RU2575707C2 - Methods of producing biofuel - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: method of producing biofuel, which includes treating an organic substance with an aqueous solvent and at least one additional catalyst selected from a group consisting of: an acid catalyst, a steam conversion catalyst, an aluminosilicate-based catalyst, a sulphide catalyst and a base catalyst, where the organic substance and aqueous solvent are provided in the form of a suspension, and said treatment is carried out in continuous flow conditions with minimal, volume-independent suspension flow rate which is greater than the settling rate of solid substance in the suspension, wherein said treatment includes: heating and raising pressure to a target temperature between about 250°C and about 400°C and to a target pressure between about 100 bar to about 300 bar to obtain biofuel; treating at the target temperature and target pressure for a defined period of time; cooling and lowering pressure in the suspension, and wherein said at least one additional catalyst is added to the organic substance after heating to said temperature and after raising pressure to said level, but before lowering pressure in the suspension; the biofuel is bio-oil and said organic substance is coal or a wood-fibre substance.

EFFECT: high efficiency of the method.

34 cl, 7 dwg, 2 ex, 13 tbl

Description

Technical field

The present invention generally relates to the field of biofuel production. More specifically, the invention relates to methods for producing biofuels from organic matter. The invention also relates to biofuel products obtained by these methods.

BACKGROUND OF THE INVENTION

Global energy demand continues to grow, while reserves of natural oil (such as oil, gas and natural gas condensate) are declining. The peak in oil production imposed by the reduction in oil reserves increases the likelihood of a global energy crisis, especially if energy demand continues to grow as predicted. Consequently, increased attention has been paid to the exploitation of previously considered unconventional fuel resources (for example, heavy oil, oil sands, oil shale) and other non-fossil energy sources (for example, wood-fiber materials).

A significant amount of research in the field of “alternative” energy production has focused on the production of biofuels from wood-fiber material. This technology increases the chances of a shift to common and renewable energy feedstocks as an alternative to depleting hydrocarbon-based feedstock. The enrichment of fossil fuels with low specific energy (for example, lignite, peat or oil shale) in high-energy fuel products also represents an attractive alternative, due to the relative abundance of these resources.

Despite having significant potential, most technologies for the production of fuels from wood-fiber material or other unconventional materials are marginal and / or unable to provide fuel products of adequate quality that are commercially viable. For example, modern processes for the production of biofuels from wood-fiber material usually require the separation of the substrate into many different components through a number of complex and time-consuming steps, and in many cases require the use of expensive hydrolytic enzymes and fermenting microorganisms. In addition to these shortcomings, modern processes are unable to use a significant part of the substrate material, which is not converted to fuel and sent to waste. In addition, fuels produced in modern processes typically contain a significantly higher oxygen content than conventional fuels. Therefore, their specific energy is relatively small and low stability makes it difficult to process them (for example, storage, mixing with conventional fuels, improving quality).

There is a need for improved methods for the production of biofuels from organic matter, which would avoid one or more of the above disadvantages.

SUMMARY OF THE INVENTION

In a first aspect, the invention provides a method for producing biofuels, the method comprising treating the organic matter with an aqueous solvent and at least one additional catalyst at a temperature between about 250 ° C and about 400 ° C and under a pressure of between about 100 bar and about 300 bar.

In a second aspect, the invention provides a method for producing biofuels, wherein the method comprises:

• providing a reaction mixture containing organic matter and an aqueous solvent, and

• treating said reaction mixture at a temperature between about 250 ° C. and about 400 ° C. and at a pressure between about 100 bar and about 300 bar in the reaction vessel;

where the specified reaction mixture contains at least one additional catalyst, the origin of which is independent of other components of the reaction mixture and from the specified vessel.

In one embodiment of the first and second aspects, the additional catalyst is not present, or is not substantially present, in any one or more organic matter, aqueous solvent, or wall of the reaction vessel.

In another embodiment of the first and second aspects, an additional catalyst is also present in any one or more organic matter, an aqueous solvent, or the wall of the reaction vessel.

In one embodiment of the first and second aspects, the additional catalyst is an additional primary catalyst.

In one embodiment of the first and second aspects, the further base catalyst is an alkali metal hydroxide catalyst or a transition metal hydroxide catalyst.

In one embodiment of the first and second aspects, the additional base catalyst is sodium hydroxide or potassium hydroxide.

In one embodiment of the first and second aspects, the biofuel is an oil product.

In one embodiment of the first and second aspects, the biofuel is bio-oil.

In one embodiment of the first and second aspects, biooil is obtained from the processing of fossilized organic material (for example, from coal, such as lignite).

In one of the embodiments of the first and second aspects, biooil is obtained from non-fossilized organic material (for example, from wood-fiber material).

In another embodiment of the first and second aspects, the organic substance and the aqueous solvent are processed in the form of a suspension.

In another embodiment of the first and second aspects, the processing is performed in a continuous stream.

In another embodiment of the first and second aspects, the suspension is exposed to:

(a) heating and raising the pressure to a target temperature and pressure,

(b) processing at a target temperature (s) and pressure (s) for a specific period of time (i.e., “retention time”), and

(c) cooling and depressurizing,

in continuous flow conditions.

In another embodiment of the first and second aspects, the minimum (volume independent) flow rate of the slurry under said continuous flow conditions is greater than the rate of deposition of the solid in the slurry.

In another embodiment of the first and second aspects, the minimum (volume independent) flow rate of the slurry under said continuous flow conditions is higher than 0.01 cm / s.

In another embodiment of the first and second aspects, the minimum (volume independent) flow rate of the slurry under said continuous flow conditions is greater than 0.05 cm / s.

In another embodiment of the first and second aspects, the minimum (volume independent) flow rate of the slurry under said continuous flow conditions is higher than about 0.5 cm / s.

In another embodiment of the first and second aspects, the minimum (volume independent) flow rate of the slurry under said continuous flow conditions is higher than about 1.5 cm / s.

In an additional embodiment of the first and second aspects, the treatment comprises the use of at least one additional catalyst that facilitates the introduction of hydrogen into the organic substance.

In one of the embodiments of the first and second aspects, an additional catalyst that facilitates the introduction of hydrogen into organic matter is selected from the group consisting of catalysts based on alkali metal formates, catalysts based on transition metal formates, catalysts based on reactive carboxylic acids, catalysts on based on transition metals, sulfide catalysts, noble metal catalysts, water vapor conversion catalysts, and combinations thereof.

In one embodiment of the first and second aspects, an additional catalyst that facilitates the incorporation of hydrogen into the organic material is sodium formate.

In a further embodiment of the first and second aspects, the treatment comprises the use of at least one further catalyst that facilitates the removal of oxygen from the organic matter.

In a further embodiment of the first and second aspects, the origin of another additional catalyst is independent of other components of the reaction mixture and of the vessel.

In one embodiment of the first and second aspects, an additional catalyst that facilitates the removal of oxygen from the organic material is selected from the group consisting of acidic catalysts, transition metal catalysts, noble metal catalysts, support transition metal catalysts, catalysts based on solid acid and mixtures thereof.

In one embodiment of the first and second aspects, the organic substance is a fossilized organic substance having a carbon content of at least 50%, and the aqueous solvent is water.

In another embodiment of the first and second aspects, the organic substance is a fossilized organic substance having a carbon content of at least 60%, and the aqueous solvent is water.

In another embodiment of the first and second aspects, the temperature is between about 320 ° C and about 360 ° C, and the pressure is between about 200 bar and about 250 bar.

In another embodiment of the first and second aspects, the fossilized organic substance is lignite, a temperature between about 340 ° C and about 360 ° C, and a pressure between about 200 bar and about 240 bar.

In one of the embodiments of the first and second aspects, biofuel contains one or more components: oil, coal component and a gaseous component containing methane, hydrogen, carbon monoxide and carbon dioxide.

In one of the embodiments of the first and second aspects, the organic substance is a wood-fiber substance, and the aqueous solvent contains alcohol.

In one of the embodiments of the first and second aspects, the wood-fiber substance contains more than about 10% of each of: lignin, cellulose and hemicellulose.

In another embodiment of the first and second aspects, the temperature is between about 270 ° C and about 360 ° C, the pressure is between about 170 bar and about 250 bar, and the solvent contains between about 5% weight. and 40% weight. alcohol.

In one of the embodiments of the first and second aspects, the organic substance is a wood-fiber material, a temperature between about 300 ° C and about 340 ° C, a pressure between about 200 bar and about 240 bar, and the solvent contains between about 10% weight. and about 30% weight. alcohol.

In one embodiment of the first and second aspects, the alcohol is ethanol.

In another embodiment of the first and second aspects, processing is performed for a period of time between about 20 minutes and about 30 minutes.

In another embodiment of the first and second aspects, the method includes the step of heating the organic substance and the aqueous solvent to the specified temperature for a period of less than about 2 minutes before the specified treatment.

In another embodiment of the first and second aspects, the method includes the step of heating and increasing the pressure to the organic substance and the aqueous solvent to the specified temperature and pressure for a period of time less than about 2 minutes before the specified treatment.

In another embodiment of the first and second aspects:

(i) an additional catalyst,

(ii) an additional catalyst that facilitates the introduction of hydrogen into organic matter; and / or

(iii) an additional catalyst that facilitates the removal of oxygen from organic matter,

added to the organic matter after the specified heating and the specified pressure increase.

In another embodiment of the first and second aspects:

(i) an additional catalyst,

(ii) an additional catalyst that facilitates the introduction of hydrogen into organic matter; and / or

(iii) an additional catalyst that facilitates the removal of oxygen from organic matter,

added to the organic matter after the specified heating and the specified pressure increase and before the specified treatment.

In another embodiment of the first and second aspects, the organic substance is lignite, and

(i) an additional catalyst,

(ii) an additional catalyst that facilitates the introduction of hydrogen into organic matter; and / or

(iii) an additional catalyst that facilitates the removal of oxygen from organic matter,

added to organic matter when said temperature is more than about 340 ° C. and said pressure is more than about 230 bar.

In another embodiment of the first and second aspects, the organic substance is a wood-fiber material, and

(i) an additional catalyst,

(ii) an additional catalyst that facilitates the introduction of hydrogen into organic matter; and / or

(iii) an additional catalyst that facilitates the removal of oxygen from organic matter,

added to organic matter when said temperature is more than about 310 ° C and said pressure is more than about 180 bar.

In another embodiment of the first and second aspects, the method includes the steps of:

(i) cooling the organic matter to a temperature between about 160 ° C and about 200 ° C for a period of less than about 30 seconds after said treatment; and

(ii) lowering the pressure and cooling the organic substance to ambient temperature by release through a pressure reducing device.

In another embodiment of the first and second aspects, the pressure reducing device is placed in water at ambient temperature.

In one embodiment of the first and second aspects, the biofuel contains an oil component having a higher heat output of more than 35 MJ / kg.

In one of the embodiments of the first and second aspects, biofuel contains an oil component containing more than about 8% by weight. hydrogen based on dry weight and less than about 10% weight. oxygen per dry weight.

In one embodiment of the first and second aspects, the biofuel contains a coal component having a higher heat output of more than 30 MJ / kg.

In a third aspect, the invention provides biofuels produced by the method according to the first and second aspect.

In one embodiment of the third aspect, biofuel is an oil product.

In one embodiment of the third aspect, the biofuel is bio-oil.

In one embodiment of the third aspect, biofuel is produced by processing fossilized organic material (e.g., coal, such as lignite).

In one embodiment of the third aspect, biofuels are obtained by processing non-fossilized organic material (e.g., wood-fiber material).

Brief Description of the Drawings

Preferred embodiments of the present invention will be described below by only one of the examples with reference to the accompanying graphic materials, where:

Figure 1 is a graph showing the weight percent of oxygen in oil obtained from wood-fiber biomass, depending on the concentration of sodium (mol per liter) (reaction conditions: processing time - 25 minutes, 320-350 ° C, 240 bar).

2 is a graph showing simulated distillation according to ASTM D7169 of a typical brown oil derived from brown coal.

Figa-3l represent proton NMR and quantitative 13C NMR spectra for fractions A-F, as shown in table 6 (first, proton NMR). Sample Code A (FIGS. 3A-3B); Sample Code B (FIG. 3C-3D); Sample Code C (FIGS. 3E-3F); Sample Code D (Fig. 3G-3H); Sample Code E (FIGS. 3I-3J); Sample code F (Fig. 3K-3L).

Figure 4 shows a 1 H NMR spectrum of a typical bio-oil obtained from radiant pine from a sample of feedstock No. 4 in Table 2B.

Figure 5 shows the normalized intensity (GPC) as a function of molecular weight for typical bio-oil products from radiant pine.

6 shows a partial analysis by gas chromatography with mass spectrometric detection (GC-MS) obtained from wood-fiber bio-oil material transported in water, showing the identification of components with the highest relative content.

Fig.7 shows a partial analysis by gas chromatography with mass spectrometric detection (GC-MS) of oil collected from the aqueous phase associated with the processing of a suspension of brown coal. The component with the highest relative content is catechin (1,2-benzenediol).

Definitions

In this context, singular forms include plural references, unless the context explicitly requires otherwise. For example, the term “catalyst” also includes many catalysts.

In this context, the term “comprising” means “comprising”. Changes to the word “comprising”, such as “contain” and “contains”, have correspondingly changed meanings. So, for example, the material “containing” lignin and cellulose may consist exclusively of lignin and cellulose or may contain other, additional substances.

In this context, the term "native catalyst" will be understood as a catalyst that is naturally present in this component of the reaction, such as, for example, in any one or more of the source of organic matter such as feedstock, aqueous solvent and / or vessel walls of the reactor device.

In this context, the term “additional catalyst” will be understood as a catalyst that is supplied in addition to the catalyst (s) that is substantially present in other components of this reaction (for example, a native catalyst present in an organic substance, an aqueous solvent and / or walls of a reactor devices).

In this context, the terms “organic matter” and “organic materials” have the same meaning and cover any material containing carbon, including fossilized and non-fossilized materials. Non-limiting examples of organic matter include biomass, wood-fiber material and materials containing hydrocarbons (e.g., lignite, oil shale and peat).

In this context, the term "biofuel" refers to energy-containing material obtained from the processing of organic matter. Non-limiting examples of biofuels include petroleum products (i.e. biooil), coal products (also known as equivalent to Pulverized Coal Product (PCI), biodiesel and alcohols (e.g. ethanol and butanol).

In this context, the term “bio-oil” will be understood as encompassing petroleum products obtained from the processing of fossilized organic material (eg, coal, such as lignite), non-fossilized organic material (eg, wood-fiber material) or mixtures thereof.

In this context, the terms “wood-fiber material” and “wood-fiber biomass” are used interchangeably and have the same meaning. The terms encompass any substance containing lignin, cellulose and hemicellulose.

In this context, the term "aqueous solvent" refers to a solvent containing at least one percent water based on the total weight of the solvent. Therefore, an “aqueous solvent” may contain between one percent water and one hundred percent water, based on the total weight of the solvent.

As used herein, the term “aqueous alcohol” refers to a solvent containing at least one percent alcohol based on the total weight of the solvent.

As used herein, the term “aqueous ethanol” refers to a solvent containing at least one percent ethanol, based on the total weight of the solvent.

In this context, the term "aqueous methanol" refers to a solvent containing at least one percent methanol, based on the total weight of the solvent.

In this context, the term “supercritical” substance (for example, a supercritical solvent) refers to a substance that is heated above its critical temperature and to which pressure is applied above its critical pressure (ie, a substance at a temperature and pressure above its critical point).

It should be understood that the use of the term "about" in this document in relation to the stated numerical value (eg, temperature or pressure) includes the stated numerical value within plus or minus ten percent of the stated numerical value.

It should be understood that the use of the term “between” in this document when referring to an interval of numerical values encompasses numerical values at each of the end points of the interval. For example, the temperature range between 10 ° C and 15 ° C includes temperatures of 10 ° C and 15 ° C.

Any description of a prior art document, or an assertion derived from or based on such a document, does not constitute recognition that the document, or the resulting assertion, is part of well-known knowledge in the related art.

For the purpose of description, all documents to which reference is made here are incorporated by reference as a whole, unless otherwise specified.

DETAILED DESCRIPTION OF THE INVENTION

Modern methods of biofuel production suffer from a number of disadvantages. Most contain a number of complex reaction steps, often requiring the addition of expensive reagents (e.g. hydrolytic enzymes). Additionally, many are unable to effectively use / convert a significant portion of the feedstock. More significantly, biofuels produced by modern technologies usually have a significantly increased oxygen content compared to traditional fuels, which reduces their specific energy and stability. Therefore, these biofuels are difficult to store and / or process for downstream applications (for example, for mixing with conventional fuels, improving quality). In light of these and other limitations, few current biofuel production methods provide a commercially viable alternative to using conventional fuels.

