method for the continuous treatment of biomass

专利摘要:
METHOD FOR CONTINUOUS TREATMENT OF BIOMASS, METHOD FOR PROCESSING BIOMASS AND METHOD FOR INCREASING THE LEVEL OF GLUCOSE PRODUCED FROM LIGNOCELLULOSIC BIOMASS. The present invention relates to methods for the continuous treatment of biomass comprising a pre-treatment step, in which said biomass is contacted with a first supercritical fluid, close to the critical or subcritical one to form a solid matrix and a first liquid fraction. ; and a hydrolysis step, in which said solid matrix formed in said pretreatment step is contacted with a second supercritical fluid or close to the critical to produce a second liquid fraction and a fraction containing insoluble lignin. Apparatus is also disclosed for the continuous conversion of biomass comprising a pretreatment reactor and a hydrolysis reactor associated with said pretreatment reactor.
公开号:BR112012017850B1
申请号:R112012017850-4
申请日:2011-01-19
公开日:2020-11-17
发明作者:Kiran L. Adam
申请人:Renmatix, Inc.；
IPC主号:

专利说明:

Cross Reference to Related Orders
[0001] This application claims priority to U.S. patent application No. 61 / 296,101 filed on January 19, 2010, the full description of which is incorporated by reference. Field of the Invention
[0002] The present invention generally relates to the supercritical or quasi-supercritical treatment of biomass. More particularly, it refers to processes for the treatment of biomass to produce fermentable sugars and lignin using supercritical, almost supercritical and / or subcritical fluids. Background of the Invention
[0003] Biomass, especially lignocellulosic biomass, is an important raw material and can be processed into fuels or industrial chemicals. Current technology technologies are time consuming and therefore require a lot of capital investment. Supercritical solvents such as supercritical water and supercritical carbon dioxide have been used in the extraction of various substances and in the facilitation of chemical reactions. The useful applications of these value-added products increase the importance of supercritical fluid technology. Modifications to prior art techniques are necessary to improve the efficiency of converting biomass from renewable sources and / or waste to more valuable products. The methods and apparatus of the present invention are aimed at these, as well as other, important purposes. SUMMARY OF THE INVENTION
[0004] In one embodiment, the invention is directed to methods for the continuous treatment of biomass, comprising: the pre-treatment step, in which said biomass is contacted with a first supercritical, almost critical or subcritical fluid to form a matrix solid and the first net fraction; wherein said first supercritical, almost critical or subcritical fluid comprises water and, optionally, CO2; and wherein said first supercritical, almost critical or subcritical fluid is substantially free of C1-C5 alcohol; and a hydrolysis step, wherein said solid matrix is contacted with a second supercritical or quasi-supercritical fluid to produce a second liquid fraction (including soluble sugars and soluble lignin) and a fraction containing insoluble lignin; wherein said second supercritical or quasi-critical fluid comprises water and, optionally, CO2; and wherein said second supercritical or quasi-critical fluid is substantially free of C1-C5 alcohols.
[0005] In another embodiment, the invention is directed to methods for the continuous treatment of biomass, comprising: a pre-treatment step, in which said biomass is contacted with a first supercritical, almost critical or subcritical fluid to form a matrix solid and the first net fraction; wherein said first supercritical, almost critical or subcritical fluid comprises water and, optionally, CO2; and wherein said first supercritical, almost critical or subcritical fluid is substantially free of C1-C5 alcohol; and a first hydrolysis step, wherein said solid matrix is contacted with a second supercritical or quasi-supercritical fluid to produce a second liquid fraction (including soluble sugars and soluble lignin) and the fraction containing insoluble lignin; wherein said second supercritical or quasi-critical fluid comprises water and, optionally, CO2; wherein said second supercritical or quasi-critical fluid is substantially free of C1-C5 alcohols; a second hydrolysis step in which said second liquid fraction is contacted with a third quasi-critical or subcritical fluid to produce a third liquid fraction comprising glucose monomers; wherein said third quasi-critical or subcritical fluid comprises water and, optionally, acid.
