WO2025117879A1 - A process for desalting, dewatering, and desolventizing an algal biomass - Google Patents
A process for desalting, dewatering, and desolventizing an algal biomass Download PDFInfo
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- WO2025117879A1 WO2025117879A1 PCT/US2024/057950 US2024057950W WO2025117879A1 WO 2025117879 A1 WO2025117879 A1 WO 2025117879A1 US 2024057950 W US2024057950 W US 2024057950W WO 2025117879 A1 WO2025117879 A1 WO 2025117879A1
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- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
- A01G33/00—Cultivation of seaweed or algae
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D11/02—Solvent extraction of solids
- B01D11/0203—Solvent extraction of solids with a supercritical fluid
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D11/00—Solvent extraction
- B01D11/02—Solvent extraction of solids
- B01D11/0215—Solid material in other stationary receptacles
- B01D11/0253—Fluidised bed of solid materials
- B01D11/0257—Fluidised bed of solid materials using mixing mechanisms, e.g. stirrers, jets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D11/02—Solvent extraction of solids
- B01D11/028—Flow sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01D11/028—Flow sheets
- B01D11/0284—Multistage extraction
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01D11/0288—Applications, solvents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/02—Solvent extraction of solids
- B01D11/0292—Treatment of the solvent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/04—Solvent extraction of solutions which are liquid
- B01D11/0403—Solvent extraction of solutions which are liquid with a supercritical fluid
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/04—Solvent extraction of solutions which are liquid
- B01D11/0426—Counter-current multistage extraction towers in a vertical or sloping position
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01D11/04—Solvent extraction of solutions which are liquid
- B01D11/0446—Juxtaposition of mixers-settlers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D11/0476—Moving receptacles, e.g. rotating receptacles
- B01D11/048—Mixing by counter-current streams provoked by centrifugal force, in rotating coils or in other rotating spaces
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- B01D39/18—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being cellulose or derivatives thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D39/2027—Metallic material
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- B01D2239/0414—Surface modifiers, e.g. comprising ion exchange groups
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- B01D2311/00—Details relating to membrane separation process operations and control
- B01D2311/04—Specific process operations in the feed stream; Feed pretreatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D2311/08—Specific process operations in the concentrate stream
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D2311/25—Recirculation, recycling or bypass, e.g. recirculation of concentrate into the feed
- B01D2311/251—Recirculation of permeate
- B01D2311/2512—Recirculation of permeate to feed side
Definitions
- Algae offers an opportunity as a crop to supply algal oil for renewable fuels derived from seawater, atmospheric CO 2 , sunlight, and nutrients. Algae can be grown on non-arable land for terrestrial crops, which is an additional benefit. Once the algal biomass has been harvested, the algal oils and the aqueous growth medium must be separated from the algal protein before either can be used for commercial purposes. [4] There is an increasing interest in using algal biomass as a key intermediate for a plethora of sustainable products, such as a source of renewable energy, as a mode to safely and efficiently capture carbon dioxide from the atmosphere for carbon sequestration, as a source of natural carotenoids and as a renewable source of chemical intermediates.
- U.S. Patent No.5,378,369 discloses a solvent-extraction of a beta carotene from algae into a vegetable oil by mixing the oil and aqueous algal suspension, allowing the beta carotene to dissolve into the oil, and separating the oil and aqueous phases by passing the oil phase through a semipermeable membrane. Using a semipermeable membrane to separate the phases can be feasible at a small scale.
- algal oil can be a source of valuable products including carotenoids, fatty acids, and other lipids
- the deoiled algal biomass produced from extraction processes can also be a source of valuable products, including protein, animal feeds, soil builder, feed for fermentation, and fuel.
- Algal biomass harvesting processes are known to involve growing the biomass in an aqueous medium containing salts, harvesting the algal biomass to produce an algal concentrate and extracting the algal concentrate in a salty environment. During the extraction process, most of the algal oils and carotenoids are removed from the algal concentrate with an extraction solvent.
- the addition of the extraction solvent causes a phase separation to occur in the algal concentrate.
- An extract layer is formed that contains the oils and carotenoids produced by the algae.
- a layer containing a lipid-depleted algal biomass is also formed.
- the layer containing the lipid-depleted algal biomass can be a rag layer that also contains water, salt, oil and residual extraction solvent.
- Attorney Docket No.0079721-000085 [8] One of the key challenges with algal biomass processing can be the presence of a high amount of salt and water in the rag layer.
- the rag layer needs to be dewatered, deoiled, dried and optionally desalted to enable further usage of the extracted algal biomass material contained therein.
- WO11053867 A1 describes a process where an algal biomass is partly dewatered before extraction.
- the extraction process involves separating a defatted biomass from an oil/solvent/water mixture, evaporating the solvent to form a water/oil mixture and then separating the oil from the water.
- this patent uses an amphiphilic solvent, which is evaporated from the oil and water mixture. The use of these solvents would not remove any residual salt from the defatted biomass.
- WO10104922 A1 describes a process where an algal biomass is pH adjusted, extracted and a biomass/water mixture is separated from a solvent phase.
- Enzymatic hydrolysis is mentioned as a treatment of defatted algal biomass, but desalting or additional dewatering/drying is not described.
- a traditional way to desalt an extracted algal biomass is to wash it with fresh water (e.g., see U.S.5,951,875).
- Several technologies can be used for that process like centrifugation, filtration, diafiltration, or membrane filtration.
- desalting is a very water intensive process.
- the extracted algal biomass is water wet and can be easily spoiled due to the lack of a salty environment that reduces microbiological growth. Additionally, drying of the extracted algal biomass is mandatory to prevent the spoilage of the algae products.
- a process for recovering algal biomass including (i.e., comprising) at least one or more of: extracting a rag layer containing an algal biomass from an algal concentrate; deoiling the rag layer to produce a deoiled algal slurry; dewatering the deoiled algal slurry to create a dewatered, deoiled algal biomass, the dewatering including contacting the deoiled algal slurry with a filtration system and washing the deoiled algal slurry with a washing media, the filtration system including at least one filtration membrane; and drying the dewatered, deoiled algal biomass.
- Also disclosed herein is a process for recovering algal biomass, the process including at least one or more of: extracting a rag layer containing an algal biomass from an algal concentrate; dewatering the rag layer to produce a dewatered algal slurry, the dewatering including contacting the rag layer with a filtration system and washing the rag layer with a washing media, the filtration system including at least one filtration membrane; deoiling the dewatered algal slurry to produce a deoiled, dewatered algal biomass; and drying the deoiled, dewatered algal biomass.
- a system for recovering algal biomass from a rag layer including at least one or more of: a dewatering zone configured to dewater an extracted rag layer and produce a dewatered algal slurry, the dewatering zone including a filtration system having at least one filtration membrane, the at least one filtration membrane including at least one hydrophilic or hydrophilic and oleophobic material; and a deoiling zone in communication with the dewatering zone, the deoiling zone being located either upstream or downstream of the dewatering zone.
- FIG.1 shows a flow diagram of an exemplary embodiment of a deoiling and dewatering process for the isolation of algal biomass in a rag layer, the process involving deoiling the rag layer to create a deoiled algal slurry and simultaneously dewatering and desalting the deoiled algal slurry.
- FIG.2 shows a flow diagram of an exemplary embodiment of a deoiling and dewatering process for the isolation of algal biomass in a rag layer, the process involving simultaneously dewatering and desalting the rag layer to create a dewatered/desalted algal slurry and deoiling the dewatered/desalted algal slurry.
- the Attorney Docket No.0079721-000085 dashed lines represent optional steps which can occur in the depicted exemplary embodiment.
- FIG.3 shows a flow diagram of an exemplary embodiment of a deoiling and dewatering process for the isolation of algal biomass in a rag layer, the process involving deoiling the rag layer to create a deoiled slurry, desalting the deoiled slurry to create a deoiled, desalted algal slurry and dewatering the deoiled, desalted algal slurry.
- the dashed lines represent optional steps which can occur in the depicted exemplary embodiment.
- FIG.4 shows a flow diagram of an exemplary embodiment of a filtration membrane system for desalting and dewatering a deoiled algal slurry.
- One aspect of the present disclosure is a process for recovering algal biomass, the process including at least one or more of: extracting a rag layer containing an algal biomass from an algal concentrate; deoiling the rag layer to produce a deoiled algal slurry; dewatering the deoiled algal slurry to create a dewatered, deoiled algal biomass, the dewatering including contacting the deoiled algal slurry with a filtration system and washing the deoiled algal slurry with a washing media, the filtration system including at least one filtration membrane; and drying the dewatered, deoiled algal biomass.
- FIG.1 shows an exemplary embodiment of the deoiling and dewatering process for the isolation of algal biomass in a rag layer.
- algae are cultured in an algal aquaculture zone (100) and are transferred to a harvesting zone (102) and a pre-harvested algal concentrate stream.
- the pre-harvested algal concentrate stream undergoes at least one harvesting process in the harvesting zone (102) to form an algal concentrate stream.
- the algal concentrate stream is then Attorney Docket No.0079721-000085 subjected to an extraction process in an extraction zone (104) that forms a rag layer containing an algal biomass.
- algal concentrate refers to a stream containing an algal biomass solution or suspension that includes natural products (e.g., algal oils, proteins, lipids, carotenoids, hydrophobic products), an aqueous solution, and a biomass.
- the algal concentrate can be derived from a feedstock source and/or a unit operation that concentrates the biomass in the algal concentrate (e.g., a harvesting zone).
- the algal concentrate is a stream originating from at least one or a combination of plant, algae, micro-organism, bacteria, or microalgae feedstock sources. Suitable algae or microalgae feedstock sources can be derived from algal aquaculture ponds.
- the algal aquaculture pond can be any type of algal aquaculture pond used to grow algae, including, but not limited to open pond, closed pond, raceway pond, enclosed or partly enclosed photobioreactor, tubular reactor, flat panel (i.e., flat-plate) reactor, column reactor, enclosed raceway, covered pond, open raceway pond, earthen pond, pond in a greenhouse, fermenter, naturally occurring body of water, solar salt pond, or any combinations thereof.
- Open algal aquaculture ponds can be configured either with or without agitation or liners.
- suitable liner materials include plastic, cement or clay.
- Plastic algal aquaculture pond liners can be formed from polyethylene, polypropylene, or polyvinyl chloride. Different types of these basic polymers can be used, for example, a linear low-density polyethylene liner can be used for algae Attorney Docket No.0079721-000085 cultivation on a large scale. These liners can also include additives, such as carbon black to provide resistance to ultraviolet radiation. These liners can also include Nylon or other fibers to provide additional structural integrity. Raven Industries (South Dakota) provides a full line of suitable liners that include one or more layers of materials. Suitable clay liners include bentonite clay.
- liners can be utilized to protect earthen borders where the hydraulic flow can be elevated.
- additional aqueous medium is periodically or continuously provided to the feedstock source to replace water that evaporates from the feedstock source and/or increase the liquid depth of the feedstock source, i.e., the depth of the algal growth medium.
- the additional aqueous medium can be combined with recycled algal growth medium to form an aqueous medium that enters a feedstock source optionally via an algal pretreatment unit to form an algal aquaculture medium.
- the algal growth medium in the feedstock source contains mineral salt
- the salinity of the additional aqueous medium fed to the feedstock source can be less than the highest salinity experienced by the algae in the feedstock source.
- the amount of the additional aqueous medium possibly added each day can depend upon several factors: salinity targets in the feedstock source, the wind speed and the relative humidity. Daily evaporation rates can be a major factor in the determination of daily water needs for the feedstock source.
- the algal concentrate includes or is an algal aquaculture medium.
- algal aquaculture medium refers to an aquaculture medium existing in an algal aquaculture pond, as well as any additional medium, such as aqueous medium, added to the algal aquaculture pond to supplement the medium already in the algal aquaculture pond.
- the algal aquaculture medium can include water and one or more of mineral salts, heavy metals, algae, algal predators, algal competitors, algal nutrients, algal biomass, natural products or residual nutrients.
- the algal aquaculture medium can also include additional aqueous medium (also sometimes referred to as make up medium) that is periodically or continuously provided to the algal aquaculture pond to supplement the algal aquaculture medium existing in the algal aquaculture pond.
- the algal concentrate contains a biomass concentration greater than about 10 ppm, 100 ppm, 0.1wt%, 1wt%, 10wt%, 20wt%, 30wt%, 40wt% or 50wt%.
- the term "about” refers to a value that is ⁇ 5% of the stated value.
- reference to a range of a first value to a second value includes the range of the stated values, e.g., a range of about 1 to Attorney Docket No.0079721-000085 about 5 also includes the more precise range of 1 to 5.
- the algal concentrate has a suitable viscosity so that it can be pumped.
- a suitable viscosity for pumping can be less than 10,000 cp, less than about 1,000 cp and/or less than 500 cp.
- the algal concentrate undergoes a harvesting process in a harvesting zone before advancing to the extraction process.
- harvesting processes can include, but are not limited to, adsorptive bubble separation, filtration, deep bed filtration, belt pressing, screw pressing, centrifugation, adsorption, sedimentation, mechanical floatation, froth flotation, flocculation and combinations thereof.
- Examples of these and other harvesting processes and equipment which can be used to condition the algal concentrate before the extraction process can be found in U.S. Pat. No.5,541,056; U. S. Pat. No.4,554,390; U.S. Pat. No.4,115,949; U.S. Pat. No.5,951,875; U.S. Pat. No.4,680,314; U.S. Pat. No. 6,524,486; U.S. Pat.
- the process includes culturing a feedstock source in an algal aquaculture pond to form a pre-harvested algal concentrate, transferring the pre-harvested algal concentrate to a harvesting zone, and Attorney Docket No.0079721-000085 performing at least one harvesting process on the pre-harvested algal concentrate to form the algal concentrate.
- the biomass e.g. in the algal concentrate can be flotation conditioned by a number of processes.
- Suitable flotation conditioning processes that can be used prior to the adsorptive bubble separation unit include, but are not limited to, adding a flotation aid, adding a frother, adding a collector, adding an activator, adding a depressor, and combinations thereof.
- Collectors selectively render one or more of the species of particles in the algal concentrate hydrophobic, thereby assisting in the process of collection by gas bubbles.
- Activators aid the adsorption of the collector to certain particles increasing the number of those particles which become hydrophobic.
- Depressors inhibit the adsorption of the collector to certain undesired particles decreasing the number of those particles which become hydrophobic.
- Sedimentation process can include the addition of alum to and/or lack agitation of the algal concentrate.
- the addition of ferric chloride can also be included in sedimentation processes to cause flocculation. Any polymer or ions that cause flocculation can also be used during sedimentation processes. Cyclones can also be used to accelerate the rate of sedimentation. Any sedimentation equipment known in the art can be used to separate the flocculated natural products from an aqueous salt solution prior to an adsorptive bubble separation process.
- Adsorption can be used as a conditioning process to reduce the volumetric flow of the algal concentrate to an adsorptive bubble separation unit.
- Some Attorney Docket No.0079721-000085 feedstock for example Dunaliella salina, can be concentrated by adsorbing the algae onto a hydrophobic surface, and then desorbing the algae with another fluid. Thus, adsorption can be used to preconcentrate the feedstock stream.
- Deep bed filtration can be used to further concentrate the algal concentrate in addition to an adsorptive bubble separation process. Deep bed filtration relies upon a bed of granular media, usually sand, through which the algal concentrate containing natural products flows downward under gravity.
- Adsorptive bubble processes can include a step of rendering material or natural products within the algal concentrate hydrophobic by treating particle surfaces with chemicals, or other techniques that selectively modify the material or natural products to be separated. In some cases, the particles or natural products are not initially hydrophobic, and need to be rendered hydrophobic to be separated or harvested from the algal concentrate.
- a flocculating agent can be utilized during adsorptive bubble separation processes to cause accumulations of algal biomass or natural products to float out during adsorptive bubble processes.
- the algal concentrate or the biomass included in the algal concentrate can also be subjected to a cell rupturing process before proceeding to the extraction process.
- the algal concentrate can include cellular material which contains natural products. In these instances, rupturing the cell wall and/or cell membrane of the Attorney Docket No.0079721-000085 cellular material can release natural products that can be purified in later processes. Cell rupturing can be achieved by a number of processes which include, but are not limited to, chemical, physical or mechanical processes.
- Chemical processes can include enzymatic digestion, detergent solubilization, lipid dissolution with a solvent, and alkali treatment (lipid saponification).
- Physical processes can include osmotic shock, decompression, sonication, heat treatment, and freeze-thawing.
- Mechanical processes can include grinding, high shear homogenization, passing the algal concentrate across a pressure drop, and pressure extrusion.
- Other cell disruption processes which can be used include pumping the algal concentrate at high pressures through a restricted orifice valve.
- An equipment which can perform this disruption process is, as an example, the MICROFLUIDIZERTM cell disruption equipment of Microfluidics, Newton, MA, US, which utilizes pressures of about 5,000 to 40,000 psig (345 - 2760 bar).
- a mill such as a vibratory mill, can also be used to rupture cellular material in the algal concentrate.
- fracking processes can be performed on the algal concentrate before the extraction process.
- the partial rupturing of algae is referred to as fracking.
- Fracked algae can be advantageous over completely ruptured algae due to the difference in size of the resulting particles.
- Particles resulting from fracking algae are larger than the particles resulting from the complete rupturing of algae and thus adsorptive bubble separation processes can be more effective when larger particles are present.
- Fracking the algae or microalgae can produce fracked cells possessing hydrophobic components while still retaining a significant portion of the intracellular material within the cellular membrane.
- algae refers to unicellular and multicellular eukaryotic algae, microalgae, diatoms, dinoflagellates, coccolithophores, cyanobacteria and combinations thereof.
- the algae or microalgae which can be present in the algal concentrate can include, but is not limited to, algae from the divisions of Bacillariophyta, Chlorophycophyta, Chrysophycophyta, Cyanophycophyta, Cryptophycophyta, Phaeophycophyta, Pyrrhophycophyta, Rhodophycophyta and combinations thereof.
- the algae or microalgae present in the algal concentrate can include, but is not limited to, species from the following genera: Acutodesmus, Achnahtes, Amphipora, Amphora, Anabaena, Ankistrodesmus, Arthrospira (also known as Spirulina), Asteromonas, Asterionella, Boekelovia, Borodinella, Botryococcus, Bracteacoccus, Carteria, Chaetoceros, Chlamydomonas, Chlorella, Chlorococcum, Chlorogonium, Chloromonas, Chroomonas, Chrysophaera, Ceratium, Closterium, Coccolithus, Coelastrella, Coscinodiscus, Cosmarium, Cricosphaera, Crocosphaera, Crypthecodinium, Cryptomonas, Cyanocystis, Cyanospira, Cyclotella, Desmodesmus, Ditylum, Dunaliella
- the algae or microalgae is selected from the group including Dunaliella sp., Dunaliella bardawil, Dunaliella salina, Dunaliella kone, Dunaliella tertiolecta, Dunaliella parva and Dunaliella viridis, and any combination thereof.
- the algae or microalgae is Dunaliella salina, Dunaliella bardawil, Dunaliella kone, or any combination thereof.
- the algae or microalgae which can be present in the algal concentrate can also include any microalgal species (including diatoms, coccolithophorids and dinoflagellates) selected from, but not limited to, Amphora sp., Ankistrodesmus sp., Arthrospira (Spirulina) plantesis, Botryococcus braunii, Chlamydomonas sp., Chlamydomonas reinhardtii, Chlorella protothecoides, Chlorella sp., Closterium sp., Cosmarium sp., Crypthecoddinium cohnii, Cyclotella sp., Dunaliella salina, Dunaliella tertiolecta, Haematococcus pluvialis, Hantzschia sp., Nannochloris sp., Nannochloropsis sp., Navicula sp., Neochloris
- the algae or microalgae which can be present in the algal concentrate can also include algae with flagella, cilia and/or eyespots.
- Flagella are a tail-like projection that protrudes from the cell body of certain algae and functions in locomotion.
- Cilia are an adaptation that allows independent cellular creatures, like algae, to move around in search of food.
- Photosensitive eyespots are found in some free-swimming unicellular algae. Photosensitive eyespots are sensitive to light. They enable the algae to move in relation to a light source. Such algae have the capability of independent motion, phototaxis, and can move towards the surface during daylight. Phototaxis is the movement of microalgae in response to light.
- Certain algae can perceive light by means of a sensitive eyespot and move to regions of higher light concentration to enhance photosynthesis.
- the algae or microalgae which can be present in the algal concentrate also include marine algae that thrive at salt concentrations above that found in seawater. Suitable marine algae can be selected from, but are not limited to, Amphora sp.
- the algae is microalgae.
- the algae or microalgae have not been genetically modified or do not originate from genetically engineered algae or microalgae.
- the algae or microalgae which can be present in the algal concentrate include a group of algae or microalgae that has not been genetically modified or does not originate from genetically engineered algae or microalgae.
- This group of algae or microalgae can include, but is not limited to, Dunaliella sp., Dunaliella bardawil, Dunaliella kone, Dunaliella salina, Dunaliella bioculata, Dunaliella granulata, Dunaliella maritima, Dunaliella minuta, Dunaliella parva, Dunaliella peircei, Dunaliella polymorpha, Dunaliella primolecta, Dunaliella pseudosalina, Dunaliella quartolecta, Dunaliella terricola, Dunaliella tertiolecta, and Dunaliella viridis.
- the extracting of the rag layer from the algal concentrate can also include extracting other natural products from the algal concentrate.
- natural products refers to products which are naturally produced or found within an environment or a living organism. Natural products can include those which are hydrophobic, hydrophilic or amphipathic.
- the natural products are those which are naturally produced by a plant, a microbe, an algae or microalgae species which can be included within the algal concentrate or biomass.
- the algal concentrate contains an aqueous salt solution.
- aqueous salt solution refers to a solution containing water and at least one salt. The salt can be any one or combination of salts found in sea water, terminal lakes, or aquifers.
- salinity refers to the total amount of dissolved salts in the aqueous solution. Salts which can be dissolved and found in the aqueous solution include, but are not limited to, those found in natural waters such as sodium chloride, magnesium chloride, calcium and magnesium sulfates, bicarbonates, and carbonates. It is a standard practice to express salinity as parts per thousand (%0), which is not a true percent but an approximation of the milligrams of salt per gram of water. In more general terms, salinity is indicated by the water source, such as a freshwater, a brackish water, a saline water, and a brine.
- Ranges of salinity are Attorney Docket No.0079721-000085 associated with these general terms and these ranges are defined as ⁇ 0.05 wt% for freshwater, 0.05 - 3 wt% for brackish water, 3 - 5 wt% for saline water, and > 5 wt% for a brine.
- Various combinations of ions found in seawater can be included in the aqueous salt solution.
- Suitable ion combinations can be derived from one or more of the following sources including: water derived from streams, lakes, rivers, or other sources associated with fresh water; water derived from underground aquifers that can include various ion concentrations; water derived from industrial, agricultural, or municipal sources that can or cannot have received treatment; or water derived from brackish sources where fresh water is combined with sea water or ocean water in various proportions; sea water or ocean water that can be derived from the various seas and oceans located around the globe; water derived from terminal lakes; or combinations thereof.
- the combination of ions for the aqueous salt solution can be derived directly from these sources, or can be derived by evaporating the desired amount of water from any of these sources to leave the desired ion-rich solution for use as the aqueous salt solution.
- An example of an ion combination source is disclosed in U.S. Pat. No.6,986,323, the contents of which are included herein by reference.
- Other examples include the evaporation of ancient sea waters that form terminal lakes, such as the Great Salt Lake in Utah, and that form various aquifers.
- the combination of ions can result up to and include crystallizers wherein sodium chloride ions are precipitated.
- the aqueous salt solution and/or the algal concentrate can have a salinity that is about 5 wt% or greater than 5 wt%, about 6 wt% or greater than 6 wt%, about 7 wt% or greater than 7 wt%, for example at least about 8 wt%, at least about 9 wt%, at least about 10 wt%, at least about 11 wt%, at least about 12 wt%, at least Attorney Docket No.0079721-000085 about 13 wt%, at least about 14 wt%, at least about 15 wt%, at least about 16 wt%, at least about 17 wt%, at least about 18 wt%, at least about 19 wt%, at least about 20 wt%, at least about 21 wt%, at least about 22 wt%, at least about 23 wt%, at least about 24 wt%, or at least about 25 wt%.
- the aqueous salt solution and/or the algal concentrate is saturated with salt.
- the aqueous salt solution and/or the algal concentrate can have a salinity that is about 5 wt% to about saturation, from about 10 wt% to saturation, from about 20 wt% to saturation, from about 5 wt% to about 20 wt%, from about 10 wt% to about 20 wt%, from about 5 wt% to about 15 wt%, from about 10 wt% to about 15 wt%, or from about 5 wt% to about 10 wt%.
- the aqueous salt solution and/or the algal concentrate has a salinity greater than 5 wt%, greater than 10 wt%, greater than 15 wt% or greater than 20 wt%.
- wt% refers to a dry mass of a component in a solution in grams divided by 100 grams of the solution.
- At least one salt can either be present in the aqueous salt solution or added to the algal concentrate to increase its salinity.
- the presence of salt, and specifically elevated salt compositions provides several advantages. First, the presence of salt in the algal concentrate can reduce solvent solubility in a raffinate layer, and thus reduce either potential solvent loss or solvent recovery costs.
- the at least one salt can be selected from, but not limited to, a sea salt, an underground salt, a salt of aquifer water, a salt of a terminal lake, sodium chloride, and/or any combination thereof.
- the biomass in any one or more of the aqueous salt solution or algal concentrate can include or be a plant biomass, a microbial biomass, an algal biomass or any combination thereof.
- All of the possible plants and/or microbes which can be included in the algal concentrate can also be included within the biomass in the aqueous salt solution.
- All of the possible plant or microbial biomass which can be included in the algal concentrate include any plant or microbial biomass.
- the biomass can also include or contain some or all of the natural products within the algal concentrate.
- the biomass content in the algal concentrate can be as low as about 0.05 wt%, greater than about 0.5 wt% and even greater than 1 wt%.
- the maximum biomass content in the algal concentrate is limited as the maximum amount of biomass that allows the algal concentrate to flow, and this is less than about 20 wt%, or less than about 10 wt%.
- the algal concentrate can contain a water content before the extraction process.
- the water content can be about 0.1 wt% to about 5 wt%, about 5 wt% to about 10 wt%, about 10 wt% to about 15 wt%, about 15 wt% to about 20 wt%, about 20 wt% to about 30 wt%, about 30 wt% to about 40 wt%, about 40 wt% to about 50 wt%, or about any range within 0.1 wt% to 50 wt% of the total weight of the algal concentrate.
- the algal concentrate can contain a water Attorney Docket No.0079721-000085 content before the extraction process that is greater than 50 wt% or about any range within 50 wt% to 99 wt%.
- the biomass can include or be a conditioned biomass.
- a conditioned biomass refers to a biomass that has been treated with one or more conditioning processes before the extraction process. Suitable conditioning processes can include, but are not limited to, fracking, adsorptive bubble separation, filtration, deep bed filtration, belt pressing, screw pressing, centrifugation, adsorption, sedimentation, mechanical floatation, froth flotation, flocculation and combinations thereof.
- the extracting of the rag layer from the algal concentrate includes performing an extraction process that produces at least two layers, one layer being the rag layer.
- the other layer can be an organic extract layer containing an organic solvent or a raffinate layer containing an aqueous solution and optionally salts.
- the extracting of the rag layer from the algal concentrate includes performing a liquid-liquid-solid extraction process on the algal concentrate, the liquid-liquid-solid extraction process including at least one or more of the following: forming a dispersion by contacting (e.g., by intimately contacting) the algal concentrate with an extraction solvent in an extraction zone; passing the dispersion to a separation zone; separating the dispersion into multiple layers, the layers including: a solvent extract layer containing at least one hydrophobic natural product and an extraction solvent, a raffinate layer containing an aqueous salt solution, and a rag layer containing a lipid-depleted biomass; and isolating at least part of the solvent extract layer, at least part of the raffinate layer and/or at least part of the rag layer.
- liquid-liquid-solid extraction refers to a process wherein an algal concentrate containing an algal biomass that includes one or more natural products is (e.g., intimately) contacted with an extraction solvent capable of extracting one or more of the hydrophobic natural products from the algal biomass.
- the term “dispersion” relates to a heterogeneous mixture containing an aqueous salt solution, algal biomass, and extraction solvent. The dispersion can exist as an emulsion.
- the extraction solvent must form a second liquid phase or layer with the algal concentrate in the extraction zone.
- Suitable extraction solvents include, but are not limited to a non-polar solvent, a non-polar organic solvent, a dense gas solvent, an aqueous two-phase solvent, a deep eutectic solvent (DES) and/or a natural deep eutectic solvent (NADES) (such as choline chloride, glucose, lactic acid, malic acid, and/or any combination thereof), an ionic liquid, or any combination thereof or any combination of solvents such as miscible solvents.
- DES deep eutectic solvent
- NADES natural deep eutectic solvent
- the extraction solvent is or includes at least one or more of a non-polar solvent, a non-polar organic solvent, a dense gas solvent, an aqueous two-phase solvent, a deep eutectic solvent (DES), a natural deep eutectic solvent (NADES), an ionic liquid, or any combination thereof.
- the extraction solvent is or includes at least one or more of a non-polar solvent, a non-polar organic solvent, a dense gas solvent, an aqueous two-phase solvent, a deep eutectic solvent (DES), a natural deep eutectic solvent (NADES), or any combination thereof.
- the extraction solvent is or includes at least one or more of a non-polar solvent, a non-polar organic solvent, a dense gas solvent, an aqueous two-phase solvent, or any combination thereof.
- Attorney Docket No.0079721-000085 [84]
- the extraction solvent is or includes at least one or more of a non-polar solvent, a non-polar organic solvent, a dense gas solvent, or any combination thereof.