Some aspects of the present invention provide methods for producing biofuels from organic matter. Unlike existing methods, the biofuel production methods described herein include a single step in which the material of the organic substrate is converted to biofuel. Separation of the substrate material into various components before performing the methods of the invention is not required. Additionally, the methods do not require the use of hydrolytic enzymes or microorganisms for the fermentation of sugars. On the contrary, to obtain a biofuel product, the substrate material mixed with an aqueous solvent is subjected to a single processing step under conditions of elevated temperature and pressure and optionally in the presence of special catalysts. Without limiting the specific mode of action, it has been postulated that the inclusion of catalysts that contribute to the maintenance of the reducing environment triggers a series of reactions in which the substrate material is cleaved and modified by oxygen reduction and the introduction of hydrogen.

Some features of the invention relate to biofuels produced by the methods of the present invention. Biofuels are characterized by low oxygen content, high specific energy and / or increased stability compared to biofuels manufactured using currently available methods. Accordingly, the biofuels according to the invention are more suitable for storage and / or mixing with conventional fuels (for example, diesel fuel) and (if necessary) their quality is more easily upgraded to higher quality fuel products.

Organic matter

The present invention provides methods for converting organic matter to biofuels. In this context, “organic matter” (also referred to herein as “organic material”) encompasses any substance containing carbon, including fossilized and non-fossilized forms of substance containing carbon.

There are no restrictions on the specific type of organic substance used in the methods of the invention, although it is contemplated that some forms of organic matter may be more suitable than others.

The organic material used in the methods of the invention can be natural organic materials (e.g., wood-fiber biomass, or fossil fuel materials, including lignite, oil shale, peat, etc.) or synthetic organic materials (e.g. synthetic rubbers, plastics, nylons, etc.).

The organic material used in the methods of the invention may be fossilized organic material (e.g., lignite), non-fossilized organic material (e.g., wood-fiber material), or a mixture thereof.

It should be understood that the organic material may contain mixtures of two or more different types of natural organic materials, two or more different types of synthetic organic materials, or a mixture of natural and synthetic organic materials. There is no limitation on the specific ratio of the various components in the mixture.

In some preferred embodiments of the invention, the organic substance used in the methods of the invention contains fossilized organic matter. "Petrified organic matter", as implied herein, covers any organic material that has been subjected to geothermal pressure and temperature for a period of time sufficient to remove water and concentrate carbon to significant levels. For example, fossilized organic material may contain more than about 10% by weight, 20% by weight, 30% by weight, 40% by weight, 50% by weight, 60% by weight, 70% by weight, 75% by weight, 80% by weight, 85% by weight, 90% by weight. or 95% weight. carbon. Preferably, the fossilized organic material may contain more than about 50% by weight. carbon, more than about 60% weight. carbon or more than about 70% weight. carbon. Non-limiting examples of such materials contain coal (e.g., anthracite such as graphite, anthracite and semi-anthracite; bituminous coal; semi-bituminous coal; lignite (i.e. brown coal), coking coal, coal tar, coal tar derivatives, semi-coke) cokes (e.g., high-temperature coke, foundry coke, low- and medium-temperature coke, pitch coke, petroleum coke, coke produced in coke oven, coke breeze, gas coke, brown coal coke, semi-coke), peat (e.g. milling torus f, formation peat), kerogen, oil sands, oil shale, shale tar, asphalts, asphalts, natural bitumen, tar sands, or any combination thereof.

In other preferred embodiments, the organic material used in the methods of the invention comprises a wood fiber material. As used herein, “wood fiber” refers to any substance containing lignin, cellulose and hemicellulose.

For example, the wood-fiber material may be a woody plant or a component thereof. Non-limiting examples of suitable woody plants include pine (e.g., radiant pine), birch, eucalyptus, bamboo, beech, spruce, fir, cedar, poplar, willow and aspen. Arboreal plants can be spruce forest plants (e.g., willow shoots, aspen shoots).

Additionally or alternatively, the wood-fiber material may be a fiber plant or a component thereof. Non-limiting examples of fibrous plants (or their components) include cereal herbs (e.g., millet twig), freshly cut grasses, flax, corn cobs, corn straw, reeds, bamboo, oilcake, hemp seed, Mexican agave, jute, hemp, hemp sowing, straw, wheat straw, abacus, cotton, kenaf, rice husk and coconut fibers.

Additionally or alternatively, wood-fiber material can be obtained from an agricultural source. Non-limiting examples of wood-fiber material from agricultural sources include crops, crop residues, and waste from grain processing plants (e.g., wheat / oat shells, maize seed, etc.). In general, wood fiber material from agricultural sources may contain hardwood, softwood, hardwood trunks, softwood trunks, nutshells, branches, shrubs, shoots, grain, corn straw, corn cobs, energy crops, forest resources , fruits, flowers, grain, cereal grasses, green crops, wheat straw, sticky millet, willow, sugarcane cake, cotton beard, foliage, bark, needles, raw timber, roots, seeds gi, forest plantations with short rotation, shrubs, switchgrass, trees, vines, cattle manure, pig waste.

Additionally or alternatively, the wood-fiber material can be obtained from production or virgin forests (e.g. trees, shoots, timber processing residues or forests, such wood waste as branches, leaves, bark, logs, roots, leaves, and products obtained from the processing of such materials, waste streams or offal from timber, rejects and scraps from sawmills and paper mills, sawdust and particle boards).

Additionally or alternatively, industrial products and by-products can be used as a source of wood-fiber material. Non-limiting examples include wood-related materials and wood waste and industrial products (e.g., pulp, pulp for paper (e.g. newsprint), cardboard, textiles and fabrics, dextran and viscose fiber).

It should be understood that the organic material used in the methods of the invention may contain a mixture of two or more different types of wood fiber material, including any combination of the individual examples presented above.

The relative proportion of lignin, hemicellulose and cellulose in the original sample will depend on the nature of the wood-fiber material.

By way of example only, the proportion of hemicellulose in a woody or fibrous plant used in the methods of the invention can be between about 15% and about 40%, the proportion of cellulose can be between about 30% and about 60%, and the lignin fraction can be between about 5% and about 40%. Preferably, the proportion of hemicellulose in the woody or fibrous plant used in the methods of the invention can be between about 23% and about 32%, the proportion of cellulose can be between about 38% and about 50%, and the proportion of lignin can be between about 15% and about 25%

In some embodiments, the wood-fiber material used in the methods of the invention may contain between about 2% and about 35% lignin, between about 15% and about 45% cellulose, and between about 10% and about 35% hemicellulose.

In other embodiments, the wood-fiber material used in the methods of the invention may include between about 20% and about 35% lignin, between about 20% and about 45% cellulose, between about 20% and about 35% hemicellulose.

In some embodiments, the wood-fiber material may contain more than about 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, or 50% lignin.

In some embodiments, the wood fiber may contain more than about 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, or 50% cellulose.

In some embodiments, the wood fiber may contain more than about 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, or 50% hemicellulose.

One skilled in the art will recognize that the methods described herein are not limited to the relative proportions of lignin, hemicellulose and cellulose in the original source of wood-fiber material.

The organic substance used in the methods of the invention may contain a mixture of fossilized organic matter and non-fossilized organic matter (e.g., wood fiber). Non-limiting examples of suitable fossilized and non-fossilized organic matter that may be included in the mixture are presented in the paragraphs above. It should be understood that there is no restriction on the relative proportion of fossilized and non-fossilized organic matter in the mixture.

In some embodiments, the mixture comprises lignite (brown coal) and wood fiber. The woody fibrous material of the mixture may, for example, contain woody plant material and / or fibrous plant material. The proportion of lignite in the mixture may be more than about 20%, 40%, 60% or 80%. Alternatively, the proportion of wood-fiber material in the mixture may be greater than about 20%, 40%, 60%, or 80%.

In some preferred embodiments, the organic material used in the methods of the invention comprises carbon-containing polymeric materials, non-limiting examples of which include rubbers (e.g., tires), plastics, and polyamides (e.g., nylons).

Non-limiting examples of suitable rubbers include natural and synthetic rubbers such as polyurethanes, styrene rubbers, neoprene, polybutadiene, fluororubber, butyl rubbers, siloxane rubbers, plantation rubbers, acrylate rubbers, thiocols and nitrile rubbers.

Non-limiting examples of suitable plastics include PVC, polyethylene, polystyrene, terephthalate, polyethylene and polypropylene.

The organic material used in the methods of the invention may include carbonaceous waste, such as wastewater, compost, or industrial or household waste.

Organic matter pretreatment

The organic substance used in the methods of the invention can optionally be processed before converting the substance to biofuel.

It should be recognized that there are no stringent requirements for the pre-processing step when using the methods of the invention. For example, pretreatment of an organic substance may not be required if it is obtained in the form of a liquid or in the form of solid particles. However, it is contemplated that in many cases, pretreatment of organic matter may be advantageous in improving the outcome of the biofuel production methods described herein.

In general, pretreatment can be used to disrupt the physical and / or chemical structure of organic matter, making it more accessible to various reagents used in the methods of the invention (e.g., aqueous solvent, catalyst) and / or other reaction parameters (e.g., heat and pressure). In some embodiments, pretreatment of the organic material may be performed to increase solubility, increase porosity, and / or reduce the crystallinity of sugar-containing components (e.g., cellulose). Pretreatment of organic matter can be carried out using a device such as, for example, an extruder, a sealed container or a batch reactor.

Pretreatment of organic matter may include physical methods, non-limiting examples of which include crushing, chipping, grinding, milling (e.g., milling in a vibrating ball mill), compression / expansion, shaking and / or pulsed electric field (PEF) treatment.

Additionally or alternatively, the pretreatment of the organic material may include physicochemical methods, non-limiting examples of which include pyrolysis, steam explosion, ammonia cellulose destruction (AFEX), ammonia cyclic filtration (ARP) and / or carbon dioxide explosion. For example, a steam explosion causes an organic substance to be exposed to high pressure vapor in a closed environment before the resulting product is released by explosion under atmospheric pressure. Steam explosion pretreatment can additionally cause the mixing of organic matter.

Additionally or alternatively, pretreatment of the organic material may include chemical methods, non-limiting examples of which include ozonolysis, acid hydrolysis (e.g. diluted acid hydrolysis using H₂SO_fourand / or HCl), alkaline hydrolysis (e.g. diluted alkali hydrolysis using sodium, potassium, calcium and / or ammonium hydroxides), oxidative delignification (i.e., biological decomposition of lignin catalyzed by a peroxidase enzyme in the presence of H₂O₂) and / or an organosolvation process (i.e., using a mixture of an organic solvent with an inorganic acid catalyst such as H₂SO_four and / or HCl, for breaking lignin-hemicellulose bonds).

Additionally or alternatively, the pretreatment of the organic matter may include biological methods, non-limiting examples of which include the addition of microorganisms (e.g. rotting fungi) capable of decomposing / causing the decomposition of some component (s) of the organic matter.

In preferred embodiments, the organic substance used in the methods of the invention is provided in the form of a suspension. A suspension can be created, for example, by generating organic matter in the form of solid particles (for example, by those physical methods mentioned above and / or other means) and mixing it with an appropriate liquid (for example, with an aqueous solvent).

The optimal particle size of the solid components and the optimal concentration of solids in the suspension may depend on factors such as, for example, the thermal conductivity of the organic substance used (i.e., the rate at which heat can be transferred to individual particles and through individual particles), the required rheological properties suspensions and / or compatibility of the suspension with the component (s) of a given device in which the methods of the invention can be carried out (for example, with a reactor pipe). The optimal particle size and / or concentration of solid components in the suspension used in the methods of the invention can be easily determined by a person skilled in the art using standard techniques. For example, a series of suspensions can be generated, each sample of the series contains particles of a different size and / or concentration of solid components that is different in comparison with other samples. Each suspension can then be processed in accordance with the methods of the invention with a continuing set of reaction conditions. The optimal particle size and / or concentration of solid components can then be determined by analyzing and comparing products generated from each suspension using methods standard for the art.

In some embodiments, the particle size of the solid components in the suspension may be between about 10 microns and about 10,000 microns. For example, the particle size may be greater than about 50, 100, 500, 750, 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000 or 9000 microns. Alternatively, the particle size may be less than about 50, 100, 500, 750, 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000 or 9000 microns. In some embodiments, the particle size is between about 10 microns and about 50 microns, between about 10 microns and about 100 microns, between about 10 microns and about 200 microns, between about 10 microns and about 500 microns, between about 10 microns and about 750 microns or between about 10 microns and about 1000 microns. In other embodiments, the implementation of the particle size is between about 100 microns and about 1000 microns, between about 100 microns and about 750 microns, between about 100 microns and about 500 microns, or between about 100 microns and about 250 microns.

In some embodiments, the concentration of solids in the suspension may be higher than about 50% in terms of weight to volume. Alternatively, the concentration of solids may be lower than, about 50% in terms of weight to volume, lower than, about 40% in terms of weight to volume, lower than, about 30% in terms of weight to volume, lower than, about 20% in terms of weight to volume, lower than about 10% in terms of weight to volume or lower than, about 5% in terms of weight to volume. In some embodiments, the implementation of the concentration of solids may be between about 2% in terms of weight to volume and about 30% in terms of weight to volume, between about 2% in terms of weight to volume and about 20% in terms of weight to volume, between about 2 % in terms of weight to volume and about 10% in terms of weight to volume, between about 5% in terms of weight to volume and about 10% in terms of weight to volume, between about 5% in terms of weight to volume and about 20% in terms of weight to volume or between about 1% in relation to weight to volume, etc. approximately 10% in terms of weight to volume.

In some embodiments, the organic material used in the methods of the invention is a wood fiber material subjected to an optional pretreatment step in which hemicellulose is recovered. Accordingly, most of the hemicellulose (or even all of the hemicellulose) can be extracted from the wood-fiber material and the remaining material (containing mainly cellulose and lignin) is used to produce biofuel according to the methods of the invention. However, it should be understood that this pre-treatment is optional, and when performing the methods of the invention, there is no requirement to separate the hemicellulose from the wood-fiber material. Suitable methods for separating hemicellulose from a fibrous material are described, for example, in PCT publication No. WO / 2010/034055, the contents of which are hereby incorporated by reference in their entirety.

For example, hemicellulose can be removed from a fibrous substance by subjecting a suspension containing wood fibrous substance (for example, with a solids concentration of 5-15% by weight to volume), treatment with weak aqueous acid (for example, with a pH of 6.5- 6.9) at a temperature between about 100 ° C and about 250 ° C, a reactive pressure between about 2 atmospheres and about 50 atmospheres, for a period of time between about 5 minutes and about 20 minutes. The soluble hemicellulosic component can be separated from the rest of the solid (containing predominantly cellulose and lignin) using any suitable means (for example, by using a filter of an appropriate size). The remaining solid can be directly used in the methods of the invention or, alternatively, for use in the methods of the invention, it can be mixed with one or more other forms of organic matter (for example, lignite).

Biofuel production

The methods of the invention include means for generating biofuels from organic matter. In general, the methods require treating the organic material with an aqueous solvent under conditions of elevated temperature and pressure and, optionally, in the presence of catalysts that support the reducing medium.

Putative reaction mechanisms

Without limiting to a specific mechanistic description, it is assumed that the organic substance used in the methods of the invention decomposes (i.e., undergoes conversion from a solid to a liquid), primarily by acid and / or basic catalyzed hydrolysis. Hydrolysis reactions can be mediated by aqueous cations (hydroxonium) and anions (hydroxide), which dissociate from water molecules at elevated temperature and pressure. The hydrolysis of the organic substrate can also be facilitated by the inclusion of additional acidic and / or basic catalysts in the mixture of the organic substance and the aqueous solvent. Examples of reactions that can be caused to hydrolyze a material include the conversion of glycoside and / or ether linkages of an organic substance to alcohols and the conversion of esters of an organic substance to carboxylic acids and alcohols.

In some embodiments, aqueous solvents used in the methods of the invention are aqueous alcohols. It is believed that at elevated temperatures and pressures, the alcohols present in the solvent can decompose organic matter by alcohol hydrolysis. Additional functions of alcohols (if present) in an aqueous solvent may contain swelling of the organic substance in order to stimulate greater reactivity and / or remove hydrolyzed particles from the surface of the substance in order to expose a fresh surface that can hydrolyze further (thereby increasing the total yield ) Alcohols in an aqueous solvent can also act as radical modifiers, reducing the frequency and / or stiffness of unwanted radical side reactions (e.g. polymerizations).

It is also assumed that the conversion of organic matter to biofuel using the methods of the invention contains the removal of oxygen from the substance. And again, without reference to specific mechanistic paths, it is assumed that the inclusion of special catalysts in a mixture of an aqueous solvent and organic matter during processing and / or thermal catalysis of a substance facilitates the elimination (dehydration) reactions (i.e. elimination of water with the formation of double bonds), decarboxylation reactions (i.e., removal of the carboxyl group (s) from organic compounds in the form of carbon dioxide) and / or decarbonylation reactions (i.e. removal of carbon monoxide from aldehydes) , each of which, when processed, can contribute to the removal of oxygen from compounds present in organic matter.

