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WO1993005186A1 - Procede de degradation de dechets urbains et de fabrication d'alcool combustible - Google Patents

Procede de degradation de dechets urbains et de fabrication d'alcool combustible Download PDF

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Publication number
WO1993005186A1
WO1993005186A1 PCT/US1991/007879 US9107879W WO9305186A1 WO 1993005186 A1 WO1993005186 A1 WO 1993005186A1 US 9107879 W US9107879 W US 9107879W WO 9305186 A1 WO9305186 A1 WO 9305186A1
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acid
separation
cellulose
waste
products
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PCT/US1991/007879
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English (en)
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James M. Easter, Iii
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    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
    • C12P7/04—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
    • C12P7/06—Ethanol, i.e. non-beverage
    • C12P7/08—Ethanol, i.e. non-beverage produced as by-product or from waste or cellulosic material substrate
    • C12P7/10—Ethanol, i.e. non-beverage produced as by-product or from waste or cellulosic material substrate substrate containing cellulosic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/001—Processes specially adapted for distillation or rectification of fermented solutions
    • B01D3/002—Processes specially adapted for distillation or rectification of fermented solutions by continuous methods
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
    • B01D61/44—Ion-selective electrodialysis
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel

Definitions

  • The- present invention relates generally to resource recovery and more particularly to the manufacture of fuels, such as ethanol, or chemicals, such as furfural, from undesired waste products from, for example, a municipal waste dump.
  • fuels such as ethanol
  • chemicals such as furfural
  • Cellulose is the raw material of numerous types of manufactured goods such as paper, cardboard, rayon, celluloid or cellophane and is the chief component in the walls of plants and trees.
  • Cellulosic content of municipal waste varies with the source of the waste: department stores discard vast amounts of paper and cardboard; restaurants throw away mostly food, cans, and plastics; domestic garbage comprises a combination of food and packaging products.
  • One ton of waste typically contains over 1/2 ton of cellulose.
  • cellulose Besides paper materials, other major sources of cellulose include cotton, wood chips, sawdust, straw, corn stover, bagasse (residue of sugar cane), rice hulls and peanut shells. Most cellulosic materials contain three primary components: cellulose, hemicellulose, and lignin.
  • Cellulose has a very tightly bonded crystalline structure and has the chemical formula
  • Hemicellulose is a combination of simple or mixed polysaccharides, including polymers of hexoses
  • Hemicellulose has a much lower molecular weight than cellulose and is amorphous rather than crystalline; its molecules separate easily and they can therefore be easily hydrolyzed.
  • the hexose sugars from glucomannans are fermentable with the glucose from the cellulose.
  • the 5-sugar xylose from xylans is not fermentable by most ordinary yeasts.
  • the xylose can be separately accumulated and, using a special yeast in a batch operation, be converted to ethanol or, it can be converted to Furfural, using heat and weak acid.
  • Furfural is the most important member of the family of heterocyclic compounds known as Furans and is characterized by a doubly unsaturated ring of four carbon atoms and one oxygen atom.
  • Furfural can be oxidized to furic acid, reduced to furfuryl alcohol and converted to furan by decarbonization.
  • Corncobs, bagasse, cottonseed hulls, oat and rice hulls are major sources of furfural.
  • Furfural is an important chemical intermediate and a selective solvent in the refining of fuels.
  • Furfural and other tetrahydrofuran compounds may be used as a selective solvent for separating saturated from unsaturated compounds in petroleum lubricating oils, gas, oil and diesel fuel, as well as vegetable oil.
  • Furfural may also be used as an ingredient in resins (particularly of the phenol- aldehyde types), as a decoloring agent for wood resin, as a resin solvent and wetting agent in the manufacture of abrasive wheels and brake linings and in the manufacture of synthetic rubber.
  • Lignin is the cementing material between adjacent cell walls of plants and trees and is a branched polymer macromolecule having three- dimensional, randomly linked polyphenolic units.
  • Lignin is generally unaffected by acid at moderate temperatures (50° C or below) and will remain as an insoluble residue along with other insoluble paper components such as coatings, fillers, etc. after the hydrolysis process.