- the extraction solvent can be chosen such that its polarity is appropriate to extract the desired natural products.
- the optimal extraction solvent for the liquid-liquid-solid extraction process can depend on which natural products are desired to be extracted.
- Any solvent system that forms a second immiscible liquid phase or layer with the algal concentrate can be used as the extraction solvent.
- These solvent systems should not adversely impact the quality or quantity of the natural products.
- These solvent systems can include, but are not limited to, synthetic and/or natural flavorants, edible oils, petrochemicals, dense gases, and combinations of these so long as the mixture of the solvent system and the algal concentrate forms two immiscible liquid phases at a desired extraction zone temperature. Some of these solvents are more desirable than others for various reasons as discussed below and the results obtained are not necessarily equivalent.
- the solvent system can include petrochemical solvents due to their low viscosity and favorable solute molecular diffusivity.
- Natural oils are soluble in petrochemical solvents and concentrated extracts are possible.
- Suitable petrochemical solvents can include those that are disclosed in "Organic Solvents: Physical Properties and Methods of Purification", edited by J. A. Riddick et al, Volume 2, Fourth Edition, ISBN Number 0-471- 08467-0, such as 2-methyl oxolane.
- the petrochemical solvents can include, but are not limited to, aliphatic hydrocarbons (such as pentane, hexane, heptane, octane, nonane, decane, dodecane, cyclohexane, petroleum ether, their isomers, and Attorney Docket No.0079721-000085 mixtures thereof), aromatic hydrocarbons (including but not limited to benzene, toluene, xylene), alcohols (including, but not limited to butanol, pentanol, hexanol, octanol, dodecanol, cyclohexanol, benzyl alcohol, their isomers, and combinations thereof), ketones (including, but not limited to methyl isobutyl ketone, hexanone, heptanone, octanone, their isomers, and combinations thereof), esters (including, but not limited to methyl acetate
- the petrochemical solvents can also contain one or more co-solvents to improve extractability of solutes.
- co-solvents include methanol, ethanol, 1-propanol, 2-propanol, 1-hexanol, 2-methoxy ethanol, acetone, tetrahydrofuran, 1,4-dioxane, acetonitrile, dichloromethane, chloroform, dimethyl sulfoxide, formic acid, carbon disulfide, methylene chloride, amines, chelating agents, phase transfer catalysts and combinations thereof.
- the co-solvents can also be added to the algal concentrate to enhance recovery of a solute or hydrophobic natural product in the extraction solvent.
- the edible oils which can be included within the solvent system can be chosen from those obtained from plant or animal sources, such as fish oils.
- Edible vegetable oil solvents include, but are not limited to, those derived from corn, olive, algae, soybean, flax, safflower, sunflower, palm, jatropha, coconut, other oils known in the art, and combinations thereof. Compared to petrochemical solvents, edible oils can be more viscous, and the solute molecular diffusivity is lower.
- the solvent system can also include synthetic and natural flavorants.
- flavorants can be more desirable than petrochemical solvents and edible oils if the natural products are to be used for human or animal consumption.
- Naturally derived flavorants have appeal in nutritional supplements. Flavorants classified by the Flavor and Extract Manufacturers Association, or FEMA, as Generally Recognized As Safe, or GRAS, do not have the drawbacks of petrochemical solvents in association with nutritional supplements. The presence of residual flavorant solvents in nutritional supplements is generally acceptable in comparison with petrochemical solvents, which reduces downstream purification and recovery costs.
- the flavorants can be chosen from those which have boiling points, viscosities, and molecular diffusivity properties comparable to petrochemical solvents.
- flavorants include, but are not limited to, methyl-, ethyl-, propyl-, butyl-, isobutyl-, benzyl-, and octyl- esters with the carboxylic acid component of the ester including acetate, ethanoate, propionate, butyrate, hexanoate, caproate, heptanoate, octanoate, decanoate, cinnamate, and isovalerate.
- Other examples of flavorants which can be used include, but are not limited to, benzaldehyde, other aldehydes, limonene, and other terpenes. Combinations of flavorants can also be used.
- Suitable dense gases which can be used as the extraction solvent include, but are not limited to, carbon dioxide, ethane, propane, butane, chlorofluorocarbons, and mixtures thereof.
- the dense gas extraction can be operated in any manner known in the art including leaching, batch extraction, and continuous countercurrent extraction as described in U.S. Pat. No.6,106,720 and U.S. Pat. No.5,932,101, the contents of which are incorporated herein by reference in their entirety.
- Additional suitable dense gases can be methane, isobutane, dimethyl ether, sulfur hexafluoride, Attorney Docket No.0079721-000085 ammonia, fluorocarbons, and mixtures thereof. Any combination of the above dense gases can also be used.
- the dense gases can also contain one or more co-solvents to improve extractability of solutes.
- co-solvents include methanol, ethanol, 1- propanol, 2-propanol, 1-hexanol, 2-methoxy ethanol, acetone, tetrahydrofuran, 1,4- dioxane, acetonitrile, dichloromethane, chloroform, dimethyl sulfoxide, formic acid, carbon disulfide, methylene chloride, amines, chelating agents, phase transfer catalysts and combinations thereof.
- Other examples of dense gases and co-solvents are listed in U.S. Pat.
- the co-solvents can also be added to the algal concentrate to enhance recovery of a solute or hydrophobic natural product in the extraction solvent.
- the solvent system can also include an ionic liquid. Suitable ionic liquids include, but are not limited to, solvent systems that are in the liquid phase at the extraction temperature, those that include a cation and an anion, and those that are immiscible with a water-rich algal concentrate phase.
- the extraction solvent is selected such that the selectivity of the extraction solvent for specific non-polar compounds versus specific salts is greater than unity (i.e., greater than 1).
- the selectivity is calculated by dividing the distribution coefficient for a specific non-polar compound of interest to the distribution coefficient for a specific salt of interest.
- the distribution coefficients are defined as the concentration of the nonpolar compound in the extract phase divided by the concentration of the nonpolar compound in the raffinate phase.
- forming the dispersion by contacting the algal concentrate with the extraction solvent involves using an algal concentrate or algal Attorney Docket No.0079721-000085 biomass to extraction solvent ratio (e.g., a volumetric ratio) of from about 8 to about 0.1, from about 5 to about 0.2, or 1 (e.g., a 1 to 1 volumetric ratio).
- the algal concentrate can contact the extraction solvent for about 1 minute to 5 hours, or for about 2 minutes to 5 hours, and the contact time can differ based on the type of contactor used in the extraction zone.
- the contact time can range from about 0.5 to 10 minutes, or less than 2 minutes.
- the contact time can range from about 1 minute to 5 hours, or between 2 and 120 minutes. Preferably, the contact time will be 5 to 60 minutes.
- the algal concentrate can contact the extraction solvent for about 2 to 180 minutes, about 5 to 180 minutes or about 10 to 60 minutes in a counter-current extraction column.
- the extraction zone can include a mixer, a static mixer, a settler, a co- current extraction column, a countercurrent extraction column, a centrifugal extractor, an emulsion phase contactor, or any combination thereof known in the art.
- Suitable mixers for the extraction zone include agitated vessels where a mechanical agitator is used to intimately contact the algal concentrate and the extraction solvent.
- the mechanical agitator can include one or more impellers on a rotating shaft.
- Suitable impellers include, but are not limited to Rushton Turbines, flat-blade turbines, pitch-blade turbines, marine propellers, hydrofoils, impellers that are sold by Chemineer (Dayton Ohio), or SPX/ Lightnin (Rochester, New York). Regardless of the type of impeller used, the degree of agitation required is important for efficient mass transfer of the solute. The degree of agitation required can be calculated by the minimum impeller speed to completely disperse one immiscible Attorney Docket No.0079721-000085 liquid in another, as defined by Skelland and Ramsay [1987 I&EC Res.26, 1, 77– 81], Skelland and Moeti [1989, I&EC Res.
- Static mixers of any design can also be used as the extraction zone. Suitable static mixers include, but are not limited to, those produced by Chemineer in their Kenics line. [99]
- the extraction zone can be followed by a separation zone, and mass transfer can continue to occur while the dispersion is separating in the separation zone. In an exemplary embodiment, there is a balance between the amount of shear energy added in the extraction zone to generate an acceptable drop size distribution in the liquid-liquid dispersion in order to achieve acceptable mass transfer kinetics in the extraction zone, and reasonable decantation kinetics in the separation zone.
- Suitable extraction columns which can be used as the extraction zone include, but are not limited to, those that are mechanically agitated and those that have stationary internals. The latter is preferred when the extraction solvent is a dense gas and/or the operating pressure of the extractor is elevated so that more expensive mechanical seals are needed.
- Suitable extraction columns with stationary internals can include, but are not limited to, packed, perforated plate, baffle tray, and combinations thereof.
- Suitable packings include structured or random packings that are known to those skilled in the art.
- Suitable mechanically agitated extraction columns can include, but are not limited to, the Karr reciprocating plate column, the York Scheibel column, and the rotating disc column, all made by Koch Modular Process Technology Corporation, which is located in Paramus, N.J., the Kuhni Attorney Docket No.0079721-000085 column, which is sold by Sulzer in Switzerland, the asymmetric rotating disc column, pulsed columns, and combinations thereof.
- the separation zone can include or be a decanter which is configured to perform at least one or more of gravity settling, centrifugal settling, and/or combinations thereof to separate the dispersion into the multiple layers.
- the separation zone can include one or more fixed or moving separation aids like mesh pad coalescers, wire pad coalescers, structured packing, inclined plates, perforated plates, baffles, ultrasonic waves, acoustic waves, and/or combinations thereof.
- the extraction zone includes a mixer and/or a countercurrent extraction column, and/or the separation zone includes a decanter.
- the extraction zone and separation zone are combined in a countercurrent extraction column.
- the raffinate layer can exit the column at one end while the solvent extract layer can exit the column at the opposite end.
- the rag layer can be removed from the countercurrent extraction column with either the raffinate layer or the solvent extract layer, or alternatively removed from the extraction column as a sidedraw. Any of the types of extraction columns described above can be used for countercurrent extraction.
- the algal concentrate can contact the extraction solvent for about 5 to 180 minutes, about 5 to 180 minutes or about 10 to 60 minutes in a counter-current extraction column.
- Suitable centrifugal extractors that can be used to provide both the extraction zone and the separation zone include, but are not limited to those produced by CINC, Alfa Lavel, Podbielniak, Robatel, Westfalia, and combinations of these centrifugal extractors.
- Suitable emulsion phase contactors that can be used to provide both the extraction zone and the separation zone include, but are not limited to, those produced by Schlumberger termed the NATCO dual frequency electrostatic treater.
- the separation of the dispersion into multiple layers can be carried out or performed under a gravitational field or by decanting.
- Separating the dispersion into multiple layers can occur in as little as 10 minutes to about 24 hours, at least 20 minutes to 12 hours, at least 30 minutes to 6 hours, or 40 minutes to 3 hours.
- Separating the dispersion into multiple layers can occur or can be performed at a pressure ranging from atmospheric to supercritical conditions for the extraction solvent.
- Separating the dispersion into multiple layers can occur or can be performed at e.g., a temperature of less than 100°C, such as about 20°C to about 90°C, about 30°C to about 90°C, about 40°C to about 90°C, about 50°C to about 90°C, about 60°C to about 90°C, about 35°C to about 80°C, about 35°C to about 70°C or about 40°C to about 70°C.
- the solvent extract layer can include at least one hydrophobic natural product present within the dispersion.
- hydrophobic natural products can include one or more selected from the group including lipids, algal lipids, carotenoids, fatty acids, algal fatty acids, triacylglycerols, diacylglycerols, monoacylglycerols, oils, algal oils and combinations thereof.
- the carotenoids can include beta-carotene, alpha-carotene, lutein, zeaxanthin, beta-cryptoxanthin, astaxanthin, phytoene, phytofluene, lycopene, and/or combinations thereof.
- the solvent extract layer can include extraction solvent, algal oil, carotenoids, trace amounts of water and salt.
- the solvent extract layer can contain extraction solvent in amounts of more than 50 wt%, such as above 60 wt% or above 70 wt% of its total weight; algal oil in amounts than less 30 wt%, such as less than 20 wt% or less than 10 wt% of its total weight; carotenoids in amounts less than 5 wt%, such as less than 3 wt% or less than 1 wt% of its total weight; water in amounts less than 10 wt%, such as less than 5 wt% or less than 2 wt% of its total weight; and/or salt in amounts less than 3 wt%, such as less than 2 wt% or less than 1 wt% of its total weight.
- extraction solvent in amounts of more than 50 wt%, such as above 60 wt% or above 70 wt% of its total weight
- algal oil in amounts than less 30 wt%, such as less than 20 wt% or less than 10 wt% of its total weight
- the solvent extract layer can include limited amounts of lipid-depleted biomass and an aqueous salt solution.
- the raffinate layer can include an aqueous salt solution depleted of hydrophobic natural products.
- the raffinate layer can possess a salt concentration of above 5 wt%, above 7 wt%, above 10 wt% above 15 wt%, above 18 wt% up to saturation.
- the raffinate layer has a salinity of about 5 wt% or greater, about 10 wt% or greater, about 15 wt% or greater, or about 20 wt% or greater.
- a salinity of the raffinate layer is about 5 wt% or greater than 5 wt%, about 6 wt% or greater than 6 wt%, about 7 wt% or greater than 7 wt%, for example at least about 8 wt%, at least about 9 wt%, at least about 10 wt%, at least about 11 wt%, at least about 12 wt%, at least about 13 wt%, at least about 14 wt%, at least about 15 wt%, at least about 16 wt%, at least about 17 wt%, at least about 18 wt%, at least about 19 wt%, at least about 20 wt%, at least about 21 wt%, at least about 22 wt%, at least about 23 wt%, at least about 24 wt%, or at least about 25 wt%.
- the raffinate layer is saturated with salt.
- the raffinate layer can have a salinity that Attorney Docket No.0079721-000085 is about 5 wt% to about saturation, from about 10 wt% to saturation, from about 20 wt% to saturation, from about 5 wt% to about 20 wt%, from about 10 wt% to about 20 wt%, from about 5 wt% to about 15 wt%, from about 10 wt% to about 15 wt%, or from about 5 wt% to about 10 wt%.
- the raffinate layer can contain algal growth medium that is depleted in algal biomass and/or algal oils.
- the raffinate layer can include water, salts, trace amounts of extraction solvent, trace amounts of algal biomass (such as less than 5 wt% or less than 1 wt% of its total weight) and/or trace amounts of algal oil (such as less than 5 wt% or less than 1 wt% of its total weight).
- the raffinate layer can contain water above 50 wt% (such as from 60 wt% to 90 wt%, 70 wt% to 85 wt% or 80 wt% to 90 wt%) or at about 50 wt% of its total weight, and/or the raffinate layer can contain salt from about 0.1 wt% to about 50 wt%, about 5 wt% to about 40 wt%, about 10 wt% to 30 wt%, and/or about 15 wt% to 26 wt% of its total weight.
- the raffinate layer can also contain trace amounts of the extraction solvent in both soluble and/or insoluble forms.
- the solubility of the extraction solvent in the raffinate layer influences the amount, or concentration, of the extraction solvent in the raffinate layer.
- the soluble amount of extraction solvent can be experimentally determined by measuring the solubility of the extraction solvent in the raffinate layer as a function of temperature, pressure, pH, salinity, and/or other factors known to those skilled in the art.
- the insoluble amount of the extraction solvent in the raffinate layer can be determined by the amount of entrainment of both extraction solvent droplets and the amount of extraction solvent that is associated with entrained algal biomass in the raffinate layer. Trace amounts of algal oil in the raffinate layer can be present in the solvent of the raffinate layer and/or in the algal biomass as unextracted oil.
- the rag layer can form at any location in a separation zone.
- the rag layer can form between, above or below solvent extract and raffinate layers.
- the rag layer can include a lipid-depleted biomass.
- the lipid-depleted biomass can include at least one or more of, chlorophyll, glycerol, phospholipids, proteins, carbohydrates, fibers, and limited amounts of lipids, carotenoids and/or raffinate relative to the dispersion or any combination thereof.
- the rag layer contains at most about 45 wt% of a solvent extract layer, about 45 wt% of a raffinate layer and about 10 wt% lipid-depleted biomass.
- the rag layer contains at most about 60 wt% of a solvent extract layer (such as from 30 wt% to 60 wt%, e.g., 40 wt% to 50 wt% or about 45 wt%), at most about 60 wt% of a raffinate layer (such as from 30 wt% to 60 wt%, e.g., 40 wt% to 50 wt% or about 45 wt%) and/or about from 2 wt% to 20 wt% lipid-depleted biomass (e.g., from 5 wt% to 10 wt%).
- the rag layer can contain a majority of the algal biomass. Reducing the volume of the rag layer can be desirable to minimize the cost of further processing the rag layer to recover any entrained algal biomass.
- the rag layer can include water, salt, extraction solvent, algae oil, and/or algal biomass.
- the rag layer is a mixture of three layers: 1) a layer containing algal biomass that has been depleted of non-polar compounds, 2) at least a portion of a solvent extract layer optionally containing at least one natural product, and 3) at least a portion of a raffinate layer. The ratio of these three layers can vary depending on the conditions used to separate the dispersion into multiple layers.
- the layer containing the algal biomass that has been depleted of non-polar compounds can vary from about 0.01 wt% of the total weight of the rag layer to about 20 wt%.
- the solvent extract layer and the raffinate layer can vary Attorney Docket No.0079721-000085 from about 1 wt% to about 99 wt% of the total weight of the rag layer.
- the layer containing algal biomass that has been depleted of non- polar compounds is between about 1 and 10 wt% of the total weight of the rag layer, and the solvent extract layer and the raffinate layer range from about 10 wt% to 90 wt% of the total weight of the rag layer.
- the rag layer includes an algal biomass having a particle distribution size from about 0.1 microns to about 1000 microns, about 0.2 microns to about 100 microns, from about 0.4 microns to about 25 microns, from about 0.4 microns to about 20 microns or at least 20 microns.
- the rag layer can have an intermediate density between the solvent extract layer and the raffinate layer, so in decantation and/or centrifugation processes, it is located between the solvent extract layer and the raffinate layer.
- the rag layer does not exist as a true thermodynamic phase and exists as a mixture of solid algal biomass, raffinate layer and solvent extract layer.
- the raffinate layer and the solvent extract layer can exist as true thermodynamic phases.
- the rag layer has a salinity greater than 5 wt%, greater than 10 wt%, greater than 15 wt% or greater than 20 wt%.
- the liquid-liquid-solid extraction process includes performing a heat exchange before the algal concentrate enters the extraction zone, before the extraction solvent enters the extraction zone, and/or before the dispersion enters the separation zone.
- the liquid-liquid-solid extraction process includes isolating at least part of the solvent extract layer, at least part of the raffinate layer and/or at least part of the rag layer.
- the solvent extract layer can be e.g., Attorney Docket No.0079721-000085 overflowed or pumped out of the separation zone, the rag layer can be pumped out of the separation zone and/or the raffinate layer can be removed e.g., from the bottom of the separation zone.
- the liquid-liquid-solid extraction process includes contacting the isolated solvent extract layer with an aqueous phase to remove any residual salt concentrations that can be present within the solvent extract layer.
- the liquid-liquid-solid extraction process includes using a coalescer after formation of the dispersion.
- the liquid-liquid-solid extraction process includes filtering the solvent extract layer after isolation to remove any entrained biomass and/or filtering the raffinate layer after isolation to remove any entrained biomass. [129] In exemplary embodiments, the liquid-liquid-solid extraction process includes evaporating the extraction solvent from the solvent extract layer after isolation of the solvent extract layer.
- the liquid-liquid-solid extraction process is performed at a temperature of about 100°C (e.g., 100 ⁇ 1-10°C) or less, about 95°C (e.g., 95 ⁇ 1-10°C) or less, about 90°C (e.g., 90 ⁇ 1-10°C) or less, about 85°C or less, about 80°C or less, about 75°C or less, about 70°C or less, about 65°C or less, about 60°C or less, or e.g., within a temperature range from 5 to 90°C, from 25 to 90°C, from 30 to 90°C, from 40 to 90°C, from 50 to 90°C, from 55 to 90°C, from 60 to 90°C, from 40 to 80°C, from 50 to 80°C, or from 60 to 80°C.
- a temperature range from 5 to 90°C, from 25 to 90°C, from 30 to 90°C, from 40 to 90°C, from 50 to 90°C, from 55 to 90°C, from 60 to
- forming the dispersion by contacting the algal concentrate with the extraction solvent in the extraction zone and separating the dispersion into multiple layers in the separation zone can be performed at the same or different temperatures.
- the separating of the dispersion into multiple layers occurs or is performed at a temperature of about 100°C or less, about 95°C or less, about 90°C or less, about 85°C or less, about 80°C or less, about 75°C or less, about 70°C or less, about 65°C or less, about 60°C or less, or within a temperature range from 35 to 90°C, from 40 to 90°C, from 45 to 90°C, from 50 to 90°C, from 55 to 90°C, from 60 to 90°C, from 30 to 80°C, from 35 to 80°C, from 40 to 80°C, from 45 to 80°C, from 50 to 80°C, from 55 to 80°C, or from 60 to 80°C, from 30 to 70°C, from 35 to 70°C, from 40 to 70°C, from 45 to 70°C, from 50 to 70°C, from 55 to 70°C, or from 60 to 70°C.
- the separating of the dispersion into multiple layers occurs or is performed at a temperature of about 100°C, less than about 100°C, of about 10°C to 90°C, 10°C to 80°C, 20°C to 90°C, 20°C to 80°C, 30°C to 90°C, 30°C to 80°C, 40°C to 90°C, 40°C to 80°C, 50°C to 90°C, 50°C to 80°C, 60°C to 90°C, 60°C to 80°C, 35°C to 80°C, 35°C to 70°C or 40°C to 70°C.
- the separating of the dispersion into multiple layers occurs or is performed at a temperature of about 40°C to 90°C, 50°C to 90°C, 60°C to 90°C, 35°C to 80°C, 35°C to 70°C or 40°C to 70°C.
- the liquid-liquid-solid extraction process can be performed without addition of salt during the forming of the dispersion and during the separating of the dispersion into the multiple layers.
- the extraction process includes performing the forming, passing, Attorney Docket No.0079721-000085 separating and isolating steps without an addition of salt.
- the biomass or algal concentrate containing the biomass in an aqueous salt solution does not include added salt.
- the liquid-liquid-solid extraction process is a continuous process.
- the liquid-liquid-solid extraction process can be configured as a continuous process wherein the forming, passing, separating and isolating steps are performed sequentially. Continuous operation can allow for the production of biofuels and/or other hydrophobic natural products with reduced capital and operating costs.
- the algal concentrate and the extraction solvent are intimately contacted so that the solvent receives the hydrophobic natural products.
- the hydrophobic natural products are either pressed from the biomass or extracted with additional algal (or vegetable) oil.
- the resulting raffinate phase and the extract phases are separated so that the hydrophobic natural products can be further processed into desirable products.
- a variety of extraction equipment components can be used for continuous extraction including, but not limited to, mixers and settlers, countercurrent extraction columns, centrifugal extractors, and other classes of extractors known in the art as described by Pratt et al., Selection, Design, PilotTesting, and Scale-Up of Extraction Equipment, Chapter 8, in Science and Practice of LiquidLiquid Extraction, Volume 1, Clarendon Press, Oxford, 1992, the contents of which are incorporated herein by reference.
- the algal concentrate and the extraction solvent can be contacted in a countercurrent or co-current flow.
- Suitable centrifugal extractors can include, but are not limited to, those manufactured by GEA Westfalia Separator GmbH, which is headquartered in Oelde, Germany; Alfa Laval, with a location in Richmond, Virginia; Robatel, which is located Attorney Docket No.0079721-000085 in Pittsfield, Massachusetts; and Podbelniak, which is manufactured by Baker Perkins of Saginaw, Michigan.
- Suitable other extraction equipment includes, but is not limited to hollow fiber membrane extractors and other novel extractor designs known in the art. In some cases, hollow fiber membrane extractors are used since they obviate the need to separate the solvent from the algal biomass.
- Gravity settling is useful in a continuous extraction process.
- a coalescer can be added to assist in the decantation.
- the raffinate layer can be coalesced to recover any additional extraction solvent that is entrained before being recycled to a bioreactor or returned to a pond, depending on the type of aquaculture practiced.
- a coalescer, liquid/liquid/solid centrifuge, flotation cell, and/or liquid/liquid cyclone can be used to recover solvent from the aqueous salt solution, or the aqueous salt solution can be recycled to a flotation device for cleanup.
- Suitable materials for the construction of the mixer, decanter, and/or extraction equipment include, but are not limited to, steel, concrete, non-ferrous material, plastics, fiberglass, fiberglass reinforced plastic such as fiberglass reinforced HDPE, and combinations thereof.
- Non-ferrous materials are advantageous due to the salt content of the algal concentrate and the raffinate layer in the extraction process.
- the salinity of these components could cause stress corrosion cracking in ferrous materials, greatly increasing the maintenance required on the mixer, decanter, and extraction equipment.
- Plastic and fiberglass equipment is resistant to the effects of the elevated salinity and can be less expensive than equipment constructed of ferrous material.
- the solvent extract layer, the lipid-depleted biomass, the rag layer, the raffinate layer and/or a combination thereof can be stabilized against degradation by any means known in the art including, but not limited to, one or more of the following processes: the addition of antioxidants, storage of the material in the absence of light exposure, storage under an inert environment such as nitrogen, argon, or carbon dioxide, chilling, and subjecting the material to a thermal cycle to destroy bacteria.
- Suitable antioxidants include, but are not limited to carotenoids, tertiary butyl hydroquinone (TBHQ), butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), vitamin E, vitamin C, rosemary extracts, and combinations thereof.
- TBHQ tertiary butyl hydroquinone
- BHA butylated hydroxyanisole
- BHT butylated hydroxytoluene
- vitamin E vitamin C
- rosemary extracts and combinations thereof.
- Exemplary advantages of performing a liquid-liquid-solid extraction process disclosed herein include, but are not limited to, not drying the biomass prior to the hydrophobic natural products being extracted, traditional liquid-liquid extraction equipment can be used instead of expensive leaching equipment, salt does not need to be removed prior to the extraction process, and/or washing of the solvent extract layer can be accomplished in traditional liquid-liquid extraction equipment.
- the rag layer forms from the extraction process in the extraction zone (104) depicted in FIG.1, the rag layer is isolated and transferred to a deoiling zone (106) wherein the rag layer is washed with an extraction solvent capable of removing any entrained oils or other hydrophobic products not extracted from the algal concentrate during the extraction process.
- Algal oils and/or other hydrophobic products can be present in the algal biomass and/or solvent extract entrained in the rag layer. These entrained natural products can be either physically separated from the rag layer and/or displaced from the rag layer with an extraction solvent.
- the deoiling zone includes or is a decanter which is configured to perform at least one or more of gravity settling, centrifugal settling, and/or combinations thereof to extract any algal oils and/or other hydrophobic products entrained in the rag layer.
- the deoiling zone can include one or more fixed or moving separation aids like mesh pad coalescers, wire pad coalescers, structured packing, inclined plates, perforated plates, baffles, ultrasonic waves, acoustic waves, and/or combinations thereof.
- the deoiling zone can include one or more gravity decantaters, coalescers, hydrocyclones, centrifuges, acoustic-based separators, electric-field based separators, other equipment known in the art to assist in physical separation of hydrophobic products from an aqueous solution, and/or combinations thereof.
- the rag layer is deoiled through contact with an extraction solvent capable of (i) forming a second liquid phase or layer with the rag layer in the deoiling zone and (ii) extracting the entrained algal oils and/or other hydrophobic products out of the rag layer into the second liquid phase or layer.
- the extraction solvent used to deoil the rag layer can either be the same as or different from the extraction solvent used to form the dispersion in the liquid-liquid-solid extraction process.
- the extraction solvent used to deoil the rag layer can include, but is not limited to, a non-polar solvent, a non-polar organic solvent, a dense gas solvent, an aqueous two-phase solvent, a deep eutectic solvent (DES) and/or a natural deep eutectic solvent (NADES), an ionic liquid, any combination thereof or any combination of solvents such as miscible solvents.
- the extraction solvent used to deoil the rag layer is any solvent system that (i) forms a second immiscible liquid phase or layer with the rag layer in the deoiling zone and (ii) extracts the entrained algal oils and/or other hydrophobic products out of the rag layer and into the second immiscible liquid phase or layer.
- solvent systems should not adversely impact the quality or quantity of the natural products.
- solvent systems can include, but are not limited to, synthetic and/or natural flavorants, edible oils, petrochemicals, dense gases, and combinations of these so long as the mixture of the solvent system and the rag layer forms two immiscible liquid phases at a desired temperature.
- the deoiling of the rag layer includes removing the second immiscible liquid phase or layer/second liquid phase or layer containing the extracted algal oils and/or other hydrophobic products from the deoiling zone.
- a deoiled algal slurry forms and is transferred to a dewatering zone (108).
- the deoiled algal slurry is transferred to at least one filtration system (110) containing at least one filtration membrane.
- the deoiled algal slurry is washed with a washing media that simultaneously removes water and/or salts from the deoiled algal slurry, thereby producing a deoiled, dewatered and/or desalted algal slurry.
- a washing media that simultaneously removes water and/or salts from the deoiled algal slurry, thereby producing a deoiled, dewatered and/or desalted algal slurry.
- the washing medium also allows the dewatered (and optionally desalted) algal biomass material to remain fluid enough Attorney Docket No.0079721-000085 for transport to other zones (e.g., a drying zone, a deoiling zone and/or a concentration zone).
- the dewatering zone includes at least one filtration system that includes a centrifuge and/or decanter configured to remove water and/or salts from the algal biomass.
- the centrifuge and/or decanter can be used to separate any water or excess washing medium by centrifugal forces, and this can be performed in one or more centrifugation steps.