An additionally proposed mechanism contributing to the conversion of organic matter to biofuels is the hydrogenation of compounds in organic matter. Hydrogenation can be simplified by special catalysts added during processing to a mixture of an aqueous solvent and organic matter. Without being limited to specific mechanisms, catalysts are provided to facilitate:

(i) hydrogenation by transferring hydrogen of aldehydes, ketones and / or unsaturated or aromatic systems in compounds of organic matter with the release of alcohol (from which oxygen can then be removed by dehydration, i.e. elimination of water) and saturated fragments; and / or

(ii) direct hydrogenation of aldehydes, ketones and / or unsaturated or aromatic systems with the release of alcohols (which can then be eliminated by removal of oxygen) and saturated fragments.

Hydrogenation and subsequent dehydration can occur in a cascade reaction system (referred to as hydrodeoxygenation).

It is assumed that hydrogen in this system can be made available by gasification of organic matter (and alcohols, if present in an aqueous solvent), giving a mixture of hydrogen, carbon monoxide and water, the last two can then undergo a water gas conversion reaction to form molecular hydrogen and dioxide carbon. In addition, carbon monoxide resulting from gasification is designed to interact with special catalysts (for example, sodium hydroxide or potassium hydroxide), which during processing can be added to a mixture of an aqueous solvent and organic matter to form formate (for example, sodium formate or formate potassium). The formate thus formed can act as a hydrogen transfer agent, facilitating the hydrogenation of compounds in organic material. Other hydrogen transfer agents that can be generated by decomposing organic matter can be low molecular weight acids, in particular formic, acetic and oxalic acids.

In general, and again without limitation to specific modes of action, the intent is to partially gasify reactive chemical particles in the presence of the catalysts described in this document, activates a cascade of interrelated reactions, the culmination of which is the generation of biofuels with high energy and stability.

In general, the concept of stability (and high specific energy) of biofuels produced by the methods of the invention arises, at least in part, due to the relatively low oxygen content and high hydrogen content, which reduces the degree of unsaturation (starting point for undesired polymerization, leading to "coking" of the material). In addition, it should be borne in mind that unsaturated or aromatic bonds present in the product may be less prone to activation by neighboring oxygen-containing groups, which further reduces the repolymerization potential.

Water solvents

The solvents used in accordance with the methods of the invention may be aqueous solvents. The specific nature of the aqueous solvent used will depend on the form of the organic substance used.

In some embodiments, the solvent may be water. For example, the use of water as a solvent may be suitable or preferred when the organic substance used in the methods consists of a significant amount, or contains a significant amount of fossilized organic matter (eg, lignite, peat, etc.).

It should be recognized that water can also be used as a solvent in the processing of other types of organic matter using the methods of the invention, although in the case of some organic materials (e.g., wood-fiber material), the results may be suboptimal.

In other embodiments, the aqueous solvent is aqueous alcohol. For example, the use of aqueous alcohol as a solvent may be suitable or preferred when the organic substance used in the methods of the invention consists or contains a significant amount of wood-fiber material and / or other materials, such as rubber and plastics, due to stronger chemical bonds in these types of organic matter.

Suitable alcohols may contain from one and about ten carbon atoms. Non-limiting examples of suitable alcohols include methanol, ethanol, isopropyl alcohol, isobutyl alcohol, pentyl alcohol, hexanol and isohexanol.

In some embodiments, the solvent comprises a mixture of two or more aqueous alcohols.

Preferably, the alcohol is ethanol, methanol, or a mixture thereof.

Aqueous alcohol will generally contain at least one percent alcohol based on the total weight of the solvent. In some embodiments, the aqueous alcohol comprises more than about 5% by weight, 10% by weight, 15% by weight, 20% by weight, 25% by weight, 30% by weight, 35% by weight, 40% by weight. , 45% weight. or 50% weight. alcohol. In other embodiments, the aqueous alcohol comprises less than about 5% by weight, 10% by weight, 15% by weight, 20% by weight, 25% by weight, 30% by weight, 35% by weight, 40% by weight. , 45% weight. or 50% weight. alcohol.

Preferably, the aqueous alcohol contains between about 1% weight. and about 50% weight. alcohol, between about 5% weight. and about 50% weight. alcohol, between about 5% weight. and about 40% weight. alcohol, between about 5% weight. and about 30% weight. alcohol, between about 5% weight. and about 20% weight. alcohol, between about 5% weight. and about 10% weight. alcohol, between about 10% weight. and about 50% weight. alcohol, between about 20% weight. and about 50% weight. alcohol, between about 25% weight. and about 50% weight. alcohol, or between about 30% weight. and about 50% weight. alcohol.

In some embodiments, the aqueous alcohol may act as an alkylating agent. Without being limited to a specific mechanism (s), the transfer of an alkyl group from aqueous alcohol to one or more components of an organic substance is intended to facilitate solvation and / or chemical stabilization of the organic substance.

In preferred embodiments, the aqueous solvent used in the methods of the invention is aqueous methanol or aqueous ethanol.

In particularly preferred embodiments, ethanol is aqueous ethanol. Preferably, aqueous ethanol comprises between about 5% weight. and about 30% weight. ethanol, more preferably between about 10% weight. and about 25% weight. ethanol, and even more preferably, between about 15% weight. and about 25% weight. ethanol.

Temperature and pressure

In accordance with the methods of the invention, for the production of biofuels, the organic substance can be treated with an aqueous solvent under conditions of elevated temperature and pressure.

The specific temperature and pressure conditions used in the practical application of the methods of the invention may depend on a large number of different factors, including, for example, the type of aqueous solvent used, the percentage of alcohol (if present) in the aqueous solvent, the type of organic substance being processing, the physical form of the organic substance being processed, the types of catalyst (s) used (if any) and their different concentration (concentration tion), retention time and / or type of device in which these methods are performed. These and other factors may vary in order to optimize the initial set of conditions so as to maximize yield and / or reduce processing time. In preferred embodiments, all, or substantially all, of the organic material used as feedstock is converted to biofuel.

The desired reaction conditions can be achieved, for example, by carrying out the reaction in a suitable device (for example, in a sub / supercritical reactor device) capable of maintaining elevated temperature and elevated pressure.

In some embodiments of the invention, the aqueous solvent used in the methods of the invention can be heated and applied beyond its critical temperature and / or beyond its critical pressure (ie, beyond the “critical point” of the solvent). Accordingly, an aqueous solvent, if it is heated and under pressure outside the “critical point” of the solvent, can be a “supercritical” aqueous solvent.

In some embodiments, the aqueous solvent used in the methods of the invention may be heated and applied to a pressure (s) below the critical temperature and pressure (ie, below the "critical point" of the solvent). Accordingly, the aqueous solvent may be a “subcritical” aqueous solvent if its maximum temperature and / or maximum pressure is below its “critical point”. Preferably, the “subcritical” aqueous solvent is heated or pressurized to a level (s) approaching the “critical point” of the solvent (for example, between about 10 ° C. and about 50 ° C. below the critical temperature and / or between about 10 atmospheres and about 50 atmospheres below its critical pressure).

In some embodiments, the aqueous solvent used in the methods of the invention can be heated and applied to pressures above and below its critical temperature and pressure (ie, heated and applied to pressures above and below the “critical point” solvent at different points in time). Accordingly, when performing these methods, the aqueous solvent can fluctuate between “subcritical” and “supercritical” states.

In some embodiments, the aqueous solvent used in the methods of the invention may be heated to a level above its critical temperature, but subjected to pressure to a level below its critical pressure. In other embodiments of the invention, the aqueous solvent used in the methods of the invention may be heated to a level below its critical temperature, but subjected to pressure to a level above its critical pressure.

Those skilled in the art will recognize that the critical temperature and critical pressure for each given aqueous solvent will depend, at least in part, on the percentage of water in the solvent. For example, if an aqueous solvent contains a predetermined percentage of water in combination with a predetermined percentage of a second component having a lower critical point than water (e.g., alcohol), the critical point of the solvent will generally be lower than that for pure water. Conversely, if the aqueous solvent contains a predetermined percentage of water in combination with a predetermined percentage of a second component having a higher critical point than water, the critical point of the solvent will generally be higher than that for pure water.

In cases where the aqueous solvent contains two main components (e.g. water and alcohol), there can be an approximately linear relationship between the percentage of alcohol present in the solvent and the critical temperature and pressure of the solvent, where the end points at one end are determined by the critical point of pure water , and on the other end - the critical point of pure alcohol. For example, if the critical point of water is defined as 374 ° C and 221 atm, and the critical point of ethanol is defined as 240 ° C and 60 atm, then the critical point of a 25% aqueous ethanol solution can be at approximately 340 ° C / 180 atm, critical point 50 A% ethanol aqueous solution can be at about 307 ° C / 140 atm, and a critical point of a 75% ethanol aqueous solution can be at about 273 ° C / 100 atm.

In cases where the aqueous solvent contains more than two main components (for example, water and two different types of alcohols), calculations of a similar essence can be used to determine the critical point of the solvent when changing the fractions of different alcohols in the solvent.

Accordingly, it should be understood that when the temperature and / or pressure (or the range of temperatures and / or pressures) is given in connection with a given aqueous solvent containing two or more major components in predetermined proportions (for example, 10% aqueous alcohol in relation to weight to volume), one can easily derive the corresponding values / ranges of temperature and / or pressure when changing the relative ratios of the main components.

It should also be understood that the critical point of this aqueous solvent will be influenced by additional factors, such as the chemical state of the organic material being processed. For example, the critical point of a given aqueous solvent is likely to change during this reaction as the feedstock solvates.

In some embodiments of the invention, the processing of organic matter for biofuel production using the methods of the invention can be carried out at a temperature (s) between about 200 ° C and about 450 ° C and under pressure (s) between about 50 bar and about 350 bar. In other embodiments, the treatment may be carried out at a temperature (s) between about 250 ° C and about 400 ° C and under pressure (s) between about 100 bar and about 300 bar. In further embodiments, the treatment may be carried out at a temperature (s) between about 275 ° C. and about 375 ° C. and under pressure (s) between about 150 bar and about 275 bar. In some preferred embodiments, the treatment may be carried out at a temperature (s) between about 300 ° C and about 375 ° C and under pressure (s) between about 175 bar and about 275 bar. In other preferred embodiments, the treatment may be carried out at a temperature (s) between about 330 ° C and about 360 ° C and under pressure (s) between about 200 bar and about 250 bar. In other preferred embodiments, the treatment may be carried out at a temperature (s) between about 340 ° C and about 360 ° C and under pressure (s) between about 200 bar and about 250 bar.

An experienced recipient will understand that between the temperature and pressure necessary to actuate the conversion of organic material to biofuel using the methods of the invention, and the fraction of an additional component (s) (e.g., alcohol) combined with water in an aqueous solvent may exist in in general, the inverse relationship. For example, the use of an aqueous solvent containing mainly water (i.e., in the absence of an additional component (s) such as alcohol) may require elevated temperatures and / or pressures to trigger the conversion of organic matter to biofuels compared to an aqueous solvent containing a greater proportion of alcohol (which may require a relatively lower temperature and / or pressure to activate the conversion). Accordingly, it should be readily apparent to a person skilled in the art that increasing the proportion of, for example, alcohol (e.g. ethanol and / or methanol) in an aqueous solvent may allow a corresponding reduction in the temperature and / or pressure required to efficiently convert organic matter to biofuel using methods inventions. Conversely, as should be readily understood, a decrease in the proportion of, for example, alcohol (e.g., ethanol and / or methanol) in an aqueous solvent may require a corresponding increase in the temperature and / or pressure required to effect an effective conversion of the organic substance to biofuel using the methods of the invention .

You should also be aware that various catalysts can be used to increase the processing efficiency, as described here (see the subsection below, entitled “Catalysts”), which, in turn, can lower the temperature and / or pressure required to trigger the conversion of organic matter to biofuels using the methods of the invention.

Retention time

The specific period of time during which the conversion of organic matter (ie, “retention time”) can be achieved when the target temperature and pressure is reached may depend on a large number of different factors, including, for example, the type of aqueous solvent used, percent the alcohol content (if present) in the aqueous solvent, such as the organic substance being treated, the physical form of the organic substance being processed, the type of catalyst (s) (if it isutstvuet) in a mixture and different concentrations (concentrations) and / or the type of device in which these methods are performed. These and other factors may vary in order to optimize the initial process so as to maximize yield and / or reduce processing time. Preferably, the retention time is sufficient to convert all, or substantially all, of the organic material used as feedstock into biofuel.

In some embodiments, the retention time is less than about 60 minutes, 45 minutes, 30 minutes, 25 minutes, 20 minutes, 15 minutes, 10 minutes, or 5 minutes. In some embodiments, the retention time is more than about 60 minutes, 45 minutes, 30 minutes, 25 minutes, 20 minutes, 15 minutes, 10 minutes, or 5 minutes. In some embodiments, the retention time is between about 1 minute and about 60 minutes. In further embodiments, the retention time is between about 5 minutes and about 45 minutes, between about 5 minutes and about 35 minutes, between about 10 minutes and about 35 minutes, or between about 15 minutes and about 30 minutes. In further embodiments, the retention time is between about 20 minutes and about 30 minutes.

Those skilled in the art will recognize that various catalysts can be used to enhance processing efficiency, as described herein (see the subsection below, entitled “Catalysts”), which, in turn, can reduce the retention time required to convert organic matter to biofuel. Similarly, the required retention time may, in some cases, be shorter when the temperature and / or pressure rises, and / or the proportion of the additional component (s) (e.g., alcohol) in the aqueous solvent rises.

The optimal retention time for a given set of reaction conditions, as described herein, can be easily determined by experienced recipients by producing and starting a series of reactions that differ only in retention time, and analyzing the yield and / or quality of the biofuel produced.

Heating / cooling, application / pressure relief

The reaction mixture (for example, in the form of a suspension) comprising an organic substance, an aqueous solvent and optionally one or more catalysts, as described herein, can be brought to the target temperature and pressure (i.e., the temperature and pressure maintained during " retention time ") for a period of time between about 30 seconds and about 30 minutes. In some embodiments, the reaction mixture may be brought to the target temperature and pressure in less than about 5 minutes, or in less than about 2 minutes. Preferably, the reaction mixture is brought to the target temperature and pressure in less than about 2 minutes.

In some embodiments of the invention, the reaction mixture can be brought to the target pressure, mainly instantly and brought to the target temperature in less than about 5 minutes. In other embodiments of the invention, the reaction mixture can be brought to the target pressure, mainly instantly and brought to the target temperature in less than about two minutes. In other embodiments of the invention, the reaction mixture may be brought to the target pressure mainly instantly and be brought to the target temperature in between about 1 and about 2 minutes.

Additionally or alternatively, after the completion of the retention time, the reaction mixture may be cooled between about 150 ° C and about 200 ° C, between about 160 ° C and about 200 ° C, preferably between about 170 ° C and about 190 ° C, and more preferably about 180 ° C. over a period of less than about 10 minutes, preferably less than about 7 minutes, more preferably less than about 6 minutes, preferably from about 4 minutes and about 6 minutes, and more preferably , about 5 minutes. Following the initial cooling period, the temperature may further decrease to ambient temperature with a concomitant decrease in pressure by rapid release into a cold aqueous medium (e.g., chilled water).

The processes of heating / pressurizing and cooling / depressurizing can be facilitated by performing the methods of the invention in a continuous flow system (see the section below, entitled "Continuous Flow").

Catalysts

In accordance with the methods of the invention, the organic substance can be treated with an aqueous solvent under conditions of elevated temperature and pressure to produce a biofuel product. In some embodiments, the organic material may be treated with a supercritical aqueous solvent. In other embodiments, the organic material may be treated with a subcritical aqueous solvent. In each case, the treatment can be facilitated by the use of one or more additional catalysts. Although the catalysts can be an intrinsic component of an organic substance (e.g., minerals), an aqueous solvent (e.g., hydroxonium / water hydroxide ions under sub / supercritical conditions) and / or the walls of a vessel of a reactor device in which organic material can be processed ( for example, transition / noble metals), to facilitate the production of biofuels from organic matter, the invention involves the use of an additional catalyst (s).

(i) “incremental” catalysts

Some embodiments of the invention relate to the production of biofuels and organic matter by treatment with an aqueous solvent under conditions of elevated temperature and pressure in the presence of at least one “additional” catalyst. By “additional catalyst” it will be understood that the catalyst is additional (ie, separate) with respect to the catalytic compounds essentially present in other components of the reaction, such as an organic substance, an aqueous solvent and / or walls of the reactor device. In other words, an “additional” catalyst, as suggested in this document, can be considered as “coming from outside” in the sense that it is delivered to the reaction as a separate component of the reaction.

For example, one embodiment of the invention in which the lignite feedstock is treated (only) with water under conditions of elevated temperature and pressure in the reactor apparatus should not be construed as using an “additional catalyst”.

On the contrary, one embodiment of the invention in which the lignite feed is treated with water in the presence of an additional base catalyst (eg sodium hydroxide) under conditions of elevated temperature and pressure in the reactor device can be considered as using an “additional catalyst”.