  • Glucose is a carbohydrate which occurs widely in nature in the food chain and can be obtained from cellulose by breaking the glyosidic bonds of cellulose by the addition of water, in the presence of an acid catalyst, creating a "hydrolysis" reaction. During hydrolysis, the polymer chain is shattered
  • xylose polymers become xylose (a five carbon sugar) . Lignin and acetic acid are also released.
  • the usual source of glucose is the hydrolysis of starch, which is amorphous and branched and thus easily converted to glucose.
  • the starch is usually obtained from corn. Once cellulose has been converted to glucose, the glucose may be more easily converted to many commercial and industrial products, including refining into pure sugar, or dextrose. When converted to glucose and then fermented and distilled, the product is ethanol alcohol. A pound of cellulose has the energy equivalent of one third of a pound of gasoline.
  • the initial product is a solution containing the glucose, water and acid. If done at high temperatures, this mix requires immediate separation of the acid from the solution.
  • Most successful commercial acid hydrolysis processes employ either sulfuric or hydrochloric acid as a catalyst.
  • the cellulose feedstock used in most past commercial processes was primarily sawdust or wood chips. Some types of cellulose convert to sugar faster than others.
  • Acid hydrolysis is a method used to break down cellulosic material into individual molecules. Mineral acids acting only as a catalyst fractures the chain of molecules allowing them to combine with water molecules. The acid is neither crystalline combined nor consumed in the process. The major factors affecting acid hydrolysis are acid strength and temperature. High acid concentration results in a high sugar yield. High temperatures must be avoided to prevent degradation of the sugars into undesirable by ⁇ products.
  • Ethanol ethyl alcohol
  • Ethanol may be produced by adding yeast to a sugar/glucose solution with an appropriate concentration of water. In the absence of oxygen, the yeast will ferment the sugar to alcohol.
  • Ethanol has the empirical formula C 2 H 5 OH and is structurally depicted as follows:
  • the compound ethanol is a carbonyl group and is a hydroxy derivative of hydrocarbons.
  • Ethanol is the primary alcohol of all the alcohol groups, as opposed to the secondary and tertiary groups. All of these alcohols comprise a very wide and important segment of organic chemistry and are extensively used in industry worldwide.
  • ethanol there are two primary markets for ethanol: the chemical and the fuel industry.
  • the fuel industry provides by far the largest market and is rapidly growing.
  • the chemical industry uses industrial grade ethanol which must be processed and refined to very high standards of purity for use in the production of solvents, detergents, pharmaceuticals, toiletries, cosmetics, plastics, paints, disinfectants, and in food and drug processing.
  • Ethanol is usually sold as a blend with gasoline in the United States, although it is often used 100% as a fuel (neat) in Brazil. This blend is called “gasohol” and consists of 10% ethanol and 90% gasoline. The ethanol increases the octane rating, combustion efficiency, and overall engine performance. Ethanol produces minimal pollution — it does not add net carbon dioxide to the atmosphere and is easily transported and stored. The demand is expected to double or triple within the next five years. Over one billion gallons of ethanol is expected to be produced in 1991. But these ethanol sales are in spite of the high cost. High cost is the chief constraint to the sales and use of ethanol sales reaching their full potential_
  • Concentrated acid hydrolysis of cellulose is effective on any substrate without pretreatment, can provide almost quantitative yields of fermentable glucose, affords more concentrated solutions for fermentation, takes place in minutes, and affords a relatively reactive lignin residue with potential by ⁇ product value.
  • neither dilute acid hydrolysis nor enzymatic hydrolysis can claim more than two of these attributes.
  • An additional object of this invention is to use certain of these by-products from the conversion process as fuel to make the operation self sufficient in both steam and electricity, if the economics dictate.
  • a further object of the invention is to reduce the cost of ethanol below that of gasoline by reducing conversion time and conversion rate through improved reactor mixing and design, reducing burnt, or caramelized, sugars, and reducing unconverted cellulose.
  • Another object of this invention is to reduce the high cost of separating the acid catalyst from the sugar syrup.
  • Another object of this invention is to develop a continuous system from start to finish, eliminating the costly and time consuming "batch" methods normally used for acid hydrolysis and fermentation.