- Suitable centrifuges and/or decanters include disc-stack centrifuges, decanter centrifuges, scrolling decanter centrifuges, or combinations thereof.
- Suitable filtration systems include, but are not limited to cross-flow microfilters, filtration membranes, depth filters, sand filters, rotary drum filters, filter presses, and combinations thereof.
- Suitable centrifuges include, but are not limited to disc-stack centrifuges, decanter centrifuges, shooting bowl centrifuges, and combinations thereof.
- the dewatering zone includes at least one filtration system that contains at least one filtration membrane.
- the dewatering zone can include a membrane filtration device selected from, but not limited to, drum filter/dryers, cross-flow filters, diafiltration units, and units where a filter cake accumulates and can be washed with a washing media such as water or a solvent.
- a membrane filtration device selected from, but not limited to, drum filter/dryers, cross-flow filters, diafiltration units, and units where a filter cake accumulates and can be washed with a washing media such as water or a solvent.
- the at least one filtration membrane includes at least one hydrophilic material and/or at least one hydrophilic and oleophobic material.
- membrane refers to a selective barrier between two phases including, but not limited to, one or more selective barriers that contain thick or thin layers, have homogeneous or heterogeneous layers, perform active or Attorney Docket No.0079721-000085 passive transport, are pressure-driven, are concentration or temperature-driven, are osmotically-driven, are electrically-driven, are natural or artificial / synthetic, are porous or non-porous (dense), are symmetric or asymmetric, are hydrophobic or hydrophilic, are oleophilic or are oleophobic and neutral or charged.
- synthetic membranes include, but are not limited to, organic membranes e.g., polymeric, e.g., glassy or rubbery and liquid membranes, inorganic membranes e.g., ceramic including, but not limited to apatite-based, silica-based, alumina-based, titania-based, zirconia-based and proton conducting dense ceramic membrane, carbon membrane including, but not limited to supported, e.g., flat, capillary and hollow fibers and unsupported, e.g., flat and tube, zeolite membrane, glass and metallic membranes, mixed matrix membranes e.g., incorporation of the dispersed phase such as additive solid material including, but not limited to zeolite, activated carbon, carbon molecular sieve, metal-organic framework, carbon nanotubes, metal oxides, mesoporous and nanoporous into a continuous phase including, but not limited to cellulose acetate, polysulfone, polycarbonate, polyamide, polyimide,
- hydrophilic membrane refers to a “water loving” membrane including membrane materials that easily adsorb water molecules due to the presence of active polar functional groups and has low water contact angle value ( ⁇ 90°).
- hydrophilic and oleophobic membrane and/or “hydrophilic/oleophobic membrane” refers to a membrane material that allows polar solvents including, but are not limited to, water, acetone, ammonia, methanol, ethanol and isopropanol to permeate through the membrane while preventing the permeation of nonpolar solvents including, but are not limited to, hexane, heptane, Attorney Docket No.0079721-000085 toluene, acetic acid and chloroform through the microporous or mesoporous membrane structure.
- Suitable hydrophilic/oleophobic membranes include, but are not limited to, ceramic membrane e.g., Ucarsep ® membrane (4 nm), Carbosep ® membrane by SFEC (now TECH-SEP, Miribel, France), Membralox ® ( Soc.Céramiques Techniques, Bazet, France), and other commercial ceramic membranes from Le Carbone Lorraine (Pagny-sur-Moselle,France), CERASIV (now Dynamit Nobel, Troisdorf, Germany), NGK (Nagoya, Japan), WhatmanTM (Little Chalfont, Buckinghamshire, UK) and DuPont (Wilmington, Delaware, USA).
- ceramic membrane e.g., Ucarsep ® membrane (4 nm), Carbosep ® membrane by SFEC (now TECH-SEP, Miribel, France), Membralox ® ( Soc.Céramiques Techniques, Bazet, France), and other commercial ceramic
- hydrophobic membrane refers to a “water hating” membrane including materials that have the opposite response to water interaction compared to hydrophilic membranes and has a high water contact angle value (>90°), are not wetted by water and no water will flow through the membrane at normal applied pressure.
- oleophobic membrane refers to a membrane that includes membrane materials that repel oils and hydrophobic liquids. Any known oleophobic membrane material can be selected, for example, a material that when exposed to n-hexadecane, a standard short-chain alkane testing fluid, produces contact angles ranging between 60° and 80°.
- water contact angle value refers to the wetting angle of a drop of water on the surface of a membrane material. If the contact angle of a water droplet on a sample of membrane material is greater than 90°, the material is considered to not be wetted by water and is thus hydrophobic.
- a membrane material becomes more hydrophilic as the contact angle decreases from 90° to 0°
- Attorney Docket No.0079721-000085 (Watanabe, T., “Wettability of ceramic surfaces – A wide range control of surface wettability from super hydrophilicity to super hydrophobicity, from static wettability to dynamic wettability”, 2009, Journal of the Ceramic Society of Japan, 117 [12], pp. 1285-1292; Somlyai-Sipos et al., “Wettability of Metals by Water”, Metals, 2022, 12 (8), 1274).
- the contact angle of the water droplet on the material is 45°, the material has good wetting properties with water and is hydrophilic.
- the at least one hydrophilic material and/or the at least one hydrophilic and oleophobic material includes at least one or more of aluminum oxide (alumina), silicone carbide, titanium dioxide, zirconium dioxide, apatite and/or combinations thereof.
- the at least one hydrophilic material and/or the at least one hydrophilic and oleophobic material includes at least one or more of a stainless-steel alloy, palladium, tungsten and/or a nickel-based alloy selected from, but not limited to, 304 stainless steel, 316 stainless steel, duplex stainless steels (e.g., duplex 2205 and super-duplex 2507), high-alloyed super-austenitic stainless steel (e.g., 254 SMO), Inconel 625, and/or Hastelloy C-276.
- a stainless-steel alloy palladium, tungsten and/or a nickel-based alloy selected from, but not limited to, 304 stainless steel, 316 stainless steel, duplex stainless steels (e.g., duplex 2205 and super-duplex 2507), high-alloyed super-austenitic stainless steel (e.g., 254 SMO), Inconel 625, and/or Hastelloy C-276.
- the at least one filtration membrane of the filtration system or filtration membrane system includes at least one hydrophilic material and/or at least one hydrophilic and oleophobic material that allows a brine mixture (i.e., a mixture of water and salts) to pass through the membrane but prevents the extraction solvent used to deoil the rag layer and/or the extraction solvent used to form the dispersion in the extraction zone from passing through the membrane.
- a brine mixture i.e., a mixture of water and salts
- the at least one filtration membrane includes at least one or more pores, wherein each pore has a pore diameter within a range of 0.001 microns to 0.2 microns, 0.001 microns to 0.1 microns, 0.001 microns to 0.05 microns, 0.001 microns to 0.01 microns, 0.001 microns to 0.008 microns, 0.008 microns to 0.2 microns, to 0.008 microns to 0.1 microns, 0.008 microns to 0.05 microns, 0.008 microns to 0.01 microns, 0.01 microns to 0.2 microns, 0.01 microns to 0.1 microns, 0.01 microns to 0.05 microns, 0.05 microns to 0.2 microns, 0.05 microns to 0.1 microns, 0.01 microns to 0.2 microns, or 0.01 microns to 0.1 microns.
- the at least one filtration membrane of the system has Molecular Weight Cut Off (MWCO) within the range of 0.2 - 10 kDa or 1 - 500 kDa.
- MWCO Molecular Weight Cut Off
- the at least one filtration membrane includes at least one or more pores, wherein each pore has a pore size-to-algal biomass size ratio of less than 1:10, less than 1:8, less than 1:4, less than 1:2 or less than 1:1.
- the membrane filtration system includes at least two, three, four, five, six or more filtration membranes.
- the washing media can include, but is not limited to, an extraction solvent, one or more other solvents, water, co-solvents and/or combinations thereof.
- Exemplary water sources that can be used in the washing media include, but are not limited to, potable water, distilled water, water derived from a sea, lake, river, ocean, aquifer, irrigation water, and/or combinations thereof.
- the washing media contains water having a salinity capable of removing salts from the rag layer.
- acceptable other solvents are a light solvent (e.g., hexane) that is combined with a more viscous solvent (e.g., vegetable oil).
- Examples of other acceptable solvents are co-solvents capable of miscibilizing the extraction solvent with the raffinate contained in the rag layer. These solvents can be identified and selected by examining the liquid-liquid equilibrium as shown on a ternary phase diagram. In a ternary phase diagram, the liquid-liquid region can be identified where the extraction solvent and the raffinate phases are immiscible, and the co-solvent serves as a coupling agent between these two different phases. Residue curve maps can be used to determine optimal mixtures of other solvents with the extraction solvent.
- the washing media is a single solvent or a combination of solvents selected from, but not limited to, those solvents described by Riddick et al. (“Organic Solvents Physical Properties and Methods of Purification”, 1986, edited by J. A. Riddick, W. B. Bunger, T. K. Sakano, ISBN 0-471-08467-0), a food grade solvent (e.g., hexane, ethyl acetate, limonene, essential oils, edible oils) or a dense gas (e.g., carbon dioxide, propane, and butane).
- a food grade solvent e.g., hexane, ethyl acetate, limonene, essential oils, edible oils
- a dense gas e.g., carbon dioxide, propane, and butane
- the washing media includes a co-solvent selected from, but not limited to, acetone, methanol, ethanol and/or combinations thereof.
- the co-solvent is a food grade solvent (e.g., acetone and ethanol).
- the washing media does not contain water.
- at least a portion of the washing media contains water.
- the washing media includes at least one or more of a C 5 -C 8 hydrocarbon, such as hexane and isomers thereof, ethyl acetate, limonene, essential oils, edible oils and/or combinations thereof, and optionally water.
- the washing media includes i) at least one or more of a C 5 -C 8 hydrocarbon, such as hexane and isomers thereof, ethyl acetate, limonene, essential oils, edible oils and/or combinations thereof, ii) water and iii) at least one a co-solvent selected from, but not limited to, acetone, methanol, ethanol and/or combinations thereof.
- a C 5 -C 8 hydrocarbon such as hexane and isomers thereof, ethyl acetate, limonene, essential oils, edible oils and/or combinations thereof
- water and iii) at least one a co-solvent selected from, but not limited to, acetone, methanol, ethanol and/or combinations thereof.
- the ratio of a C 5 -C 8 hydrocarbon, such as hexane and isomers thereof, ethyl acetate, limonene, essential oils, edible oils and/or combinations thereof, to water is 20:1 - 1:20, 10:1 - 1:10 or 5:1 - 1:5.
- the washing media contains at least one of the following properties: a heat of vaporization less than that of water, a permeability through a selected membrane that is less than water or brine, a polarity that allows the washing media to be separated from algal oil, and immiscible with the algal biomass over a temperature range of 0°C to 100°C, and/or a viscosity of less than 100 centipoise when subjected to the temperature range.
- the washing media has a lower boiling point than the algal oils contained in the rag layer.
- the washing media includes at least one pH adjustment chemical, optionally including but not limited to organic acids, inorganic acids, organic bases, and inorganic bases.
- Suitable organic acids include but are not limited to carnosic acid, formic acid, acetic acid, citric acid, and ascorbic acid.
- Suitable inorganic acids include but are not limited to perchloric acid, hydrochloric acid, sulfuric acid, and nitric acid.
- Suitable inorganic bases include but are not limited to sodium hydroxide, potassium hydroxide, and calcium hydroxide.
- the combination of the at least one filtration membrane material and washing media allow water and/or salts to selectively pass through the membrane and prevent the algal biomass and/or solvent extract layer from passing through the membrane.
- the combination of the at least one filtration membrane material and washing media allow the solvent extract layer to pass through the membrane.
- Selection of the washing media and the filtration membrane material can depend on the salt concentration in the rag layer, the extraction solvent used in the extraction zone, the operating temperature in the dewatering zone, and/or the operating pH in the dewatering zone.
- the selection of the washing media can be based on the washing media’s ability to selectively extract desired solutes (e.g., water and/or salts) from the algal biomass in the rag layer.
- the selection of the washing media can also be based on the Hansen Solubility Parameters of the desired solutes with that of the solvents used in the washing media.
- the co-solvent can be selected to more closely match the Hansen Solubility Parameters of the desired solutes with that of the mixed solvent system by the process described by Archer (Industrial Solvents Handbook, 1996, ISBN # 0-8247-9718-3).
- the selection of the filtration membrane material can be based on the salt level or salinity of the algal concentrate and/or raffinate.
- the salt level in the algal concentrate and/or raffinate could be quantified so that the materials of construction for the filtration system and/or the at least one filtration membrane can be selected to where minimum damage to the filtration system and/or the at least one filtration membrane occurs.
- the presence of chloride salts in the algal concentrate and/or raffinate can impact the material of construction for the filtration system and/or the at least one filtration membrane since chloride salts are known to eliminate or degrade some metals (e.g., carbon steel).
- Attorney Docket No.0079721-000085 [189] The selection of the filtration membrane material can also be based on the chemical compatibility of the material with washing media. The washing media could allow for the removal of desired solutes (e.g., water and salts) in the algal biomass without the loss of algal biomass material. Most chemical compatibility selection charts can be used to assist with this selection. One example of this type of chart is shown in Table 2.
- ETFE ethylene tetrafluoroethylene
- FEP/TFE/PFA fluorinated ethylene propylene/ tetrafluoroethylene/ perfluoroalkoxy alkane
- FLPE fluorinated high density polyethylene
- FLPP fluorinated high density polypropylene
- HDPE high density polyethylene
- LDPE low density polyethylene
- PC polycarbonate
- PETG glycol modified polyethylene terephthalate
- PP polypropylene
- PVC polyvinyl chloride
- TPE thermoplastic elastomer.
- the configuration of the filtration system and/or the at least one filtration membrane can be based on the type and concentration of solids initially contained in the rag layer.
- spiral wound membranes are not preferred when the concentration of solids is significant because the membrane can foul. Different types of solids impact membrane fouling in their own way, but in general it is not preferred to operate a spiral wound membrane system with more than about one weight percent solids.
- plate, Attorney Docket No.0079721-000085 frame and tubular membrane configurations are preferred when the solids concentration is above about one percent.
- the washing media is or includes hexane and/or the at least one filtration membrane is constructed of ceramic aluminum oxide in the tubular form.
- the washing media is or includes a mixture of heptane and ethanol, and/or the at least one filtration membrane is constructed of PTFE in a plate and frame form.
- the algal biomass and/or rag layer is washed with water after being washed with washing media to reduce the salinity of the rag layer and/or biomass that remains in the membrane filtration system. In some of these exemplary embodiments, at least a portion of the raffinate passes through the at least one filtration membrane.
- the washing media includes a solvent and/or solvent system that allows raffinate to pass through the at least one filtration membrane and/or filtration system.
- a surprisingly unexpected advantage of these embodiments is that the washing media can essentially desalt and dewater the rag layer and/or algal biomass at the same time.
- membrane filtration systems capable of removing brine (i.e., water and salt) from a deoiled algal slurry, rag layer and/or algal biomass with reduced fresh water and energy usage were surprisingly discovered.
- the exemplary process depicted in FIG.1 also depicts the deoiled, dewatered and/or desalted algal slurry being transferred to a drying zone (112) to remove any residual solvents and produce a dry algal powder that can be used in downstream processes to produce valuable products.
- the drying zone can include any dryer or dryer system known in the art. Suitable dryer types include, but are not limited to, those described by Moyers et al. (Moyers, C. G., and G. W. Baldwin, “Psychometry, Evaporative Cooling, and Solids Drying” Section 12 in Perry’s Chemical Engineer’s Handbook, 7th Edition, Edited by R. H. Perry and D. W.
- Suitable dryers that rely on an inert gas to evaporate a solvent include, but are not limited to, spray dryers, fluidized solid bed dryers, and rotary dryers.
- Suitable dryers that rely on steam to evaporate a solvent include, but are not limited to, rotary dryers and desolventizer-toasters.
- Suitable dryers also include direct-contact dryers, where the dewatered, desalted and deoiled algal slurry is contacted with a hot solid surface to evaporate a solvent.
- Examples of this type of dryer are drum dryers and double drum dryers with a hot surface dried thermally.
- the drying of the dewatered and deoiled algal biomass includes using a dryer gas (e.g., a condensable gas, such as steam) capable of removing solvent from the dewatered and deoiled algal biomass and recycling the solvent back to the extraction step.
- a dryer gas e.g., a condensable gas, such as steam
- the Attorney Docket No.0079721-000085 slurry can optionally be transferred to a concentration zone (114) to remove any residual solvents that have become entrained in the slurry during the deoiling and/or dewatering processes.
- the concentrated deoiled, dewatered and/or desalted algal slurry formed in the concentration zone (114) is then transferred to the drying zone (112).
- the concentration zone can include at least one of the following: a gravity separator, a decanter, a coalescer, a hydroclone, a centrifuge, a filter, a membrane, a flotation device, an adsorptive bubble separation device, and/or combinations thereof.
- the concentrating of the deoiled and dewatered/desalted algal slurry includes using at least one of the following concentration processes to affect concentration: gravitational fields, electrical fields, acoustic fields, and/or combinations thereof.
- the concentrating of the deoiled and dewatered/desalted algal slurry includes reducing the concentration of solvent in the deoiled and dewatered/desalted algal slurry to less than about 95wt%, less than about 90wt% or less than about 85wt%.
- the minimum residual solvent concentration that remains in the deoiled and dewatered/desalted algal slurry can be the concentration at which spoilage of the algal biomass is prevented.
- the process for recovering deoiled and dewatered algal biomass can also include dewatering and/or desalting the rag layer and/or algal biomass before the deoiling of the rag layer and/or algal biomass.
- another aspect of the present disclosure is a process for recovering algal biomass, the process including at least one or more of: extracting a rag layer containing an algal biomass from an algal concentrate; dewatering the rag layer to produce a dewatered algal slurry, the dewatering including intimately contacting the rag layer with a filtration system and washing the rag layer with a washing media, the filtration system including at least one filtration membrane; deoiling the dewatered algal slurry to produce a deoiled, dewatered algal biomass; and drying the deoiled, dewatered algal biomass.
- FIG.2 shows an exemplary embodiment of the deoiling and dewatering process wherein the dewatering of the rag layer occurs before the deoiling.
- an algal concentrate stream is first subjected to an extraction process in an extraction zone (200) that forms a rag layer containing an algal biomass, raffinate (i.e., a solution containing water and salts) and extraction solvent.
- the rag layer is then transferred from the extraction zone (200) to a dewatering zone (202).
- the rag layer is transferred to at least one filtration system (204).
- the rag layer is washed with a washing media that simultaneously removes water and/or salts from the rag layer, thereby producing a dewatered and/or desalted algal slurry.
- the dewatered and/or desalted algal slurry is then transferred from the dewatering zone (202) to a deoiling zone (206).
- the dewatered and/or desalted algal slurry is washed with an extraction solvent capable of removing any entrained oils or other hydrophobic products not extracted from the rag layer during the extraction process.
- the deoiled, dewatered and/or desalted algal slurry produced in the deoiling zone (206) is then transferred to a drying zone (208) to remove any residual Attorney Docket No.0079721-000085 solvents and produce a dry algal powder that can be used in downstream processes to produce valuable products.
- the slurry can optionally be transferred to a concentration zone (210) to remove any residual solvents that have become entrained in the slurry during the deoiling and/or dewatering processes.
- the at least one filtration system includes at least one filtration membrane having at least one hydrophilic material and/or at least one hydrophilic and oleophobic material disclosed herein.
- the at least one filtration system includes at least one filtration membrane having at least one pore, wherein each pore has a pore diameter within a range of 0.001 microns to 0.2 microns, 0.001 microns to 0.1 microns, 0.001 microns to 0.05 microns, 0.001 microns to 0.01 microns, 0.001 microns to 0.008 microns, 0.008 microns to 0.2 microns, to 0.008 microns to 0.1 microns, 0.008 microns to 0.05 microns, 0.008 microns to 0.01 microns, 0.01 microns to 0.2 microns, 0.01 microns to 0.1 microns, 0.01 microns to 0.05 microns, 0.05 microns to 0.2 microns, 0.05 microns to 0.1 microns, 0.01 microns to 0.2 microns, or 0.01 microns to 0.1 microns.
- the at least one filtration membrane of the system has Molecular Weight Cut Off (MWCO) within the range of 0.2 - 10 kDa or 1 - 500 kDa.
- MWCO Molecular Weight Cut Off
- the at least one filtration system includes at least two, three, four, five, or six filtration membranes.
- the process for recovering deoiled and dewatered algal biomass includes selecting a washing media to has at least one or more of the following properties: a heat of vaporization less than that of water, a permeability through a selected membrane that is less than water or brine, a polarity that allows the washing media to be separated from algal oil, and immiscible with the algal biomass over a temperature range of 0°C to 100°C, and a viscosity of less than 100 centipoise when subjected to the temperature range.
- the washing media contains at least one or more of hexane, ethyl acetate, limonene, essential oils, edible oils and/or combinations thereof and optionally water.
- the washing media contains at least one co- solvent selected from acetone, methanol, ethanol and combinations thereof.
- the washing media contains i) at least one or more of hexane, ethyl acetate, limonene, essential oils, edible oils and/or combinations thereof, ii) water, and iii) at least one co-solvent selected from acetone, methanol, ethanol and combinations thereof.
- the extracting of the rag layer containing the algal biomass from the algal concentrate includes at least one or more of the following: forming a dispersion by contacting the algal concentrate with an extraction solvent in an extraction zone, passing the dispersion to a separation zone, and separating the dispersion into multiple layers, the layers including a solvent extract layer containing at least one hydrophobic natural product and the extraction solvent, a raffinate layer containing an aqueous salt solution, and the rag layer containing the algal biomass.
- the extracting of the rag layer is carried out or occurs at a temperature of about 100°C, less than about 100°C, of about 10°C to 90°C, 10°C to 80°C, 20°C to 90°C, 20°C to 80°C, 30°C to 90°C, 30°C to 80°C, 40°C to 90°C, 40°C to 80°C, 50°C to 90°C, 50°C to 80°C, 60°C to 90°C, 60°C to 80°C, 35°C to 80°C, 35°C to 70°C or 40°C to 70°C.
- the extracting of the rag layer containing the algal biomass from the algal concentrate includes separating the dispersion into multiple layers at a pressure ranging from atmospheric to supercritical conditions for the extraction solvent.
- the extracting of the rag layer containing the algal biomass from the algal concentrate includes separating the dispersion into multiple layers at a temperature of less than about 100°C, less than about 90°C, less than about 80°C, less than about 70°C, less than about 60°C or less than about 50°C, such e.g.
- the algal concentrate has a salinity greater than 5 wt%, greater than 10 wt%, greater than 15 wt% or greater than 20 wt% e.g., 15 wt% to 25 wt%.
- the process for recovering deoiled and dewatered algal biomass can also include desalting the rag layer in a separate desalting zone before the rag layer is transferred to the dewatering zone and/or deoiling zone.
- the algal biomass is desalted with water having a salinity of at most 25 wt%, a salinity that is ⁇ 0.05 wt%, a salinity ranging from 0.05 - 3 wt%, a salinity ranging from 3 - 5 wt%, a salinity of at least 5 wt%, a Attorney Docket No.0079721-000085 salinity ranging from 5-25 wt%, a salinity ranging from 10-25wt%, a salinity ranging from 15-25 wt% or a salinity ranging from 20-25wt%.
- FIG.3 shows an exemplary embodiment of the deoiling and dewatering process wherein the desalting of the rag layer occurs in a desalting zone.
- an algal concentrate stream is first subjected to an extraction process in an extraction zone (300) that forms a rag layer containing an algal biomass, raffinate (i.e., a solution containing water and salts) and extraction solvent.
- the rag layer is then transferred from the extraction zone (300) to a deoiling zone (302).
- the rag layer is washed with an extraction solvent capable of removing any entrained oils or other hydrophobic products not extracted from the algal concentrate in the extraction zone (300).
- a deoiled algal slurry forms and is transferred to a desalting zone (304).
- the deoiled algal slurry is washed with fresh water to remove any salts that were not removed during the extraction process.
- salt can be removed from the raffinate phase that is part of the rag layer or algal slurry. The removal of salt can be accomplished by contacting the rag layer or algal slurry with fresh water, thus dissolving the salt that is in the rag layer or algal slurry into the added fresh water.
- the resulting aqueous phase can be separated from the algal slurry or rag layer to reduce the level of salt in the washed rag layer or algal slurry. This desalting process can be repeated until a target level of residual salt relative to algal biomass in the rag layer and/or algal slurry is achieved.
- the desalting of the rag layer and/or algal slurry can be accomplished in any equipment known in the art for washing solids, such as, but not limited to, Attorney Docket No.0079721-000085 agitated vessels, static mixers, ultrasonic mixers, high-shear mixers, in-line mixers, other agitation devices known in the art, gravity decanters, decanters, coalescers, hydrocyclones, electrically-enhanced settlers, acoustically-enhanced settlers, other settler devices known in the art, and/or combinations thereof.
- Attorney Docket No.0079721-000085 agitated vessels such as, but not limited to, Attorney Docket No.0079721-000085 agitated vessels, static mixers, ultrasonic mixers, high-shear mixers, in-line mixers, other agitation devices known in the art, gravity decanters, decanters, coalescers, hydrocyclones, electrically-enhanced settlers, acous
- the deoiled, desalted algal slurry is transferred to a dewatering zone (306) containing at least one filtration system (308).
- a dewatering zone (306) containing at least one filtration system (308).
- the deoiled, desalted algal slurry is washed with a washing media that simultaneously removes water and/or salts from the deoiled, desalted algal slurry, thereby producing a dewatered, desalted and deoiled algal slurry.
- the dewatered, desalted and deoiled algal slurry is then transferred to a drying zone (310) to remove any residual solvents and produce a dry algal powder that can be used in downstream processes to produce valuable products.
- the slurry can optionally be transferred to a concentration zone (312) to remove any residual solvents that have become entrained in the slurry during the deoiling, desalting and/or dewatering processes.
- the concentrated deoiled, dewatered and desalted algal slurry formed in the concentration zone (312) is then transferred to the drying zone (310) to remove any residual solvents.
- any of a variety of products can be made from the biomass or lipid- depleted biomass, or from the oil obtained by deoiling the rag layer, including, but not limited to, biofuels, nutraceuticals, cosmaceuticals, wastewater treatment processes, spa products, animal feeds, animal feed ingredients, human food, human food ingredients, soil builders, chemical intermediates, renewable plastics, Attorney Docket No.0079721-000085 renewable polymers, renewable chemicals, specialty lipids, solar salt, soaps or components of a soap or detergent compositions, spa products, and cosmetic ingredients (e.g., carotenoids, omega fatty acids, and other lipids) and combinations thereof.
- biofuels nutraceuticals, cosmaceuticals
- wastewater treatment processes spa products
- animal feeds animal feed ingredients
- human food human food ingredients
- soil builders chemical intermediates
- renewable plastics Attorney Docket No.0079721-000085 renewable polymers, renewable chemicals, specialty lipids, solar salt, soaps or components of a soap or detergent compositions, spa products,
- the process for recovering deoiled and dewatered algal biomass includes desalting the rag layer with washing media and/or fresh water.
- the process for recovering deoiled and dewatered algal biomass includes desalting the rag layer and/or the algal slurry before dewatering the rag layer and/or the algal slurry, the desalting including contacting the rag layer with water (e.g., fresh water) to form an aqueous phase containing dissolved salts, an interface containing algal biomass and an organic phase containing extraction solvent; and separating the aqueous phase from the organic phase and the algal biomass.
- water e.g., fresh water
- FIG.4 depicts an exemplary embodiment wherein the permeate formed from dewatering an algal slurry in a dewatering zone (402) is used to desalt algal slurries entering a desalting zone (400).
- Another aspect of the present disclosure is a system for recovering algal biomass from a rag layer, the system including at least one of the following: a dewatering zone configured to dewater an extracted rag layer and produce a dewatered algal slurry, the dewatering zone including a filtration system having at least one filtration membrane, the at least one filtration membrane including at least Attorney Docket No.0079721-000085 one hydrophilic or hydrophilic and oleophobic material; and a deoiling zone in communication with the dewatering zone, the deoiling zone being located either upstream or downstream of the dewatering zone.
- the at least one hydrophilic material and/or the at least one hydrophilic and oleophobic material of the at least one filtration membrane of the system includes at least one or more of a polyacrylonitrile, a polyethylene, a high-density polyethylene, a polypropylene, a polyethylsulfone, a polysulfone, a polytetrafluoroethylene, a polyvinylidine difluoride, a polyester, a polycarbonate, a polyethylene terephthalate, a modified polyethylene terephthalate, a cellulose acetate, a cellulose propionate, a cellulose butyrate and/or combinations thereof.
- the at least one hydrophilic material and/or the at least one hydrophilic and oleophobic material of the at least one filtration membrane of the system includes at least one or more of aluminum oxide (alumina), silicone carbide, titanium dioxide, zirconium dioxide and/or combinations thereof.
- the at least one hydrophilic and/or the at least one hydrophilic and oleophobic material of the at least one filtration membrane of the system includes a stainless-steel alloy and/or a nickel-based alloy.
- the at least one filtration membrane of the system has at least one pore, wherein each pore has a pore diameter within a range of 0.001 microns to 0.2 microns, 0.001 microns to 0.1 microns, 0.001 microns to 0.05 microns, 0.001 microns to 0.01 microns, 0.001 microns to 0.008 microns, 0.008 microns to 0.2 microns, to 0.008 microns to 0.1 microns, 0.008 microns to 0.05 microns, 0.008 microns to 0.01 microns, 0.01 microns to 0.2 microns, 0.01 microns Attorney Docket No.0079721-000085 to 0.1 microns, 0.01 microns to 0.05 microns, 0.05 microns to 0.2 microns, 0.05 microns to 0.1 microns, 0.01 microns to 0.2 microns, or 0.01 microns to 0.1 micro
- the at least one filtration membrane of the system has Molecular Weight Cut Off (MWCO) within the range of 0.2 - 10 kDa or 1 - 500 kDa.