An additional catalyst, as suggested herein, can be any catalyst that facilitates the formation of biofuels from organic matter using the methods of the invention, non-limiting examples of which include basic catalysts, acid catalysts, alkali metal hydroxide catalysts, transition metal hydroxide catalysts, alkali metal formate catalysts, transition metal formate catalysts, p-based catalysts aktsionnosposobnyh carboxylic acids, catalysts based on transition metal sulfide catalysts, the catalysts based on noble metals, the catalysts of the water gas shift, and combinations thereof.

The methods of the invention can be performed using an “additional” catalyst (s) in combination with an “own” catalyst (s).

The optimal amount of additive catalyst used in the methods of the invention may depend on many different factors, including, for example, the type of organic substance being treated, the volume of organic substance being processed, the aqueous solvent used, the particular temperature and pressure used during reactions, type of catalyst, and desired properties of the biofuel product. Following the methods of the invention, the optimal amount of additional catalyst to be used can be determined by a person skilled in the art without inventive effort.

In some embodiments, an additional catalyst, or a combination of additional catalysts, can be used in an amount of from about 0.1% in terms of weight to volume to about 10% in terms of weight to volume, between about 0.1% in terms of weight to volume and about 7.5% weight to volume ratio, between about 0.1% in terms of weight to volume and about 5% in terms of weight to volume, between about 0.1% in terms of weight to volume and about 2.5% in the ratio of weight to volume, between about 0.1% in the ratio of weight to volume and about 1% in the ratio and weight to volume or between about 0.1% in terms of weight to volume and about 0.5% in terms of weight to volume (relative to an aqueous solvent).

In some embodiments, the “additional” catalyst used in the reaction may be alkali or alkaline earth metal salts (eg, potassium, calcium and / or sodium salts). For example, as shown herein, alkali metal hydroxides and carbonates can be effective in reducing the oxygen content of a bio-oil product, where all conditions except the concentration of the additional catalyst are constant. In one embodiment, the optimal catalyst concentration based on (in the reaction itself) alkali metal hydroxide and / or alkali metal carbonate, for a given set of other, generally constant reaction conditions, can range from about 0.1 mol / l to about 1 mol / L. In preferred embodiments, the concentration may be from about 0.1 mol / L to about 0.3 mol / L. Preferably, the concentration of the alkali metal hydroxide and / or alkali metal carbonate catalyst provides a low oxygen product (for example, less than about 11% by weight; between about 6% by weight and about 11% by weight).

In general, catalysts can be used to create a reducing environment or to promote the formation and / or maintenance of a reducing environment that favors the conversion of organic matter to biofuels. The reducing medium may favor the hydrolysis of organic matter, the activation of oxygen substitution with hydrogen and / or the stabilization of the resulting biofuel.

Treatment with a subcritical aqueous solvent (as opposed to a supercritical aqueous solvent) may be preferable in that less energy is required to carry out the methods and the solvent can be better preserved during processing. When a subcritical aqueous solvent is used, it is contemplated that the additional use of one or more catalysts may be particularly useful to increase the yield and / or quality of biofuels. Additionally, the cost-effectiveness of reducing the input energy (i.e., to maintain subcritical rather than supercritical conditions) and preserve the solvent can significantly outweigh the added cost that the additional inclusion of one or more of the catalysts described herein carries.

It is assumed that under conditions of elevated temperature and pressure, water molecules in an aqueous solvent can dissociate into acid (hydroxonium) and basic (hydroxyl) ions, which facilitate the hydrolysis of the solid being processed (i.e., the conversion of solid into liquid). In some embodiments of the invention, the temperature and pressure at which the reaction is performed may be high enough so that the required levels of hydrolysis occur without the use of additional catalysts. Additionally or alternatively, the particular organic material used can be relatively easily hydrolyzed (and additional catalysts are therefore not required). For example, sufficient hydrolysis of a fossilized organic substance, such as lignite, can be achieved using subcritical water without the additional addition of catalysts described herein. However, the introduction of these catalysts can be used as a means of increasing the yield and / or quality of biofuels produced.

In other cases, the temperature and pressure at which the reaction is performed may not be high enough to achieve the desired levels of hydrolysis without additional catalysts being added. Additionally or alternatively, the particular organic material used may be difficult to hydrolyze due to its specific chemical structure (e.g., wood-fiber material).

Accordingly, hydrolysis catalysts may be added in order to facilitate (i.e., increase and / or accelerate) the hydrolysis of the solid to be treated (i.e., hydrolysis catalysis).

In some embodiments, the hydrolysis catalysts may be basic catalysts. Any suitable basic catalyst may be used.

Non-limiting examples of suitable basic catalysts include alkali metal salts, transition metal salts, organic bases, and mixtures thereof.

Alkali metal salts or transition metal salts may include any inorganic anion (s), non-limiting examples of which include sulfate, sulfite, sulfide, disulfide, phosphate, aluminate, nitrate, nitrite, silicate, hydroxide, methoxide, ethoxide, alkoxide, carbonate and oxide. Preferred alkali or transition metal salts are salts of sodium, potassium, iron, calcium and barium, and they may include one or more anions selected from phosphate, aluminate, silicate, hydroxide, methoxide, ethoxide, carbonate, sulfate, sulfide, disulfide and oxide .

Non-limiting examples of suitable organic bases include ammonia, basic and polar amino acids (e.g. lysine, histidine, arginine), benzathine, benzimidazole, betaine, cichonin, diethylamine, diisopropylethylamine, ethanolamine, ethylenediamine, imidazole, methylamine, N-methylguanidine, N-methylguanidine -methylmorpholine, N-methylpiperidine, phosphazene bases, picoline, piperazine, procaine, pyridine, quinidine, quinoline, trialkylamine, tributylamine, triethylamine, trimethylamine and mixtures thereof.

In some embodiments, the hydrolysis catalysts may be acidic catalysts, although it should be recognized that acidic catalysts may generally be slower in catalyzing the hydrolysis of organic matter than basic catalysts. Any suitable acid catalyst may be used.

Non-limiting examples of suitable acid catalysts for hydrolysis include liquid mineral acids, organic acids, and mixtures thereof. Liquid mineral acids and organic acids may include any inorganic anion (s), non-limiting examples of which include aluminate, sulfate, sulfite, sulfide, phosphate, phosphite, nitrate, nitrite, silicate, hydroxide and alkoxide (under supercritical or near supercritical conditions ), carbonate and anions of carboxyl groups.

Non-limiting examples of suitable organic acids include acetic acid, butyric acid, caproic acid, citric acid, formic acid, glycolic acid, 3-hydroxypropionic acid, lactic acid, oxalic acid, propionic acid, succinic acid, uric acid, and mixtures thereof.

In some embodiments, the acid catalyst (s) for hydrolysis may be present in the minerals of an organic substance and / or obtained from a reaction mixture of a carboxylic and / or phenolic acid compound during a processing process.

In some embodiments, a mixture of one or more acid hydrolysis catalysts or one or more basic hydrolysis catalysts may be used to facilitate hydrolysis of the solid to be treated.

The methods of the invention can use catalysts for hydrolysis of organic matter (as described in the preceding paragraphs). Additionally or alternatively, the methods can use catalysts that increase and / or accelerate the removal of oxygen (both directly and indirectly) from compounds in the organic material being processed. The removal of oxygen can provide a large number of beneficial effects, such as, for example, increasing the energy intensity and stability of the produced biofuel.

An acidic catalyst can be used to facilitate the removal of oxygen, for example, by dehydration (elimination) of water. Accordingly, in some embodiments of the invention, the acid catalyst may be used to facilitate hydrolysis and to facilitate the removal of oxygen from the organic material to be treated.

Any suitable acid catalyst may be used to facilitate oxygen removal. Non-limiting examples of suitable acid catalysts for oxygen removal include liquid mineral acids, organic acids, and mixtures thereof. Liquid mineral acids and organic acids may include any inorganic anion (s), non-limiting examples of which include aluminate, sulfate, sulfite, sulfide, phosphate, phosphite, nitrate, nitrite, silicate, hydroxide and alkoxide (under supercritical or near supercritical conditions ), carbonate and anions of carboxyl groups.

Non-limiting examples of suitable organic acids include acetic acid, butyric acid, caproic acid, citric acid, formic acid, glycolic acid, 3-hydroxypropionic acid, lactic acid, oxalic acid, propionic acid, succinic acid, uric acid, and mixtures thereof.

In some embodiments, aluminosilicates comprising hydrated atoms (eg, zeolites) can be used during the processing of organic matter to facilitate dehydration (elimination) of water.

Additionally or alternatively, the removal of oxygen can be facilitated by thermal means, including decarbonylation, for example, aldehydes (giving R ₃ CH and gaseous CO) and decarboxylation of carboxylic acids (giving R ₃ CH and gaseous CO ₂ ) in the material to be processing. The speed of these reactions can be increased by adding acid and / or transition (noble) metal as a catalyst. Any transition or noble metal may be used, including metals on a solid acid support. Non-limiting examples include Pt / Al ₂ O ₃ / SiO ₂ , Pd / Al ₂ O ₃ / SiO ₂ , Ni / Al ₂ O ₃ / SiO _2, and mixtures thereof.

Additionally or alternatively, to facilitate the removal of oxygen, a combined hydrogenation acid catalyst may be used, for example, by hydrodeoxygenation (i.e. eliminating water (via an acidic component) and saturating double bonds (via a metal component)). Any suitable acidic hydrogenation catalyst may be used, including catalysts on a solid acid support. Non-limiting examples include Pt / Al ₂ O3 / SiO ₂ , Pd / Al ₂ O ₃ / SiO ₂ , Ni / Al ₂ O ₃ / SiO ₂ , NiO / MoO ₃ , CoO / MoO ₃ , NiO / WO ₂ , zeolites filled with noble metals (e.g. ZSM-5, Beta, ITQ-2), and mixtures thereof.

The methods of the invention may involve catalysts that facilitate the hydrolysis of the organic matter to be treated and / or catalysts that facilitate the removal of oxygen from compounds in the organic matter (as discussed in the preceding paragraphs). Additionally or alternatively, the methods can use catalysts that facilitate the concentration of hydrogen (both directly and indirectly) in the compounds in the organic material to be processed. Concentration of hydrogen can provide many beneficial effects, such as, for example, increasing the energy intensity and stability of biofuels produced.

To facilitate the concentration of hydrogen in compounds of the organic matter to be treated, for example by hydrogenation by hydrogen transfer or by generating hydrogen in situ, a hydrogenation catalyst by hydrogen transfer can be used.

Any suitable hydrogenation catalyst by hydrogen transfer can be used to concentrate hydrogen. Non-limiting examples of suitable hydrogen transfer hydrogenation catalysts include alkali metal hydroxides (e.g. sodium hydroxide), transition metal hydroxides, alkali metal formates (e.g. sodium formate), transition metal formates, reactive carboxylic acids, transition or noble metals and their mixtures.

The alkali metal hydroxide or formate may include any suitable alkali metal. Preferred alkali metals include sodium, potassium, and mixtures thereof. The transition metal hydroxide or formate may include any suitable transition metal, preferred examples include Fe and Ru. Reactive carboxylic acid may be any carboxylic acid, preferred examples include formic acid, acetic acid, and mixtures thereof. The transition or noble metal may be any suitable transition or noble metal, preferred examples include platinum, palladium, nickel, ruthenium, rhodium, and mixtures thereof.

Additionally or alternatively, a transition metal catalyst may be used to facilitate the concentration of hydrogen in the organic material to be treated, for example by hydrogenation of H ₂ . Non-limiting examples of suitable transition metals as catalysts for hydrogenation of H ₂ include nullovalent metals (e.g., platinum, palladium and nickel), transition metal sulfides (e.g., iron sulfide (FeS, Fe _x S _y )) and mixtures thereof.

Additionally or alternatively, a water gas conversion catalyst may be used to facilitate the concentration of hydrogen in the organic material to be treated (i.e., through a water gas conversion reaction). Any suitable water gas conversion catalyst (WGS) can be used, for example, transition metals, transition metal oxides and mixtures thereof (e.g. magnetite, platinum-based WGS catalysts, finely dispersed copper and nickel).

Additionally or alternatively, the concentration of hydrogen in the organic material to be treated can be facilitated by in situ gasification (i.e., by thermal catalysis). In situ gasification can be facilitated by the addition of transition metals. Any suitable transition metal may be used, including transition metals on a solid acid support (e.g., Pt / Al ₂ O ₃ / SiO ₂ , Pd / Al ₂ O ₃ / SiO ₂ , Ni / Al ₂ O ₃ / SiO _2, and mixtures thereof ) and sulfides of transition metals (for example, Fe _x S _y , FeS / Al ₂ O ₃ , FeS / SiO ₂ , FeS / Al ₂ O ₃ / SiO ₂ and mixtures thereof). Table 1 below provides a summary of examples of catalysts that can be used in the methods of the invention and in the corresponding reactions that they can catalyze.

Table 1 Catalyst Summary and Related Reactions Reaction type Catalyst Catalyst family Typical example (examples) Preferred Catalysts / Comments Hydrolysis Main catalysts Sub / supercritical water Hydroxide ion in sub / supercritical water All alkali and transition metal salts, as well as cations and anions, can contribute. Includes all well-known inorganic anions M = any alkali or transition metal
A = anions, including: aluminate, sulfate, sulfite, sulfide, phosphate, phosphite, nitrate, nitrite, silicate, hydroxide, alkoxide, carbonate, oxide M = Na, K, Fe, Ca, Ba
A = aluminate, phosphate, silicate, hydroxide, methoxide, ethoxide, carbonate, sulfate, sulfide, disulfide (FeS ₂ ), oxide Any organic base Ammonia, pyridine, etc.

Hydrolysis Acid Catalysis (slower) Sub / supercritical water Hydroxonium ion in sub / supercritical water Any liquid mineral or organic acid ON where
A = anions, including: aluminate, sulfate, sulfite, sulfide, phosphate, phosphite, nitrate, nitrite, silicate, hydroxide, alkoxide, carbonate, carboxyl group Acids can form as a result of the formation of reaction mixtures of carboxylic acids and phenolic resins and minerals present Dehydration (elimination) Acid catalysis Sub / supercritical water Hydroxonium ion in sub / supercritical water

Any liquid mineral or organic acid ON where
A = anions, including: aluminate, sulfate, sulfite, sulfide, phosphate, phosphite, nitrate, nitrite, silicate, hydroxide, alkoxide, carbonate, carboxyl group Acids can form as a result of the formation of reaction mixtures of carboxylic acids and phenolic resins and the minerals present.
zeolites or aluminosilicates can generally be added Hydrogenation by transferring hydrogen or generating H ₂ reaction mixture Proton Hydrogenation Catalysts All hydroxides of alkali and transition metals and formates
All reactive carboxylic acids
All transition and noble metals M = any alkali or transition metal
A = hydroxide, formate M = Na, K
A = hydroxide
formate
formic, vinegar
M = Pd, Pd, Ni, Ru, Rh

Decarboxylation High heat Acids and catalysts based on transition (noble) metals reported to facilitate the process All transition and noble metals on a solid acid substrate Pt / Al ₂ O ₃ / SiO ₂ , Pd / Al ₂ O ₃ / SiO ₂ , Ni / Al ₂ O ₃ / SiO ₂ Decarbonylation High heat As for decarboxylation As for decarboxylation As for decarboxylation Gasification of the reaction mixture High heat Transition metals Transition metals on the substrate
sulfides Pt / Al ₂ O ₃ / SiO ₂ , Pd / Al ₂ O ₃ / SiO ₂ , Ni / Al ₂ O ₃ / SiO ₂
Fe _x S _y , FeS / Al ₂ O ₃ , FeS / SiO ₂ , FeS / Al ₂ O ₃ / SiO ₂ Water gas conversion WGS catalysts WGS Standard Catalysts As in the literature As in the literature Direct hydrogenation with H ₂ Transition metals Zero-valent metals
Sulfides Pt, P, Ni in zero valency
FeS, Fe_xS_y

Hydrodeoxygenation Combined Acid and Hydrogenation Catalyst Transition metal and solid acid M = transition metal
A = acid solid Pt / Al ₂ O ₃ / SiO ₂ , Pd / Al ₂ O ₃ / SiO ₂ , Ni / Al ₂ O ₃ / SiO ₂ ,
NiO / MoO ₃ ,
CoO / MoO ₃ ,
NiO / WO ₂
Noble metal zeolites, e.g. ZSM-5, Beta, ITQ-2

Catalysts for use in the methods of the invention can be produced using chemical methods known in the art and / or purchased from commercial sources.

It should be understood that there are no restrictions on the point in time at which the additional catalyst (s) can be used in carrying out the methods of the invention. For example, the catalyst (s) may be added to an organic substance, an aqueous solvent, or mixtures thereof (i.e., to a suspension) before heating / applying pressure to a target temperature and pressure, during heating / raising pressure to a target temperature and pressure and / or after reaching temperature and reaction pressure. The catalyst addition time may depend on the reactivity of the feed used. For example, a highly reactive feed can benefit from the addition of a catalyst near the target reaction temperature and pressure or at a target reaction temperature and pressure, while a less reactive feed can have a wider process range for adding catalysts (i.e., catalysts can be added before achievement of the target temperature and reaction pressure).