  • PROCESS FOR THE DISPOSAL OF WASTE AND MANUFACTURE OF FUEL FROM WASTE BY RECYCLING AND CONVERTING WASTE TO USEFUL BY-PRODUCTS which generally comprises: (1) separation for further treatment of cellulosic material feedstock from waste material brought to a processing facility; (2) an acid hydrolysis process using an acid catalyst to convert the feedstock into simple sugars which can be fermented into ethanol via a continuous operation; (3) recovery of the acid from the hydrolyzate by electrodialysis to provide concentrated sugar solutions for fermentation and to recycle the acid catalyst; and (4) continuous fermentation of the sugars combined with the continuous distillation of the ethanol produced.
  • Figure 1 is a flow chart for the production and separation of cellulose from solid waste
  • Figure 2 is a graphical drawing of the production and separation of cellulose from solid waste
  • SUBSTITUTESHEET Figure 3 is a perspective view of a primary disk screen
  • Figure 4 is a cross sectional view of screen disk elements of a primary disc screen
  • FIG. 5 is a perspective view of an air table used in conjunction with the waste separation system
  • Figure 6 is a perspective view of a primary shredder
  • Figure 7 is a perspective view of an air knife used in conjunction with the waste separation system
  • Figure 8 is a flow chart of the acid hydrolysis process
  • Figure 9 is a perspective view of a twin screw extruder used for acid hydrolysis
  • Figure 10 is a cross-sectional view of an electrodialysis unit
  • Figure 11 is a schematic of a Delta-t continuous fermentation/distillation ⁇ system.
  • Figure 12 is a flow chart depicting the production of ethanol and also various by-products which may be obtained.
  • the preferred embodiment of the present invention of conversion of municipal waste or other undesirable waste products to fuel, such as ethanol, involves generally the steps of: (a) separating from municipal solid waste the usable cellulosic feedstock;
  • products of the cellulosic conversion process can be used for the production of energy, such as electricity, by: (a) anaerobicy digesting biodegradable sludges left from the cellulose conversion process and ethanol production;
  • SUBSTITUTESHEET WASTE SEPARATION The process of separation of commercial and residential waste for ultimately the production of ethanol is schematically depicted in Figure 1 and graphically depicted in Figure 2 and begins once the waste is delivered onto a "tipping" floor via collection vehicles.
  • the tipping floor is designed to handle a high volume of trucks and solid waste and usually has a series of traffic lights over an entry door. These lights are controlled by operators located in a main control room overlooking the tipping floor to control the flow of trucks and front end loaders and other traffic.
  • the infeed apron conveyor 200 such as one manufactured by Beloit-Rader, regulates the amount of material entering the separation system and elevates the solid waste to a primary disc screen 300.
  • the conveyor 200 is equipped with a variable speed motor which will regulate conveyor speed from 0 to 50 feet per minute.
  • Bag rippers placed along the infeed apron conveyor 200, facilitate opening of plastic trash bags, which, of course, contain a significant percentage of municipal solid waste, to expose their contents for separation.
  • preliminary sorting operations will be performed at the conveyor.
  • One such operation is simply "hand sorting” (not shown) — i.e. removing large pieces by hand.
  • a flat/round separator (not shown) is also employed to separate out large flat pieces from the process of stream. Once the large pieces are sorted out of the stream, easier access is provided to a magnet (not shown) which removes the non- cellulosic, metallic content waste.
  • a hysteresis unit may also be used at this stage to remove the non-ferrous metals.
  • Additional hand sorting may be performed with respect to the diverted flat pieces.
  • next step involves advancing the material over primary disc screens 300 (see also Figures 3 and
  • Primary disc screens 300 have variable speed hydraulic drives which rotate the screen disks 310 (see Figure 4) to optimize their performance.
  • the overflow from the disk screen will be material having a diameter of greater than 5 inches and will typically comprise paper and plastic products, while the underflow typically will comprise cans, glass and waste and grass clippings with other fibrous materials.
  • An underflow belt 320 (below the Primary Disk Screens) (Fig. 2), such as one manufactured by National
  • the ferrous products typically comprise about 4% of the total material feed.
  • a secondary underbelt 350 such as one manufactured by National Resource Recovery Systems, Inc. will receive material underflow from a second disc screen 360 similar to the primary disc screen.