- MWCO Molecular Weight Cut Off
- the at least one filtration system of the system has at least two, three, four, five, or six filtration membranes.
- the system includes an extraction zone and/or a drying zone, the extraction zone including an algal concentrate inlet configured to receive an algal concentrate and a rag layer outlet in communication with the dewatering zone or the deoiling zone, the rag layer outlet being configured to transfer a rag layer from the extraction zone to either the dewatering zone or the deoiling zone; and the drying zone including a drying inlet in communication with either an outlet of the dewatering zone, an outlet of the deoiling zone or an outlet of a concentration zone configured to concentrate a dewatered and deoiled algal biomass, the drying inlet being configured to receive a deoiled and dewatered algal biomass.
- the deoiling zone includes an algal slurry outlet and a rag layer inlet, the rag layer inlet being in communication with the rag layer outlet of the extraction zone and configured to receive a rag layer from the extraction zone, and the algal slurry outlet being in communication with an inlet of the dewatering zone and configured to transfer a deoiled algal biomass to the dewatering zone; and the dewatering zone includes an outlet configured to transport a deoiled and dewatered algal biomass to either the drying zone or the concentration zone.
- the dewatering zone includes an algal slurry outlet and a rag layer inlet, the rag layer inlet being in communication with the rag layer outlet of the extraction zone and configured to receive a rag layer from the extraction zone, and the algal slurry outlet being in communication with an inlet of the deoiling zone and configured to transfer a dewatered algal biomass to the deoiling zone; and the deoiling zone includes an outlet configured to transport a deoiled and dewatered algal biomass to either the drying zone or the concentration zone.
- the system includes a washing media input line, wherein the washing media input line is in communication with the dewatering zone and is configured to transfer a washing media from a washing media storage container to the dewatering zone.
- the system includes a first extraction solvent input line, wherein the first extraction solvent input line is in communication with the extraction zone and is configured to transfer an extraction solvent from a first extraction solvent storage container to the extraction zone.
- the system includes a second extraction solvent input line, wherein the second extraction solvent input line is in communication with the deoiling zone and is configured to transfer an extraction solvent from a second extraction solvent storage container to the deoiling zone.
- the system includes a desalting zone configured to desalt a rag layer or an algal slurry, the desalting zone being located upstream of, downstream of or within the dewatering zone.
- Attorney Docket No.0079721-000085 [255]
- the system includes a desalting zone configured to desalt a rag layer or an algal slurry, the desalting zone being located upstream of the dewatering zone.
- the system includes a freshwater input line, wherein the freshwater input line is in communication with the desalting zone and is configured to transfer freshwater from a freshwater storage container to the desalting zone.
- the system includes at least one harvesting zone configured to operatively communicate with an extraction zone and at least one algal aquaculture zone configured to operatively communicate with the at least one harvesting zone.
- the at least one harvesting zone is configured to perform an adsorptive bubble separation process on an algal concentrate.
- the dry algal powder formed from the systems and processes disclosed herein can be used to produce various products including, but not limited to, biofuels, animal feed, animal feed ingredients, human food, human food ingredients, renewable plastics, renewable polymers, renewable chemicals, nutraceuticals, cosmaceuticals, soaps or components of a soap or detergent compositions, and cosmetic ingredients (e.g., carotenoids, omega fatty acids, and other lipids).
- Biofuels that can be produced from high temperature processing of the dry algal powder include, but are not limited to, biodiesel, green diesel, renewable diesel, methane, alcohols, and dried algal biomass.
- Algal biodiesel is produced via any transesterification process known in the art, including those which utilize two immiscible liquid phases, and those that utilize a solid acid catalyst.
- Green diesel can be produced by hydrogenation, cracking, or a combination thereof of the algal oil or Attorney Docket No.0079721-000085 any derivative thereof in order to produce hydrocarbons that can be used directly in the existing diesel distribution system.
- Methane and/or hydrogen can be produced from the dry algal powder by any anaerobic process known in the art. Fermentation of the dry algal powder by any process known in the art can be used to produce methanol, ethanol, butanol, n-butanol, i-butanol, other alcohols, and combinations thereof.
- the dry algal powder can be torrified for the production of a soil builder or for use in combination with coal for power or steam generation.
- the dry algal powder can be gasified or combusted either by itself or in combination with coal or biomass.
- Suitable animal feeds include, but are not limited to, feeds for shrimp, fish, shellfish, brine shrimp, chickens, poultry, cows, ducks, dogs, pigs, sheep, goats, and combinations thereof.
- Suitable dietary supplements include, but are not limited to alpha carotene, betacarotene, lutein, zeaxanthin, cryptoxanthin, phytoene, phytofluene, and the various cis- and trans-isomers and the various alpha, beta, gamma, delta isomers of the various carotenoids, and combinations thereof.
- Suitable methods of carbon storage include, but are not limited to, burying the dry algal powder, sinking it, torifying it and using it as a soil builder, or combinations thereof.
- Suitable methods for water and wastewater treatment include, but are not limited to, removal of BOD (biological oxygen demand), and or TOC (total organic carbon) from a water stream.
- Suitable methods to process the dry algal powder into useful compounds include, but are not limited to, torification, gasification, liquefaction, fermentation, Attorney Docket No.0079721-000085 drying, combustion, burial, and combinations thereof.
- Suitable applications of the torified algal powder includes, but is not limited to, a soil builder and a material to be combined with coal, wood, or other combustible material for power generation.
- Suitable applications of gasified algal powder include, but are not limited to, the production of the entire suite of products that can be produced via syngas chemistry, as described by the Gasification Technologies Council.
- Suitable products from syngas include, but are not limited to, chemicals, fertilizers, power generation, substitute natural gas, hydrogen, and transportation fuels.
- Suitable chemicals include, but are not limited to, hydrogen, carbon monoxide, methanol, dimethyl ether, acetic acid, propionic acid, butyric acid, acetic anhydride, methyl acetate, ethylene, propylene, olefins, and combinations thereof.
- Suitable fertilizers that can be produced from the syngas include, but are not limited to ammonia, ammonium nitrate, urea, and others known in the art.
- Suitable substitute natural gas can be generated from the syngas produced by gasifying the algal powder, and this includes methane.
- Suitable liquid fuels include gasoline, diesel fuel, jet fuels, and combinations thereof. All of the chemicals that are produced by Eastman Chemicals and by Sasol via their gasification processes can also be produced by the gasification of the algal powder. Products produced by the utilization of syngas can also be produced by gasification of the algal powder. Illustrative processes are described in U. S. Pat.
- No.6,310,260 the contents of which are incorporated herein by reference in their entirety, include, for example, hydroformylation, hydroacylation (intramolecular and intermolecular), hydrocyanation, hydroamidation, hydroesterification, aminolysis, alcoholysis, hydrocarbonylation, reductive hydroformylation, hydrogenation, olefin oligomerization, hydroxycarbonylation, carbonylation, olefin isomerization, transfer hydrogenation and the like.
- exemplary embodiments of the processes and systems disclosed herein can deoil, dewater, desalt and dry an algal biomass with reduced freshwater usage, reduced potential spoilage of the algal biomass and/or reduced energy consumption.
- the total water consumption of the dewatering (and optionally desalting) processes averages around 28 t/h.
- the deoiled and dewatered algal biomass can be desolventized and/or dried to a moisture content of around 8 wt%.
- the heat used to evaporate the solvent and water can average 6.2 MW.
- these exemplary embodiments can reduce freshwater consumption, for example, up to 55% (consumption drops from 63 t/h to 35 t/h) and the heat required for vaporization, for example, up to 73% (required heat drops from 22 MW to 6.2 MW).
- any of the systems disclosed herein can also be used for treating an algal biomass. Any of the processes disclosed herein can be used in combination with the systems disclosed herein to treat algal biomass.
- Example 1 Dunaliella salina algal biomass was grown in an algal aquaculture system and harvested with an adsorptive bubble separation unit to generate an algal concentrate. In extraction, the algal concentrate including water, salt, and algal biomass was contacted with hexane as the extraction solvent to transfer the algal oil and carotenoid solutes into the extract phase. The resulting raffinate phase contained a majority of the water and salt, and it was depleted of algal biomass, algal oil, and carotenoids.
- the resulting rag layer (containing algal biomass, extract and raffinate) was separated from the bulk extract and raffinate phases by gravity decantation.
- the rag layer was washed with the hexane extraction solvent and passed through a centrifuge to remove a majority of the extract and raffinate phases and to produce a deoiled algal slurry that was fed to a membrane system.
- the membrane system contained two similar cross-flow membrane filtration units in series. In both of these units, the membrane material was selected so that permeability of salt and water was high, and permeability of solvent was low. In the first membrane unit, salt concentration of deoiled algal biomass was lowered by dilution with recycled permeate from the second membrane unit and filtration.
- both the salt and water concentration were lowered by displacement with a washing media.
- the washing media used in the process contained extraction solvent, water and the cosolvent acetone.
- Attorney Docket No.0079721-000085 [272] The deoiled algae slurry (from the extraction and deoiling processes including algae, salt, water and extraction solvent) and the permeate from the second membrane unit (including salt and water) was fed to the first membrane unit at ambient temperature and at neutral pH. Salt and water permeated through the membrane and were collected. [273] Concentrate from the first membrane unit (including algae and extraction solvent) was mixed with washing liquid prior to feeding to the second membrane unit. Salt and water permeate through the second membrane were collected.
- the collected permeate was counter-currently fed to the first membrane unit, where it was used as washing liquid since the salt concentration was lower compared to the deoiled algae slurry.
- the washing media to feed mass ratio in the 2nd membrane unit was 1.5.
- Example 2 involves the use of an exemplary process for recovering algal biomass from a rag layer, the process including: extracting a rag layer containing an algal biomass from an algal concentrate; deoiling the rag layer to produce a deoiled algal slurry; dewatering the deoiled algal slurry to create a dewatered, deoiled algal biomass; and drying the dewatered, deoiled algal biomass.
- the dewatering includes contacting the deoiled algal slurry with a filtration system and washing the deoiled algal slurry with a washing media.
- the filtration system includes at least one filtration membrane. The drying of the dewatered, deoiled algal biomass was tested at laboratory scale.
- the rag layer was washed with heptane, the extraction solvent and passed through a centrifuge to remove a majority of the extract and raffinate phases and to produce a deoiled algal slurry.
- Sample was evaporated to remove the extraction solvent to generate a more standardized sample, but this step is not essential to the process.
- the deoiled algal slurry was desalted with fresh water to produce a deoiled and desalted algal slurry.
- Two different samples were taken from the deoiled and desalted algal slurry fraction and dewatered with the same lab scale membrane filtration unit.150 kDa polyethersulfone was used as the membrane material.
- the first sample (Sample 1) including algae and water was dewatered without adding any washing media and the second sample (Sample 2) was dewatered by first mixing Sample 2 with the heptane extraction solvent and then filtering the mixture including algae, extraction solvent and water. Both tests were done at room temperature and low pH. pH ranges from 2 – 9 are suitable. [279] With both tests, experiments were continued until the mixing inside the lab scale membrane unit was working in a sufficient manner. With both tests, water permeated through the membrane and was collected as a permeate and analyzed. Attorney Docket No.0079721-000085 With Sample 1, the deoiled, desalted and dewatered algal slurry, that included algae and remaining water, was collected and analyzed.
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Abstract
Systems and processes for recovering algal biomass are disclosed. These processes include extracting a rag layer containing an algal biomass from an algal concentrate; deoiling the rag layer to produce a deoiled algal slurry; dewatering the deoiled algal slurry to create a dewatered, deoiled algal biomass, the dewatering including contacting the deoiled algal slurry with a filtration system and washing the deoiled algal slurry with a washing media, the filtration system including at least one filtration membrane; and drying the dewatered, deoiled algal biomass. Processes and systems wherein the dewatering occurs before the deoiling are also disclosed.
Description
Attorney Docket No.0079721-000085 A PROCESS FOR DESALTING, DEWATERING, AND DESOLVENTIZING AN ALGAL BIOMASS CROSS-REFERENCE TO RELATED APPLICATION [1] This application claims priority to U.S. Provisional Patent Application No. 63/604,265 filed on November 30, 2023, and to Finnish Patent Application No. 20245068 filed on January 24, 2024, the contents of which are incorporated herein by reference in their entirety for all purposes. FIELD [2] The present disclosure relates to processes and systems for recovering a deoiled and dewatered algal biomass from a rag layer. Also, the present disclosure relates to uses of a system for treating algal biomass. BACKGROUND INFORMATION [3] Algae offers an opportunity as a crop to supply algal oil for renewable fuels derived from seawater, atmospheric CO2, sunlight, and nutrients. Algae can be grown on non-arable land for terrestrial crops, which is an additional benefit. Once the algal biomass has been harvested, the algal oils and the aqueous growth medium must be separated from the algal protein before either can be used for commercial purposes. [4] There is an increasing interest in using algal biomass as a key intermediate for a plethora of sustainable products, such as a source of renewable energy, as a mode to safely and efficiently capture carbon dioxide from the atmosphere for carbon sequestration, as a source of natural carotenoids and as a renewable source of chemical intermediates. For example, an algal concentrate that
Attorney Docket No.0079721-000085 is produced by a harvester is often passed through an extraction process to separate the algal oil from the algal biomass. [5] U.S. Patent No.5,378,369 discloses a solvent-extraction of a beta carotene from algae into a vegetable oil by mixing the oil and aqueous algal suspension, allowing the beta carotene to dissolve into the oil, and separating the oil and aqueous phases by passing the oil phase through a semipermeable membrane. Using a semipermeable membrane to separate the phases can be feasible at a small scale. However, scaling up membrane separation processes for applications such as industrial production of algal oil for biofuels or production of large quantities of carotenoids for dietary supplements, is difficult. [6] Though algal oil can be a source of valuable products including carotenoids, fatty acids, and other lipids; the deoiled algal biomass produced from extraction processes can also be a source of valuable products, including protein, animal feeds, soil builder, feed for fermentation, and fuel. [7] Algal biomass harvesting processes are known to involve growing the biomass in an aqueous medium containing salts, harvesting the algal biomass to produce an algal concentrate and extracting the algal concentrate in a salty environment. During the extraction process, most of the algal oils and carotenoids are removed from the algal concentrate with an extraction solvent. The addition of the extraction solvent causes a phase separation to occur in the algal concentrate. An extract layer is formed that contains the oils and carotenoids produced by the algae. Additionally, a layer containing a lipid-depleted algal biomass is also formed. The layer containing the lipid-depleted algal biomass can be a rag layer that also contains water, salt, oil and residual extraction solvent.
Attorney Docket No.0079721-000085 [8] One of the key challenges with algal biomass processing can be the presence of a high amount of salt and water in the rag layer. The rag layer needs to be dewatered, deoiled, dried and optionally desalted to enable further usage of the extracted algal biomass material contained therein. [9] WO11053867 A1 describes a process where an algal biomass is partly dewatered before extraction. The extraction process involves separating a defatted biomass from an oil/solvent/water mixture, evaporating the solvent to form a water/oil mixture and then separating the oil from the water. There is no discussion regarding the handling of the defatted biomass and desalting is not mentioned. Furthermore, this patent uses an amphiphilic solvent, which is evaporated from the oil and water mixture. The use of these solvents would not remove any residual salt from the defatted biomass. [10] WO10104922 A1 describes a process where an algal biomass is pH adjusted, extracted and a biomass/water mixture is separated from a solvent phase. Enzymatic hydrolysis is mentioned as a treatment of defatted algal biomass, but desalting or additional dewatering/drying is not described. [11] A traditional way to desalt an extracted algal biomass is to wash it with fresh water (e.g., see U.S.5,951,875). Several technologies can be used for that process like centrifugation, filtration, diafiltration, or membrane filtration. Unfortunately, desalting is a very water intensive process. Furthermore, after salt is washed away, the extracted algal biomass is water wet and can be easily spoiled due to the lack of a salty environment that reduces microbiological growth. Additionally, drying of the extracted algal biomass is mandatory to prevent the spoilage of the algae products. The energy requirement to dry water wet algal biomass material is high due to the amount of heat energy needed. Traditional
Attorney Docket No.0079721-000085 desalt/dewater technologies are also limited with algal concentration achieved leading to the fact that water concentration is high before drying. Process hygiene also needs to be taken into account and that usually complicates the overall extraction and recovery process. [12] Thus, to address the foregoing issues, a more economical and efficient process for recovering algal biomass material from a layer containing lipid-depleted algal biomass and optionally water, salt, oil and residual extraction solvent, formed via an extraction process is desirable. SUMMARY [13] Disclosed herein is a process for recovering algal biomass, the process including (i.e., comprising) at least one or more of: extracting a rag layer containing an algal biomass from an algal concentrate; deoiling the rag layer to produce a deoiled algal slurry; dewatering the deoiled algal slurry to create a dewatered, deoiled algal biomass, the dewatering including contacting the deoiled algal slurry with a filtration system and washing the deoiled algal slurry with a washing media, the filtration system including at least one filtration membrane; and drying the dewatered, deoiled algal biomass. [14] Also disclosed herein is a process for recovering algal biomass, the process including at least one or more of: extracting a rag layer containing an algal biomass from an algal concentrate; dewatering the rag layer to produce a dewatered algal slurry, the dewatering including contacting the rag layer with a filtration system and washing the rag layer with a washing media, the filtration system including at least one filtration membrane; deoiling the dewatered algal slurry to produce a deoiled, dewatered algal biomass; and drying the deoiled, dewatered algal biomass.
Attorney Docket No.0079721-000085 [15] Disclosed herein is a system for recovering algal biomass from a rag layer, the system including at least one or more of: a dewatering zone configured to dewater an extracted rag layer and produce a dewatered algal slurry, the dewatering zone including a filtration system having at least one filtration membrane, the at least one filtration membrane including at least one hydrophilic or hydrophilic and oleophobic material; and a deoiling zone in communication with the dewatering zone, the deoiling zone being located either upstream or downstream of the dewatering zone. [16] Disclosed herein is also a use of the systems and processes of the present disclosure for treating (e.g., deoiling, dewatering and/or drying) algal biomass. BRIEF DESCRIPTION OF THE DRAWINGS [17] Other features and advantages of the processes and systems disclosed herein will be apparent to those skilled in the art reading the following detailed description in conjugation with the exemplary embodiments illustrated in the drawings, wherein: [18] FIG.1 shows a flow diagram of an exemplary embodiment of a deoiling and dewatering process for the isolation of algal biomass in a rag layer, the process involving deoiling the rag layer to create a deoiled algal slurry and simultaneously dewatering and desalting the deoiled algal slurry. The dashed lines represent optional steps which can occur in the depicted exemplary embodiment. [19] FIG.2 shows a flow diagram of an exemplary embodiment of a deoiling and dewatering process for the isolation of algal biomass in a rag layer, the process involving simultaneously dewatering and desalting the rag layer to create a dewatered/desalted algal slurry and deoiling the dewatered/desalted algal slurry. The
Attorney Docket No.0079721-000085 dashed lines represent optional steps which can occur in the depicted exemplary embodiment. [20] FIG.3 shows a flow diagram of an exemplary embodiment of a deoiling and dewatering process for the isolation of algal biomass in a rag layer, the process involving deoiling the rag layer to create a deoiled slurry, desalting the deoiled slurry to create a deoiled, desalted algal slurry and dewatering the deoiled, desalted algal slurry. The dashed lines represent optional steps which can occur in the depicted exemplary embodiment. [21] FIG.4 shows a flow diagram of an exemplary embodiment of a filtration membrane system for desalting and dewatering a deoiled algal slurry. DETAILED DESCRIPTION [22] One aspect of the present disclosure is a process for recovering algal biomass, the process including at least one or more of: extracting a rag layer containing an algal biomass from an algal concentrate; deoiling the rag layer to produce a deoiled algal slurry; dewatering the deoiled algal slurry to create a dewatered, deoiled algal biomass, the dewatering including contacting the deoiled algal slurry with a filtration system and washing the deoiled algal slurry with a washing media, the filtration system including at least one filtration membrane; and drying the dewatered, deoiled algal biomass. [23] FIG.1 shows an exemplary embodiment of the deoiling and dewatering process for the isolation of algal biomass in a rag layer. In this embodiment, algae are cultured in an algal aquaculture zone (100) and are transferred to a harvesting zone (102) and a pre-harvested algal concentrate stream. The pre-harvested algal concentrate stream undergoes at least one harvesting process in the harvesting zone (102) to form an algal concentrate stream. The algal concentrate stream is then
Attorney Docket No.0079721-000085 subjected to an extraction process in an extraction zone (104) that forms a rag layer containing an algal biomass. [24] The expression “algal concentrate” refers to a stream containing an algal biomass solution or suspension that includes natural products (e.g., algal oils, proteins, lipids, carotenoids, hydrophobic products), an aqueous solution, and a biomass. The algal concentrate can be derived from a feedstock source and/or a unit operation that concentrates the biomass in the algal concentrate (e.g., a harvesting zone). [25] In exemplary embodiments, the algal concentrate is a stream originating from at least one or a combination of plant, algae, micro-organism, bacteria, or microalgae feedstock sources. Suitable algae or microalgae feedstock sources can be derived from algal aquaculture ponds. These algal aquaculture ponds can be operated in batch, continuous, semi-continuous or other modes known in the art to produce the desired algae in the algal concentrate. [26] The algal aquaculture pond can be any type of algal aquaculture pond used to grow algae, including, but not limited to open pond, closed pond, raceway pond, enclosed or partly enclosed photobioreactor, tubular reactor, flat panel (i.e., flat-plate) reactor, column reactor, enclosed raceway, covered pond, open raceway pond, earthen pond, pond in a greenhouse, fermenter, naturally occurring body of water, solar salt pond, or any combinations thereof. [27] Open algal aquaculture ponds can be configured either with or without agitation or liners. When present, suitable liner materials include plastic, cement or clay. Plastic algal aquaculture pond liners can be formed from polyethylene, polypropylene, or polyvinyl chloride. Different types of these basic polymers can be used, for example, a linear low-density polyethylene liner can be used for algae
Attorney Docket No.0079721-000085 cultivation on a large scale. These liners can also include additives, such as carbon black to provide resistance to ultraviolet radiation. These liners can also include Nylon or other fibers to provide additional structural integrity. Raven Industries (South Dakota) provides a full line of suitable liners that include one or more layers of materials. Suitable clay liners include bentonite clay. However, when algal aquaculture ponds are flooded, components in the water, especially saline, can often form a barrier that seals the algal aquaculture pond. It can also be desirable to include liners in just a portion of the algal aquaculture pond where they are specifically needed. For example, liners can be utilized to protect earthen borders where the hydraulic flow can be elevated. [28] In exemplary embodiments, additional aqueous medium is periodically or continuously provided to the feedstock source to replace water that evaporates from the feedstock source and/or increase the liquid depth of the feedstock source, i.e., the depth of the algal growth medium. The additional aqueous medium can be combined with recycled algal growth medium to form an aqueous medium that enters a feedstock source optionally via an algal pretreatment unit to form an algal aquaculture medium. If the algal growth medium in the feedstock source contains mineral salt, the salinity of the additional aqueous medium fed to the feedstock source can be less than the highest salinity experienced by the algae in the feedstock source. [29] The amount of the additional aqueous medium possibly added each day can depend upon several factors: salinity targets in the feedstock source, the wind speed and the relative humidity. Daily evaporation rates can be a major factor in the determination of daily water needs for the feedstock source. If evaporation rates are high, then the salinity of the feedstock source will increase, and water will be
Attorney Docket No.0079721-000085 required to make up for the losses and to maintain the salinity target for each feedstock source. Wind tends to accelerate evaporation rates, and thus the higher the wind speed, the higher the evaporation rates for a given salinity. The amount of moisture in the atmosphere is termed the relative humidity, and the lower this value the higher the evaporation rates when all other factors are constant. Consequently, the rate and amount of evaporation directly influences the daily demand for additional aqueous medium. [30] In exemplary embodiments, the algal concentrate includes or is an algal aquaculture medium. [31] As used herein, the term “algal aquaculture medium” refers to an aquaculture medium existing in an algal aquaculture pond, as well as any additional medium, such as aqueous medium, added to the algal aquaculture pond to supplement the medium already in the algal aquaculture pond. The algal aquaculture medium can include water and one or more of mineral salts, heavy metals, algae, algal predators, algal competitors, algal nutrients, algal biomass, natural products or residual nutrients. The algal aquaculture medium can also include additional aqueous medium (also sometimes referred to as make up medium) that is periodically or continuously provided to the algal aquaculture pond to supplement the algal aquaculture medium existing in the algal aquaculture pond. [32] In exemplary embodiments, the algal concentrate contains a biomass concentration greater than about 10 ppm, 100 ppm, 0.1wt%, 1wt%, 10wt%, 20wt%, 30wt%, 40wt% or 50wt%. [33] As used herein, the term "about" refers to a value that is ± 5% of the stated value. In addition, it is understood that reference to a range of a first value to a second value includes the range of the stated values, e.g., a range of about 1 to
Attorney Docket No.0079721-000085 about 5 also includes the more precise range of 1 to 5. It is also understood that the ranges disclosed herein include any selected subrange within the stated range, e.g., a subrange of about 50 to about 60 is contemplated in a disclosed range of about 1 to about 100. [34] In exemplary embodiments, the algal concentrate has a suitable viscosity so that it can be pumped. A suitable viscosity for pumping can be less than 10,000 cp, less than about 1,000 cp and/or less than 500 cp. [35] In exemplary embodiments, the algal concentrate undergoes a harvesting process in a harvesting zone before advancing to the extraction process. These harvesting processes can include, but are not limited to, adsorptive bubble separation, filtration, deep bed filtration, belt pressing, screw pressing, centrifugation, adsorption, sedimentation, mechanical floatation, froth flotation, flocculation and combinations thereof. Examples of these and other harvesting processes and equipment which can be used to condition the algal concentrate before the extraction process can be found in U.S. Pat. No.5,541,056; U. S. Pat. No.4,554,390; U.S. Pat. No.4,115,949; U.S. Pat. No.5,951,875; U.S. Pat. No.4,680,314; U.S. Pat. No. 6,524,486; U.S. Pat. No.6,405,948; U.S. Pat. No.5,776,349; U.S. Pat. No. 6,000,551; U.S. Pat. No.8,512,998; U.S. Pat. No.4,397,741; U.S. Pat. No. 4,938,865; U.S. Pat. No.5,188,726; U.S. Pat. No.5,332,100; WO 2008/156,795; WO 2008/156,835; U.S. Pat. No.4,981,582; U.S. Pat. No.5,167,798; all the contents of which are incorporated herein by reference in their entireties. [36] In exemplary embodiments, the process includes culturing a feedstock source in an algal aquaculture pond to form a pre-harvested algal concentrate, transferring the pre-harvested algal concentrate to a harvesting zone, and
Attorney Docket No.0079721-000085 performing at least one harvesting process on the pre-harvested algal concentrate to form the algal concentrate. [37] In exemplary embodiments, prior to an adsorptive bubble separation process, the biomass e.g. in the algal concentrate can be flotation conditioned by a number of processes. Suitable flotation conditioning processes that can be used prior to the adsorptive bubble separation unit include, but are not limited to, adding a flotation aid, adding a frother, adding a collector, adding an activator, adding a depressor, and combinations thereof. [38] Collectors selectively render one or more of the species of particles in the algal concentrate hydrophobic, thereby assisting in the process of collection by gas bubbles. Activators aid the adsorption of the collector to certain particles increasing the number of those particles which become hydrophobic. Depressors inhibit the adsorption of the collector to certain undesired particles decreasing the number of those particles which become hydrophobic. Also, frothing agents and frothers can be added to the algal concentrate to assist in the formation of a stable froth on the surface of a liquid. [39] Sedimentation process can include the addition of alum to and/or lack agitation of the algal concentrate. The addition of ferric chloride can also be included in sedimentation processes to cause flocculation. Any polymer or ions that cause flocculation can also be used during sedimentation processes. Cyclones can also be used to accelerate the rate of sedimentation. Any sedimentation equipment known in the art can be used to separate the flocculated natural products from an aqueous salt solution prior to an adsorptive bubble separation process. [40] Adsorption can be used as a conditioning process to reduce the volumetric flow of the algal concentrate to an adsorptive bubble separation unit. Some
Attorney Docket No.0079721-000085 feedstock, for example Dunaliella salina, can be concentrated by adsorbing the algae onto a hydrophobic surface, and then desorbing the algae with another fluid. Thus, adsorption can be used to preconcentrate the feedstock stream. [41] Deep bed filtration can be used to further concentrate the algal concentrate in addition to an adsorptive bubble separation process. Deep bed filtration relies upon a bed of granular media, usually sand, through which the algal concentrate containing natural products flows downward under gravity. The natural products are deposited in the pores of the granular media and in the interstitial spaces between the grains of media. Deep bed filtration should not be confused with straining filtration. Straining takes place on the surface of a mesh or fabric, and is only suitable to further concentrate the algal concentrate with natural products that will not blind the filtration equipment. [42] Adsorptive bubble processes can include a step of rendering material or natural products within the algal concentrate hydrophobic by treating particle surfaces with chemicals, or other techniques that selectively modify the material or natural products to be separated. In some cases, the particles or natural products are not initially hydrophobic, and need to be rendered hydrophobic to be separated or harvested from the algal concentrate. [43] A flocculating agent can be utilized during adsorptive bubble separation processes to cause accumulations of algal biomass or natural products to float out during adsorptive bubble processes. [44] The algal concentrate or the biomass included in the algal concentrate can also be subjected to a cell rupturing process before proceeding to the extraction process. The algal concentrate can include cellular material which contains natural products. In these instances, rupturing the cell wall and/or cell membrane of the
Attorney Docket No.0079721-000085 cellular material can release natural products that can be purified in later processes. Cell rupturing can be achieved by a number of processes which include, but are not limited to, chemical, physical or mechanical processes. Chemical processes can include enzymatic digestion, detergent solubilization, lipid dissolution with a solvent, and alkali treatment (lipid saponification). Physical processes can include osmotic shock, decompression, sonication, heat treatment, and freeze-thawing. Mechanical processes can include grinding, high shear homogenization, passing the algal concentrate across a pressure drop, and pressure extrusion. [45] Other cell disruption processes which can be used include pumping the algal concentrate at high pressures through a restricted orifice valve. An equipment which can perform this disruption process is, as an example, the MICROFLUIDIZER™ cell disruption equipment of Microfluidics, Newton, MA, US, which utilizes pressures of about 5,000 to 40,000 psig (345 - 2760 bar). [46] A mill, such as a vibratory mill, can also be used to rupture cellular material in the algal concentrate. [47] In exemplary embodiments wherein the algal concentrate contains algae or microalgae, fracking processes can be performed on the algal concentrate before the extraction process. The partial rupturing of algae is referred to as fracking. Fracked algae can be advantageous over completely ruptured algae due to the difference in size of the resulting particles. Particles resulting from fracking algae are larger than the particles resulting from the complete rupturing of algae and thus adsorptive bubble separation processes can be more effective when larger particles are present. Fracking the algae or microalgae can produce fracked cells possessing hydrophobic components while still retaining a significant portion of the intracellular material within the cellular membrane. This can result in increased recovery of the
Attorney Docket No.0079721-000085 intracellular material. Fracking can take place in any device known in the art in which algae or microalgae can be partially ruptured including, but not limited to, a vibratory mill, a French press, a pump, an agitated vessel, or combinations thereof. [48] As used herein, the term “algae” refers to unicellular and multicellular eukaryotic algae, microalgae, diatoms, dinoflagellates, coccolithophores, cyanobacteria and combinations thereof. [49] The algae or microalgae which can be present in the algal concentrate can include, but is not limited to, algae from the divisions of Bacillariophyta, Chlorophycophyta, Chrysophycophyta, Cyanophycophyta, Cryptophycophyta, Phaeophycophyta, Pyrrhophycophyta, Rhodophycophyta and combinations thereof. The algae or microalgae present in the algal concentrate can include, but is not limited to, species from the following genera: Acutodesmus, Achnahtes, Amphipora, Amphora, Anabaena, Ankistrodesmus, Arthrospira (also known as Spirulina), Asteromonas, Asterionella, Boekelovia, Borodinella, Botryococcus, Bracteacoccus, Carteria, Chaetoceros, Chlamydomonas, Chlorella, Chlorococcum, Chlorogonium, Chloromonas, Chroomonas, Chrysophaera, Ceratium, Closterium, Coccolithus, Coelastrella, Coscinodiscus, Cosmarium, Cricosphaera, Crocosphaera, Crypthecodinium, Cryptomonas, Cyanocystis, Cyanospira, Cyclotella, Desmodesmus, Ditylum, Dunaliella, Ellipsoidon, Emiliania, Eremosphaera, Euglena, Fragilaria, Franceia, Galdieria, Gracilaria, Graesiella, Guinardia, Haematococcus, Halocafeteria, Halospirulina, Hantzschia, Hymenomonas, Isochrysis, Lepocinclis, Limnothrix, Micractinium, Microactinium, Microcystis, Monochrysis, Monodus, Monoraphidium, Muriellopsis, Nannochloris, Nannochloropsis, Navicula, Neochloris, Neospongiococcum, Nephrochloris, Nephroselmis, Nitzschia, Nodularia, Nostoc, Ochromonas, Oedogonium, Oocystis, Oscillatoria, Ostreococcus, Parachlorella,
Attorney Docket No.0079721-000085 Pavlova, Peridinium, Phaeodactylum, Picochlorum, Platymonas, Pleurochrysis, Pleurococcus, Porphyra, Porphyridium, Prochlorococcus, Prototheca, Prymnesium, Pseudanabaena, Pseudochlorella, Pseudochoricystis, Pseudoneochloris, Pyramimonas, Pyrobotrys, Rhodomonas, Scenedesmus, Schizochytrium, Scytonema, Skeletonema, Spirogyra, Stichococcus, Synechococcus, Tetrachlorella, Tetradesmus, Tetraselmis, Thalassiosira, Tisochrysis, Tolypothrix, Tribonema, Trichodesmium, Ulothrix, Vaucheria, Viridiella, Volvox, and genetically-engineered varieties or combinations (mixtures, mixed cultures, co-cultures or synthetic co- cultures) thereof. In exemplary embodiments, the algae or microalgae is selected from the group including Dunaliella sp., Dunaliella bardawil, Dunaliella salina, Dunaliella kone, Dunaliella tertiolecta, Dunaliella parva and Dunaliella viridis, and any combination thereof. In exemplary embodiments, the algae or microalgae is Dunaliella salina, Dunaliella bardawil, Dunaliella kone, or any combination thereof. [50] The algae or microalgae which can be present in the algal concentrate can also include any microalgal species (including diatoms, coccolithophorids and dinoflagellates) selected from, but not limited to, Amphora sp., Ankistrodesmus sp., Arthrospira (Spirulina) plantesis, Botryococcus braunii, Chlamydomonas sp., Chlamydomonas reinhardtii, Chlorella protothecoides, Chlorella sp., Closterium sp., Cosmarium sp., Crypthecoddinium cohnii, Cyclotella sp., Dunaliella salina, Dunaliella tertiolecta, Haematococcus pluvialis, Hantzschia sp., Nannochloris sp., Nannochloropsis sp., Navicula sp., Neochloris oleoabundans, Nitzschia sp., Phaeodactylum tricornutum, Scenedesmus sp., Schiochytrium limacinum, Stichococcus sp., Tetraselmis suecica, and Thalassiosira pseudonana, and genetically-engineered varieties or combinations (mixtures, or mixed cultures) of these microalgal species.