(ii) “proprietary” catalysts

Some embodiments of the invention relate to the production of biofuels from organic matter by treatment with an aqueous solvent under conditions of elevated temperature and pressure in the presence of at least one “additional” catalyst. As noted above, by “additional” catalyst is meant an indication that the catalyst is supplied in addition to the catalysts substantially present in the other component (s) of the reaction.

Additionally or alternatively, the production of biofuels from organic matter in accordance with the methods of the invention can be facilitated in the presence of “proprietary” catalyst (s) that are initially present in a given reaction component, such as, for example, any one or more sources of organic matter as feedstock, in an aqueous solvent and / or in the walls of a vessel of a reactor device in which organic matter can be processed.

Additionally, the methods of the invention can be performed using an “additional” catalyst (s) in combination with an “own” catalyst (s) or using one “own” catalyst (s).

The optimal amount of proprietary catalyst used in the methods of the invention may depend on many different factors, including, for example, the type of organic substance being treated, the amount of organic substance being processed, the aqueous solvent used, the particular temperature and pressure involved in the reaction, type catalyst and the required properties of the biofuel product.

In some embodiments, a proprietary catalyst, or a combination of proprietary and additional catalysts, can be used in an amount of between about 0.1% in terms of weight to volume and about 10% in terms of weight to volume, between about 0.1% in terms of weight to volume and about 7.5% in terms of weight to volume, between about 0.1% in terms of weight to volume and about 5% in terms of weight to volume, between about 0.1% in terms of weight to volume and about 2.5 % in terms of weight to volume, between about 0.1% in terms of weight to volume mu and about 1% in terms of weight to volume, or between about 0.1 weight% in relation to volume and about 0.5% in terms of weight to volume (relative to the aqueous solvent).

In some embodiments, the “proprietary” catalyst used in the reaction may be an alkali and / or alkaline earth metal salt (eg, potassium, calcium and / or sodium salts). For example, alkali metal hydroxides and carbonates can be effective in reducing the oxygen content in a bio-oil product. In one embodiment, the optimal concentration of the catalyst (in the reaction itself) based on alkali metal hydroxide and / or alkali metal carbonate, for a given set of substantially constant other reaction conditions, can range from about 0.1 mol / l to about 1 mol / l In preferred embodiments, the concentration may be from about 0.1 mol / L to about 0.3 mol / L. Preferably, the concentration of the alkali metal hydroxide and / or alkali metal carbonate catalyst used provides a low oxygen product (for example, less than about 11% by weight; between about 6% by weight and about 11% by weight).

One or more other types of catalysts may be present in the organic material used as the starting material for the reaction. Non-limiting examples of these catalysts include minerals and / or salts of alkali and / or alkaline earth metals. In some embodiments, the potassium and / or calcium salt present in the organic material of the feed can provide catalytic activity in the reaction.

For example, wood-fiber biomass may include a variable amount of ash (e.g., between about 0.1% and about 50% ash), and ash, in turn, may include variable amounts of alkali metal salts (e.g., potassium and / or calcium salts) ) (see, for example, Stanislav et al., "An Overview of the Chemical Composition of Biomass", Fuel 89 (2010), 913-933). For example, ash may include between about 0.2% and about 64% potassium (as potassium oxide) and / or between about 1% to about 83% calcium (as calcium oxide). Alkali metal salts present in the feedstock, such as, for example, potassium or calcium salts, can be catalysts for a number of reactions under the reaction conditions of the present invention, including in the reactions described above in table 1.

Additionally or alternatively, the aqueous solvent used in the methods of the invention can supply its own catalysts to the reaction. Non-limiting examples of these catalysts include hydroxonium and / or hydroxide ions from water.

Additionally or alternatively, “proprietary” catalysts can be provided by the vessel walls of a reactor device in which organic matter can be processed. Non-limiting examples of materials that are commonly used to design reactors (i.e., including vessel walls) are iron alloys with other metals, including chromium, nickel, manganese, vanadium, molybdenum, titanium, and silicon. Non-limiting examples of suitable steel grades are 310, 316 and alloy 625.

In some embodiments, the “proprietary” catalysts that can be provided by the vessel walls of the reactor device are transition / noble metals.

Non-limiting examples of “proprietary” catalysts that can be provided by the vessel walls of a reactor apparatus include metallic iron, iron hydroxides, iron oxides, iron carbonates, iron hydrogen carbonates, iron acetates; nickel metal, nickel hydroxides, nickel oxides, nickel carbonates, nickel hydrogen carbonates; metal chromium, chromium hydroxides, chromium oxides, chromium carbonates, chromium hydrogen carbonates; metallic manganese, metallic manganese hydroxides, metallic manganese oxides, metallic manganese carbonates and / or metallic manganese hydrogen carbonates. Hydroxides may be present due to the reaction of metals with water and alkaline “auxiliary” catalysts. Oxides may be present due to the reaction of metals with oxygen-containing compounds and as passivating layers. Carbonates and bicarbonates may be present due to reactions of metals, metal oxides and / or metal hydroxides with carbon dioxide generated in situ in decarboxylation reactions. Metal acetates may be present due to reactions of metals, metal oxides, metal hydroxides, metal hydrogen carbonates and metal carbonates with acetic acid generated in situ by hydrolysis of organic matter.

Metals and metal compounds bonded to surfaces made of steel and similar materials can catalyze various reactions, including, but not limited to, one or more of the reactions described above in Table 1. For example, catalysts can catalyze such hydrothermal reactions, such as decarboxylation reactions (see, for example, Maiella and Brill, Spectroscopy of Hydrothermal Reactions. 10. Evidence of Wall Effects in Decarboxylation Kinetics of l.00 m HC0 ₂ X (X = H, Na) at 280-330 ° C and 275 bar ", J. Phys. Chem. A (1998), 102, 5886-5891) and transport reactions in hydrogen (see, for example, Onwudili and Williams, "Hydrothermal reactions of sodium formate and sodium acetate as model intermediate products of the sodium hydroxide-promoted hydrothermal gasification of biomass", Green Chem., (2010), 12, 2214-2224) .

(iii) catalyst recycling

The catalysts according to the invention can be recycled for use in subsequent reactions for the conversion of organic matter into biofuel as a feedstock. Recycled catalysts may be “additional” catalysts and / or “proprietary” catalysts, as described herein.

As a non-limiting example, proprietary catalysts (e.g., alkaline salts such as potassium and calcium salts) can be transferred to the aqueous liquid phase during the reaction. Since significant concentrations of such catalysts (e.g., alkaline potassium and calcium salts) may be present in the organic material as a feedstock processed in accordance with the methods of the invention, in some embodiments aqueous phases containing dissolved catalysts (e.g., potassium salts and / or calcium).

Accordingly, in some embodiments, proprietary catalysts from any of the reaction component (s) (for example, from one or more sources of organic matter such as feedstock, aqueous solvent and / or walls of the reactor device) can be renewed by the reaction mixture, mitigating or reducing the need in providing “additional” catalysts in subsequent conversion cycles of the feedstock. This may be particularly advantageous in embodiments of the invention relating to continuous operation with scales at or above the scale level of the pilot plant. In general, it is assumed that the disposal of proprietary catalysts present in such reaction components as organic matter as feedstock (eg, alkaline salts) may allow a situation where “additional” catalysts are required only during commissioning.

In preferred embodiments, the “proprietary” catalyst recirculated during the reaction is an alkali and / or alkaline earth metal salt (eg, potassium, calcium and / or sodium salt).

Examples of reaction conditions

In some embodiments, the organic material processed using the methods of the invention is (or includes) a fossilized organic substance (see "Organic Substance" section above). For example, the processed organic substance may be lignite.

The conversion of fossilized organic matter to biofuel can be carried out, for example, using an aqueous solvent at a temperature (temperatures) of from about 200 ° C to about 400 ° C and under pressure (pressures) of from about 150 bar to about 350 bar; preferably at a temperature (s) of from about 250 ° C to about 375 ° C and under pressure (s) of from about 175 bar to about 300 bar; more preferably, at a temperature (s) of from about 300 ° C to about 375 ° C and under pressure (s) of from about 200 bar to about 250 bar; more preferably, at a temperature (s) of from about 320 ° C to about 360 ° C and under pressure (s) of from about 200 bar to about 250 bar; and even more preferably, at a temperature (s) of from about 340 ° C to about 360 ° C and under a pressure (s) of from about 200 bar to about 240 bar.

Preferably, the aqueous solvent is water or an aqueous alcohol (e.g., aqueous ethanol or methanol), comprising between about 1% in terms of weight to volume and about 5% in terms of weight to volume of alcohol, aqueous alcohol (e.g., aqueous ethanol or methanol), comprising between about 1% in terms of weight to volume and about 10% in terms of weight to volume of alcohol, between about 5% in terms of weight to volume and about 15% in terms of weight to volume of alcohol, or between about 5% in terms of weight to volume and about 20% in terms of weight to volume of alcohol.

Preferably, the retention time is between about 15 minutes and about 45 minutes, more preferably between about 15 minutes and about 40 minutes, and even more preferably, between about 20 minutes and about 30 minutes.

The conversion of fossilized organic matter to biofuels can be facilitated by the addition of one or more catalysts (see the subsection entitled “Catalysts” above). For example, conversion can be facilitated by adding a hydrogenation catalyst by transferring hydrogen (e.g., formic acid, sodium formate and / or sodium hydroxide (in a reducing atmosphere)) or a direct hydrogenation catalyst (e.g., Ni, Pt, Pd on silica or coal (in reducing atmosphere)).

Accordingly, in some embodiments, the biofuel can be produced from an organic material including fossilized organic material (e.g., lignite) using water as a solvent, at a temperature (s) between about 300 ° C and about 375 ° C and under pressure ( pressures) between about 200 bar and about 250 bar, with a retention time of more than about 15 minutes. Optionally, conversion can be facilitated by the addition of one or more catalysts, as described herein. The catalyst may include one or more hydrogenation catalysts by transferring hydrogen (e.g., sodium formate, sodium hydroxide (in a reducing atmosphere), formic acid and / or formate).

In some embodiments, the reaction includes an alkali metal hydroxide and / or alkali metal carbonate catalyst (e.g., sodium hydroxide and / or sodium carbonate) in the range of about 0.1 mol / L to about 1 mol / L (in the reaction) . In preferred embodiments, the concentration may be from about 0.1 mol / L to about 0.3 mol / L. In some embodiments, the organic material processed using the methods of the invention is (or includes) wood-fiber material (see the section entitled “Organic Material” above). For example, the wood-fiber material being processed may be radiant pine.

The conversion of wood-fiber material into biofuel can be carried out, for example, using an aqueous solvent at a temperature (temperatures) between about 200 ° C to about 400 ° C and under pressure (pressures) between about 150 bar to about 350 bar; preferably at a temperature (s) of from about 250 ° C to about 375 ° C and under pressure (s) of from about 150 bar to about 250 bar; more preferably, at a temperature (s) of from about 270 ° C to about 360 ° C and under pressure (s) of from about 170 bar to about 250 bar; and, more preferably, at a temperature (s) of from about 300 ° C to about 340 ° C and under pressure (s) of from about 200 bar to about 240 bar.

Preferably, the aqueous solvent is selected from aqueous alcohols (e.g., aqueous ethanol and aqueous methanol), comprising from about 1% by weight to volume to about 50% by weight to volume of alcohol, from about 5% by weight to volume to about 50% in terms of weight to volume of alcohol, from about 5% in terms of weight to volume to about 35% in terms of weight to volume of alcohol, from about 5% in terms of weight to volume to about 30% in terms of weight to volume of alcohol, from about 10% in terms of weight to volume up to about 30% in terms of weight to the volume of alcohol, from about 15% in terms of weight to volume to about 25% in terms of weight to volume of alcohol, or from about 18% in terms of weight to volume to about 22% in terms of weight to volume of alcohol.

The conversion of wood fiber to biofuels can be facilitated by the addition of one or more catalysts (see the subsection entitled “Catalysts” above). For example, conversion can be facilitated by adding a hydrogenation catalyst by transferring hydrogen (e.g., formic acid, sodium formate and / or sodium hydroxide).

In some embodiments, the reaction comprises an alkali metal hydroxide and / or an alkali metal carbonate as a catalyst (e.g., sodium hydroxide and / or sodium carbonate) in the range of from about 0.1 mol / L to about 1 mol / L (in the reaction). In preferred embodiments, the concentration may be from about 0.1 mol / L to about 0.3 mol / L.

Accordingly, in some embodiments, the biofuel can be produced from an organic material including wood fiber material using from about 5% by weight to volume to about 50% by weight to volume of aqueous alcohol (e.g., aqueous methanol or ethanol ) at a temperature (s) of from about 250 ° C to about 400 ° C and under pressure (s) of from about 150 bar to about 250 bar with a retention time of more than about 15 minutes. Optionally, conversion can be facilitated by the addition of one or more catalysts, as described herein. The catalyst may include one or more hydrogenation catalysts by hydrogen transfer (for example, formic acid, formate and / or sodium hydroxide).

Continuous stream

The production of biofuels from organic matter using the methods of the invention can be facilitated by the implementation of the methods under continuous flow conditions.

Despite the fact that the methods of the invention do not need to be performed under continuous flow conditions, such an implementation can provide many useful effects. For example, a continuous flow can simplify the accelerated implementation and / or elimination of heat and / or pressure applied to the suspension. This can help to achieve the required rates of mass and heat transfer, heating / cooling and / or increase / decrease pressure. Continuous flow can also allow close control of retention times. Without limiting the specific mode of action, it is postulated that the increased heating / cooling and / or pressure increase / decrease rate simplified by continuous flow, along with the ability to closely control the retention time, helps to prevent undesired side reactions (e.g. polymerization) from occurring when the suspension is heated / the pressure rises and / or the pressure cools / decreases. It is also believed that continuous flow facilitates the reactions responsible for the conversion of organic matter to biofuels by virtue of the generation of mixing and shear forces, which are believed to promote emulsification, which may be an important mechanism involved in the transfer and “storage” of generated oils away from reactive surfaces of the feedstock.

Accordingly, in preferred embodiments, the methods of the invention are carried out under continuous flow conditions. In this context, the term "continuous stream" refers to a process in which an organic substance mixed with an aqueous solvent in the form of a suspension (with or without additional catalysts) is subjected to:

(d) heating and raising the pressure to a target temperature and pressure,

(e) processing at a target temperature (s) and under pressure (s) for a specified period of time (i.e., “retention time”), and

(f) cooling and depressurization,

while the suspension is maintained in a stream in continuous motion along the length (or partial length) of a given surface. It should be understood that the conditions of "continuous flow", as assumed in this document, are determined by the starting point of heating and applying pressure (i.e. (a) above) and the end point of cooling and pressure relief (i.e. (c) above) .

Continuous flow conditions, as suggested herein, do not imply any particular limitation on the flow rate of the suspension, provided that it is maintained during continuous movement.

Preferably, the minimum (volume-independent) flow rate of the suspension along a given surface is greater than the rate of deposition of a solid in the suspension (i.e., the final rate at which a suspended particle having a density higher than the density of the surrounding aqueous solution moves (under gravity) to the lower parts of the suspension flow).

For example, the minimum slurry flow rate may be higher than about 0.01 cm / s, higher than about 0.05 cm / s, preferably higher than about 0.5 cm / s, and more preferably higher than about 1.5 cm / s. Factors such as volumetric flow rate and / or retention time may influence the upper limit of the flow rate. This, in turn, is influenced by the components of a particular reactor device used to maintain continuous flow conditions.

Continuous flow conditions can be simplified, for example, by performing the methods of the invention in a suitable reactor device. A suitable reactor device will generally include heating / cooling, pressure increase / decrease, and reaction components in which a continuous stream is maintained.

The use of a suitable flow rate (under continuous flow conditions) may be advantageous to prevent scale formation along the length of the specific surface along which the slurry moves (for example, the walls of the vessel of the reactor device), and / or to generate an effective mixing mode for efficient heat transfer in and out from suspension.

Biofuel products

The methods of the invention can be used to produce biofuels from organic matter.

The nature of the biofuel product may depend on many different factors, including organic material as feedstock and / or reaction conditions / reagents used in the methods.

In some embodiments, the biofuel product may include one or more biooil, petroleum coal (e.g., soot with associated oils), soluble light oil, a gaseous product (e.g., methane, hydrogen, carbon monoxide and / or carbon dioxide), alcohol (e.g. , ethanol, methanol, etc.) and biodiesel.

In some embodiments, the biofuel may be made from fossilized organic matter, such as, for example, lignite (brown coal), peat, or oil shale.

Biofuels can include solid, liquid and gas phases. The solid phase may include high carbon black (equivalent to high quality carbon for PCI). The liquid phase may include biooil. The gaseous product may include methane, hydrogen, carbon monoxide and / or carbon dioxide.