[0006] In yet another modality, the invention is directed to methods for the continuous treatment of biomass, comprising: a pre-treatment step, in which said biomass is contacted with a first supercritical, almost critical or subcritical fluid to form a solid matrix and the first liquid fraction; wherein said first supercritical, almost critical or subcritical fluid comprises water and, optionally, CO2; and wherein said first supercritical, almost critical or subcritical fluid is substantially free of C1-C5 alcohol; a hydrolysis step; wherein said solid matrix is contacted with a second supercritical or quasi-supercritical fluid to produce a second liquid fraction (including soluble sugars and soluble lignin, if present) and a fraction containing insoluble lignin; wherein said second supercritical or quasi-critical fluid comprises water and, optionally, CO2; and wherein said second supercritical or quasi-critical fluid is substantially free of C1-C5 alcohols; and a xylooligosaccharide hydrolysis step, wherein said first liquid fraction is contacted with a fourth quasi-critical or subcritical fluid to produce a fourth liquid fraction comprising xylose monomers.
[0007] In another embodiment, the present invention is directed to methods for the continuous treatment of biomass, comprising: a pre-treatment step, in which said biomass is contacted with a first supercritical, almost critical or subcritical fluid to form a pretreated slurry comprising a solid matrix and a first liquid fraction comprising xylooligosaccharides; a first separation step, wherein said solid matrix and said first liquid fraction are separated; a first hydrolysis step, wherein said solid matrix is contacted with a second supercritical or quasi-critical fluid to form a fraction containing insoluble lignin and a second liquid fraction comprising cell oligosaccharides; a second separation step, wherein said fraction containing insoluble lignin and said second liquid fraction are separated; and a second hydrolysis step, wherein said second liquid fraction is contacted with a third quasi-critical or subcritical fluid to form a product comprising glucose monomers; and optionally, a third hydrolysis step, wherein said first liquid fraction is contacted with a fourth quasi-critical or subcritical fluid to form a second product comprising xylose monomers.
[0008] In yet other embodiments, the invention is directed to methods of increasing the level of xylose produced from biomass, comprising: the fractionation of said biomass to form: a solid fraction comprising: cellulose; and insoluble lignin; and the first liquid fraction at a first temperature and at a first pressure comprising:
[0009] A soluble C5 saccharide selected from the group consisting of xylooligosaccharides, xylose, and mixtures thereof; separating said solid fraction from said first liquid fraction at a second pressure; wherein said first pressure and said second pressure are substantially the same; adding to said first liquid fraction an aqueous acid to increase the level of said soluble Cs soluble in said liquid fraction to form a second liquid fraction at a second temperature; and optionally, hydrolysis of said second liquid fraction to form xylose.
[0010] In another embodiment, the invention is directed to the apparatus adapted to continuously convert the biomass comprising a pretreatment reactor and a hydrolysis reactor associated with said pretreatment reactor. BRIEF DESCRIPTION OF THE DRAWINGS
[0011] The attached drawings, which are included to provide an additional understanding of the invention and are incorporated into and constitute a part of this report, illustrate modalities of the invention and together with the description serve to explain the principles of the invention. In the drawings:
[0012] Figure 1 is a block diagram showing an embodiment of the method of the present invention.
[0013] Figure 2 is a block diagram showing an embodiment of the biomass pretreatment portion of the present invention.
[0014] Figure 3 describes a schematic representation of the introduction of biomass in a pretreatment reactor by extrusion according to an embodiment of the present invention.
[0015] Figure 4 is a sectional representation of a twin screw extruder useful for introducing biomass into a pretreatment reactor in a modality of the present invention.
[0016] Figure 5 shows typical yields (as a percentage of theoretical maximum for each component) for certain components of the resulting mixture obtained from the pre-treatment of biomass, according to a modality of the present invention.