  • the refuse falling onto this screen will typically comprise broken glass, ceramics, dirt and small organic materials such as grass clippings.
  • the glass particles from the secondary belt will be recovered by an air table density separation system 400 comprising a series of air tables (see Figure 5).
  • the material from the Primary Disc Screen overflow will be discharged onto a slow moving shredder feed belt 500 (see Figure 2), which will allow hand sorting of non-processable materials and the option of gathering up of cardboard and mixed paper.
  • the material moving along the shredder feed belt will be fed to the primary shredder 600 (see Figure 6). If the cardboard and mixed paper are removed, they could be shredded and fed directly to the hydrolysis operation.
  • the primary shredder 600 such as one manufactured by National Waste Recovery Systems, Inc., is located in a separate primary shredder building 700 and may be employed to reduce the oversize screen products, which are mostly non-cellulosic, into uniform sized particles.
  • a final ferrous removal magnet (not shown), used in conjunction with the primary shredder, will extract the remaining amounts of iron still present in the prepared feed stock.
  • the shredder building 700 will be equipped with pressure reduction (blow out) explosion containment walls.
  • the blow-out wall design will aid in rapid pressure relief in the event of an explosion.
  • the building should be equipped with Hydrocarbon sensors which will detect explosive and most toxic gasses. This detection system will be connected to the electrical system to stop material movement, preventing its return into the screening building where operators are present.
  • the shredder building should have limited access and precautions should be taken not to allow operators inside during normal operations.
  • the building should be equipped with plant air, water, intercom, phone, electrical outlets (to include welding plugs) and television monitoring equipment.
  • the shredded material will then be passed over five air tables (single air tables are depicted in Figures 2 and 5) , such as one manufactured by Beloit- Rader, each of which are actually air classifiers which permit the further recovery of the glass products through density separation and permit light materials (such as grass clippings) to be vacuumed off the screen bed and into a cyclone separator.
  • Each air table will facilitate removal of the heavy materials which will primarily comprise "grids" - i.e., metals, dirt, rock and ceramics.
  • the air table will also separate the heavy glass fraction from the waste.
  • the glass material will comprise a mixed color of clear, amber and green and will be used for the manufacture of fiber glass.
  • a manual aluminum hand-picking station will follow the air tables and precede the air knife equipment as also shown in Figure 8. Each person on the aluminum picking station will be capable of picking an average of 40 to 50 cans per minute.
  • the remaining material will be processed through the air knife 800 (see Figure 7), which is equipped with a. hot air plenum 810 directly in front of the separation chamber.
  • the air has different effects on different particles based upon particle weight and density and therefore serves as a classifier.
  • baling is necessary where the hydrolysis units and ethanol production units are in separate locations. The majority of the feed stock of the conversion plant will be compacted bales. An automatic baler is used to compress the high concentration of cellulose material into bales. DESCRIPTION OF THE HYDROLYSIS PROCESS
  • FIG. 8 A schematic flow sheet for the overall process is shown in Figure 8. The process steps are described in the following sections.
  • the lignocellulose from waste paper comprising the raw material for the process will vary in composition depending on its source and prior treatment.
  • Cellulose itself will be the most abundant component, but will range from about 40% of mechanically pulped softwoods (newsprint) to 75% of unbleached kraft (linerboard) to 80% of bleached kraft.
  • Hemicelluloses differ greatly according to origin.
  • the glucomannans can vary from 3% in hardwood mechanical pulps to about 10% in softwood chemical pulps to 17% in softwood mechanical pulps.
  • Xylans can vary from 8% in softwood mechanical pulps to about 10% in softwood chemical -pulps to as high as 30% in hardwood mechanical pulps.
  • Lignin content can vary from 0% in bleached chemical pulps to 6% in unbleached chemical pulps to
  • the requirements for the hydrolysis reactor are that it bring together the cellulosic raw material and the concentrated hydrochloric acid that will hydrolyze it to sugars, have sufficient capacity for the desired rate of production, provide adequate residence time at the desired reaction temperature, provide positive mixing and mechanical disruption of cellulose gels, and withstand corrosion from the acid.