Attorney Docket No.0079721-000085 [51] The algae or microalgae which can be present in the algal concentrate can also include algae with flagella, cilia and/or eyespots. Flagella are a tail-like projection that protrudes from the cell body of certain algae and functions in locomotion. Cilia are an adaptation that allows independent cellular creatures, like algae, to move around in search of food. Photosensitive eyespots are found in some free-swimming unicellular algae. Photosensitive eyespots are sensitive to light. They enable the algae to move in relation to a light source. Such algae have the capability of independent motion, phototaxis, and can move towards the surface during daylight. Phototaxis is the movement of microalgae in response to light. Certain algae (e.g., Dunaliella) can perceive light by means of a sensitive eyespot and move to regions of higher light concentration to enhance photosynthesis. [52] The algae or microalgae which can be present in the algal concentrate also include marine algae that thrive at salt concentrations above that found in seawater. Suitable marine algae can be selected from, but are not limited to, Amphora sp. (diatom), Arthrospira sp., Arthrospira (Spirulina) obliquus, Arthrospira (Spirulina) platensis, Chlorella sp., Chlorella fusca, Chlorella protothecoides, Chlorella pyrenoidosa, Chlorella stigmataphora, Chlorella vulgaris, Chlorella zofingiensis, Dunaliella sp., Dunaliella bardawil, Dunaliella salina, Dunaliella tertiolecta, Dunaliella viridis, Isochrysis galbana, Microcystis sp., Nannochloropsis sp., Nannochloropsis salina, Navicula sp. (diatom), Navicula saprophila (diatom), Nitzschia laevis (diatom), Nitzschia alba (diatom), Nitzschia communis (diatom), Nitzschia paleacea (diatom), Nitzschia closterium (diatom), Nitzschia palea, (diatom), and genetically-engineered varieties or combinations (mixtures, or mixed cultures) of these algal species.
Attorney Docket No.0079721-000085 [53] In exemplary embodiments, the algae is microalgae. In other exemplary embodiments, the algae or microalgae have not been genetically modified or do not originate from genetically engineered algae or microalgae. [54] In exemplary embodiments, the algae or microalgae which can be present in the algal concentrate include a group of algae or microalgae that has not been genetically modified or does not originate from genetically engineered algae or microalgae. This group of algae or microalgae can include, but is not limited to, Dunaliella sp., Dunaliella bardawil, Dunaliella kone, Dunaliella salina, Dunaliella bioculata, Dunaliella granulata, Dunaliella maritima, Dunaliella minuta, Dunaliella parva, Dunaliella peircei, Dunaliella polymorpha, Dunaliella primolecta, Dunaliella pseudosalina, Dunaliella quartolecta, Dunaliella terricola, Dunaliella tertiolecta, and Dunaliella viridis. [55] All of the possible algae and microalgae which can be included in the algal concentrate can also be included within any biomass present in the algal concentrate. [56] In exemplary embodiments, the extracting of the rag layer from the algal concentrate can also include extracting other natural products from the algal concentrate. [57] The expression “natural products” refers to products which are naturally produced or found within an environment or a living organism. Natural products can include those which are hydrophobic, hydrophilic or amphipathic. [58] In exemplary embodiments, the natural products are those which are naturally produced by a plant, a microbe, an algae or microalgae species which can be included within the algal concentrate or biomass. These natural products can include one or more of lipids, algal lipids, carotenoids, fatty acids, algal fatty acids,
Attorney Docket No.0079721-000085 triacylglycerols, diacylglycerols, monoacylglycerols, oils, algal oils, chlorophyll, glycerol, phospholipids, carbohydrates, fibers, and proteins. [59] In exemplary embodiments, the algal concentrate contains an aqueous salt solution. [60] The expression “aqueous salt solution” refers to a solution containing water and at least one salt. The salt can be any one or combination of salts found in sea water, terminal lakes, or aquifers. In exemplary embodiments the aqueous salt solution is or includes culture medium of the algal concentrate. [61] The aqueous salt solution can include combinations of ions found in seawater. [62] The aqueous salt solution can contain concentrations of salts which range from trace amounts to saturating amounts. Suitable terms to describe the salinity or salt concentration of the aqueous salt solution range from fresh water, brackish water, salt water, brine, and saturated brine, respectively, as the salt concentration in the aqueous salt solution increase. The desired concentration of salt in the aqueous salt solution will depend on the type of feedstock (e.g., algae species) present in the algal concentrate. [63] The expression “salinity” refers to the total amount of dissolved salts in the aqueous solution. Salts which can be dissolved and found in the aqueous solution include, but are not limited to, those found in natural waters such as sodium chloride, magnesium chloride, calcium and magnesium sulfates, bicarbonates, and carbonates. It is a standard practice to express salinity as parts per thousand (%0), which is not a true percent but an approximation of the milligrams of salt per gram of water. In more general terms, salinity is indicated by the water source, such as a freshwater, a brackish water, a saline water, and a brine. Ranges of salinity are
Attorney Docket No.0079721-000085 associated with these general terms and these ranges are defined as < 0.05 wt% for freshwater, 0.05 - 3 wt% for brackish water, 3 - 5 wt% for saline water, and > 5 wt% for a brine. [64] Various combinations of ions found in seawater can be included in the aqueous salt solution. Suitable ion combinations can be derived from one or more of the following sources including: water derived from streams, lakes, rivers, or other sources associated with fresh water; water derived from underground aquifers that can include various ion concentrations; water derived from industrial, agricultural, or municipal sources that can or cannot have received treatment; or water derived from brackish sources where fresh water is combined with sea water or ocean water in various proportions; sea water or ocean water that can be derived from the various seas and oceans located around the globe; water derived from terminal lakes; or combinations thereof. The combination of ions for the aqueous salt solution can be derived directly from these sources, or can be derived by evaporating the desired amount of water from any of these sources to leave the desired ion-rich solution for use as the aqueous salt solution. An example of an ion combination source is disclosed in U.S. Pat. No.6,986,323, the contents of which are included herein by reference. Other examples include the evaporation of ancient sea waters that form terminal lakes, such as the Great Salt Lake in Utah, and that form various aquifers. The combination of ions can result up to and include crystallizers wherein sodium chloride ions are precipitated. [65] The aqueous salt solution and/or the algal concentrate can have a salinity that is about 5 wt% or greater than 5 wt%, about 6 wt% or greater than 6 wt%, about 7 wt% or greater than 7 wt%, for example at least about 8 wt%, at least about 9 wt%, at least about 10 wt%, at least about 11 wt%, at least about 12 wt%, at least
Attorney Docket No.0079721-000085 about 13 wt%, at least about 14 wt%, at least about 15 wt%, at least about 16 wt%, at least about 17 wt%, at least about 18 wt%, at least about 19 wt%, at least about 20 wt%, at least about 21 wt%, at least about 22 wt%, at least about 23 wt%, at least about 24 wt%, or at least about 25 wt%. In exemplary embodiments the aqueous salt solution and/or the algal concentrate is saturated with salt. In other exemplary embodiments, the aqueous salt solution and/or the algal concentrate can have a salinity that is about 5 wt% to about saturation, from about 10 wt% to saturation, from about 20 wt% to saturation, from about 5 wt% to about 20 wt%, from about 10 wt% to about 20 wt%, from about 5 wt% to about 15 wt%, from about 10 wt% to about 15 wt%, or from about 5 wt% to about 10 wt%. In exemplary embodiments, the aqueous salt solution and/or the algal concentrate has a salinity greater than 5 wt%, greater than 10 wt%, greater than 15 wt% or greater than 20 wt%. [66] As used herein, wt% refers to a dry mass of a component in a solution in grams divided by 100 grams of the solution. [67] At least one salt can either be present in the aqueous salt solution or added to the algal concentrate to increase its salinity. The presence of salt, and specifically elevated salt compositions provides several advantages. First, the presence of salt in the algal concentrate can reduce solvent solubility in a raffinate layer, and thus reduce either potential solvent loss or solvent recovery costs. Second, the presence of salt in the algal concentrate can increase the density of a raffinate layer, thus enhancing phase separation rates that lead to reduced decanter sizes. Third, the presence of salt in the aqueous salt solution can retard spoilage of the biomass in the processing step. All of these advantages, alone or in combination adds significant value to the processes disclosed herein.
Attorney Docket No.0079721-000085 [68] The at least one salt can be selected from, but not limited to, a sea salt, an underground salt, a salt of aquifer water, a salt of a terminal lake, sodium chloride, and/or any combination thereof. [69] The biomass in any one or more of the aqueous salt solution or algal concentrate can include or be a plant biomass, a microbial biomass, an algal biomass or any combination thereof. [70] All of the possible plants and/or microbes which can be included in the algal concentrate can also be included within the biomass in the aqueous salt solution. [71] All of the possible plant or microbial biomass which can be included in the algal concentrate include any plant or microbial biomass. [72] The biomass can also include or contain some or all of the natural products within the algal concentrate. [73] The biomass content in the algal concentrate can be as low as about 0.05 wt%, greater than about 0.5 wt% and even greater than 1 wt%. The maximum biomass content in the algal concentrate is limited as the maximum amount of biomass that allows the algal concentrate to flow, and this is less than about 20 wt%, or less than about 10 wt%. [74] The algal concentrate can contain a water content before the extraction process. The water content can be about 0.1 wt% to about 5 wt%, about 5 wt% to about 10 wt%, about 10 wt% to about 15 wt%, about 15 wt% to about 20 wt%, about 20 wt% to about 30 wt%, about 30 wt% to about 40 wt%, about 40 wt% to about 50 wt%, or about any range within 0.1 wt% to 50 wt% of the total weight of the algal concentrate. In exemplary embodiments, the algal concentrate can contain a water
Attorney Docket No.0079721-000085 content before the extraction process that is greater than 50 wt% or about any range within 50 wt% to 99 wt%. [75] The biomass can include or be a conditioned biomass. As used herein “a conditioned biomass” refers to a biomass that has been treated with one or more conditioning processes before the extraction process. Suitable conditioning processes can include, but are not limited to, fracking, adsorptive bubble separation, filtration, deep bed filtration, belt pressing, screw pressing, centrifugation, adsorption, sedimentation, mechanical floatation, froth flotation, flocculation and combinations thereof. [76] In exemplary embodiments, the extracting of the rag layer from the algal concentrate includes performing an extraction process that produces at least two layers, one layer being the rag layer. The other layer can be an organic extract layer containing an organic solvent or a raffinate layer containing an aqueous solution and optionally salts. [77] In exemplary embodiments, the extracting of the rag layer from the algal concentrate includes performing a liquid-liquid-solid extraction process on the algal concentrate, the liquid-liquid-solid extraction process including at least one or more of the following: forming a dispersion by contacting (e.g., by intimately contacting) the algal concentrate with an extraction solvent in an extraction zone; passing the dispersion to a separation zone; separating the dispersion into multiple layers, the layers including: a solvent extract layer containing at least one hydrophobic natural product and an extraction solvent, a raffinate layer containing an aqueous salt solution, and a rag layer containing a lipid-depleted biomass; and isolating at least part of the solvent extract layer, at least part of the raffinate layer and/or at least part of the rag layer.
Attorney Docket No.0079721-000085 [78] The expression “liquid-liquid-solid extraction” refers to a process wherein an algal concentrate containing an algal biomass that includes one or more natural products is (e.g., intimately) contacted with an extraction solvent capable of extracting one or more of the hydrophobic natural products from the algal biomass. [79] The term “dispersion” relates to a heterogeneous mixture containing an aqueous salt solution, algal biomass, and extraction solvent. The dispersion can exist as an emulsion. [80] The extraction solvent must form a second liquid phase or layer with the algal concentrate in the extraction zone. Suitable extraction solvents include, but are not limited to a non-polar solvent, a non-polar organic solvent, a dense gas solvent, an aqueous two-phase solvent, a deep eutectic solvent (DES) and/or a natural deep eutectic solvent (NADES) (such as choline chloride, glucose, lactic acid, malic acid, and/or any combination thereof), an ionic liquid, or any combination thereof or any combination of solvents such as miscible solvents. [81] In an exemplary embodiment, the extraction solvent is or includes at least one or more of a non-polar solvent, a non-polar organic solvent, a dense gas solvent, an aqueous two-phase solvent, a deep eutectic solvent (DES), a natural deep eutectic solvent (NADES), an ionic liquid, or any combination thereof. [82] In another exemplary embodiment, the extraction solvent is or includes at least one or more of a non-polar solvent, a non-polar organic solvent, a dense gas solvent, an aqueous two-phase solvent, a deep eutectic solvent (DES), a natural deep eutectic solvent (NADES), or any combination thereof. [83] In another exemplary embodiment, the extraction solvent is or includes at least one or more of a non-polar solvent, a non-polar organic solvent, a dense gas solvent, an aqueous two-phase solvent, or any combination thereof.
Attorney Docket No.0079721-000085 [84] In another exemplary embodiment, the extraction solvent is or includes at least one or more of a non-polar solvent, a non-polar organic solvent, a dense gas solvent, or any combination thereof. [85] The extraction solvent can be chosen such that its polarity is appropriate to extract the desired natural products. Thus, the optimal extraction solvent for the liquid-liquid-solid extraction process can depend on which natural products are desired to be extracted. [86] Any solvent system that forms a second immiscible liquid phase or layer with the algal concentrate can be used as the extraction solvent. These solvent systems should not adversely impact the quality or quantity of the natural products. These solvent systems can include, but are not limited to, synthetic and/or natural flavorants, edible oils, petrochemicals, dense gases, and combinations of these so long as the mixture of the solvent system and the algal concentrate forms two immiscible liquid phases at a desired extraction zone temperature. Some of these solvents are more desirable than others for various reasons as discussed below and the results obtained are not necessarily equivalent. [87] The solvent system can include petrochemical solvents due to their low viscosity and favorable solute molecular diffusivity. Natural oils are soluble in petrochemical solvents and concentrated extracts are possible. Suitable petrochemical solvents can include those that are disclosed in "Organic Solvents: Physical Properties and Methods of Purification", edited by J. A. Riddick et al, Volume 2, Fourth Edition, ISBN Number 0-471- 08467-0, such as 2-methyl oxolane. In exemplary embodiments, the petrochemical solvents can include, but are not limited to, aliphatic hydrocarbons (such as pentane, hexane, heptane, octane, nonane, decane, dodecane, cyclohexane, petroleum ether, their isomers, and
Attorney Docket No.0079721-000085 mixtures thereof), aromatic hydrocarbons (including but not limited to benzene, toluene, xylene), alcohols (including, but not limited to butanol, pentanol, hexanol, octanol, dodecanol, cyclohexanol, benzyl alcohol, their isomers, and combinations thereof), ketones (including, but not limited to methyl isobutyl ketone, hexanone, heptanone, octanone, their isomers, and combinations thereof), esters (including, but not limited to methyl acetate, ethyl acetate, propyl acetate, butyl acetate, pentyl acetate, hexyl acetate, ethyl propionate, ethyl butyrate, ethyl valerate, their isomers, and combinations thereof), and/or ethers (including but not limited to 2- methyltetrahydrofuran, diisopropyl ether, methyl tert-butyl ether, cyclopentyl methyl ether, and combinations thereof). Combinations of petrochemical solvents can also be used if desired. [88] The petrochemical solvents can also contain one or more co-solvents to improve extractability of solutes. Examples of these co-solvents include methanol, ethanol, 1-propanol, 2-propanol, 1-hexanol, 2-methoxy ethanol, acetone, tetrahydrofuran, 1,4-dioxane, acetonitrile, dichloromethane, chloroform, dimethyl sulfoxide, formic acid, carbon disulfide, methylene chloride, amines, chelating agents, phase transfer catalysts and combinations thereof. The co-solvents can also be added to the algal concentrate to enhance recovery of a solute or hydrophobic natural product in the extraction solvent. [89] The edible oils which can be included within the solvent system can be chosen from those obtained from plant or animal sources, such as fish oils. Edible vegetable oil solvents include, but are not limited to, those derived from corn, olive, algae, soybean, flax, safflower, sunflower, palm, jatropha, coconut, other oils known in the art, and combinations thereof. Compared to petrochemical solvents, edible oils can be more viscous, and the solute molecular diffusivity is lower.
Attorney Docket No.0079721-000085 [90] The solvent system can also include synthetic and natural flavorants. These flavorants can be more desirable than petrochemical solvents and edible oils if the natural products are to be used for human or animal consumption. Naturally derived flavorants have appeal in nutritional supplements. Flavorants classified by the Flavor and Extract Manufacturers Association, or FEMA, as Generally Recognized As Safe, or GRAS, do not have the drawbacks of petrochemical solvents in association with nutritional supplements. The presence of residual flavorant solvents in nutritional supplements is generally acceptable in comparison with petrochemical solvents, which reduces downstream purification and recovery costs. The flavorants can be chosen from those which have boiling points, viscosities, and molecular diffusivity properties comparable to petrochemical solvents. Examples of such flavorants include, but are not limited to, methyl-, ethyl-, propyl-, butyl-, isobutyl-, benzyl-, and octyl- esters with the carboxylic acid component of the ester including acetate, ethanoate, propionate, butyrate, hexanoate, caproate, heptanoate, octanoate, decanoate, cinnamate, and isovalerate. Other examples of flavorants which can be used include, but are not limited to, benzaldehyde, other aldehydes, limonene, and other terpenes. Combinations of flavorants can also be used. [91] Suitable dense gases which can be used as the extraction solvent include, but are not limited to, carbon dioxide, ethane, propane, butane, chlorofluorocarbons, and mixtures thereof. The dense gas extraction can be operated in any manner known in the art including leaching, batch extraction, and continuous countercurrent extraction as described in U.S. Pat. No.6,106,720 and U.S. Pat. No.5,932,101, the contents of which are incorporated herein by reference in their entirety. Additional suitable dense gases can be methane, isobutane, dimethyl ether, sulfur hexafluoride,
Attorney Docket No.0079721-000085 ammonia, fluorocarbons, and mixtures thereof. Any combination of the above dense gases can also be used. [92] The dense gases can also contain one or more co-solvents to improve extractability of solutes. Examples of these co-solvents include methanol, ethanol, 1- propanol, 2-propanol, 1-hexanol, 2-methoxy ethanol, acetone, tetrahydrofuran, 1,4- dioxane, acetonitrile, dichloromethane, chloroform, dimethyl sulfoxide, formic acid, carbon disulfide, methylene chloride, amines, chelating agents, phase transfer catalysts and combinations thereof. Other examples of dense gases and co-solvents are listed in U.S. Pat. Nos.4,345,976 and 5,490,884, the contents of which are incorporated herein by reference in their entirety. The co-solvents can also be added to the algal concentrate to enhance recovery of a solute or hydrophobic natural product in the extraction solvent. [93] The solvent system can also include an ionic liquid. Suitable ionic liquids include, but are not limited to, solvent systems that are in the liquid phase at the extraction temperature, those that include a cation and an anion, and those that are immiscible with a water-rich algal concentrate phase. [94] In exemplary embodiments, the extraction solvent is selected such that the selectivity of the extraction solvent for specific non-polar compounds versus specific salts is greater than unity (i.e., greater than 1). The selectivity is calculated by dividing the distribution coefficient for a specific non-polar compound of interest to the distribution coefficient for a specific salt of interest. The distribution coefficients are defined as the concentration of the nonpolar compound in the extract phase divided by the concentration of the nonpolar compound in the raffinate phase. [95] In exemplary embodiments, forming the dispersion by contacting the algal concentrate with the extraction solvent involves using an algal concentrate or algal
Attorney Docket No.0079721-000085 biomass to extraction solvent ratio (e.g., a volumetric ratio) of from about 8 to about 0.1, from about 5 to about 0.2, or 1 (e.g., a 1 to 1 volumetric ratio). [96] The algal concentrate can contact the extraction solvent for about 1 minute to 5 hours, or for about 2 minutes to 5 hours, and the contact time can differ based on the type of contactor used in the extraction zone. When a centrifugal extractor is used for the extraction zone, the contact time can range from about 0.5 to 10 minutes, or less than 2 minutes. When an agitated vessel is used for the extraction zone, the contact time can range from about 1 minute to 5 hours, or between 2 and 120 minutes. Preferably, the contact time will be 5 to 60 minutes. The algal concentrate can contact the extraction solvent for about 2 to 180 minutes, about 5 to 180 minutes or about 10 to 60 minutes in a counter-current extraction column. In exemplary embodiments the dispersion is retained in the countercurrent extraction column for a residence time of about 2 minutes to about 2 hours. [97] The extraction zone can include a mixer, a static mixer, a settler, a co- current extraction column, a countercurrent extraction column, a centrifugal extractor, an emulsion phase contactor, or any combination thereof known in the art. [98] Suitable mixers for the extraction zone include agitated vessels where a mechanical agitator is used to intimately contact the algal concentrate and the extraction solvent. The mechanical agitator can include one or more impellers on a rotating shaft. Suitable impellers include, but are not limited to Rushton Turbines, flat-blade turbines, pitch-blade turbines, marine propellers, hydrofoils, impellers that are sold by Chemineer (Dayton Ohio), or SPX/ Lightnin (Rochester, New York). Regardless of the type of impeller used, the degree of agitation required is important for efficient mass transfer of the solute. The degree of agitation required can be calculated by the minimum impeller speed to completely disperse one immiscible
Attorney Docket No.0079721-000085 liquid in another, as defined by Skelland and Ramsay [1987 I&EC Res.26, 1, 77– 81], Skelland and Moeti [1989, I&EC Res. 28, 1, 122–127] and Skelland and Kanel [1993, I&EC Res.29, 7, 1300–1306]. Static mixers of any design can also be used as the extraction zone. Suitable static mixers include, but are not limited to, those produced by Chemineer in their Kenics line. [99] The extraction zone can be followed by a separation zone, and mass transfer can continue to occur while the dispersion is separating in the separation zone. In an exemplary embodiment, there is a balance between the amount of shear energy added in the extraction zone to generate an acceptable drop size distribution in the liquid-liquid dispersion in order to achieve acceptable mass transfer kinetics in the extraction zone, and reasonable decantation kinetics in the separation zone. Since the separation zone can be larger in volume than the extraction zone, it is advantageous not to add too much shear that generates a small drop size distribution that would increase the size of the decanter. [100] Suitable extraction columns which can be used as the extraction zone include, but are not limited to, those that are mechanically agitated and those that have stationary internals. The latter is preferred when the extraction solvent is a dense gas and/or the operating pressure of the extractor is elevated so that more expensive mechanical seals are needed. Suitable extraction columns with stationary internals can include, but are not limited to, packed, perforated plate, baffle tray, and combinations thereof. Suitable packings include structured or random packings that are known to those skilled in the art. Suitable mechanically agitated extraction columns can include, but are not limited to, the Karr reciprocating plate column, the York Scheibel column, and the rotating disc column, all made by Koch Modular Process Technology Corporation, which is located in Paramus, N.J., the Kuhni
Attorney Docket No.0079721-000085 column, which is sold by Sulzer in Switzerland, the asymmetric rotating disc column, pulsed columns, and combinations thereof. [101] The separation zone can include or be a decanter which is configured to perform at least one or more of gravity settling, centrifugal settling, and/or combinations thereof to separate the dispersion into the multiple layers. In exemplary embodiments, the separation zone can include one or more fixed or moving separation aids like mesh pad coalescers, wire pad coalescers, structured packing, inclined plates, perforated plates, baffles, ultrasonic waves, acoustic waves, and/or combinations thereof. [102] In an exemplary embodiment, the extraction zone includes a mixer and/or a countercurrent extraction column, and/or the separation zone includes a decanter. [103] In exemplary embodiments, the extraction zone and separation zone are combined in a countercurrent extraction column. In these exemplary embodiments, the raffinate layer can exit the column at one end while the solvent extract layer can exit the column at the opposite end. The rag layer can be removed from the countercurrent extraction column with either the raffinate layer or the solvent extract layer, or alternatively removed from the extraction column as a sidedraw. Any of the types of extraction columns described above can be used for countercurrent extraction. The algal concentrate can contact the extraction solvent for about 5 to 180 minutes, about 5 to 180 minutes or about 10 to 60 minutes in a counter-current extraction column. [104] Suitable centrifugal extractors that can be used to provide both the extraction zone and the separation zone include, but are not limited to those produced by CINC, Alfa Lavel, Podbielniak, Robatel, Westfalia, and combinations of these centrifugal extractors.