In other embodiments, the biofuel may be made from an organic substance, including wood-fiber material. Biofuels may include a liquid phase including biooil.

Biofuels made in accordance with the methods of the invention can include many useful properties, non-limiting examples include low oxygen, high hydrogen, increased specific energy and increased stability.

A bio-oil product (also referred to herein as an “oil product”) made in accordance with the methods of the invention may contain an energy intensity of more than about 25 MJ / kg, preferably more than about 30 MJ / kg, more preferably more than about 32 MJ / kg, even more preferably more than about 35 MJ / kg, and even more preferably more than about 37 MJ / kg, 38 MJ / kg or 39 MJ / kg. The bio-oil product may include less than about 15% weight. oxygen per dry weight, preferably less than about 10% by weight. oxygen per dry weight, more preferably less than about 8% by weight. oxygen based on dry weight, and even more preferably, less than about 7% by weight. oxygen per dry weight. The bio-oil product may include more than about 6% weight. hydrogen per dry weight, preferably more than about 7% by weight. hydrogen per dry weight, more preferably more than about 8% by weight. hydrogen calculated on dry weight, and even more preferably, more than about 9% by weight. hydrogen per dry weight. The molar ratio of hydrogen: carbon in bio-oil according to the invention can be less than about 1.5, less than about 1.4, less than about 1.3, or less than about 1.2.

Bio-oil produced in accordance with the methods of the invention may include, for example, any of one or more of the following classes of compounds: phenols, aromatic and aliphatic acids, ketones, aldehydes, hydrocarbons, alcohols, esters, ethers, furans, furfurols, terpenes, polycyclic compounds, oligo- and polymers from each of the above classes, plant steroid alcohols, modified steroid alcohols, asphaltenes, pre-asphaltenes and waxes.

A coal or petroleum coal product produced in accordance with the methods of the invention may contain an energy intensity of more than about 20 MJ / kg, preferably more than about 25 MJ / kg, more preferably more than about 30 MJ / kg, and even more preferably more than about 31 MJ / kg or 32 MJ / kg. The coal, or petroleum coal, product may include less than about 20% by weight. oxygen per dry weight, preferably less than about 15% by weight. oxygen per dry weight, more preferably less than about 10% by weight. oxygen based on dry weight, and even more preferably, less than about 9% by weight. oxygen per dry weight. The coal, or petroleum coal, product may include more than about 2% by weight. hydrogen per dry weight, preferably more than about 3% by weight. hydrogen per dry weight, more preferably more than about 4% by weight. hydrogen calculated on dry weight, and even more preferably, more than about 5% weight. hydrogen per dry weight. The molar ratio of hydrogen: carbon in the carbonized or petroleum coal product of the invention may be less than about 1.0, less than about 0.9, less than about 0.8, less than about 0.7, or less than about 0, 6.

A coal or petroleum coal product produced in accordance with the methods of the invention may include, for example, any of one or more of the following classes of compounds: phenols, aromatic and aliphatic acids, ketones, aldehydes, hydrocarbons, alcohols, esters, ethers, furans , furfurals, terpenes, polycyclic compounds, oligo- and polymers from each of the above classes, asphaltenes, pre-asphaltenes and waxes.

The carbon product (equivalent to high-quality coal for PCI) produced in accordance with the methods of the invention may include, for example, a mixture of amorphous carbon and graphite with partially oxidized end groups giving rise to carboxyl and alkoxyl groups on the surface, as well as carbonyl and ester groups.

Biofuels produced in accordance with the methods of the invention can be purified and / or separated into individual components using standard methods known in the art.

For example, the solid and liquid phases of a biofuel product (for example, during coal conversion) at the first stage of separation of solid and liquid can be filtered through a pressure filter or a rotating vacuum drum filter. The resulting solid product may include high carbon black with associated oils. In some embodiments, the oil may be separated from the carbon black, for example, by thermal distillation or by solvent extraction. The resulting liquid product may contain a small percentage of light oils, which can be concentrated and released using an evaporator.

The bio-oil product (for example, during the conversion of wood-fiber material) can be extracted by decantation or by density separation. Water soluble light oils can be concentrated and released using an evaporator. Bio-oil obtained in accordance with the methods of the invention can be clarified, or distilled, to remove any residual water or to prepare for further processing.

Biofuels obtained in accordance with the methods of the invention can be used in many applications. For example, biofuels can be mixed with other fuels, including, for example, ethanol, diesel fuel, etc. Additionally or alternatively, biofuels can be upgraded to higher grade fuel products. Additionally or alternatively, biofuels can be used directly, for example, as petroleum products, etc.

Those skilled in the art will recognize that numerous changes and / or modifications can be made to the invention, as shown in specific embodiments of the invention, without departing from the spirit or scope of the invention as broadly described. Therefore, the present embodiments of the invention should be considered in all features as illustrative and non-limiting.

EXAMPLES

Below the invention will be described with reference to specific examples, which, in any case, should not be construed as limiting.

Example 1: Conversion of Organic Matter to Biofuel

(i) Device

The device partially consists of an elongated continuous flow reactor installation with a high surface area constructed of 310 grade stainless steel. Due to the high degree of interaction of the reacting materials with the reactor wall under continuous flow conditions, i.e. turbulent with a small radius (maximum - 21.4 mm, and minimum - 4.25 mm), and considerable length (only 84 meters), the following “proprietary" catalysts were present in each of the various reactions described (that is, regardless whether “additional” catalysts were introduced): metallic iron, iron hydroxides, iron oxides, iron carbonates, iron hydrogen carbonates, iron acetates; nickel metal, nickel hydroxides, nickel oxides, nickel carbonates, nickel hydrogen carbonates; metal chromium, chromium hydroxides, chromium oxides, chromium carbonates, chromium hydrogen carbonates; metallic manganese, hydroxides of metallic manganese, oxides of metallic manganese, carbonates of metallic manganese, hydrogen carbonates of metallic manganese. Hydroxides were present due to the reaction of metals with water and alkaline “additional” catalysts. Oxides were present due to the reaction of metals with oxygen-containing compounds and as passivating layers. Carbonates and bicarbonates were present due to reactions of metals, metal oxides and / or metal hydroxides with carbon dioxide generated in-situ during decarboxylation reactions. Metal acetates were present due to reactions of metals, metal oxides, metal hydroxides, metal hydrogen carbonates and metal carbonates with acetic acid generated in situ during the hydrolysis of organic matter.

(ii) Preparation of the suspension

The feed was ground to a micron level suitable for injection. The injection process was wet or dry depending on the nature of the feedstock (i.e., lignite or wood-fiber biomass). The milled feed was passed through a screening system to remove any remaining larger particles or foreign objects. The feedstock was then suspended in water in the supply tanks and maintained in a state of readiness for processing. In some cases, ethanol (20% by weight) was added to the suspension (wood-fiber biomass samples as feedstock No. 1-4: see table 2B).

Below, steps (ii) - (iv) were carried out under continuous flow conditions.

(iii) Heating and pressure increase

The suspension of the feedstock was removed from the supply tanks and brought to the target reaction pressure (see tables 2A and 2B) using a two-stage injection system. The first stage used a low pressure pump to feed the slurry into the second stage of the high pressure pump. A high pressure pump was used to bring the suspension to the desired reaction pressure (subsecond interval). Then the suspension was passed through a five-stage concentric tube heating system. Each heating stage has a separate control for adjusting process temperatures and heating rates. The suspension was brought to the reaction temperature for a period of 1-2 minutes (approximately 6-7 ° C per second), then, where applicable, catalysts were added (samples of lignite feedstock No. 4, 6, 7, 8, 9, 10 - see table 2A; samples of wood-fiber feedstock No. 2, 3, 4 - see table 2B), and the mixture was transferred to the reactor.

A summary of the feedstock used and the parameters with which it was processed is shown in Tables 2A and 2B below. Radiant pine lignin / cellulose fractions (feedstock samples Nos. 1 and 2 in Table 2B) were generated by extracting hemicellulose from wood-fiber starting material (radiant pine) using the methods described in PCT publication No. WO / 2010/034055, the contents of which reference is fully incorporated into the present description.

Table 2A Lignite feedstock and flow conditions Raw material sample number Type of feedstock Solids in suspension (% wt.) Temperature (° C) Pressure (bar) Hold (min) Additives one Lignite 22.00 350 240 twenty No 2 Lignite 11.50 350 240 twenty No 3 Lignite 8.00 250 220 25 No four Lignite 9.10 350 220 25 1.3% weight. HCOONa 5 Lignite 11.50 350 240 25 No 6 Lignite 12.73 350 240 25 0.2 mol / L NaOH 7 Lignite 12.00 350 220 25 1.5% weight. HCOONa 8 Lignite / wood-fiber biomass (Banna Grass) 11.00 350 220 25 4 g / l NaOH; 10% Banna Grass 9 Lignite 10 340 230 25 0.35 l / h NaOH, CO, 23.8 g / min 10 Lignite 16.00 330 240 5 0.1 mol / L NaOH eleven Lignite 5 260 240 twenty No 12 Lignite 15.0 350 240 25 No 13 Lignite 20,0 340 240 25 No fourteen Lignite 22.0 350 240 25 1% weight. solid iron oxide, 0.03 mol / l NaOH fifteen Lignite and sucrose 16,0 350 240 25 1% Fe ₂ O ₃ / 0.33 mol / L NaOH / 10% sucrose 16 Lignite and wood-fiber biomass 26.5 340 240 25 0.5% iron oxide, 6% Banna grass, 20% lignite 17 Lignite 25.0 350 240 25 No eighteen Lignite 25.0 350 240 25 0.07 mol / L NaOH 19 Lignite 25.0 350 240 25 0.03 mol / L NaOH twenty Lignite 25.0 350 240 13 No 21 Lignite 25.0 350 240 13 0.015 mol / L NaOH 22 Lignite 25.0 280 240 13 No 23 Lignite 22.0 350 240 25 2% weight. iron pyrites

Table 2B Wood-fibrous biomass as feedstock and flow conditions Raw material sample number Type of feedstock Solids in suspension (% wt.) Temperature (° C) Pressure (bar) Stay (min) Additives one Lignin / cellulose fraction (radiant pine), semi-recovered 8.00 330 180 10 20% weight. ethanol 2 Lignin / cellulose fraction (radiant pine), semi-recovered 8.00 320 180 thirty 20% weight. ethanol; 1 mol / L sodium hydroxide 3 Wood fiber (elephant grass) / lignite 12.00 350 220 25 20% weight. ethanol, 4 g / l sodium hydroxide; 10% weight. Banna Grass (calculated on dry weight) four Wood-fibrous substance (radiant pine) 10.00 320 190 thirty 20% weight. ethanol; 0.2 mol / L sodium hydroxide 5 Coated-seed (duckweed) 10.00 320 200 3.0 20% weight. ethanol 6 Wood-fibrous substance (radiant pine) 10.00 320 240 25.0 20% ethanol, 0.07 mol / L sodium hydroxide 7 Wood-fibrous substance (radiant pine) 10.00 320 240 25.0 20% ethanol, 0.13 mol / L sodium hydroxide 8 Wood-fibrous substance (radiant pine) 10.00 350 240 25.0 20% ethanol, 0.13 mol / L sodium hydroxide 9 Wood-fibrous substance (radiant pine) 10.00 350 240 25.0 16.6% methanol, 0.13M sodium hydroxide 10 Wood-fibrous substance (radiant pine) 10.00 350 240 25.0 20% ethanol, 0.13 mol / L sodium hydroxide eleven Wood-fibrous substance (radiant pine) 10.00 350 240 25.0 20% ethanol, 0.13 mol / L sodium hydroxide 12 Wood-fibrous substance (radiant pine) 10.00 350 240 12.5 20% ethanol 13 Wood-fibrous substance (radiant pine) 10.00 350 240 12.5 No fourteen Wood-fibrous substance (radiant pine) 10.00 350 240 12.5 0.03 mol / L NaOH fifteen Wood-fibrous substance (radiant pine) 10.00 350 240 12.5 20% ethanol, 0.03 mol / L sodium hydroxide 16 Wood-fibrous substance (radiant pine) 10.00 350 240 12.5 20% ethanol, 0.02 mol / L sodium carbonate 17 Wood-fibrous substance (radiant pine) 10.00 350 240 25.0 No eighteen Wood-fibrous substance (radiant pine) 10.00 350 240 25.0 No 19 Wood-fibrous substance (radiant pine) 10.00 350 240 25.0 0.13 mol / L NaOH twenty Wood-fibrous substance (radiant pine) 10.00 350 240 25.0 0.13 mol / L NaOH

(iv) Conversion Reaction

The reactor used is designed to maintain laminar flow over a specific residence time (ie, “retention time”). The reactor includes rows of several tubular reaction vessels that can be connected and disconnected to adjust the total residence time. The residence time used depended on the time required for a sufficient conversion of the feedstock to take place, and, in some cases, it varied depending on the nature of the feedstock, the nature of the aqueous solvent used and / or the presence / absence of additional catalysts in the suspension ( see tables 2A and 2B). The reactor used used external satellite heating so that precise temperature profile control could be performed.

(v) Cooling and depressurization

After a sufficient reaction, the suspension exited the reactor and was passed through a concentric tube cooling module. The cooling module was used as a heat exchanger in order to reduce the process temperature to levels suitable for a pressure reduction system and in order to provide the possibility of heat recovery in order to improve the overall thermal efficiency.

The suspension was cooled to about 180 ° C. over a period of about 5-30 seconds (preferably 25 seconds), the cooling rate was optimized to minimize the formation and precipitation of solids. The suspension was passed through a pressure reduction system that lowered the pressure to atmospheric levels and sent the product to a collection tank. The pressure reducing system included switched parallel paths with a constant cross section, as well as a control valve with a variable flow area. The collection tank uses a water jacket to cool the slurry back to ambient temperature. Accordingly, the pressure reduction system and the water jacket of the collection tank facilitate an almost instantaneous depressurization to ambient pressure and a rapid decrease in temperature from about 180 ° C to ambient temperature.

(vi) Biofuel processing

The biofuel product is then processed for separation and purification. In the case of a lignite feedstock, the biofuel product was filtered through a pressure filter or a rotating vacuum drum filter to facilitate the first stage of separation of solid and liquid. The solid product includes high carbon ash with associated oils. The oil was separated from the ash either by thermal distillation or by solvent extraction. The liquid product contains a low percentage of light oils, which are concentrated and separated using an evaporator.

In the case of wood-fiber biomass as a feedstock (or a cellulose / lignin fraction as a feedstock), the product may be oil (i.e. no solid) depending on the processing conditions and nature of the feedstock (ash content, etc. .). Most were isolated by decantation or by density separation. A small percentage of water-soluble light oils were also present, which were concentrated and separated by means of an evaporator. Petroleum products can be further clarified, or distilled, to remove all residual water or to prepare for further processing.

Example 2: Analysis of biofuel products

The analysis of biofuel products was carried out using standard methods, according to the following brief descriptions:

Coal / Coal Substance Analysis:

Rapid analysis, including the percentage of moisture, ash, volatiles and bound carbon, was carried out in accordance with Australian standard procedures AS2434.1,2 and 8.

A complete analysis, including carbon, hydrogen, nitrogen, and total sulfur, was carried out in accordance with Australian standard procedures AS1038.6.4 and AS1038.6.3.2.

The specific heat was determined in accordance with the Australian standard method AS1038.5.

Ash analysis was carried out in accordance with the Australian standard method AS1038.14.

The melting temperatures of the ash in an oxidizing atmosphere were determined in accordance with the Australian standard procedure AS1038.15.

Oil Analysis:

A complete analysis, including carbon, hydrogen and nitrogen, was carried out in accordance with the Australian standard method AS1038.6.4.

Analysis of total sulfur was performed in accordance with US Environmental Protection Agency (USEPA) No. 5050 followed by inductively coupled plasma atomic emission spectroscopy (ICPAES).

The specific heat was determined in accordance with the Australian standard method AS1038.5.

Determination of the total moisture content in the oils was carried out in accordance with the current ASTM D6304 standard.

Table 3 below provides details regarding the properties of the feedstock materials used in the biofuel generation process. Tables 4a, 4b and 5 below provide details regarding the properties of biofuels produced in accordance with the process.