  • Cellulose slurries can only be stirred up to consistencies of about 15%. This upper limit corresponds to an acid to cellulose ratio of 5.7:1, which is prohibitive as far as recovery system cost is concerned.
  • reaction kinetic studies have shown that in the absence of agitation to break up the swollen cellulose gels formed during decrystalization of the cellulose, the hydrolysis reaction often stops short of complete conversion with only 50-60% of the cellulose hydrolyzed. With proper agitation, however, the reaction proceeds to over 90% conversion at rates as much as 20 times greater than the diffusion controlled rates in the absence of agitation.
  • a Werner-Pfleiderer twin screw extruder is used to continuously mix, transport, and by inference effect gel disruption of cellulose and water mixtures with a 2:1 liquor to cellulose ratio. This ratio is used in the acid recovery discussions below.
  • reaction kinetic studies have also shown that over 90% of the cellulose is hydrolyzed in ten minutes at 50°C. A reactor residence time of 15 minutes at 50°C has been adopted to ensure that the hydrolysis does proceed to completion.
  • sugars are present in the form of oligomers.
  • the lignocellulose material either the separated fraction taken from municipal solid waste, newsprint, food waste, or vegetable matter such as corn stover or bagasse, must first be finely shredded.
  • this raw material is forced by a "stuffer” or "packer” into a receiving hopper of the reactor. The grinding-ileights of the screws draw the material into the barrel and begin to crush it.
  • a continuous but closely controlled and measured amount of hydrochloric acid flows into the barrel and mixes with the cellulose. As the acid comes into contact with the cellulose, the molecules of the crystalline structure begin to dissociate.
  • Lignin has not been affected by the acid at this low temperature and is not soluble in the sugar/acid mixture.
  • the lignin must be separated from the mix and the HCl must be separated from the sugars to permit fermentation and to reduce processing costs by recovery and recycling of the HCl.
  • the end product of the reaction in the reactor are sugar oligomer and 43% concentration of HCl solution.
  • the hydrolyzate solution leaving the reactor contains all of the HCl added to the reactor. The HCl must be separated from the sugars, to permit fermentation.
  • the hydrolyzate solution leaving the reactor still contains all the HCl added to the reactor. This must be separated from the sugars, not only to permit fermentation, but also to reduce processing costs by recovery and recycle of the HCl.
  • the volatility of HCl gas allows it to be stripped from the hydrolyzate at reduced pressure. With pure water this can be carried all the way to the azeotrope at 20.2% HCl.
  • the HCl binds to the sugars in the hydrolyzate as well as the water leading to a reduction in HCl volatility and an upward shift in the aesotropic composition in addition to that which also occurs at the reduced pressure. Compensation for reduced HCl volatility by increasing the temperature in the stripper is limited to the 50°C temperature adopted for the reactor to prevent the degradation of the sugars that would occur at higher temperatures.
  • HCl gas would be compressed sufficiently to bring the solution leaving the absorber up to the 45% concentration entering the reactor, as well as to maintain this concentration at the moderate temperature
  • the hydrolyzate containing sugar oligomers and residual HCl must be freed of insoluble solids before it can be introduced into the electrodialysis unit.
  • These solids will consist of lignin, unhydrolyzed cellulose, and inert materials such as ink, coating pigments, fillers, and dirt. Any trash that had not been previously separated from municipal solid waste would also be present.
  • Removal of the solids can conveniently be accomplished by centrifuging. Some dilution with water is necessary here to reduce the viscosity enough to expedite sedimentation and to wash residual sugars from the sediment. Thus the acid concentration leaving the centrifuge will be less than 20%, which also conforms to optimum electrodialysis conditions. A filtration step to remove fines that might plug the electrodialysis membranes is also appropriate at this point. Sugar oligomers and less than 20% concentration of HCl are then passed to the electrodialysis unit (see Fig. 10), which is typically the most expensive component of the hydrolysis plant.
  • Dialysis is a concentration gradient- driven separation process.
  • the dialysis system utilizes a unique ion exchange membrane permeable to anionic species and H+, but rejects other cationic species.
  • the dialysis technique is used to separate and purify acids from salts by selectively permeating acids through special anion permselective membranes driven by the concentration difference of the solutions. In this way hydrochloric and other acids can efficiently be recovered.