Attorney Docket No.0079721-000085 [105] Suitable emulsion phase contactors that can be used to provide both the extraction zone and the separation zone include, but are not limited to, those produced by Schlumberger termed the NATCO dual frequency electrostatic treater. [106] The separation of the dispersion into multiple layers can be carried out or performed under a gravitational field or by decanting. [107] Separating the dispersion into multiple layers can occur in as little as 10 minutes to about 24 hours, at least 20 minutes to 12 hours, at least 30 minutes to 6 hours, or 40 minutes to 3 hours. [108] Separating the dispersion into multiple layers can occur or can be performed at a pressure ranging from atmospheric to supercritical conditions for the extraction solvent. [109] Separating the dispersion into multiple layers can occur or can be performed at e.g., a temperature of less than 100°C, such as about 20°C to about 90°C, about 30°C to about 90°C, about 40°C to about 90°C, about 50°C to about 90°C, about 60°C to about 90°C, about 35°C to about 80°C, about 35°C to about 70°C or about 40°C to about 70°C. [110] The solvent extract layer can include at least one hydrophobic natural product present within the dispersion. These hydrophobic natural products can include one or more selected from the group including lipids, algal lipids, carotenoids, fatty acids, algal fatty acids, triacylglycerols, diacylglycerols, monoacylglycerols, oils, algal oils and combinations thereof. [111] The carotenoids can include beta-carotene, alpha-carotene, lutein, zeaxanthin, beta-cryptoxanthin, astaxanthin, phytoene, phytofluene, lycopene, and/or combinations thereof.
Attorney Docket No.0079721-000085 [112] The solvent extract layer can include extraction solvent, algal oil, carotenoids, trace amounts of water and salt. The solvent extract layer can contain extraction solvent in amounts of more than 50 wt%, such as above 60 wt% or above 70 wt% of its total weight; algal oil in amounts than less 30 wt%, such as less than 20 wt% or less than 10 wt% of its total weight; carotenoids in amounts less than 5 wt%, such as less than 3 wt% or less than 1 wt% of its total weight; water in amounts less than 10 wt%, such as less than 5 wt% or less than 2 wt% of its total weight; and/or salt in amounts less than 3 wt%, such as less than 2 wt% or less than 1 wt% of its total weight. [113] The solvent extract layer can include limited amounts of lipid-depleted biomass and an aqueous salt solution. [114] The raffinate layer can include an aqueous salt solution depleted of hydrophobic natural products. The raffinate layer can possess a salt concentration of above 5 wt%, above 7 wt%, above 10 wt% above 15 wt%, above 18 wt% up to saturation. In an exemplary embodiment, the raffinate layer has a salinity of about 5 wt% or greater, about 10 wt% or greater, about 15 wt% or greater, or about 20 wt% or greater. In exemplary embodiments a salinity of the raffinate layer is about 5 wt% or greater than 5 wt%, about 6 wt% or greater than 6 wt%, about 7 wt% or greater than 7 wt%, for example at least about 8 wt%, at least about 9 wt%, at least about 10 wt%, at least about 11 wt%, at least about 12 wt%, at least about 13 wt%, at least about 14 wt%, at least about 15 wt%, at least about 16 wt%, at least about 17 wt%, at least about 18 wt%, at least about 19 wt%, at least about 20 wt%, at least about 21 wt%, at least about 22 wt%, at least about 23 wt%, at least about 24 wt%, or at least about 25 wt%. In other exemplary embodiments the raffinate layer is saturated with salt. In more exemplary embodiments, the raffinate layer can have a salinity that
Attorney Docket No.0079721-000085 is about 5 wt% to about saturation, from about 10 wt% to saturation, from about 20 wt% to saturation, from about 5 wt% to about 20 wt%, from about 10 wt% to about 20 wt%, from about 5 wt% to about 15 wt%, from about 10 wt% to about 15 wt%, or from about 5 wt% to about 10 wt%. [115] The raffinate layer can contain algal growth medium that is depleted in algal biomass and/or algal oils. [116] The raffinate layer can include water, salts, trace amounts of extraction solvent, trace amounts of algal biomass (such as less than 5 wt% or less than 1 wt% of its total weight) and/or trace amounts of algal oil (such as less than 5 wt% or less than 1 wt% of its total weight). The raffinate layer can contain water above 50 wt% (such as from 60 wt% to 90 wt%, 70 wt% to 85 wt% or 80 wt% to 90 wt%) or at about 50 wt% of its total weight, and/or the raffinate layer can contain salt from about 0.1 wt% to about 50 wt%, about 5 wt% to about 40 wt%, about 10 wt% to 30 wt%, and/or about 15 wt% to 26 wt% of its total weight. The raffinate layer can also contain trace amounts of the extraction solvent in both soluble and/or insoluble forms. The solubility of the extraction solvent in the raffinate layer influences the amount, or concentration, of the extraction solvent in the raffinate layer. The soluble amount of extraction solvent can be experimentally determined by measuring the solubility of the extraction solvent in the raffinate layer as a function of temperature, pressure, pH, salinity, and/or other factors known to those skilled in the art. The insoluble amount of the extraction solvent in the raffinate layer can be determined by the amount of entrainment of both extraction solvent droplets and the amount of extraction solvent that is associated with entrained algal biomass in the raffinate layer. Trace amounts of algal oil in the raffinate layer can be present in the solvent of the raffinate layer and/or in the algal biomass as unextracted oil.
Attorney Docket No.0079721-000085 [117] The rag layer can form at any location in a separation zone. For example, the rag layer can form between, above or below solvent extract and raffinate layers. The rag layer can include a lipid-depleted biomass. The lipid-depleted biomass can include at least one or more of, chlorophyll, glycerol, phospholipids, proteins, carbohydrates, fibers, and limited amounts of lipids, carotenoids and/or raffinate relative to the dispersion or any combination thereof. In exemplary embodiments, the rag layer contains at most about 45 wt% of a solvent extract layer, about 45 wt% of a raffinate layer and about 10 wt% lipid-depleted biomass. In an exemplary embodiment, the rag layer contains at most about 60 wt% of a solvent extract layer (such as from 30 wt% to 60 wt%, e.g., 40 wt% to 50 wt% or about 45 wt%), at most about 60 wt% of a raffinate layer (such as from 30 wt% to 60 wt%, e.g., 40 wt% to 50 wt% or about 45 wt%) and/or about from 2 wt% to 20 wt% lipid-depleted biomass (e.g., from 5 wt% to 10 wt%). [118] The rag layer can contain a majority of the algal biomass. Reducing the volume of the rag layer can be desirable to minimize the cost of further processing the rag layer to recover any entrained algal biomass. [119] The rag layer can include water, salt, extraction solvent, algae oil, and/or algal biomass. In exemplary embodiments, the rag layer is a mixture of three layers: 1) a layer containing algal biomass that has been depleted of non-polar compounds, 2) at least a portion of a solvent extract layer optionally containing at least one natural product, and 3) at least a portion of a raffinate layer. The ratio of these three layers can vary depending on the conditions used to separate the dispersion into multiple layers. The layer containing the algal biomass that has been depleted of non-polar compounds can vary from about 0.01 wt% of the total weight of the rag layer to about 20 wt%. The solvent extract layer and the raffinate layer can vary
Attorney Docket No.0079721-000085 from about 1 wt% to about 99 wt% of the total weight of the rag layer. In exemplary embodiments, the layer containing algal biomass that has been depleted of non- polar compounds is between about 1 and 10 wt% of the total weight of the rag layer, and the solvent extract layer and the raffinate layer range from about 10 wt% to 90 wt% of the total weight of the rag layer. [120] In exemplary embodiments, the rag layer includes an algal biomass having a particle distribution size from about 0.1 microns to about 1000 microns, about 0.2 microns to about 100 microns, from about 0.4 microns to about 25 microns, from about 0.4 microns to about 20 microns or at least 20 microns. [121] The rag layer can have an intermediate density between the solvent extract layer and the raffinate layer, so in decantation and/or centrifugation processes, it is located between the solvent extract layer and the raffinate layer. [122] In exemplary embodiments, the rag layer does not exist as a true thermodynamic phase and exists as a mixture of solid algal biomass, raffinate layer and solvent extract layer. The raffinate layer and the solvent extract layer can exist as true thermodynamic phases. [123] In exemplary embodiments, the rag layer has a salinity greater than 5 wt%, greater than 10 wt%, greater than 15 wt% or greater than 20 wt%. [124] In exemplary embodiments, the liquid-liquid-solid extraction process includes performing a heat exchange before the algal concentrate enters the extraction zone, before the extraction solvent enters the extraction zone, and/or before the dispersion enters the separation zone. [125] In exemplary embodiments, the liquid-liquid-solid extraction process includes isolating at least part of the solvent extract layer, at least part of the raffinate layer and/or at least part of the rag layer. The solvent extract layer can be e.g.,
Attorney Docket No.0079721-000085 overflowed or pumped out of the separation zone, the rag layer can be pumped out of the separation zone and/or the raffinate layer can be removed e.g., from the bottom of the separation zone. [126] In exemplary embodiments, the liquid-liquid-solid extraction process includes contacting the isolated solvent extract layer with an aqueous phase to remove any residual salt concentrations that can be present within the solvent extract layer. [127] In exemplary embodiments, the liquid-liquid-solid extraction process includes using a coalescer after formation of the dispersion. [128] In exemplary embodiments, the liquid-liquid-solid extraction process includes filtering the solvent extract layer after isolation to remove any entrained biomass and/or filtering the raffinate layer after isolation to remove any entrained biomass. [129] In exemplary embodiments, the liquid-liquid-solid extraction process includes evaporating the extraction solvent from the solvent extract layer after isolation of the solvent extract layer. [130] In exemplary embodiments, the liquid-liquid-solid extraction process is performed at a temperature of about 100°C (e.g., 100 ± 1-10°C) or less, about 95°C (e.g., 95 ± 1-10°C) or less, about 90°C (e.g., 90 ± 1-10°C) or less, about 85°C or less, about 80°C or less, about 75°C or less, about 70°C or less, about 65°C or less, about 60°C or less, or e.g., within a temperature range from 5 to 90°C, from 25 to 90°C, from 30 to 90°C, from 40 to 90°C, from 50 to 90°C, from 55 to 90°C, from 60 to 90°C, from 40 to 80°C, from 50 to 80°C, or from 60 to 80°C. It is advantageous to operate the extraction at a temperature below 100°C to preserve the algal oils and carotenoids.
Attorney Docket No.0079721-000085 [131] In exemplary embodiments, forming the dispersion by contacting the algal concentrate with the extraction solvent in the extraction zone and separating the dispersion into multiple layers in the separation zone can be performed at the same or different temperatures. [132] In exemplary embodiments, the separating of the dispersion into multiple layers occurs or is performed at a temperature of about 100°C or less, about 95°C or less, about 90°C or less, about 85°C or less, about 80°C or less, about 75°C or less, about 70°C or less, about 65°C or less, about 60°C or less, or within a temperature range from 35 to 90°C, from 40 to 90°C, from 45 to 90°C, from 50 to 90°C, from 55 to 90°C, from 60 to 90°C, from 30 to 80°C, from 35 to 80°C, from 40 to 80°C, from 45 to 80°C, from 50 to 80°C, from 55 to 80°C, or from 60 to 80°C, from 30 to 70°C, from 35 to 70°C, from 40 to 70°C, from 45 to 70°C, from 50 to 70°C, from 55 to 70°C, or from 60 to 70°C. [133] In an exemplary embodiment the separating of the dispersion into multiple layers occurs or is performed at a temperature of about 100°C, less than about 100°C, of about 10°C to 90°C, 10°C to 80°C, 20°C to 90°C, 20°C to 80°C, 30°C to 90°C, 30°C to 80°C, 40°C to 90°C, 40°C to 80°C, 50°C to 90°C, 50°C to 80°C, 60°C to 90°C, 60°C to 80°C, 35°C to 80°C, 35°C to 70°C or 40°C to 70°C. [134] In exemplary embodiments, the separating of the dispersion into multiple layers occurs or is performed at a temperature of about 40°C to 90°C, 50°C to 90°C, 60°C to 90°C, 35°C to 80°C, 35°C to 70°C or 40°C to 70°C. [135] In exemplary embodiments, the liquid-liquid-solid extraction process can be performed without addition of salt during the forming of the dispersion and during the separating of the dispersion into the multiple layers. For some exemplary embodiments, the extraction process includes performing the forming, passing,
Attorney Docket No.0079721-000085 separating and isolating steps without an addition of salt. In other exemplary embodiments, the biomass or algal concentrate containing the biomass in an aqueous salt solution does not include added salt. [136] In exemplary embodiments, the liquid-liquid-solid extraction process is a continuous process. The liquid-liquid-solid extraction process can be configured as a continuous process wherein the forming, passing, separating and isolating steps are performed sequentially. Continuous operation can allow for the production of biofuels and/or other hydrophobic natural products with reduced capital and operating costs. In exemplary embodiments, the algal concentrate and the extraction solvent are intimately contacted so that the solvent receives the hydrophobic natural products. In other exemplary embodiments, the hydrophobic natural products are either pressed from the biomass or extracted with additional algal (or vegetable) oil. The resulting raffinate phase and the extract phases are separated so that the hydrophobic natural products can be further processed into desirable products. [137] A variety of extraction equipment components can be used for continuous extraction including, but not limited to, mixers and settlers, countercurrent extraction columns, centrifugal extractors, and other classes of extractors known in the art as described by Pratt et al., Selection, Design, PilotTesting, and Scale-Up of Extraction Equipment, Chapter 8, in Science and Practice of LiquidLiquid Extraction, Volume 1, Clarendon Press, Oxford, 1992, the contents of which are incorporated herein by reference. The algal concentrate and the extraction solvent can be contacted in a countercurrent or co-current flow. [138] Suitable centrifugal extractors can include, but are not limited to, those manufactured by GEA Westfalia Separator GmbH, which is headquartered in Oelde, Germany; Alfa Laval, with a location in Richmond, Virginia; Robatel, which is located
Attorney Docket No.0079721-000085 in Pittsfield, Massachusetts; and Podbelniak, which is manufactured by Baker Perkins of Saginaw, Michigan. [139] Suitable other extraction equipment includes, but is not limited to hollow fiber membrane extractors and other novel extractor designs known in the art. In some cases, hollow fiber membrane extractors are used since they obviate the need to separate the solvent from the algal biomass. [140] Gravity settling is useful in a continuous extraction process. Separation of the multiple layers can be achieved in a centrifugal or gravitational force field, but gravity settling is usually of lower cost. A coalescer can be added to assist in the decantation. The raffinate layer can be coalesced to recover any additional extraction solvent that is entrained before being recycled to a bioreactor or returned to a pond, depending on the type of aquaculture practiced. A coalescer, liquid/liquid/solid centrifuge, flotation cell, and/or liquid/liquid cyclone can be used to recover solvent from the aqueous salt solution, or the aqueous salt solution can be recycled to a flotation device for cleanup. [141] Suitable materials for the construction of the mixer, decanter, and/or extraction equipment include, but are not limited to, steel, concrete, non-ferrous material, plastics, fiberglass, fiberglass reinforced plastic such as fiberglass reinforced HDPE, and combinations thereof. Non-ferrous materials are advantageous due to the salt content of the algal concentrate and the raffinate layer in the extraction process. The salinity of these components could cause stress corrosion cracking in ferrous materials, greatly increasing the maintenance required on the mixer, decanter, and extraction equipment. Plastic and fiberglass equipment is resistant to the effects of the elevated salinity and can be less expensive than equipment constructed of ferrous material.
Attorney Docket No.0079721-000085 [142] The solvent extract layer, the lipid-depleted biomass, the rag layer, the raffinate layer and/or a combination thereof can be stabilized against degradation by any means known in the art including, but not limited to, one or more of the following processes: the addition of antioxidants, storage of the material in the absence of light exposure, storage under an inert environment such as nitrogen, argon, or carbon dioxide, chilling, and subjecting the material to a thermal cycle to destroy bacteria. Suitable antioxidants include, but are not limited to carotenoids, tertiary butyl hydroquinone (TBHQ), butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), vitamin E, vitamin C, rosemary extracts, and combinations thereof. [143] Exemplary advantages of performing a liquid-liquid-solid extraction process disclosed herein include, but are not limited to, not drying the biomass prior to the hydrophobic natural products being extracted, traditional liquid-liquid extraction equipment can be used instead of expensive leaching equipment, salt does not need to be removed prior to the extraction process, and/or washing of the solvent extract layer can be accomplished in traditional liquid-liquid extraction equipment. [144] Once the rag layer forms from the extraction process in the extraction zone (104) depicted in FIG.1, the rag layer is isolated and transferred to a deoiling zone (106) wherein the rag layer is washed with an extraction solvent capable of removing any entrained oils or other hydrophobic products not extracted from the algal concentrate during the extraction process. [145] Algal oils and/or other hydrophobic products can be present in the algal biomass and/or solvent extract entrained in the rag layer. These entrained natural products can be either physically separated from the rag layer and/or displaced from the rag layer with an extraction solvent.
Attorney Docket No.0079721-000085 [146] In exemplary embodiments, the deoiling zone includes or is a decanter which is configured to perform at least one or more of gravity settling, centrifugal settling, and/or combinations thereof to extract any algal oils and/or other hydrophobic products entrained in the rag layer. In exemplary embodiments, the deoiling zone can include one or more fixed or moving separation aids like mesh pad coalescers, wire pad coalescers, structured packing, inclined plates, perforated plates, baffles, ultrasonic waves, acoustic waves, and/or combinations thereof. [147] In exemplary embodiments, the deoiling zone can include one or more gravity decantaters, coalescers, hydrocyclones, centrifuges, acoustic-based separators, electric-field based separators, other equipment known in the art to assist in physical separation of hydrophobic products from an aqueous solution, and/or combinations thereof. [148] In exemplary embodiments, the rag layer is deoiled through contact with an extraction solvent capable of (i) forming a second liquid phase or layer with the rag layer in the deoiling zone and (ii) extracting the entrained algal oils and/or other hydrophobic products out of the rag layer into the second liquid phase or layer. The extraction solvent used to deoil the rag layer can either be the same as or different from the extraction solvent used to form the dispersion in the liquid-liquid-solid extraction process. [149] The extraction solvent used to deoil the rag layer can include, but is not limited to, a non-polar solvent, a non-polar organic solvent, a dense gas solvent, an aqueous two-phase solvent, a deep eutectic solvent (DES) and/or a natural deep eutectic solvent (NADES), an ionic liquid, any combination thereof or any combination of solvents such as miscible solvents.
Attorney Docket No.0079721-000085 [150] In exemplary embodiments, the extraction solvent used to deoil the rag layer is any solvent system that (i) forms a second immiscible liquid phase or layer with the rag layer in the deoiling zone and (ii) extracts the entrained algal oils and/or other hydrophobic products out of the rag layer and into the second immiscible liquid phase or layer. These solvent systems should not adversely impact the quality or quantity of the natural products. These solvent systems can include, but are not limited to, synthetic and/or natural flavorants, edible oils, petrochemicals, dense gases, and combinations of these so long as the mixture of the solvent system and the rag layer forms two immiscible liquid phases at a desired temperature. [151] In exemplary embodiments, the deoiling of the rag layer includes removing the second immiscible liquid phase or layer/second liquid phase or layer containing the extracted algal oils and/or other hydrophobic products from the deoiling zone. [152] After the rag layer has been deoiled by the extraction solvent in the deoiling zone (106) depicted in FIG.1, a deoiled algal slurry forms and is transferred to a dewatering zone (108). In the dewatering zone (108), the deoiled algal slurry is transferred to at least one filtration system (110) containing at least one filtration membrane. Once all of the deoiled algal slurry has entered the at least one filtration system (110), the deoiled algal slurry is washed with a washing media that simultaneously removes water and/or salts from the deoiled algal slurry, thereby producing a deoiled, dewatered and/or desalted algal slurry. [153] In the dewatering zone, water (and optionally salts) is displaced from the algal biomass material with a washing medium that selectively removes the water (and/or salts) from the algal biomass material. The washing medium also allows the dewatered (and optionally desalted) algal biomass material to remain fluid enough
Attorney Docket No.0079721-000085 for transport to other zones (e.g., a drying zone, a deoiling zone and/or a concentration zone). [154] In exemplary embodiments, the dewatering zone includes at least one filtration system that includes a centrifuge and/or decanter configured to remove water and/or salts from the algal biomass. The centrifuge and/or decanter can be used to separate any water or excess washing medium by centrifugal forces, and this can be performed in one or more centrifugation steps. Suitable centrifuges and/or decanters include disc-stack centrifuges, decanter centrifuges, scrolling decanter centrifuges, or combinations thereof. Suitable filtration systems include, but are not limited to cross-flow microfilters, filtration membranes, depth filters, sand filters, rotary drum filters, filter presses, and combinations thereof. Suitable centrifuges include, but are not limited to disc-stack centrifuges, decanter centrifuges, shooting bowl centrifuges, and combinations thereof. [155] In exemplary embodiments, the dewatering zone includes at least one filtration system that contains at least one filtration membrane. [156] The dewatering zone can include a membrane filtration device selected from, but not limited to, drum filter/dryers, cross-flow filters, diafiltration units, and units where a filter cake accumulates and can be washed with a washing media such as water or a solvent. [157] In exemplary embodiments, the at least one filtration membrane includes at least one hydrophilic material and/or at least one hydrophilic and oleophobic material. [158] The expression “membrane” refers to a selective barrier between two phases including, but not limited to, one or more selective barriers that contain thick or thin layers, have homogeneous or heterogeneous layers, perform active or
Attorney Docket No.0079721-000085 passive transport, are pressure-driven, are concentration or temperature-driven, are osmotically-driven, are electrically-driven, are natural or artificial / synthetic, are porous or non-porous (dense), are symmetric or asymmetric, are hydrophobic or hydrophilic, are oleophilic or are oleophobic and neutral or charged. Examples of synthetic membranes include, but are not limited to, organic membranes e.g., polymeric, e.g., glassy or rubbery and liquid membranes, inorganic membranes e.g., ceramic including, but not limited to apatite-based, silica-based, alumina-based, titania-based, zirconia-based and proton conducting dense ceramic membrane, carbon membrane including, but not limited to supported, e.g., flat, capillary and hollow fibers and unsupported, e.g., flat and tube, zeolite membrane, glass and metallic membranes, mixed matrix membranes e.g., incorporation of the dispersed phase such as additive solid material including, but not limited to zeolite, activated carbon, carbon molecular sieve, metal-organic framework, carbon nanotubes, metal oxides, mesoporous and nanoporous into a continuous phase including, but not limited to cellulose acetate, polysulfone, polycarbonate, polyamide, polyimide, polyacrylonitrile and polyurethane and/or combinations thereof. [159] The expression “hydrophilic membrane” refers to a “water loving” membrane including membrane materials that easily adsorb water molecules due to the presence of active polar functional groups and has low water contact angle value (<90°). [160] The expression “hydrophilic and oleophobic membrane” and/or “hydrophilic/oleophobic membrane” refers to a membrane material that allows polar solvents including, but are not limited to, water, acetone, ammonia, methanol, ethanol and isopropanol to permeate through the membrane while preventing the permeation of nonpolar solvents including, but are not limited to, hexane, heptane,
Attorney Docket No.0079721-000085 toluene, acetic acid and chloroform through the microporous or mesoporous membrane structure. Suitable hydrophilic/oleophobic membranes include, but are not limited to, ceramic membrane e.g., Ucarsep ® membrane (4 nm), Carbosep ® membrane by SFEC (now TECH-SEP, Miribel, France), Membralox ® ( Soc.Céramiques Techniques, Bazet, France), and other commercial ceramic membranes from Le Carbone Lorraine (Pagny-sur-Moselle,France), CERASIV (now Dynamit Nobel, Troisdorf, Germany), NGK (Nagoya, Japan), Whatman™ (Little Chalfont, Buckinghamshire, UK) and DuPont (Wilmington, Delaware, USA). [161] The expression “hydrophobic membrane” refers to a “water hating” membrane including materials that have the opposite response to water interaction compared to hydrophilic membranes and has a high water contact angle value (>90°), are not wetted by water and no water will flow through the membrane at normal applied pressure. [162] The expression “oleophobic membrane” refers to a membrane that includes membrane materials that repel oils and hydrophobic liquids. Any known oleophobic membrane material can be selected, for example, a material that when exposed to n-hexadecane, a standard short-chain alkane testing fluid, produces contact angles ranging between 60° and 80°. When pure water (deionized water) is exposed to an oleophobic membrane, contact angles between 105° and 120° are formed. [163] The expression “water contact angle value” refers to the wetting angle of a drop of water on the surface of a membrane material. If the contact angle of a water droplet on a sample of membrane material is greater than 90°, the material is considered to not be wetted by water and is thus hydrophobic. A membrane material becomes more hydrophilic as the contact angle decreases from 90° to 0°
Attorney Docket No.0079721-000085 (Watanabe, T., “Wettability of ceramic surfaces – A wide range control of surface wettability from super hydrophilicity to super hydrophobicity, from static wettability to dynamic wettability”, 2009, Journal of the Ceramic Society of Japan, 117 [12], pp. 1285-1292; Somlyai-Sipos et al., “Wettability of Metals by Water”, Metals, 2022, 12 (8), 1274). When the contact angle of the water droplet on the material is 45°, the material has good wetting properties with water and is hydrophilic. If the contact angle is 0°, the material is completely wetted by water, and is completely hydrophilic. [164] A list of water contact angles for some exemplary membrane materials that can be used in the filtration membrane and filtration systems disclosed herein is provided below. Table 1: Water Contact Angles of Exemplary Membrane Materials Material Water Contact Angle Polyvinyl alcohol (PVOH) 20°-51° Polyamide 31-46° Polypiperazineamide 36° Cross-linked aromatic polyamide 42-47° Polyethersulphone 54-88° Polyvinyl acetate (PVA) 60.8° Nylon 6 (polycaprolactum, aramid 6) 62.6° Polyethylene oxide (PEO, PEG, 63° polyethylene glycol) Nylon 6.6 68.3° Nylon 7.7 70° Polysulfone (PSU) 70.5° Polymethyl methacrylate 70.9° (PMMA, acrylic, plexiglass)
Attorney Docket No.0079721-000085 Material Water Contact Angle Nylon 12 72.4° Polyethylene terephthalate (PET) 72.5° Epoxies 76.3° Polyoxymethylene (POM, polyacetal, 76.8° polymethylene oxide) Polyvinylidene chloride (PVDC, Saran) 80° Polyphenylene sulfide (PPS) 80.3° Acrylonitrile butadiene styrene (ABS) 80.9° Nylon 11 82° Polycarbonate (PC) 82° Polyvinyl fluoride (PVF) 84.5° Polyvinyl chloride (PVC) 85.6° Nylon 8.8 86° Nylon 9.9 86° Polystyrene (PS) 87.4° [165] In exemplary embodiments, the at least one hydrophilic material and/or the at least one hydrophilic and oleophobic material includes at least one or more of a polyacrylonitrile, a polyethylene, a high-density polyethylene, a polypropylene, a polyethylsulfone, a polysulfone, a polytetrafluoroethylene, a polyvinylidine difluoride, a polyester, a polycarbonate, a polyethylene terephthalate, a modified polyethylene terephthalate, a cellulose acetate, a cellulose propionate, a cellulose butyrate and/or combinations thereof.
Attorney Docket No.0079721-000085 [166] In exemplary embodiments, the at least one hydrophilic material and/or the at least one hydrophilic and oleophobic material includes at least one or more of aluminum oxide (alumina), silicone carbide, titanium dioxide, zirconium dioxide, apatite and/or combinations thereof. [167] In exemplary embodiments, the at least one hydrophilic material and/or the at least one hydrophilic and oleophobic material includes at least one or more of a stainless-steel alloy, palladium, tungsten and/or a nickel-based alloy selected from, but not limited to, 304 stainless steel, 316 stainless steel, duplex stainless steels (e.g., duplex 2205 and super-duplex 2507), high-alloyed super-austenitic stainless steel (e.g., 254 SMO), Inconel 625, and/or Hastelloy C-276. [168] In exemplary embodiments, the at least one filtration membrane of the filtration system or filtration membrane system includes at least one hydrophilic material and/or at least one hydrophilic and oleophobic material that allows a brine mixture (i.e., a mixture of water and salts) to pass through the membrane but prevents the extraction solvent used to deoil the rag layer and/or the extraction solvent used to form the dispersion in the extraction zone from passing through the membrane. [169] In exemplary embodiments, the at least one filtration membrane includes at least one or more pores, wherein each pore has a pore diameter within a range of 0.001 microns to 0.2 microns, 0.001 microns to 0.1 microns, 0.001 microns to 0.05 microns, 0.001 microns to 0.01 microns, 0.001 microns to 0.008 microns, 0.008 microns to 0.2 microns, to 0.008 microns to 0.1 microns, 0.008 microns to 0.05 microns, 0.008 microns to 0.01 microns, 0.01 microns to 0.2 microns, 0.01 microns to 0.1 microns, 0.01 microns to 0.05 microns, 0.05 microns to 0.2 microns, 0.05 microns to 0.1 microns, 0.01 microns to 0.2 microns, or 0.01 microns to 0.1 microns.