Table 3 Analysis of the properties of the feedstock Feedstock VUT (MJ / kg based on dry weight) Carbon (% weight based on dry weight) Hydrogen (% weight based on dry weight) Nitrogen (% weight based on dry weight) Sulfur (% weight based on dry weight) Ash (% weight based on dry weight) Oxygen (% weight based on dry weight) H / C molar ratio Numbers of samples of lignite feedstock 12 25.6 66.3 4.4 0.6 0.2 3,1 25,4 0.8 3, 4 25,4 67.1 4.2 0.7 0.2 2,4 25,4 0.7 eleven 24.1 62,2 5,4 0.6 3.8 12.9 15.1 1,0 5, 6, 7, 8 25.5 65.5 4.6 0.7 0.3 2.2 26.8 0.8 9, 10 24.7 63,4 4.4 0.5 0.3 3.6 27.8 0.8 Numbers of samples of wood-fiber material as feedstock 1, 2, 3, 4 17.8 48.0 5,6 0.1 0,0 0.5 45.7 1.4

Table 3 (continued) Analysis of the properties of the feedstock Feedstock VUT (MJ / kg based on dry weight) Carbon (% weight based on dry weight) Hydrogen (% weight based on dry weight) Nitrogen (% weight based on dry weight) Sulfur (% weight based on dry weight) Oxygen (% weight based on dry weight) H / C molar ratio Numbers of samples of lignite feedstock 12 25.64 66.30 4.35 0.63 0.23 25.39 0.78 13-17, 23 24.70 63.40 4.40 0.48 0.33 27.79 0.83 18-22 26.00 64.30 4.90 0.79 0.70 23.31 0.91 Numbers of samples of wood-fiber material as feedstock 5 19.40 46.40 6.20 3.48 0.30 37.52 1,59 6-20 17.81 48.00 5.61 0.13 0.02 45.74 1.39

Table 4b Analysis of lignite-derived (carbon) product equivalent to high-quality coal for PCI Lignite Feed Number Analyzed product Express analysis Full analysis and analysis of UT Moisture (% wt. Ar) Ash (% wt. Based on dry weight) Volatile substances (% wt. Calculated on dry weight) Associated With (% wt. Calculated on dry weight) VUT (MJ / kg based on dry weight) Carbon (% wt. Based on dry weight) Hydrogen (% wt. Based on dry weight) Nitrogen (% wt. Based on dry weight) Sulfur (% wt. Based on dry weight) Oxygen (% wt. Based on dry weight) Molar ratio
N / a 2 PCI 4.60 2.70 26.2 71.1 30.62 78.9 3.57 0.89 0.31 13.6 0.54 3 PCI 2.20 3.30 27.6 66.9 31.12 78.1 4.18 0.90 0.18 13.3 0.64 four PCI 1,60 2.60 20.5 76.9 33.30 84.5 3.80 0.89 0.10 8.1 0.54 5 PCI 2.60 3.70 29.3 67.1 30,20 77.8 3.70 0.75 0.18 13.9 0.57 6 PCI 1.80 6.30 22.1 71.6 31.80 80.1 3.80 0.75 0.23 8.8 0.57 7 PCI 1.40 5.00 25.1 69.9 32.30 81.0 4.10 0.74 0.18 9.0 0.60 8 PCI 0.80 3.80 26.6 69.5 31.40 79.9 4.10 0.75 0.20 11.3 0.61 9 PCI 1.00 4.20 26.9 68.9 31.6 79.1 4.40 0.88 0.22 16.7 0.71 10 PCI 3.80 5.20 32.8 62.0 28.90 73,4 4.10 0.83 0.28 16,2 0.67 eleven PCI 6.00 14.3 30.1 55.6 27.52 69.9 3.47 0.79 2.59 8.9 0.59

Table 4b (continued) Analysis of lignite-derived (carbon) product equivalent to high-quality coal for PCI Lignite Feed Number Analyzed product Component ash SiO ₂ (% wt. Calculated on dry weight) Al ₂ O ₃ (% wt. Calculated on dry weight) Fe ₂ O ₃ (% wt. Calculated on dry weight) TiO ₂ (% wt. Calculated on dry weight) K ₂ O (% wt. Calculated on dry weight) MgO (% wt. Calculated on dry weight) Na ₂ O (% wt. Calculated on dry weight) CaO (% wt. Based on dry weight) SO ₂ (% wt. Based on dry weight) P ₂ O ₅ (% wt. Calculated on dry weight) Mn ₃ O ₄ (% wt. Calculated on dry weight) SrO (% wt. Based on dry weight) BaO (% wt. Based on dry weight) ZnO (% wt. Calculated on dry weight) V ₂ O ₅ (% wt. Calculated on dry weight) 2 PCI 17.70 7.70 12.80 0.64 0.66 15.60 0.90 22.60 20.50 1.00 0.12 0.23 0.14 <0.01 0,07 3 PCI 16.80 5.80 13.60 20.00 0.68 0.44 0.55 25.60 17.30 0.40 0.19 0.56 0.17 0.01 0.06 four PCI 11.10 4.80 18.50 0.39 0.77 18.40 13.00 16.90 18.40 5 PCI 6.60 4.30 52.00 0.30 0.40 13.80 1.70 5.40 10.90 6 PCI 4.90 3.10 34.30 0.21 0.21 11.60 28.10 3,50 10,20 7 PCI 8 PCI 6.80 2,50 42.10 0.26 0.55 15.40 12.10 6.50 13.70 0.48 9 PCI 6.40 3.60 45.40 0.32 0.23 15.60 6.60 7.20 12.90 0.10 10 PCI 13.40 7.20 31.90 0.53 11.70 10,20 12.50 11.70 0.68 eleven PCI 9.50 10.30 18.50 0.25 0.08 2.20 0.39 23.30 33.30 0.11 0.09 0.11 0.05 0,03

Table 4b (continued) Analysis of lignite-derived (carbon) product equivalent to high-quality coal for PCI Lignite Feed Number Analyzed product Ash melting point AFT-Ox DT (єC) AFT-Ox ST (єC) AFT-Ox HT (єC) AFT-Ox FT (єC) 2 PCI 3 PCI four PCI 5 PCI 6 PCI 7 PCI 8 PCI 9 PCI 10 PCI > 1550 > 1550 > 1550 > 1550 eleven PCI

Table 4b (continued) Analysis of lignite-derived (carbon) product equivalent to high-quality coal for PCI Sample Number Analyzed product Express analysis Full analysis and analysis of UT Moisture (% wt. Ar) Ash (% wt. Based on dry weight) Volatile substances (% wt. Calculated on dry weight) Associated With (% wt. Calculated on dry weight) VUT (MJ / kg based on dry weight) Carbon (% wt. Based on dry weight) Hydrogen (% wt. Based on dry weight) Nitrogen (% wt. Based on dry weight) Sulfur (% wt. Based on dry weight) Oxygen (% wt. Based on dry weight) H / C molar ratio 12 PCI 2.00 4.90 28.1 67.0 29.9 76.3 3.90 0.80 0.28 13.8 0.61 13 PCI 1.40 5.10 27.1 67.9 30.1 76,4 4.10 0.87 0.27 13.3 0.64 fourteen PCI 0.70 6.80 27.4 65.9 29.8 75.8 4.20 0.87 0.27 12.1 0.66 fifteen PCI 7.00 5.50 40.3 54,2 30,2 74.6 5.00 0.74 0.26 13.9 0.80 16 PCI 1.20 7.20 26.9 65.8 29.6 74.5 3.90 0.85 0.26 13.3 0.62 17 PCI 0.40 7.80 26.8 65,4 30,2 76.5 4.10 0.95 0.49 10,2 0.64 eighteen PCI 0.60 7.30 24.6 37.8 30.8 77.8 4.00 0.90 0.50 9.5 0.61 19 PCI 0.90 7.30 29.0 63.7 30,2 76,2 4.20 0.89 0.34 11.1 0.66 twenty PCI 0.90 6.50 30.5 63.0 29.7 75.9 4.40 1,03 12,2 0.69 21 PCI 1.20 7.20 29.7 63.1 30,0 75.8 4.30 1,03 0.46 11,2 0.68 22 PCI 36.40 6.90 43.6 49.6 28.0 69.9 5.10 0.91 0.69 16.5 0.87 23 PCI - -

Table 4b (continued) Analysis of lignite-derived (carbon) product equivalent to high-quality coal for PCI Sample Number Component ash SiO ₂ (% wt. Calculated on dry weight) Al ₂ O ₃ (% wt. Calculated on dry weight) Fe ₂ O ₃ (% wt. Calculated on dry weight) TiO ₂ (% wt. Calculated on dry weight) K ₂ O (% wt. Calculated on dry weight) MgO (% wt. Calculated on dry weight) Na ₂ O (% wt. Calculated on dry weight) CaO
(% wt. based on dry weight) SO ₃
(% wt. based on dry weight) P ₂ O ₅ (% wt. Calculated on dry weight) Mn ₃ O ₄ (% wt. Calculated on dry weight) SrO (% wt. Based on dry weight) Bao
(% wt. based on dry weight) ZnO (% wt. Calculated on dry weight) V ₂ O ₅ (% wt. Calculated on dry weight) 12 18.70 9.40 37.90 0.68 0.58 12.10 2.20 8.90 8.20 0.23 13 18.50 9.40 38.70 0.78 0.57 10.90 1.70 7.80 8.40 0.24 fourteen 11.9 6.6 47.2 0.50 0.66 10 4.4 7.7 9.5 0.16 fifteen 19.00 8.30 45.50 0.79 0.49 8.60 2,30 6.80 6.30 0.17 16 26.10 8.60 46.90 0.63 0.90 6.60 1.80 5.60 3.90 0.77 17 23.00 7.30 29.90 0.44 0.38 7.10 0.60 18.50 14.20 0.05 eighteen 24.80 8.20 29.00 0.56 0.41 9.10 1,60 16.30 12.40 0.10 19 28.80 9.00 28.00 0.66 0.40 9.80 1,60 14.80 8.00 0.11 twenty 17.00 6.90 24.50 0.43 0.30 8.20 0.50 25.90 18.00 0.10 21 23.00 7.30 24.00 0.46 0.24 8.00 1.20 24.40 13.30 0.05 22 23

Table 4b (continued) Analysis of lignite-derived (carbon) product equivalent to high-quality coal for PCI Sample Number Ash melting point AFT-Ox DT (° C) AFT-Ox ST (° C) AFT-Ox HT (° C) AFT-Ox FT (° C) 12 13 fourteen fifteen 1,410 1,430 1,460 1,480 16 17 eighteen 1,180 1,190 1,190 1,200 19 1,030 1,050 1,060 1,170 twenty 1,290 1,300 1,310 1,320 21 1,160 1,200 1,210 1,210 22 23

Table 5 Analysis of bio-oil product obtained from wood-fiber material Woodfiber Feed Number Analyzed product Oil distillate VUT (MJ / kg based on dry weight) Carbon (% wt. Based on dry weight) Hydrogen (% wt. Based on dry weight) Nitrogen (% wt. Based on dry weight) Sulfur (% wt. Based on dry weight) Ash (% wt. Based on dry weight) Oxygen (% wt. Based on dry weight) H / C molar ratio one Bio oil + 98% 74.71 6.39 18.04 1,0 2 Bio oil + 98% 37.5 82,2 8.6 0.4 0.1 0.4 8.3 1.3 3 Bio oil 36.6 82.6 6.7 0.9 0.6 - 9.1 1,0 four Bio oil + 98% 34.9 81.0 9.5 0.5 0.1 - 8.7 1.4

Table 5 (continued) Analysis of bio-oil product obtained from wood-fiber material Sample Number Analyzed product Oil output indication VUT (MJ / kg based on dry weight) Carbon (% wt. Based on dry weight) Hydrogen (% wt. Based on dry weight) Nitrogen (% wt. Based on dry weight) Sulfur (% wt. Based on dry weight) Ash (% wt. Based on dry weight) Oxygen (% wt. Based on dry weight) H / C molar ratio 5 Bio oil 25-40% 31.87 69.25 7.43 3.70 0.42 10.39 8.82 1.28 6 Bio oil 25-40% 38.86 78.98 6.77 0.18 0,07 - 14.00 1,02 7 Bio oil 25-40% 35.93 78.64 6.86 0.17 0,03 - 14.30 1,04 8 Bio oil 25-40% 34.93 78.87 7.20 0.20 0.04 1.70 11.99 1.09 9 Bio oil 25-40% 34.86 79.09 7.02 0.16 0,03 1,02 12.67 1.06 10 Bio oil 25-40% 34.16 77.95 7.19 0.18 0,03 0.70 13.95 1.10 eleven Bio oil 25-40% 34.74 78.91 7.39 0.11 0.04 1.10 12.45 1.12 12 Bio oil 25-40% 31.56 71.84 6.99 0.14 0,07 0.30 20.65 1.16 13 Bio oil 25-40% 30.49 69.90 6.69 0.09 0,03 0.10 23.19 1.14 fourteen Bio oil 25-40% 31.97 73.50 6.88 0.08 0,03 0.10 19.42 1,11 fifteen Bio oil 25-40% 30.37 69.37 6.69 0.10 0.02 0.10 23.72 1.15 16 Bio oil 25-40% 31.78 73.08 6.79 0.11 0.02 0.20 19.80 1,11 17 Bio oil 25-40% 32,20 74.94 6.79 0.14 - - 18.13 1,08 eighteen Bio oil 25-40% 33.14 74.92 6.58 0.11 - - 18.39 1.05 19 Bio oil 25-40% 35.15 81.22 7.19 0.06 0.02 1.20 10.30 1.06 twenty Bio oil 25-40% 35.50 82.33 7.19 0.08 0.01 0.30 10.09 1,04

Table 5 (continued) Analysis of bio-oil product obtained from wood-fiber material Sample Number Component ash SiO ₂ (% wt. Calculated on dry weight) Al ₂ O ₃ (% wt. Calculated on dry weight) Fe ₂ O ₃ (% wt. Calculated on dry weight) TiO ₂ (% wt. Calculated on dry weight) K ₂ O (% wt. Calculated on dry weight) MgO (% wt. Calculated on dry weight) Na ₂ O (% wt. Calculated on dry weight) CaO (% wt. Based on dry weight) SO ₃
(% wt. based on dry weight) P ₂ O ₅ (% wt. Calculated on dry weight) Mn ₃ O ₄ (% wt. Calculated on dry weight) SrO (% wt. Based on dry weight) BaO (% wt. Based on dry weight) ZnO (% wt. Calculated on dry weight) V ₂ O ₅ (% wt. Calculated on dry weight) 5 6.20 1.70 7.40 0.36 0.36 5.00 0.60 40.60 4.30 34.60 6 7 8 9.60 8.40 7.80 0.21 0.56 5.30 34.50 20.80 3,50 8.10 9 15.30 12.10 14.50 0.49 0.40 9.90 2.20 28.00 6.10 13.10 10 eleven 12 13 fourteen fifteen 16 17 eighteen 19 twenty

The effect of alkali metal hydroxides and carbonates on the oxygen content:

Figure 1 demonstrates the effectiveness of alkali metal hydroxides and carbonates in reducing the oxygen content in a bio-oil product, where all conditions are constant, except for the concentration of an additional catalyst. The optimal concentration of the catalyst based on sodium hydroxide or sodium carbonate under these conditions lies in the range of about 0.1 mol / L to 1 mol / L, since this gives a product with a low oxygen content (8-10% by weight) without the use of excessively high concentrations of catalyst.

Additional characteristics of coal oil obtained from lignite:

As shown in table 6 below and figure 2, the simulated distillation of a typical coal oil obtained from lignite (table 2A - sample feedstock No. 20), illustrated the similarity of the product with crude oil. 99% of the product is recovered from a GC column used for simulated distillation at 620 ° C, which indicates that the product does not contain a significant amount of low volatility residue.

Table 6 Percentage of mass release at different temperatures Report Number / Number COQ 322196 Way The properties Units D7169 Initial boiling point ° C 123.0 1% of the mass is regenerated when ° C 157.5 5% of the mass is regenerated when ° C 218.5 10% of the mass is regenerated when ° C 252.5 20% of the mass is regenerated when ° C 294.0 30% of the mass is regenerated when ° C 332.5 40% of the mass is regenerated when ° C 387.0 50% of the mass is regenerated when ° C 428.0 60% of the mass is regenerated when ° C 459.5 70% of the mass is regenerated when ° C 484.5 80% of the mass is regenerated when ° C 508.0 90% of the mass is regenerated when ° C 537.5 95% of the mass is regenerated when ° C 560.5 99% of the mass is regenerated when ° C 620.5 Final boiling point ° C 676.5 % regenerated at 360єC % by weight 35,2 % regenerated at 370єC % by weight 37.0 % regenerated at 555єC % by weight 94.0

The properties of lignite coal oil were also studied using 1H and quantitative 13C NMR spectroscopy. For this test, the oil was accelerated over various boiling ranges, and NMR spectra for the fractions were recorded. The fractions in this example were designated as follows

Table 7 Fraction Designation for NMR Sample Code Approximate boiling range / ° C The approximate relative content,% weight. A 60-300, mainly 250-300 17 B 300-340 ° C 17 C 160-200 at approximately 1-10 mbar 9 D 200-250 at approximately 1-10 mbar 24 E 250-300 at approximately 1-10 mbar fifteen F Up to 620 eighteen

Proton NMR and quantitative 13C NMR spectra are shown for each fraction mentioned in Table 7 as FIGS. 3A-3L (first, proton NMR). Sample Code A (FIGS. 3A-3B); Sample Code B (FIG. 3C-3D); Sample Code C (FIGS. 3E-3F); Sample Code D (Fig. 3G-3H); Sample Code E (FIGS. 3I-3J); Sample code F (Fig. 3K-3L).