  • the feed solution is supplied to the dialysis unit at the bottom portion of one side of a vertical anion permselective membrane and made to flow upwards, while water is made to flow countercurrently through the top and flows downward on the other side of the membrane.
  • the concentration of the acid in the feed solution drops when acid permeates to the water side with purified acid being recovered in the water stream.
  • the almost pure acid/sugar mix continues to the electrodialysis unit.
  • Electrodialysis is an electric current driven separation process that utilizes specially designed, thin ion exchange membranes for desalting, concentration and ion separation. Electrodialysis may be performed on a batch basis, a once-through continuous basis, or a feed-and-bleed basis.
  • a feed stream is passed between a cation permeable membrane that allows passage of positively charged ions and an anion permeable membrane that allows passage of negatively charged ions.
  • Numerous cell pairs consisting of a cation permeable membrane, a flow distribution spacer, an anion permeable membrane, and another spacer are arranged as a stack in a plate and frame configuration between a positively charged electrode and a negatively charged electrode.
  • D.C. current is passed between the electrodes through the solution, electrolytically disassociated positive ions migrate toward the cathode, penetrate the cation permeable membrane and enter the next cell where migration is blocked by the anion-exchange membrane.
  • the separation of HCl from the sugar in the hydrolyzates by electrodialysis should provide a maximum yield of recovered acid in maximum concentration at minimum power consumption with minimum membrane area.
  • the experimental results made it obvious that these conditions cannot be met simultaneously.
  • the final acid concentration in the concentrate solution is too low.
  • the percentage of acid transferred falls off and power consumption and membrane area are high.
  • the remaining independent operating variable is current density, the current per unit of effective area of the membrane through which the current passes.
  • the experiments reported above were conducted at a current density of 116 mA/sq cm.
  • the optimum current density may be determined from balancing initial and replacement membrane costs which fall with increasing current density against power costs which rise with current density. Without knowing the actual values for capital, membrane, and power costs the site-specific optimum current density cannot be determined.
  • HCl As HCl passes through the membranes, water is also transferred by osmotic forces. The volume of this acid and its associated water increases the volume of the recovery stream and decreases the volume of the hydrolyzate stream. Since the sugars are retained, their concentration increases as already noted to as high as 60%. The HCl concentration in the hydrolyzate at the end of electrodialysis based on acid and water alone is about 3%.
  • the sugar solutions obtained have two additional significant advantages over those obtainable from high temperature dilute acid hydrolysis beyond the improved yield. Since the processing temperatures are mild (not exceeding 50°C), the solutions are readily fermentable without the need for removal of inhibitors formed at high temperatures. And the high concentration of sugars allows significant energy savings in fermentation and ethanol distillation when coupled with the BIOSTIL or Delta-T process for ethanol production.
  • the CHEMATUR (Sweden) BIOSTIL or Delta-T (American) process is a continuous fermentation process for ethanol production, combining fermentation with simultaneous ethanol distillation.
  • a concentrated substrate such as a 55% sugar solution is fed to the fermenter at a rate that maintains the residual sugars in the fermenter at a very low concentration. Immediate conversion of sugars to ethanol occurs, but the alcohol concentration is maintained constant at about 5% by ethanol removal from a circulating beer stream. Only a single fermenter is needed for continuous operation.
  • Fermented liquid (beer) is fed to a centrifugal yeast separator and the separated yeast slurry fraction is returned to the fermenter.
  • De- yeasted beer enters a primary distillation column where about 90% of the ethanol is removed.
  • the ethanol-water vapor (about 40% ethanol) goes to a rectification column.
  • the exhausted liquid (weak beer) passes through a heat exchanger and cooler and is returned to the fermenter.
  • a minor stream passes to the stripping section of a beer column. Concentrated stillage is removed at the bottom of the stripping section.
  • the process permits the use of more concentrated feedstocks, provides a more concentrated stillage, and improves ethanol yields.
  • Sugar losses are considerably smaller, glycerol formation is inhibited, and yeast is recycled.
  • the operations are very resistant to bacterial infection, and can accept unpasteurized substrates.