Attorney Docket No.0079721-000085 [170] In exemplary embodiments, the at least one filtration membrane of the system has Molecular Weight Cut Off (MWCO) within the range of 0.2 - 10 kDa or 1 - 500 kDa. [171] In exemplary embodiments, the at least one filtration membrane includes at least one or more pores, wherein each pore has a pore size-to-algal biomass size ratio of less than 1:10, less than 1:8, less than 1:4, less than 1:2 or less than 1:1. [172] In exemplary embodiments, the membrane filtration system includes at least two, three, four, five, six or more filtration membranes. [173] The washing media can include, but is not limited to, an extraction solvent, one or more other solvents, water, co-solvents and/or combinations thereof. Exemplary water sources that can be used in the washing media include, but are not limited to, potable water, distilled water, water derived from a sea, lake, river, ocean, aquifer, irrigation water, and/or combinations thereof. In exemplary embodiments, the washing media contains water having a salinity capable of removing salts from the rag layer. Examples of acceptable other solvents are a light solvent (e.g., hexane) that is combined with a more viscous solvent (e.g., vegetable oil). Examples of other acceptable solvents are co-solvents capable of miscibilizing the extraction solvent with the raffinate contained in the rag layer. These solvents can be identified and selected by examining the liquid-liquid equilibrium as shown on a ternary phase diagram. In a ternary phase diagram, the liquid-liquid region can be identified where the extraction solvent and the raffinate phases are immiscible, and the co-solvent serves as a coupling agent between these two different phases. Residue curve maps can be used to determine optimal mixtures of other solvents with the extraction solvent.
Attorney Docket No.0079721-000085 [174] In exemplary embodiments, the washing media is a single solvent or a combination of solvents selected from, but not limited to, those solvents described by Riddick et al. (“Organic Solvents Physical Properties and Methods of Purification”, 1986, edited by J. A. Riddick, W. B. Bunger, T. K. Sakano, ISBN 0-471-08467-0), a food grade solvent (e.g., hexane, ethyl acetate, limonene, essential oils, edible oils) or a dense gas (e.g., carbon dioxide, propane, and butane). [175] In exemplary embodiments, the washing media includes a co-solvent selected from, but not limited to, acetone, methanol, ethanol and/or combinations thereof. In exemplary embodiments, the co-solvent is a food grade solvent (e.g., acetone and ethanol). [176] In exemplary embodiments, the washing media does not contain water. [177] In exemplary embodiments, at least a portion of the washing media contains water. [178] In exemplary embodiments, the washing media includes at least one or more of a C5 -C8 hydrocarbon, such as hexane and isomers thereof, ethyl acetate, limonene, essential oils, edible oils and/or combinations thereof, and optionally water. [179] In exemplary embodiments, the washing media includes i) at least one or more of a C5 -C8 hydrocarbon, such as hexane and isomers thereof, ethyl acetate, limonene, essential oils, edible oils and/or combinations thereof, ii) water and iii) at least one a co-solvent selected from, but not limited to, acetone, methanol, ethanol and/or combinations thereof. [180] In an exemplary embodiment the ratio of a C5 -C8 hydrocarbon, such as hexane and isomers thereof, ethyl acetate, limonene, essential oils, edible oils and/or combinations thereof, to water is 20:1 - 1:20, 10:1 - 1:10 or 5:1 - 1:5.
Attorney Docket No.0079721-000085 [181] In exemplary embodiments, the washing media contains at least one of the following properties: a heat of vaporization less than that of water, a permeability through a selected membrane that is less than water or brine, a polarity that allows the washing media to be separated from algal oil, and immiscible with the algal biomass over a temperature range of 0°C to 100°C, and/or a viscosity of less than 100 centipoise when subjected to the temperature range. [182] In exemplary embodiments, the washing media has a lower boiling point than the algal oils contained in the rag layer. [183] In exemplary embodiments, the washing media includes at least one pH adjustment chemical, optionally including but not limited to organic acids, inorganic acids, organic bases, and inorganic bases. Suitable organic acids include but are not limited to carnosic acid, formic acid, acetic acid, citric acid, and ascorbic acid. Suitable inorganic acids include but are not limited to perchloric acid, hydrochloric acid, sulfuric acid, and nitric acid. Suitable inorganic bases include but are not limited to sodium hydroxide, potassium hydroxide, and calcium hydroxide. [184] Proper selection of the at least one filtration membrane material and washing media is crucial for the performance of the dewatering processes disclosed herein. In exemplary embodiments, the combination of the at least one filtration membrane material and washing media allow water and/or salts to selectively pass through the membrane and prevent the algal biomass and/or solvent extract layer from passing through the membrane. [185] In exemplary embodiments, the combination of the at least one filtration membrane material and washing media allow the solvent extract layer to pass through the membrane. An advantage of these embodiments is that the solvent concentration in the rag layer can decrease to a point where the rag layer and/or
Attorney Docket No.0079721-000085 algal biomass can be dried in a dryer that is not rated for operation in an explosion- proof area. [186] Selection of the washing media and the filtration membrane material can depend on the salt concentration in the rag layer, the extraction solvent used in the extraction zone, the operating temperature in the dewatering zone, and/or the operating pH in the dewatering zone. [187] The selection of the washing media can be based on the washing media’s ability to selectively extract desired solutes (e.g., water and/or salts) from the algal biomass in the rag layer. The selection of the washing media can also be based on the Hansen Solubility Parameters of the desired solutes with that of the solvents used in the washing media. In exemplary embodiments wherein the washing media contains a co-solvent, the co-solvent can be selected to more closely match the Hansen Solubility Parameters of the desired solutes with that of the mixed solvent system by the process described by Archer (Industrial Solvents Handbook, 1996, ISBN # 0-8247-9718-3). [188] The selection of the filtration membrane material can be based on the salt level or salinity of the algal concentrate and/or raffinate. The salt level in the algal concentrate and/or raffinate could be quantified so that the materials of construction for the filtration system and/or the at least one filtration membrane can be selected to where minimum damage to the filtration system and/or the at least one filtration membrane occurs. For example, the presence of chloride salts in the algal concentrate and/or raffinate can impact the material of construction for the filtration system and/or the at least one filtration membrane since chloride salts are known to eliminate or degrade some metals (e.g., carbon steel).
Attorney Docket No.0079721-000085 [189] The selection of the filtration membrane material can also be based on the chemical compatibility of the material with washing media. The washing media could allow for the removal of desired solutes (e.g., water and salts) in the algal biomass without the loss of algal biomass material. Most chemical compatibility selection charts can be used to assist with this selection. One example of this type of chart is shown in Table 2. Table 2: Chemical Compatibilities of Select Materials with Select Solvents [190] E = 30 days of constant exposure causes no damage. Plastic can tolerate for years. G = Little or no damage after 30 days of constant exposure to the reagent. F = Some effect after 7 days exposure to the reagent. The effect can be crazing, cracking, loss of strength or discoloration. N = Not recommended. Immediate
Attorney Docket No.0079721-000085 damage can occur. Depending on the plastic, the effect can be severe crazing, cracking, loss of strength, discoloration, deformation, dissolution or permeation loss. [191] ETFE = ethylene tetrafluoroethylene, FEP/TFE/PFA = fluorinated ethylene propylene/ tetrafluoroethylene/ perfluoroalkoxy alkane, FLPE = fluorinated high density polyethylene, FLPP = fluorinated high density polypropylene, HDPE = high density polyethylene, LDPE = low density polyethylene, PC = polycarbonate, PETG = glycol modified polyethylene terephthalate, PP = polypropylene, PVC = polyvinyl chloride, TPE = thermoplastic elastomer. [192] Not all combinations of solvents, co-solvents, and aqueous compositions are compatible with all types of membrane materials and salt levels. Table 3 below provides exemplary cases of systems that can be used to dewater and/or desalt the algal biomass in the dewatering zone.
Attorney Docket No.0079721-000085 Table 3: Exemplary Washing Media and Membrane Systems [193] The configuration of the filtration system and/or the at least one filtration membrane can be based on the type and concentration of solids initially contained in the rag layer. In an exemplary embodiment, spiral wound membranes are not preferred when the concentration of solids is significant because the membrane can foul. Different types of solids impact membrane fouling in their own way, but in general it is not preferred to operate a spiral wound membrane system with more than about one weight percent solids. In another exemplary embodiment, plate,
Attorney Docket No.0079721-000085 frame and tubular membrane configurations are preferred when the solids concentration is above about one percent. [194] In an exemplary embodiment, the washing media is or includes hexane and/or the at least one filtration membrane is constructed of ceramic aluminum oxide in the tubular form. [195] In an exemplary embodiment, the washing media is or includes a mixture of heptane and ethanol, and/or the at least one filtration membrane is constructed of PTFE in a plate and frame form. [196] In exemplary embodiments, the algal biomass and/or rag layer is washed with water after being washed with washing media to reduce the salinity of the rag layer and/or biomass that remains in the membrane filtration system. In some of these exemplary embodiments, at least a portion of the raffinate passes through the at least one filtration membrane. [197] In exemplary embodiments, the washing media includes a solvent and/or solvent system that allows raffinate to pass through the at least one filtration membrane and/or filtration system. A surprisingly unexpected advantage of these embodiments is that the washing media can essentially desalt and dewater the rag layer and/or algal biomass at the same time. [198] By utilizing the hydrophilic and/or hydrophilic/oleophobic membrane materials and membrane pore sizes disclosed herein in combination with the washing media mixtures and solvents disclosed herein, membrane filtration systems capable of removing brine (i.e., water and salt) from a deoiled algal slurry, rag layer and/or algal biomass with reduced fresh water and energy usage were surprisingly discovered.
Attorney Docket No.0079721-000085 [199] The exemplary process depicted in FIG.1 also depicts the deoiled, dewatered and/or desalted algal slurry being transferred to a drying zone (112) to remove any residual solvents and produce a dry algal powder that can be used in downstream processes to produce valuable products. [200] The drying zone can include any dryer or dryer system known in the art. Suitable dryer types include, but are not limited to, those described by Moyers et al. (Moyers, C. G., and G. W. Baldwin, “Psychometry, Evaporative Cooling, and Solids Drying” Section 12 in Perry’s Chemical Engineer’s Handbook, 7th Edition, Edited by R. H. Perry and D. W. Green, ISBN # 0-07-115448-5 (1997)) including, but not limited to, those that use an inert gas to evaporate a solvent, those that use steam to supply energy to evaporate a solvent, and those that rely on direct contact of the dewatered, desalted and deoiled algal slurry with a hot surface. Suitable dryers that rely on an inert gas to evaporate a solvent include, but are not limited to, spray dryers, fluidized solid bed dryers, and rotary dryers. Suitable dryers that rely on steam to evaporate a solvent include, but are not limited to, rotary dryers and desolventizer-toasters. Suitable dryers also include direct-contact dryers, where the dewatered, desalted and deoiled algal slurry is contacted with a hot solid surface to evaporate a solvent. Examples of this type of dryer are drum dryers and double drum dryers with a hot surface dried thermally. [201] In exemplary embodiments, the drying of the dewatered and deoiled algal biomass includes using a dryer gas (e.g., a condensable gas, such as steam) capable of removing solvent from the dewatered and deoiled algal biomass and recycling the solvent back to the extraction step. [202] Before the deoiled, dewatered and/or desalted algal slurry depicted in the exemplary process illustrated in FIG.1 is transferred to the drying zone (112), the
Attorney Docket No.0079721-000085 slurry can optionally be transferred to a concentration zone (114) to remove any residual solvents that have become entrained in the slurry during the deoiling and/or dewatering processes. The concentrated deoiled, dewatered and/or desalted algal slurry formed in the concentration zone (114) is then transferred to the drying zone (112). [203] The concentration zone can include at least one of the following: a gravity separator, a decanter, a coalescer, a hydroclone, a centrifuge, a filter, a membrane, a flotation device, an adsorptive bubble separation device, and/or combinations thereof. [204] In exemplary embodiments, the concentrating of the deoiled and dewatered/desalted algal slurry includes using at least one of the following concentration processes to affect concentration: gravitational fields, electrical fields, acoustic fields, and/or combinations thereof. An advantage of reducing the concentration of the solvent prior to the drying step is that lower energy is required during the drying of the deoiled and dewatered/desalted algal slurry. [205] In exemplary embodiments, the concentrating of the deoiled and dewatered/desalted algal slurry includes reducing the concentration of solvent in the deoiled and dewatered/desalted algal slurry to less than about 95wt%, less than about 90wt% or less than about 85wt%. The minimum residual solvent concentration that remains in the deoiled and dewatered/desalted algal slurry can be the concentration at which spoilage of the algal biomass is prevented. [206] The process for recovering deoiled and dewatered algal biomass can also include dewatering and/or desalting the rag layer and/or algal biomass before the deoiling of the rag layer and/or algal biomass.
Attorney Docket No.0079721-000085 [207] Accordingly, another aspect of the present disclosure is a process for recovering algal biomass, the process including at least one or more of: extracting a rag layer containing an algal biomass from an algal concentrate; dewatering the rag layer to produce a dewatered algal slurry, the dewatering including intimately contacting the rag layer with a filtration system and washing the rag layer with a washing media, the filtration system including at least one filtration membrane; deoiling the dewatered algal slurry to produce a deoiled, dewatered algal biomass; and drying the deoiled, dewatered algal biomass. [208] FIG.2 shows an exemplary embodiment of the deoiling and dewatering process wherein the dewatering of the rag layer occurs before the deoiling. In this embodiment, an algal concentrate stream is first subjected to an extraction process in an extraction zone (200) that forms a rag layer containing an algal biomass, raffinate (i.e., a solution containing water and salts) and extraction solvent. The rag layer is then transferred from the extraction zone (200) to a dewatering zone (202). [209] In the dewatering zone (202), the rag layer is transferred to at least one filtration system (204). Once transferred to the at least one filtration system (204) the rag layer is washed with a washing media that simultaneously removes water and/or salts from the rag layer, thereby producing a dewatered and/or desalted algal slurry. [210] The dewatered and/or desalted algal slurry is then transferred from the dewatering zone (202) to a deoiling zone (206). In the deoiling zone (206), the dewatered and/or desalted algal slurry is washed with an extraction solvent capable of removing any entrained oils or other hydrophobic products not extracted from the rag layer during the extraction process. [211] The deoiled, dewatered and/or desalted algal slurry produced in the deoiling zone (206) is then transferred to a drying zone (208) to remove any residual
Attorney Docket No.0079721-000085 solvents and produce a dry algal powder that can be used in downstream processes to produce valuable products. [212] Before the deoiled, dewatered and/or desalted algal slurry is transferred to the drying zone (208), the slurry can optionally be transferred to a concentration zone (210) to remove any residual solvents that have become entrained in the slurry during the deoiling and/or dewatering processes. The concentrated deoiled, dewatered and/or desalted algal slurry formed in the concentration zone (210) is then transferred to the drying zone (208) to remove any residual solvents. [213] In exemplary embodiments, the at least one filtration system includes at least one filtration membrane having at least one hydrophilic material and/or at least one hydrophilic and oleophobic material disclosed herein. [214] In exemplary embodiments, the at least one filtration system includes at least one filtration membrane having at least one pore, wherein each pore has a pore diameter within a range of 0.001 microns to 0.2 microns, 0.001 microns to 0.1 microns, 0.001 microns to 0.05 microns, 0.001 microns to 0.01 microns, 0.001 microns to 0.008 microns, 0.008 microns to 0.2 microns, to 0.008 microns to 0.1 microns, 0.008 microns to 0.05 microns, 0.008 microns to 0.01 microns, 0.01 microns to 0.2 microns, 0.01 microns to 0.1 microns, 0.01 microns to 0.05 microns, 0.05 microns to 0.2 microns, 0.05 microns to 0.1 microns, 0.01 microns to 0.2 microns, or 0.01 microns to 0.1 microns. [215] In exemplary embodiments, the at least one filtration membrane of the system has Molecular Weight Cut Off (MWCO) within the range of 0.2 - 10 kDa or 1 - 500 kDa. [216] In exemplary embodiments, the at least one filtration system includes at least two, three, four, five, or six filtration membranes.
Attorney Docket No.0079721-000085 [217] In exemplary embodiments, the process for recovering deoiled and dewatered algal biomass includes selecting a washing media to has at least one or more of the following properties: a heat of vaporization less than that of water, a permeability through a selected membrane that is less than water or brine, a polarity that allows the washing media to be separated from algal oil, and immiscible with the algal biomass over a temperature range of 0°C to 100°C, and a viscosity of less than 100 centipoise when subjected to the temperature range. [218] In exemplary embodiments, the washing media contains at least one or more of hexane, ethyl acetate, limonene, essential oils, edible oils and/or combinations thereof and optionally water. [219] In exemplary embodiments, the washing media contains at least one co- solvent selected from acetone, methanol, ethanol and combinations thereof. [220] In exemplary embodiments, the washing media contains i) at least one or more of hexane, ethyl acetate, limonene, essential oils, edible oils and/or combinations thereof, ii) water, and iii) at least one co-solvent selected from acetone, methanol, ethanol and combinations thereof. [221] In exemplary embodiments, the extracting of the rag layer containing the algal biomass from the algal concentrate includes at least one or more of the following: forming a dispersion by contacting the algal concentrate with an extraction solvent in an extraction zone, passing the dispersion to a separation zone, and separating the dispersion into multiple layers, the layers including a solvent extract layer containing at least one hydrophobic natural product and the extraction solvent, a raffinate layer containing an aqueous salt solution, and the rag layer containing the algal biomass.
Attorney Docket No.0079721-000085 [222] In exemplary embodiments, the extracting of the rag layer is carried out or occurs at a temperature of about 100°C, less than about 100°C, of about 10°C to 90°C, 10°C to 80°C, 20°C to 90°C, 20°C to 80°C, 30°C to 90°C, 30°C to 80°C, 40°C to 90°C, 40°C to 80°C, 50°C to 90°C, 50°C to 80°C, 60°C to 90°C, 60°C to 80°C, 35°C to 80°C, 35°C to 70°C or 40°C to 70°C. [223] In exemplary embodiments, the extracting of the rag layer containing the algal biomass from the algal concentrate includes separating the dispersion into multiple layers at a pressure ranging from atmospheric to supercritical conditions for the extraction solvent. [224] In exemplary embodiments, the extracting of the rag layer containing the algal biomass from the algal concentrate includes separating the dispersion into multiple layers at a temperature of less than about 100°C, less than about 90°C, less than about 80°C, less than about 70°C, less than about 60°C or less than about 50°C, such e.g. about 40°C to about 90°C, about 50°C to about 90°C, about 60°C to about 90°C, about 35°C to about 80°C, about 35°C to about 70°C or about 40°C to about 70°C. [225] In exemplary embodiments, the algal concentrate has a salinity greater than 5 wt%, greater than 10 wt%, greater than 15 wt% or greater than 20 wt% e.g., 15 wt% to 25 wt%. [226] The process for recovering deoiled and dewatered algal biomass can also include desalting the rag layer in a separate desalting zone before the rag layer is transferred to the dewatering zone and/or deoiling zone. [227] In exemplary embodiments, the algal biomass is desalted with water having a salinity of at most 25 wt%, a salinity that is < 0.05 wt%, a salinity ranging from 0.05 - 3 wt%, a salinity ranging from 3 - 5 wt%, a salinity of at least 5 wt%, a
Attorney Docket No.0079721-000085 salinity ranging from 5-25 wt%, a salinity ranging from 10-25wt%, a salinity ranging from 15-25 wt% or a salinity ranging from 20-25wt%. [228] FIG.3 shows an exemplary embodiment of the deoiling and dewatering process wherein the desalting of the rag layer occurs in a desalting zone. In this embodiment, an algal concentrate stream is first subjected to an extraction process in an extraction zone (300) that forms a rag layer containing an algal biomass, raffinate (i.e., a solution containing water and salts) and extraction solvent. The rag layer is then transferred from the extraction zone (300) to a deoiling zone (302). [229] In the deoiling zone (302), the rag layer is washed with an extraction solvent capable of removing any entrained oils or other hydrophobic products not extracted from the algal concentrate in the extraction zone (300). [230] After the rag layer has been deoiled by the extraction solvent in the deoiling zone (302), a deoiled algal slurry forms and is transferred to a desalting zone (304). In the desalting zone (304), the deoiled algal slurry is washed with fresh water to remove any salts that were not removed during the extraction process. [231] In the desalting zone, salt can be removed from the raffinate phase that is part of the rag layer or algal slurry. The removal of salt can be accomplished by contacting the rag layer or algal slurry with fresh water, thus dissolving the salt that is in the rag layer or algal slurry into the added fresh water. The resulting aqueous phase can be separated from the algal slurry or rag layer to reduce the level of salt in the washed rag layer or algal slurry. This desalting process can be repeated until a target level of residual salt relative to algal biomass in the rag layer and/or algal slurry is achieved. [232] The desalting of the rag layer and/or algal slurry can be accomplished in any equipment known in the art for washing solids, such as, but not limited to,
Attorney Docket No.0079721-000085 agitated vessels, static mixers, ultrasonic mixers, high-shear mixers, in-line mixers, other agitation devices known in the art, gravity decanters, decanters, coalescers, hydrocyclones, electrically-enhanced settlers, acoustically-enhanced settlers, other settler devices known in the art, and/or combinations thereof. [233] After the deoiled algal slurry has been desalted in the desalting zone (304) depicted in FIG.3, the deoiled, desalted algal slurry is transferred to a dewatering zone (306) containing at least one filtration system (308). Once transferred to the at least one filtration system (308), the deoiled, desalted algal slurry is washed with a washing media that simultaneously removes water and/or salts from the deoiled, desalted algal slurry, thereby producing a dewatered, desalted and deoiled algal slurry. [234] The dewatered, desalted and deoiled algal slurry is then transferred to a drying zone (310) to remove any residual solvents and produce a dry algal powder that can be used in downstream processes to produce valuable products. [235] Before the dewatered, desalted and deoiled algal slurry is transferred to the drying zone (310), the slurry can optionally be transferred to a concentration zone (312) to remove any residual solvents that have become entrained in the slurry during the deoiling, desalting and/or dewatering processes. The concentrated deoiled, dewatered and desalted algal slurry formed in the concentration zone (312) is then transferred to the drying zone (310) to remove any residual solvents. [236] Any of a variety of products can be made from the biomass or lipid- depleted biomass, or from the oil obtained by deoiling the rag layer, including, but not limited to, biofuels, nutraceuticals, cosmaceuticals, wastewater treatment processes, spa products, animal feeds, animal feed ingredients, human food, human food ingredients, soil builders, chemical intermediates, renewable plastics,
Attorney Docket No.0079721-000085 renewable polymers, renewable chemicals, specialty lipids, solar salt, soaps or components of a soap or detergent compositions, spa products, and cosmetic ingredients (e.g., carotenoids, omega fatty acids, and other lipids) and combinations thereof. [237] In exemplary embodiments, the process for recovering deoiled and dewatered algal biomass includes desalting the rag layer with washing media and/or fresh water. [238] In exemplary embodiments, the process for recovering deoiled and dewatered algal biomass includes desalting the rag layer and/or the algal slurry before dewatering the rag layer and/or the algal slurry, the desalting including contacting the rag layer with water (e.g., fresh water) to form an aqueous phase containing dissolved salts, an interface containing algal biomass and an organic phase containing extraction solvent; and separating the aqueous phase from the organic phase and the algal biomass. [239] In exemplary embodiments, the permeate resulting from the dewatering of a rag layer or algal slurry is recycled and used to further dewater and/or desalt the rag layer and/or the algal slurry. [240] FIG.4 depicts an exemplary embodiment wherein the permeate formed from dewatering an algal slurry in a dewatering zone (402) is used to desalt algal slurries entering a desalting zone (400). [241] Another aspect of the present disclosure is a system for recovering algal biomass from a rag layer, the system including at least one of the following: a dewatering zone configured to dewater an extracted rag layer and produce a dewatered algal slurry, the dewatering zone including a filtration system having at least one filtration membrane, the at least one filtration membrane including at least
Attorney Docket No.0079721-000085 one hydrophilic or hydrophilic and oleophobic material; and a deoiling zone in communication with the dewatering zone, the deoiling zone being located either upstream or downstream of the dewatering zone. [242] In exemplary embodiments, the at least one hydrophilic material and/or the at least one hydrophilic and oleophobic material of the at least one filtration membrane of the system includes at least one or more of a polyacrylonitrile, a polyethylene, a high-density polyethylene, a polypropylene, a polyethylsulfone, a polysulfone, a polytetrafluoroethylene, a polyvinylidine difluoride, a polyester, a polycarbonate, a polyethylene terephthalate, a modified polyethylene terephthalate, a cellulose acetate, a cellulose propionate, a cellulose butyrate and/or combinations thereof. [243] In exemplary embodiments, the at least one hydrophilic material and/or the at least one hydrophilic and oleophobic material of the at least one filtration membrane of the system includes at least one or more of aluminum oxide (alumina), silicone carbide, titanium dioxide, zirconium dioxide and/or combinations thereof. [244] In exemplary embodiments, the at least one hydrophilic and/or the at least one hydrophilic and oleophobic material of the at least one filtration membrane of the system includes a stainless-steel alloy and/or a nickel-based alloy. [245] In exemplary embodiments, the at least one filtration membrane of the system has at least one pore, wherein each pore has a pore diameter within a range of 0.001 microns to 0.2 microns, 0.001 microns to 0.1 microns, 0.001 microns to 0.05 microns, 0.001 microns to 0.01 microns, 0.001 microns to 0.008 microns, 0.008 microns to 0.2 microns, to 0.008 microns to 0.1 microns, 0.008 microns to 0.05 microns, 0.008 microns to 0.01 microns, 0.01 microns to 0.2 microns, 0.01 microns
Attorney Docket No.0079721-000085 to 0.1 microns, 0.01 microns to 0.05 microns, 0.05 microns to 0.2 microns, 0.05 microns to 0.1 microns, 0.01 microns to 0.2 microns, or 0.01 microns to 0.1 microns. [246] In exemplary embodiments, the at least one filtration membrane of the system has Molecular Weight Cut Off (MWCO) within the range of 0.2 - 10 kDa or 1 - 500 kDa. [247] In exemplary embodiments, the at least one filtration system of the system has at least two, three, four, five, or six filtration membranes. [248] In exemplary embodiments, the system includes an extraction zone and/or a drying zone, the extraction zone including an algal concentrate inlet configured to receive an algal concentrate and a rag layer outlet in communication with the dewatering zone or the deoiling zone, the rag layer outlet being configured to transfer a rag layer from the extraction zone to either the dewatering zone or the deoiling zone; and the drying zone including a drying inlet in communication with either an outlet of the dewatering zone, an outlet of the deoiling zone or an outlet of a concentration zone configured to concentrate a dewatered and deoiled algal biomass, the drying inlet being configured to receive a deoiled and dewatered algal biomass. [249] In exemplary embodiments, the deoiling zone includes an algal slurry outlet and a rag layer inlet, the rag layer inlet being in communication with the rag layer outlet of the extraction zone and configured to receive a rag layer from the extraction zone, and the algal slurry outlet being in communication with an inlet of the dewatering zone and configured to transfer a deoiled algal biomass to the dewatering zone; and the dewatering zone includes an outlet configured to transport a deoiled and dewatered algal biomass to either the drying zone or the concentration zone.
Attorney Docket No.0079721-000085 [250] In exemplary embodiments, the dewatering zone includes an algal slurry outlet and a rag layer inlet, the rag layer inlet being in communication with the rag layer outlet of the extraction zone and configured to receive a rag layer from the extraction zone, and the algal slurry outlet being in communication with an inlet of the deoiling zone and configured to transfer a dewatered algal biomass to the deoiling zone; and the deoiling zone includes an outlet configured to transport a deoiled and dewatered algal biomass to either the drying zone or the concentration zone. [251] In exemplary embodiments, the system includes a washing media input line, wherein the washing media input line is in communication with the dewatering zone and is configured to transfer a washing media from a washing media storage container to the dewatering zone. [252] In exemplary embodiments, the system includes a first extraction solvent input line, wherein the first extraction solvent input line is in communication with the extraction zone and is configured to transfer an extraction solvent from a first extraction solvent storage container to the extraction zone. [253] In exemplary embodiments, the system includes a second extraction solvent input line, wherein the second extraction solvent input line is in communication with the deoiling zone and is configured to transfer an extraction solvent from a second extraction solvent storage container to the deoiling zone. [254] In exemplary embodiments, the system includes a desalting zone configured to desalt a rag layer or an algal slurry, the desalting zone being located upstream of, downstream of or within the dewatering zone.