The 1 H NMR spectra were combined into three regions of chemical shifts, which are broadly designated as follows:

"Aromatic" 9.5-6.2 ppm "Olefin" 6.2-3.5 ppm "Aliphatic" below 3.5 ppm

In practice, olefin protons can have shifts of up to 7.1 ppm. or higher depending on the substitution patterns, therefore, there may be overlap between the “olefin” and “aromatic” protons. For 1H NMR, the integral is approximately proportional to the number of protons present in each individual region of chemical shifts. Integrals were used to establish the ratio of “aromatic”, “olefin” and “aliphatic” protons present in fractions.

Table 8 Properties of oil derived from lignite Fraction id Approximate Boiling Range / ° C Appearance Relative content of proton types /% aromatic olefin "aliphatic" A 150-300 Mobile oil fourteen 6 81 B 300-340 Mobile oil 12 four 84 C 160-200 @ @ O (mbar) Paraffin oil 13 3 84 D 200-250 @ @ O (mbar) Voskopodobny 12 3 85 E 250-300 @ @ O (mbar) Voskopodobny 10 2 87 F > 300 at @ O (mbar) Bitumen 13 2 85

As expected, 1 H NMR spectra show a wide variety of chemical environments for protons in fractions. Of course, the most common environment in all fractions is the environment near 1.4 ppm, typical of methylene (-CH ₂ -) proton in a straight alkyl chain. This suggests the prevalence of direct hydrocarbon chains, which is an indication of high-quality bio-oil, the quality of which is relatively easily increased to such a “poured” fuel, such as diesel fuel or gasoline.

13C NMR spectra mean that the ratio of (aromatic and olefin): aliphatic carbon environments is approximately 1: 1 in most fractions, with the exception of fraction E, where it most likely is 2: 3. Fraction A includes the relative content of carbonyl environments.

In general, a combination of 1H and 13C data means that, in general, coal oil may be a mixture of substituted mono-, di- and triaromatic compounds and straight chain hydrocarbons, where most of the remaining oxygen is associated with aromatic compounds. It also means high quality bio-oil, the quality of which can be relatively easily improved by hydrotreating / hydrocracking to “refuel” fuel, such as diesel fuel, jet fuel or gasoline. The relative content of carbon atoms bonded to a heteroatom such as oxygen decreases with increasing boiling point, and this is confirmed by elemental analysis (table 9 below). This means that most of the oxygen can be in monocyclic aromatic structures, for example, phenols, and this means that relatively mild hydrotreating conditions can be effective in removing the remaining oxygen from coal oil.

Table 9 Elemental analysis of fractions of oil obtained from lignite Fraction Carbon Hydrogen Nitrogen % Sulfur O - by difference % the weight. upon receipt % the weight. upon receipt % the weight. upon receipt % the weight. upon receipt % the weight. upon receipt A 80.7 9.1 0.29 0.30 9.61 B 83.3 9.1 0.32 0.30 6.98 C 84.6 9.0 0.27 0.34 5.79 D 84.7 9.2 0.39 0.29 5.42 E 86.1 9,4 0.36 0.22 3.92 F 92 8.0 0.26 0.27 0.00

An additional characteristic of bio-oil obtained from wood-fiber material (radiant pine):

The 1 H NMR spectrum of a typical bio-oil sample is shown in FIG. 4. The spectrum shows broad peaks, the ratio (aromatic plus olefin): aliphatic protons is approximately 1: 4, which is similar to the ratios found for fractions of coal oil. Proton environments are present near 4 ppm, which means methoxy (-OCH ₃ ) protons. These protons are less noticeable in coal oil fractions.

Of course, the most common environment in all fractions is near 1.4 ppm, which is typical for a methylene proton (-CH ₂ -) in a straight alkyl chain. This means the prevalence of direct hydrocarbon chains, which is an indication of high-quality biofuels, the quality of which can be relatively easily increased to such “fuel” as diesel fuel or gasoline.

Figure 5 shows the range of molecular weight distributions determined by gel permeation chromatography for typical biooils produced from radiant pine. The molecular weight distribution varies according to processing conditions; longer residence times tend to generate wider molecular weight distributions.

The peaks in the molecular weight distributions are about 200-300 daltons, which means a significant amount of material in the molecular weight range, similar to the interval for diesel fuel (cetane has a molecular weight of 226 daltons). It also means high quality biooil.

Characterization of water-soluble organic materials

Despite the relatively low relative content, organic molecules contained in the aqueous phase associated with the production of bio-oil are of interest as a starting chemical raw material. Water-soluble compounds can be accumulated by, for example, liquid extraction (LLE) with suitable solvents (eg, ethers, ketones, acetates, toluene) or by evaporation of water, or by a combination of these steps.

Table 10 shows typical elemental analyzes of biooil accumulated from the aqueous phase for lignite feedstock and wood-fiber material (radiant pine) as feedstock.

Table 10 Specific heat and elemental composition of bio-oil accumulated from aqueous phases Type of feedstock VUT (MJ / kg based on dry weight) Carbon (% wt. Based on dry weight) Hydrogen
(% wt. based on dry weight) Nitrogen (% wt. Based on dry weight) Sulfur (% wt. Based on dry weight) Ash (% wt. Based on dry weight) Oxygen (% wt. Based on dry weight) H / C molar ratio Radiant pine 31.27 65.87 7.66 0.04 0.01 - 26,42 1.38 Radiant pine 32.09 67.05 7.80 0.48 0.10 - 24.58 1.39 Radiant pine 31.67 69.80 7.61 0,07 0,03 - 22.49 1.30 Lignite 28.48 67.88 6.76 0.01 0.09 - 25.26 1.19

Analysis by gas chromatography with mass spectrometric detection (GC-MS) shows that the oils accumulated from the aqueous phases of the processed wood-fiber material, such as suspensions of radiant pine, contain valuable raw materials and intermediates, including those used in food and perfumery industry. Non-limiting examples of such compounds are phenol; phenol, 2-methoxy- (guaiacol); phenol, 4-ethyl-2-methoxy- (4-ethyl guaiacol); phenol, 2-methoxy-4-propyl- (dihydroevgenol); vanillin; phenol, 2-methoxy-4- (1-propenyl) - (isoeugenol); eugenol.

6 shows a partial GC-MS analysis of a typical sample. The peak information corresponding to FIG. 6 is shown below.

Total Ion Peak Report Peak number Retention time Start time End time Area Area, % Height Title one 4,110 4,083 4,158 1892961 1.10 1048103 2-Hepten, (E) - 2 5,551 5,525 5,600 4845322 2.82 3361465 2-cyclopenten-1-one, 2-methyl- 3 6,176 6,150 6,208 1836161 1,07 1328869 2-cyclopenten-1-one, 2,3-dimethyl- four 6,925 6,900 6,958 5118173 2.98 4399064 Phenol 5 7,174 7,117 7,217 2212872 1.29 1363247 2-cyclopenten-1-one, 2,3-dimethyl- 6 7,999 7,975 8,042 4111643 2,39 3678258 Phenol 3-methyl 7 8,264 8,208 8,308 5505584 3.20 2978128 Phenol 3-methyl 8 8,472 8,442 8.517 24317667 14.15 20429867 Phenol, 2-methoxy 9 9,167 9,142 9,200 2169182 1.26 1291213 Phenol, 2,5-dimethyl 10 9,367 9,342 9,417 2291667 1.33 1407891 Phenol 3-ethyl eleven 9,699 9,667 9,750 26143596 15.22 23765767 2,3-dimethylhydroquinone 12 10,367 10,325 10,408 6205053 3.61 5239459 1,2-Benzenediol, 4-methyl- 13 10,603 10,492 10,625 11674941 6.80 9207746 Phenol, 4-ethyl-2-methoxy- fourteen 10,649 10,625 10,692 9139019 5.32 8685435 1,2-Benzenediol, 4-methyl- fifteen 11,158 11,133 11,175 5024156 2.92 4774011 1,4-Benzenediol, 2-methyl- 16 11,270 11,175 11,292 2962108 1.72 1531083 2,5-dimethylhydroquinone 17 11,457 11,342 11,492 6551464 3.81 4601891 Phenol 2-methoxy-4-propyl- I8 11,547 11,492 11,600 8491644 4.94 5946841 4-ethylcatechol 19 11,757 11,742 11,817 2958977 1.72 1869419 Vinitin twenty 11,915 11,875 11,950 2381124 1.39 1213818 1,3-benzenediol, 4-ethyl 21 12,108 12,000 12,133 2438145 1.42 719577 Phenol, 4-ethyl 2-methoxy- 22 12,200 12,133 12,225 1762113 1,03 706135 Phenol, 2-methoxy-4- (1-
propenyl) -, (Z) - 23 12,281 12,233 12,300 1752692 1,02 1284826 Phenol, 2-methoxy-4-propyl-

24 12,366 12,300 12,383 6740063 3.92 5519653 1,3-benzenediol, 4-propyl- 25 12,403 12,383 12,442 2804791 1,63 2064444 Phenol, 2-methoxy-4- (1-propenyl) -, (E) - 26 12,525 12,442 12,542 1818747 1.06 1125844 Ethanone, 1- (4-hydroxy-3-methoxyphenyl) - 27 12,710 12,667 12,742 2391608 1.39 1887661 1,2-dimethoxy-4-n-propylbenzene 28 12,902 12,875 12,933 2804803 1,63 2228508 5-methoxycarbonylpyridine-2-carboxylic acid 29th 13,154 13,125 13,183 10441687 6.08 8068955 Benzoic acid, 2,3-dimethyl- thirty 13,832 13,808 13,858 3020188 1.76 2467624 Eugenol

Bio-oil accumulated from the aqueous phase generated during the processing of lignite suspensions is generally richer in catechins and phenols and contains less methoxy-substituted compounds. These materials are a valuable raw material for the chemical industry. 7 shows a partial GC-MS analysis of such an oil. The peak information corresponding to FIG. 7 is shown below.

Total Ion Peak Report Peak number Retention time Start time End time Area Area, % Height Title one 3,599 3,583 3,658 1470437 4.16 1189280 2-hexanol, 2-methyl- 2 4,749 4,733 4,817 2767299 7.83 3347650 Phenol 3 5,159 5,142 5,183 516144 1.46 713147 Phenol 3-methyl four 5,259 5,183 5,308 1600549 4,53 1552532 Phenol 3-methyl 5 5,325 5,308 5,375 1642620 4.65 2096663 Phenol, 2-methoxy 6 5,644 5,617 5,683 858510 2.43 614175 Phenol 2,3-dimethyl 7 5,748 5,683 5,892 9552121 27.04 9352902 1,2-Benzenediol 8 5,974 5,892 6.025 2548485 7.21 1635189 1,2-Benzenediol, 4-methyl- 9 6,067 6.025 6,133 4619295 13.07 3752632 1,2-Benzenediol, 4-methyl- 10 6,268 6,208 6,292 2364042 6.69 891727 2-methoxy-6-methylphenol eleven 6,325 6,292 6,383 2903853 8.22 536646 1,4-Benzenediol, 2-methyl- 12 6,477 6,458 6,517 891055 2,52 481187 1,4-Benzenediol, 2,6-dimethyl- 13 6,533 6,517 6,575 1382085 3.91 874823 Methanol, (4-carbomethoxy) benzoyl

Inclusion by reference

This application claims the priority of provisional patent application Australia No. 2010901473, filed April 7, 2010, the contents of which are incorporated by reference in their entirety.

Claims (34)

1. A method of producing biofuels, the method comprising:
treating the organic matter with an aqueous solvent and at least one additional catalyst, which is selected from the group consisting of: an acid catalyst, a water vapor conversion catalyst, an aluminosilicate catalyst, a sulfide catalyst, and a basic catalyst,
where the organic substance and the aqueous solvent are provided in the form of a suspension, and said treatment is carried out under continuous flow conditions with a minimum, volume-independent, suspension flow rate greater than the sedimentation rate of the solid in the suspension,
wherein said processing includes:
heating and increasing the pressure to a target temperature between about 250 ° C and about 400 ° C and to a target pressure between about 100 bar and about 300 bar to produce biofuel;
processing at the target temperature and target pressure for a certain period of time; and
cooling and lowering the pressure in the suspension,
and wherein:
the specified at least one additional catalyst is added to the organic substance after heating to the specified temperature and after increasing the pressure to the specified level, but before the specified decrease in pressure in the suspension,
biofuel is bio-oil, and
said organic matter is coal or wood fiber. 2. The method according to p. 1, where the specified additional basic catalyst is an oxide, hydroxide, carbonate or sulfide. 3. The method of claim 1, wherein said further base catalyst is an additional transition metal catalyst, an alkali metal salt catalyst, or an alkaline earth metal salt catalyst. 4. The method of claim 3, wherein said additional transition metal catalyst is an additional transition metal catalyst on a substrate. 5. The method of claim 3, wherein said additional transition metal catalyst is an additional transition metal salt catalyst. 6. The method of claim 5, wherein said further transition metal salt catalyst is carbonate or sulfide. 7. The method of claim 5, wherein said additional transition metal salt catalyst is an additional transition metal formate catalyst. 8. The method of claim 3, wherein said additional alkali metal salt catalyst or alkaline earth metal salt catalyst is carbonate or sulfide. 9. The method according to p. 3, where the specified additional catalyst based on an alkali metal salt is an additional catalyst based on alkali metal carbonate or a catalyst based on alkali metal formate. 10. The method according to p. 1, where the specified additional catalyst is an additional solid acid catalyst. 11. The method of claim 1, wherein said additional aluminosilicate-based catalyst is a zeolite. 12. The method of claim 1, wherein said further base catalyst is an alkali metal hydroxide catalyst or a transition metal hydroxide catalyst. 13. The method of claim 1, wherein said further base catalyst is sodium hydroxide or potassium hydroxide. 14. The method of claim 9, wherein said additional alkali metal carbonate catalyst is sodium carbonate or potassium carbonate. 15. The method of claim 1, wherein said treatment comprises the use of at least one additional catalyst that facilitates the introduction of hydrogen into said organic substance. 16. The method of claim 1, wherein said additional catalyst is a transition metal. 17. The method of claim 1, wherein said alkali metal formate catalyst is sodium formate or potassium formate. 18. The method of claim 1, wherein said treatment comprises using at least one additional catalyst that facilitates the removal of oxygen from said organic substance. 19. The method according to p. 1, where the specified additional catalyst is a metal iron, iron oxide or iron sulfide. 20. The method of claim 1, wherein said organic substance is a fossilized organic substance having a carbon content of at least 50% and said aqueous solvent is water. 21. The method of claim 1, wherein said organic substance is a fossilized organic substance having a carbon content of at least 60% and said aqueous solvent is water. 22. The method according to any one of paragraphs. 1-21, wherein said temperature is between about 320 ° C. and about 360 ° C. and said pressure is between about 200 bar and about 250 bar. 23. The method according to any one of paragraphs. 1-21, wherein said fossilized organic substance is lignite, said temperature is between about 340 ° C. and about 360 ° C., and said pressure is between about 200 bar and about 240 bar. 24. The method according to any one of paragraphs. 1-21, where the specified biofuel contains one or more of the following components: an oil component, a coal component and a gaseous component comprising methane, hydrogen, carbon monoxide and carbon dioxide. 25. The method according to any one of paragraphs. 1-21, where the specified organic substance is a wood-fiber substance and the specified aqueous solvent contains alcohol. 26. The method according to p. 25, where the specified wood-fiber material contains more than about 10% of each of lignin, cellulose and hemicellulose. 27. The method of claim 25, wherein said temperature is between about 270 ° C. and about 360 ° C., said pressure is between about 170 bar and about 250 bar, and said solvent contains between about 5% weight. and 40% weight. alcohol. 28. The method of claim 25, wherein said temperature is between about 300 ° C. and about 340 ° C., said pressure is between about 200 bar and about 240 bar, and said solvent contains between about 10% weight. and about 30% weight. alcohol. 29. The method of claim 25, wherein said alcohol is ethanol. 30. The method according to any one of paragraphs. 1-19, where the specified processing takes place over a period of time ranging from about 20 minutes to about 30 minutes. 31. The method according to any one of paragraphs. 1-19, where the specified method includes the step of heating the organic matter and the aqueous solvent to the specified temperature for a period of time of less than about 2 minutes, before the specified treatment. 32. The method according to any one of paragraphs. 1-19, where the specified method includes the steps:
(i) cooling the organic matter to a temperature between about 160 ° C and about 200 ° C for a period of time of less than about 30 seconds after said treatment; and
(ii) lowering the pressure and cooling the organic matter to ambient temperature by releasing through a pressure reducing device. 33. The method according to any one of paragraphs. 1-19, where the specified biofuel contains an oil component characterized by a higher specific heat capacity of more than about 35 MJ / kg 34. The method according to any one of paragraphs. 1-19, where the specified biofuel contains an oil component containing more than about 8% weight. hydrogen based on dry weight and less than about 10% weight. oxygen per dry weight.

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