  • the lignin residue may comprise-as much as 25% of the starting material. It has been demonstrated that the lignin from concentrated
  • HCl hydrolysis shows high reactivity to phenol.
  • the phenolated lignin has excellent resin-forming capability and shows superior performance as an adhesive component (15). However, if highly contaminated with other insoluble residue components the lignin may only be suitable for burning to provide some of the process energy requirements.
  • Carbon dioxide is a major by-product of fermentation, with about one pound produced for each pound of ethanol. Its value varies with plant location.
  • Furfural is obtainable from the xylose that is not fermentable by Saccharomyces.
  • the Furfural yield could be as high as half the ethanol yield. Even at lower xylose contents, Furfural can be a valuable co-product.
  • Furfural is produced by heating xylose in a weak acid solution.
  • Delta-T fermentation and distillation process which were designed for use with molasses or grain feedstocks, and would not be applicable to dilute sugar solutions from cellulose hydrolysis.

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Abstract

Un procédé de conversion de la cellulose provenant de déchets urbains a été développé. Les caractéristiques importantes de ce procédé sont: (1) l'utilisation d'acide chlorhydrique concentré à des températures modérées, aliée à une action mécanique pour hydrolyser la cellulose en glucose; (2) la récupération de l'acide à partir de l'hydrolysat par électrodialyse pour produire des solutions de sucre concentrées destinées à la fermentation; et (3) la distillation continue de l'éthanol produit.
PCT/US1991/007879 1991-09-11 1991-10-31 Procede de degradation de dechets urbains et de fabrication d'alcool combustible Ceased WO1993005186A1 (fr)

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US757,846 1991-09-11

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Cited By (18)

* Cited by examiner, † Cited by third party
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US7408056B2 (en) 1999-06-22 2008-08-05 Xyleco, Inc. Cellulosic and lignocellulosic materials and compositions and composites made therefrom
WO2008111045A1 (fr) * 2007-03-15 2008-09-18 Hcl Cleantech Ltd. Procédé de récupération d'hcl dans une solution diluée de celui-ci
WO2009125400A3 (fr) * 2008-04-08 2010-01-28 Hcl Cleantech Ltd. Procédé pour la récupération d'hcl à partir d'une solution diluée de celui-ci et composition d'agent d'extraction destinée à être utilisée dans celui-ci
WO2010026572A1 (fr) * 2008-09-02 2010-03-11 Hcl Cleantech Ltd. Procédé pour la production d'hcl gazeux à partir de sels de chlorure et pour la production de glucides
JP2012183031A (ja) * 2011-03-07 2012-09-27 Kawasaki Heavy Ind Ltd 電気透析方法及び電気透析装置
US8404355B2 (en) 2010-12-09 2013-03-26 Virdia Ltd Methods and systems for processing lignocellulosic materials and related compositions
RU2541037C2 (ru) * 2009-08-11 2015-02-10 ЭфПиИННОВЕЙШНЗ Фракционирование потока жидких отходов от производства нанокристаллической целлюлозы
US9115467B2 (en) 2010-08-01 2015-08-25 Virdia, Inc. Methods and systems for solvent purification
US9410216B2 (en) 2010-06-26 2016-08-09 Virdia, Inc. Sugar mixtures and methods for production and use thereof
US9476106B2 (en) 2010-06-28 2016-10-25 Virdia, Inc. Methods and systems for processing a sucrose crop and sugar mixtures
US9512495B2 (en) 2011-04-07 2016-12-06 Virdia, Inc. Lignocellulose conversion processes and products
WO2017039439A1 (fr) * 2015-08-31 2017-03-09 Avantium Knowledge Centre B.V. Procédé de récupération d'acide chlorhydrique
US9617608B2 (en) 2011-10-10 2017-04-11 Virdia, Inc. Sugar compositions