Attorney Docket No.0079721-000085 [255] In exemplary embodiments, the system includes a desalting zone configured to desalt a rag layer or an algal slurry, the desalting zone being located upstream of the dewatering zone. [256] In exemplary embodiments, the system includes a freshwater input line, wherein the freshwater input line is in communication with the desalting zone and is configured to transfer freshwater from a freshwater storage container to the desalting zone. [257] In exemplary embodiments, the system includes at least one harvesting zone configured to operatively communicate with an extraction zone and at least one algal aquaculture zone configured to operatively communicate with the at least one harvesting zone. In exemplary embodiments, the at least one harvesting zone is configured to perform an adsorptive bubble separation process on an algal concentrate. [258] The dry algal powder formed from the systems and processes disclosed herein can be used to produce various products including, but not limited to, biofuels, animal feed, animal feed ingredients, human food, human food ingredients, renewable plastics, renewable polymers, renewable chemicals, nutraceuticals, cosmaceuticals, soaps or components of a soap or detergent compositions, and cosmetic ingredients (e.g., carotenoids, omega fatty acids, and other lipids). [259] Biofuels that can be produced from high temperature processing of the dry algal powder include, but are not limited to, biodiesel, green diesel, renewable diesel, methane, alcohols, and dried algal biomass. Algal biodiesel is produced via any transesterification process known in the art, including those which utilize two immiscible liquid phases, and those that utilize a solid acid catalyst. Green diesel can be produced by hydrogenation, cracking, or a combination thereof of the algal oil or
Attorney Docket No.0079721-000085 any derivative thereof in order to produce hydrocarbons that can be used directly in the existing diesel distribution system. Methane and/or hydrogen can be produced from the dry algal powder by any anaerobic process known in the art. Fermentation of the dry algal powder by any process known in the art can be used to produce methanol, ethanol, butanol, n-butanol, i-butanol, other alcohols, and combinations thereof. The dry algal powder can be torrified for the production of a soil builder or for use in combination with coal for power or steam generation. The dry algal powder can be gasified or combusted either by itself or in combination with coal or biomass. [260] Suitable animal feeds include, but are not limited to, feeds for shrimp, fish, shellfish, brine shrimp, chickens, poultry, cows, ducks, dogs, pigs, sheep, goats, and combinations thereof. [261] Suitable dietary supplements include, but are not limited to alpha carotene, betacarotene, lutein, zeaxanthin, cryptoxanthin, phytoene, phytofluene, and the various cis- and trans-isomers and the various alpha, beta, gamma, delta isomers of the various carotenoids, and combinations thereof. [262] Suitable methods of carbon storage include, but are not limited to, burying the dry algal powder, sinking it, torifying it and using it as a soil builder, or combinations thereof. [263] Suitable methods for water and wastewater treatment include, but are not limited to, removal of BOD (biological oxygen demand), and or TOC (total organic carbon) from a water stream. This can be useful for municipal wastewater treatment processes, and it can be important for the treatment of brines being used for the production of sodium chloride salt and other salts via evaporation. [264] Suitable methods to process the dry algal powder into useful compounds include, but are not limited to, torification, gasification, liquefaction, fermentation,
Attorney Docket No.0079721-000085 drying, combustion, burial, and combinations thereof. Suitable applications of the torified algal powder includes, but is not limited to, a soil builder and a material to be combined with coal, wood, or other combustible material for power generation. Suitable applications of gasified algal powder include, but are not limited to, the production of the entire suite of products that can be produced via syngas chemistry, as described by the Gasification Technologies Council. Suitable products from syngas include, but are not limited to, chemicals, fertilizers, power generation, substitute natural gas, hydrogen, and transportation fuels. Suitable chemicals include, but are not limited to, hydrogen, carbon monoxide, methanol, dimethyl ether, acetic acid, propionic acid, butyric acid, acetic anhydride, methyl acetate, ethylene, propylene, olefins, and combinations thereof. Suitable fertilizers that can be produced from the syngas include, but are not limited to ammonia, ammonium nitrate, urea, and others known in the art. Suitable substitute natural gas can be generated from the syngas produced by gasifying the algal powder, and this includes methane. Suitable liquid fuels include gasoline, diesel fuel, jet fuels, and combinations thereof. All of the chemicals that are produced by Eastman Chemicals and by Sasol via their gasification processes can also be produced by the gasification of the algal powder. Products produced by the utilization of syngas can also be produced by gasification of the algal powder. Illustrative processes are described in U. S. Pat. No.6,310,260, the contents of which are incorporated herein by reference in their entirety, include, for example, hydroformylation, hydroacylation (intramolecular and intermolecular), hydrocyanation, hydroamidation, hydroesterification, aminolysis, alcoholysis, hydrocarbonylation, reductive hydroformylation, hydrogenation, olefin oligomerization, hydroxycarbonylation, carbonylation, olefin isomerization, transfer hydrogenation and the like. Other
Attorney Docket No.0079721-000085 processes involve the reaction of organic compounds with carbon monoxide, or with carbon monoxide and a third reactant, e.g., hydrogen, or with hydrogen cyanide, in the presence of a catalytic amount of a metal-organophosphorus ligand complex catalyst. More advantageous processes include hydroformylation, hydrocyanation, hydrocarbonylation, hydroxycarbonylation and carbonylation. [265] It has now been surprisingly discovered that the systems and processes disclosed herein can more efficiently recover an algal biomass from a rag layer. For example, exemplary embodiments of the processes and systems disclosed herein can deoil, dewater, desalt and dry an algal biomass with reduced freshwater usage, reduced potential spoilage of the algal biomass and/or reduced energy consumption. [266] In exemplary embodiments, the total water consumption of the dewatering (and optionally desalting) processes averages around 28 t/h. After the dewatering and optionally the desalting, the deoiled and dewatered algal biomass can be desolventized and/or dried to a moisture content of around 8 wt%. The heat used to evaporate the solvent and water can average 6.2 MW. When compared with known industrial processes, these exemplary embodiments can reduce freshwater consumption, for example, up to 55% (consumption drops from 63 t/h to 35 t/h) and the heat required for vaporization, for example, up to 73% (required heat drops from 22 MW to 6.2 MW). [267] Exemplary uses of the systems, processes, products, components and compositions disclosed herein are also encompassed by the present disclosure. For example, any of the systems disclosed herein can also be used for treating an algal biomass. Any of the processes disclosed herein can be used in combination with the systems disclosed herein to treat algal biomass. Examples
Attorney Docket No.0079721-000085 [268] The present disclosure will be described in more detail with reference to the following Examples, which shows exemplary embodiments in accordance with the present disclosure. The present disclosure is not limited to these exemplary embodiments. [269] Example 1 [270] Dunaliella salina algal biomass was grown in an algal aquaculture system and harvested with an adsorptive bubble separation unit to generate an algal concentrate. In extraction, the algal concentrate including water, salt, and algal biomass was contacted with hexane as the extraction solvent to transfer the algal oil and carotenoid solutes into the extract phase. The resulting raffinate phase contained a majority of the water and salt, and it was depleted of algal biomass, algal oil, and carotenoids. The resulting rag layer (containing algal biomass, extract and raffinate) was separated from the bulk extract and raffinate phases by gravity decantation. The rag layer was washed with the hexane extraction solvent and passed through a centrifuge to remove a majority of the extract and raffinate phases and to produce a deoiled algal slurry that was fed to a membrane system. [271] The membrane system contained two similar cross-flow membrane filtration units in series. In both of these units, the membrane material was selected so that permeability of salt and water was high, and permeability of solvent was low. In the first membrane unit, salt concentration of deoiled algal biomass was lowered by dilution with recycled permeate from the second membrane unit and filtration. In the second membrane unit, both the salt and water concentration were lowered by displacement with a washing media. The washing media used in the process contained extraction solvent, water and the cosolvent acetone.
Attorney Docket No.0079721-000085 [272] The deoiled algae slurry (from the extraction and deoiling processes including algae, salt, water and extraction solvent) and the permeate from the second membrane unit (including salt and water) was fed to the first membrane unit at ambient temperature and at neutral pH. Salt and water permeated through the membrane and were collected. [273] Concentrate from the first membrane unit (including algae and extraction solvent) was mixed with washing liquid prior to feeding to the second membrane unit. Salt and water permeate through the second membrane were collected. The collected permeate was counter-currently fed to the first membrane unit, where it was used as washing liquid since the salt concentration was lower compared to the deoiled algae slurry. The washing media to feed mass ratio in the 2nd membrane unit was 1.5. [274] During this process, 97% of salt was removed from the deoiled algal slurry, 60% by washing and 40% by displacing. Fresh water usage in this example was 57% of that when only water was used as a washing media. [275] Example 2 [276] This example involves the use of an exemplary process for recovering algal biomass from a rag layer, the process including: extracting a rag layer containing an algal biomass from an algal concentrate; deoiling the rag layer to produce a deoiled algal slurry; dewatering the deoiled algal slurry to create a dewatered, deoiled algal biomass; and drying the dewatered, deoiled algal biomass. The dewatering includes contacting the deoiled algal slurry with a filtration system and washing the deoiled algal slurry with a washing media. The filtration system includes at least one filtration membrane. The drying of the dewatered, deoiled algal biomass was tested at laboratory scale.
Attorney Docket No.0079721-000085 [277] Dunaliella salina algal biomass was grown in an algal aquaculture system and harvested with a centrifuge to generate an algal concentrate. In extraction, the algal concentrate including water, salt, and algal biomass was contacted with heptane as the extraction solvent to transfer the algal oil and carotenoid solutes into the extract phase. The resulting raffinate phase contained a majority of the water and salt, and it was depleted of algal biomass, algal oil, and carotenoids. The rag layer (containing algal biomass, extract and raffinate) was separated from the bulk extract and raffinate phases by gravity decantation. The rag layer was washed with heptane, the extraction solvent and passed through a centrifuge to remove a majority of the extract and raffinate phases and to produce a deoiled algal slurry. Sample was evaporated to remove the extraction solvent to generate a more standardized sample, but this step is not essential to the process. After evaporation, the deoiled algal slurry was desalted with fresh water to produce a deoiled and desalted algal slurry. [278] Two different samples were taken from the deoiled and desalted algal slurry fraction and dewatered with the same lab scale membrane filtration unit.150 kDa polyethersulfone was used as the membrane material. The first sample (Sample 1) including algae and water was dewatered without adding any washing media and the second sample (Sample 2) was dewatered by first mixing Sample 2 with the heptane extraction solvent and then filtering the mixture including algae, extraction solvent and water. Both tests were done at room temperature and low pH. pH ranges from 2 – 9 are suitable. [279] With both tests, experiments were continued until the mixing inside the lab scale membrane unit was working in a sufficient manner. With both tests, water permeated through the membrane and was collected as a permeate and analyzed.
Attorney Docket No.0079721-000085 With Sample 1, the deoiled, desalted and dewatered algal slurry, that included algae and remaining water, was collected and analyzed. With Sample 2, the deoiled, desalted and dewatered algal slurry, that included algae, extraction solvent and remaining water, was collected and concentrated by gravity decantation so that an extraction solvent layer was collected from the top phase. The resulting bottom phase of the deoiled, desalted and dewatered algal slurry was collected and analyzed separately. [280] No extraction solvent was detected from both permeates based on headspace gas chromatography analysis, visual observation and odor, thereby indicating that only water permeated through the membrane. With Sample 1, the water removal during the dewatering process was 65 wt% and with Sample 2, the water removal during the dewatering process was 82 wt%. Use of the washing media improved the water removal in the dewatering step of the process. [281] It will be appreciated by those skilled in the art that the present disclosure can be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The presently disclosed embodiments are therefore considered in all respects to be illustrative and not restricted. The scope of the disclosure is indicated by the appended claims rather than the foregoing description and all changes that come within the meaning and range and equivalence thereof are intended to be embraced therein.
Claims
Attorney Docket No.0079721-000085 WHAT IS CLAIMED IS: 1. A process for recovering algal biomass from a rag layer, the process comprising: extracting a rag layer containing an algal biomass from an algal concentrate; deoiling the rag layer to produce a deoiled algal slurry; dewatering the deoiled algal slurry to create a dewatered, deoiled algal biomass, the dewatering including contacting the deoiled algal slurry with a filtration system and washing the deoiled algal slurry with a washing media, the filtration system including at least one filtration membrane; and drying the dewatered, deoiled algal biomass. 2. The process of claim 1, wherein the at least one filtration membrane comprises: at least one hydrophilic material or at least one hydrophilic and oleophobic material. 3. The process of claim 2, wherein the at least one hydrophilic material or the at least one hydrophilic and oleophobic material comprises: at least one or more of a polyacrylonitrile, a polyethylene, a high- density polyethylene, a polypropylene, a polyethylsulfone, a polysulfone, a polytetrafluoroethylene, a polyvinylidine difluoride, a polyester, a polycarbonate, a polyethylene terephthalate, a modified polyethylene terephthalate, a cellulose acetate, a cellulose propionate, a cellulose butyrate and/or combinations thereof.
Attorney Docket No.0079721-000085 4. The process of claim 2, wherein the at least one hydrophilic material or the at least one hydrophilic and oleophobic material comprises: at least one or more of aluminum oxide (alumina), silicone carbide, titanium dioxide, zirconium dioxide and/or combinations thereof. 5. The process of claim 2, wherein the at least one hydrophilic material or the at least one hydrophilic and oleophobic material comprises: a stainless-steel alloy and/or a nickel-based alloy. 6. The process of any one of the previous claims, wherein the at least one filtration membrane comprises: at least one pore, wherein each pore has a pore diameter within a range of at least one or more of 0.001 microns to 0.2 microns, 0.001 microns to 0.1 microns, 0.001 microns to 0.05 microns, 0.001 microns to 0.01 microns, 0.001 microns to 0.008 microns, 0.008 microns to 0.2 microns, 0.008 microns to 0.1 microns, 0.008 microns to 0.05 microns, 0.008 microns to 0.01 microns, 0.01 microns to 0.2 microns, 0.01 microns to 0.1 microns, 0.01 microns to 0.05 microns, 0.05 microns to 0.2 microns, 0.05 microns to 0.1 microns, 0.01 microns to 0.2 microns, and/or 0.01 microns to 0.1 microns. 7. The process of any one of the previous claims, wherein the filtration system comprises: at least two, three, four, five, or six filtration membranes.
Attorney Docket No.0079721-000085 8. The process of any one of the previous claims, comprising: selecting the washing media to have a heat of vaporization less than that of water, a permeability through a selected membrane that is less than water or brine, a polarity that allows the washing media to be separated from algal oil, and immiscible with the algal biomass over a temperature range of 0°C to 100°C, and a viscosity of less than 100 centipoise when subjected to the temperature range. 9. The process of any one of the previous claims, wherein the washing media comprises: at least one or more of hexane, ethyl acetate, limonene, essential oils, edible oils and/or combinations thereof, and optionally water. 10. The process of any one of the previous claims, wherein the washing media comprises: a co-solvent selected from the group consisting of acetone, methanol, ethanol and combinations thereof. 11. The process of any one of the previous claims, wherein the dewatering comprises: desalting the deoiled algal slurry with the washing media. 12. The process of any one of the previous claims, comprising: desalting the deoiled algal slurry before the dewatering, wherein the desalting includes intimately contacting the deoiled algal slurry with water to form an
Attorney Docket No.0079721-000085 aqueous phase including dissolved salts and an organic phase including deoiled algal biomass, wherein the water has a salinity of at most 25 wt%; and separating the aqueous phase from the organic phase. 13. The process of any one of the previous claims, wherein the extracting of the rag layer from the algal concentrate comprises: forming a dispersion by contacting the algal concentrate with a first extraction solvent in an extraction zone; passing the dispersion to a separation zone; and separating the dispersion into multiple layers optionally at a temperature of at least one or more of less than 100°C and/or about 30°C to about 90°C, the layers including: a solvent extract layer containing at least one hydrophobic natural product and the first extraction solvent, a raffinate layer containing an aqueous salt solution, and the rag layer containing the algal biomass. 14. The process according to claim 13, comprising: performing the separating at a pressure ranging from atmospheric to supercritical conditions for the first extraction solvent. 15. The process of any one of claims 1-14, wherein the separating of the dispersion into multiple layers and/or the extracting of the rag layer occurs at a temperature of at least one or more of about 100°C, less than about 100°C, of about 10°C to 90°C, 10°C to 80°C, 20°C to 90°C, 20°C to 80°C, 30°C to 90°C, 30°C to 80°C, 40°C to 90°C, 40°C to 80°C, 50°C to 90°C, 50°C to 80°C, 60°C to 90°C, 60°C to 80°C, 35°C to 80°C, 35°C to 70°C and/or 40°C to 70°C.
Attorney Docket No.0079721-000085 16. The process of any one of the previous claims, wherein the algal concentrate has a salinity of at least one or more of greater than 5 wt%, greater than 10 wt%, greater than 15 wt% and/or greater than 20 wt%. 17. The process of any one of the previous claims, wherein the rag layer has a salinity of at least one or more of greater than 5 wt%, greater than 10 wt%, greater than 15 wt% and/or greater than 20 wt%. 18. The process of any one of the previous claims, the deoiling comprising: contacting the rag layer with a second extract solvent, wherein the second extract solvent forms a second liquid phase or layer with the rag layer in a deoiling zone; and extracting entrained algal oils and/or other hydrophobic products from the rag layer into the second liquid phase or layer. 19. The process of any one of the previous claims, the process comprising: culturing a feedstock source in an algal aquaculture pond to form a pre- harvested algal concentrate; transferring the pre-harvested algal concentrate to a harvesting zone; and performing at least one harvesting process on the pre-harvested algal concentrate to form the algal concentrate.
Attorney Docket No.0079721-000085 20. A process for recovering algal biomass from a rag layer, the process comprising: extracting a rag layer containing an algal biomass from an algal concentrate; dewatering the rag layer to produce a dewatered algal slurry, the dewatering including contacting the rag layer with a filtration system and washing the rag layer with a washing media, the filtration system including at least one filtration membrane; deoiling the dewatered algal slurry to produce a deoiled, dewatered algal biomass; and drying the deoiled, dewatered algal biomass. 21. The process of claim 20, wherein the at least one filtration membrane comprises: at least one hydrophilic material or at least one hydrophilic and oleophobic material. 22. The process of claim 21, wherein the at least one hydrophilic material or the at least one hydrophilic and oleophobic material comprises: at least one or more of a polyacrylonitrile, a polyethylene, a high- density polyethylene, a polypropylene, a polyethylsulfone, a polysulfone, a polytetrafluoroethylene, a polyvinylidine difluoride, a polyester, a polycarbonate, a polyethylene terephthalate, a modified polyethylene terephthalate, a cellulose acetate, a cellulose propionate, a cellulose butyrate and/or combinations thereof.
Attorney Docket No.0079721-000085 23. The process of claim 21, wherein the at least one hydrophilic material or the at least one hydrophilic and oleophobic material comprises: at least one or more of aluminum oxide (alumina), silicone carbide, titanium dioxide, zirconium dioxide and/or combinations thereof. 24. The process of claim 21, wherein the at least one hydrophilic material or the at least one hydrophilic and oleophobic material comprises: a stainless-steel alloy and/or a nickel-based alloy. 25. The process of any one of claims 20-24, wherein the at least one filtration membrane comprises: at least one pore, wherein each pore has a pore diameter within a range of at least one or more of 0.001 microns to 0.2 microns, 0.001 microns to 0.1 microns, 0.001 microns to 0.05 microns, 0.001 microns to 0.01 microns, 0.001 microns to 0.008 microns, 0.008 microns to 0.2 microns, to0.008 microns to 0.1 microns, 0.008 microns to 0.05 microns, 0.008 microns to 0.01 microns, 0.01 microns to 0.2 microns, 0.01 microns to 0.1 microns, 0.01 microns to 0.05 microns, 0.05 microns to 0.2 microns, 0.05 microns to 0.1 microns, 0.01 microns to 0.2 microns, and/or 0.01 microns to 0.1 microns. 26. The process of any one of claims 20-25, wherein the filtration system comprises: at least two, three, four, five, or six filtration membranes.
Attorney Docket No.0079721-000085 27. The process of any one of claims 20-26, comprising: selecting the washing media to have a heat of vaporization less than that of water, a permeability through a selected membrane that is less than water or brine, a polarity that allows the washing media to be separated from algal oil, and immiscible with the algal biomass over a temperature range of 0°C to 100°C, and a viscosity of less than 100 centipoise when subjected to the temperature range. 28. The process of any one of claims 20-27, wherein the washing media comprises: at least one or more of hexane, ethyl acetate, limonene, essential oils, edible oils and/or combinations thereof, and optionally water. 29. The process of any one of claims 20-28, wherein the washing media comprises: a co-solvent selected from the group consisting of acetone, methanol, ethanol and combinations thereof. 30. The process of any one of claims 20-29, wherein the dewatering comprises: desalting the rag layer with the washing media. 31. The process of any one of claims 20-30, comprising: desalting the rag layer before the dewatering, wherein the desalting includes intimately contacting the rag layer with water to form an aqueous phase including dissolved salts and an organic phase including algal biomass; and
Attorney Docket No.0079721-000085 separating the aqueous phase from the organic phase. 32. The process of any one of claims 20-31, wherein the extracting comprises: forming a dispersion by contacting the algal concentrate with an extraction solvent in an extraction zone; passing the dispersion to a separation zone; and separating the dispersion into multiple layers optionally at a temperature of at least one or more of less than 100°C and/or about 30°C to about 90°C, the layers including: a solvent extract layer containing at least one hydrophobic natural product and the extraction solvent, a raffinate layer containing an aqueous salt solution, and the rag layer containing the algal biomass. 33. The process according to claim 32, comprising: performing the separating at a pressure ranging from atmospheric to supercritical conditions for the extraction solvent. 34. The process of any one of claims 20-33, wherein the separating of the dispersion into multiple layers and/or the extracting of the rag layer occurs at a temperature of at least one or more of about 100°C, less than about 100°C, of about 10°C to 90°C, 10°C to 80°C, 20°C to 90°C, 20°C to 80°C, 30°C to 90°C, 30°C to 80°C, 40°C to 90°C, 40°C to 80°C, 50°C to 90°C, 50°C to 80°C, 60°C to 90°C, 60°C to 80°C, 35°C to 80°C, 35°C to 70°C and/or 40°C to 70°C.
Attorney Docket No.0079721-000085 35. The process of any one of claims 20-34, wherein the algal concentrate has a salinity of at least one or more of greater than 5 wt%, greater than 10 wt%, greater than 15 wt% and/or greater than 20 wt%. 36. The process of any one of claims 20-35, wherein the rag layer has a salinity of at least one or more of greater than 5 wt%, greater than 10 wt%, greater than 15 wt% and/or greater than 20 wt%. 37. The process of any one of claims 20-36, the deoiling comprising: contacting the rag layer with a second extract solvent, wherein the second extract solvent forms a second liquid phase or layer with the rag layer in a deoiling zone; and extracting entrained algal oils and/or other hydrophobic products from the rag layer into the second liquid phase or layer. 38. The process of any one of claims 20 to 37, the process comprising: culturing a feedstock source in an algal aquaculture pond to form a pre- harvested algal concentrate; transferring the pre-harvested algal concentrate to a harvesting zone; and performing at least one harvesting process on the pre-harvested algal concentrate to form the algal concentrate 39. A system for recovering algal biomass from a rag layer, the system comprising:
Attorney Docket No.0079721-000085 a dewatering zone configured to dewater an extracted rag layer and produce a dewatered algal slurry, the dewatering zone including a filtration membrane system having at least one filtration membrane, the at least one filtration membrane including at least one hydrophilic or hydrophilic and oleophobic material; and a deoiling zone in communication with the dewatering zone, the deoiling zone being located either upstream or downstream of the dewatering zone. 40. The system of claim 39, wherein the at least one hydrophilic material or the at least one hydrophilic and oleophobic material comprises: at least one or more of a polyacrylonitrile, a polyethylene, a high-density polyethylene, a polypropylene, a polyethylsulfone, a polysulfone, a polytetrafluoroethylene, a polyvinylidine difluoride, a polyester, a polycarbonate, a polyethylene terephthalate, a modified polyethylene terephthalate, a cellulose acetate, a cellulose propionate, a cellulose butyrate and/or combinations thereof. 41. The system of claim 39, wherein the at least one hydrophilic material or the at least one hydrophilic and oleophobic material comprises: at least one or more of aluminum oxide (alumina), silicone carbide, titanium dioxide, zirconium dioxide and/or combinations thereof. 42. The system of claim 39, wherein the at least one hydrophilic material or the at least one hydrophilic and oleophobic material comprises: a stainless-steel alloy and/or a nickel-based alloy.
Attorney Docket No.0079721-000085 43. The system of any one of claims 39 to 42, wherein the at least one filtration membrane comprises: at least one pore, wherein each pore has a pore diameter within a range of at least one or more of 0.001 microns to 0.2 microns, 0.001 microns to 0.1 microns, 0.001 microns to 0.05 microns, 0.001 microns to 0.01 microns, 0.001 microns to 0.008 microns, 0.008 microns to 0.2 microns, 0.008 microns to 0.1 microns, 0.008 microns to 0.05 microns, 0.008 microns to 0.01 microns, 0.01 microns to 0.2 microns, 0.01 microns to 0.1 microns, 0.01 microns to 0.05 microns, 0.05 microns to 0.2 microns, 0.05 microns to 0.1 microns, 0.01 microns to 0.2 microns, and/or 0.01 microns to 0.1 microns. 44. The system of any one of claims 39 to 43, wherein the filtration membrane system comprises: at least two, three, four, five, or six filtration membranes. 45. The system of any one of claims 39 to 44, comprising: an extraction zone and/or a drying zone, wherein the extraction zone optionally includes an algal concentrate inlet configured to receive an algal concentrate and a rag layer outlet in communication with the dewatering zone or the deoiling zone, the rag layer outlet being configured to transfer a rag layer from the extraction zone to either the dewatering zone or the deoiling zone, wherein the drying zone optionally includes a drying inlet in communication with either an outlet of the dewatering zone, an outlet of the deoiling zone or an outlet of a concentration zone configured to concentrate a dewatered and
Attorney Docket No.0079721-000085 deoiled algal biomass, the drying inlet being configured to receive a deoiled and dewatered algal biomass. 46. The system of claim 45, wherein the deoiling zone includes an algal slurry outlet and a rag layer inlet, the rag layer inlet being in communication with the rag layer outlet of the extraction zone and configured to receive a rag layer from the extraction zone, and the algal slurry outlet being in communication with an inlet of the dewatering zone and configured to transfer a deoiled algal biomass to the dewatering zone; and wherein the dewatering zone contains an outlet configured to transport a deoiled and dewatered algal biomass to either the drying zone or the concentration zone. 47. The system of claim 45, wherein the dewatering zone includes an algal slurry outlet and a rag layer inlet, the rag layer inlet being in communication with the rag layer outlet of the extraction zone and configured to receive a rag layer from the extraction zone, and the algal slurry outlet being in communication with an inlet of the deoiling zone and configured to transfer a dewatered algal biomass to the deoiling zone; and wherein the deoiling zone contains an outlet configured to transport a deoiled and dewatered algal biomass to either the drying zone or the concentration zone.
Attorney Docket No.0079721-000085 48. The system of any one of claims 39 to 47, comprising: a washing media input line, wherein the washing media input line is in communication with the dewatering zone and is configured to transfer a washing media from a washing media storage container to the dewatering zone. 49. The system of any one of claims 39 to 48, comprising: a first extraction solvent input line, wherein the first extraction solvent input line is in communication with the extraction zone and is configured to transfer an extraction solvent from a first extraction solvent storage container to the extraction zone. 50. The system of any one of claims 39 to 49, comprising: a second extraction solvent input line, wherein the second extraction solvent input line is in communication with the deoiling zone and is configured to transfer an extraction solvent from a second extraction solvent storage container to the deoiling zone. 51. The system of any one of claims 39 to 50, comprising: a desalting zone configured to desalt a rag layer, the desalting zone being located upstream of or within the dewatering zone. 52. The system of claim 51, wherein the desalting zone is located upstream of the dewatering zone or upstream of the deoiling zone.
Attorney Docket No.0079721-000085 53. The system of claim 52, comprising: a freshwater input line, wherein the freshwater input line is in communication with the desalting zone and is configured to transfer freshwater from a freshwater storage container to the desalting zone. 54. The system of any one of claims 45 to 53, comprising: at least one harvesting zone configured to operatively communicate with the extraction zone; and at least one algal aquaculture zone configured to operatively communicate with the at least one harvesting zone, wherein the at least one harvesting zone is optionally configured to perform an adsorptive bubble separation process on an algal concentrate. 55. Use of the system of any one of claims 39 - 54 for treating an algal biomass.
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| CN103570198B (en) * | 2013-11-22 | 2015-12-09 | 沈阳工业大学 | A kind of processing method utilizing sanitary sewage to cultivate fast-growing algae production biofuel |
| US20170334751A1 (en) * | 2016-05-18 | 2017-11-23 | New Jersey Institute Of Technology | Reactive electrochemical membrane filtration |
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|---|---|---|---|---|
| MX2012007901A (en) * | 2010-01-15 | 2012-08-03 | Univ Texas | NON-DISPERSIVE PROCESS FOR THE RECOVERY OF INSOLUBLE OIL FROM WATERPROOF SUSPENTIONS. |
| ITMI20131915A1 (en) * | 2013-11-19 | 2015-05-20 | Eni Spa | PROCEDURE FOR THE EXTRACTION OF LIPIDS AND SUGAR FROM ALGAL BIOMASS |
| EP4422387A1 (en) * | 2021-10-29 | 2024-09-04 | Sinkco Labs | Circular methods for manufacturing products from algal biomass and atmospheric carbon removal with long-lived storage using algae residual biomass using packing and spreaded sinkage |
| US20250361460A1 (en) * | 2022-06-13 | 2025-11-27 | Neste Oyj | A liquid-liquid-solid extraction process for isolating natural products from a feedstock stream |
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- 2024-11-29 WO PCT/US2024/057950 patent/WO2025117879A1/en active Pending
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| US5378369A (en) * | 1993-02-11 | 1995-01-03 | Sasol Chemical Industries (Proprietary) Limited | Solvent extraction |
| US8765983B2 (en) * | 2009-10-30 | 2014-07-01 | Aurora Algae, Inc. | Systems and methods for extracting lipids from and dehydrating wet algal biomass |
| US20140099684A1 (en) * | 2011-05-26 | 2014-04-10 | Council Of Scientific & Industrial Research | Engine worthy fatty acid methyl ester (biodiesel) from naturally occuring marine microalgal mats and marine microalgae cultured in open salt pans together with value addition of co-products |
| CN102911278B (en) * | 2012-10-18 | 2014-05-14 | 成都连接流体分离科技有限公司 | Membrane concentration process used for carrageenan production |
| CN103570198B (en) * | 2013-11-22 | 2015-12-09 | 沈阳工业大学 | A kind of processing method utilizing sanitary sewage to cultivate fast-growing algae production biofuel |
| US20150251194A1 (en) * | 2014-02-26 | 2015-09-10 | James Madison Innovations, Inc. | Method and apparatus for recovering non-hydrophilic components from algae-containing water |
| US20170334751A1 (en) * | 2016-05-18 | 2017-11-23 | New Jersey Institute Of Technology | Reactive electrochemical membrane filtration |
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| FI20245068A1 (en) | 2025-05-31 |
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