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WO1994029475A1 (fr) * 1993-06-11 1994-12-22 Midwest Research Institute Masse cellulaire provenant de cuves de fermentation et utilisee comme source de nutrition dans la conversion de biomasse en ethanol
US7408056B2 (en) 1999-06-22 2008-08-05 Xyleco, Inc. Cellulosic and lignocellulosic materials and compositions and composites made therefrom
US7537826B2 (en) 1999-06-22 2009-05-26 Xyleco, Inc. Cellulosic and lignocellulosic materials and compositions and composites made therefrom
US10059035B2 (en) 2005-03-24 2018-08-28 Xyleco, Inc. Fibrous materials and composites
AU2008224486B2 (en) * 2007-03-15 2011-10-20 Hcl Cleantech Ltd. A process for the recovery of HCl from a dilute solution thereof
WO2008111045A1 (fr) * 2007-03-15 2008-09-18 Hcl Cleantech Ltd. Procédé de récupération d'hcl dans une solution diluée de celui-ci
WO2009125400A3 (fr) * 2008-04-08 2010-01-28 Hcl Cleantech Ltd. Procédé pour la récupération d'hcl à partir d'une solution diluée de celui-ci et composition d'agent d'extraction destinée à être utilisée dans celui-ci
WO2010026572A1 (fr) * 2008-09-02 2010-03-11 Hcl Cleantech Ltd. Procédé pour la production d'hcl gazeux à partir de sels de chlorure et pour la production de glucides
RU2541037C2 (ru) * 2009-08-11 2015-02-10 ЭфПиИННОВЕЙШНЗ Фракционирование потока жидких отходов от производства нанокристаллической целлюлозы
US9410216B2 (en) 2010-06-26 2016-08-09 Virdia, Inc. Sugar mixtures and methods for production and use thereof
US10752878B2 (en) 2010-06-26 2020-08-25 Virdia, Inc. Sugar mixtures and methods for production and use thereof
US9963673B2 (en) 2010-06-26 2018-05-08 Virdia, Inc. Sugar mixtures and methods for production and use thereof
US9476106B2 (en) 2010-06-28 2016-10-25 Virdia, Inc. Methods and systems for processing a sucrose crop and sugar mixtures
US10760138B2 (en) 2010-06-28 2020-09-01 Virdia, Inc. Methods and systems for processing a sucrose crop and sugar mixtures
US11242650B2 (en) 2010-08-01 2022-02-08 Virdia, Llc Methods and systems for solvent purification
US9115467B2 (en) 2010-08-01 2015-08-25 Virdia, Inc. Methods and systems for solvent purification
US10240217B2 (en) 2010-09-02 2019-03-26 Virdia, Inc. Methods and systems for processing sugar mixtures and resultant compositions
US9663836B2 (en) 2010-09-02 2017-05-30 Virdia, Inc. Methods and systems for processing sugar mixtures and resultant compositions
US8404355B2 (en) 2010-12-09 2013-03-26 Virdia Ltd Methods and systems for processing lignocellulosic materials and related compositions
JP2012183031A (ja) * 2011-03-07 2012-09-27 Kawasaki Heavy Ind Ltd 電気透析方法及び電気透析装置
US9512495B2 (en) 2011-04-07 2016-12-06 Virdia, Inc. Lignocellulose conversion processes and products
US11667981B2 (en) 2011-04-07 2023-06-06 Virdia, Llc Lignocellulosic conversion processes and products
US10876178B2 (en) 2011-04-07 2020-12-29 Virdia, Inc. Lignocellulosic conversion processes and products
US10041138B1 (en) 2011-10-10 2018-08-07 Virdia, Inc. Sugar compositions
US9617608B2 (en) 2011-10-10 2017-04-11 Virdia, Inc. Sugar compositions
US9976194B2 (en) 2011-10-10 2018-05-22 Virdia, Inc. Sugar compositions
US9845514B2 (en) 2011-10-10 2017-12-19 Virdia, Inc. Sugar compositions
US10543460B2 (en) 2013-03-08 2020-01-28 Xyleco, Inc. Upgrading process streams
US9637802B2 (en) 2013-03-08 2017-05-02 Xyleco, Inc. Upgrading process streams
US9925496B2 (en) 2013-03-08 2018-03-27 Xyleco, Inc. Upgrading process streams
US11078548B2 (en) 2015-01-07 2021-08-03 Virdia, Llc Method for producing xylitol by fermentation
WO2017039439A1 (fr) * 2015-08-31 2017-03-09 Avantium Knowledge Centre B.V. Procédé de récupération d'acide chlorhydrique

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