[0017] Figure 6 describes a schematic representation of the solid-liquid separation achieved by the use of an extruder according to an embodiment of the present invention.
[0018] Figure 7 describes a schematic representation of the treatment of a solid matrix produced from the pre-treatment of biomass according to an embodiment of the present invention.
[0019] Figure 8 shows an example in the schematic form of incorporation of a solid matrix produced by pretreating biomass in a treatment reactor using an extruder and an eductor in accordance with an embodiment of the present invention.
[0020] Figure 9 describes a conical treatment reactor according to an embodiment of the present invention.
[0021] Figure 10 describes a continuously stirred treatment reactor according to an embodiment of the present invention.
[0022] Figure 11 describes an alternative embodiment of a continuously stirred treatment reactor according to one embodiment of the present invention.
[0023] Figure 12 shows yields (as a percentage of theoretical maximum for each component) for certain components of a mixture produced by treating a pre-treated solid matrix at 377 ° C as a function of residence time according to a embodiment of the present invention.
[0024] Figure 13 shows typical glucose monomer yields (as a percentage of the theoretical maximum glucose yield) as a function of the hydrolysis temperature according to an embodiment of the present invention.
[0025] Figure 14 shows total xylose monomer yields (as a percentage of the theoretical maximum xylose yield) as a function of the hydrolysis temperature at various residence times according to one embodiment of the present invention (continuous pretreatment of biomass).
[0026] Figure 15 shows xylose monomer yields (as a percentage of the theoretical maximum xylose yield) as a function of the hydrolysis temperature at various residence times with varying levels of sulfuric acid according to an embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION
[0027] As an employee above and through the description, it should be understood that the following terms, unless otherwise stated, have the following meanings.
[0028] As used here, the singular forms "one (s) / one (s)", and "o (s) / a (s)" include the plural reference unless the context clearly indicates otherwise.
[0029] Although the present invention is capable of being configured in various forms, the description below of several modalities is made with the understanding that the present description should be considered as an example of the invention, and is not intended to limit the invention to specific modalities illustrated. Titles are provided for convenience only and should not be constructed to limit the invention in any way. Modalities illustrated under any title can be combined with modalities illustrated under any other title.
[0030] The use of numerical values in the various quantitative values specified in this specification, unless expressly stated otherwise, are determined as approximations as difficult as the minimum and maximum values within the determined ranges were both preceded by the word "about ". In this way, slight variations of a determined value can be used to achieve substantially the same results as the determined value. The description of the ranges is also intended to be a continuous range including any value between the minimum and maximum values listed as well as any ranges that may be formed by such values. Also described here are any and all reasons (and ranges of any such reasons) that may be formed by dividing an enumerated numerical value into any other enumerated numerical value. Consequently, the person skilled in the art will appreciate that many such reasons, ranges, and ranges of ratios can be ambiguously derived from the numerical values presented here and in all cases such as ratios, ranges, and ranges of ratios represent various embodiments of the present invention.
[0031] As used herein, the term "substantially free of" refers to a composition having less than about 1% by weight, preferably less than about 0.5% by weight, and more preferably less than about 0.1% by weight, based on the total weight of the composition, of the material determined. Biomass
[0032] Biomass is a renewable energy source usually comprising carbon-based biological material derived from recently living organisms. The organisms may have been plants, animals, fungi, etc. Examples of biomass include, without limitation, wood, municipal solid waste, manufacturing waste, food waste, black solution (a by-product of wood pulping processes), etc. Fossil fuels are not generally considered to be biomass, although they are especially derived from carbon-based biological material. The term "biomass", as used here, does not include sources of fossil fuel.
[0033] Biomass can be processed to yield many different chemicals. Generally, biomass can be converted using thermal processes, chemical processes, enzymatic processes, or combinations thereof. Supercritical, subcritical and quasi-critical fluids.
[0034] A supercritical fluid is a fluid at a temperature above its critical temperature and at a pressure above its critical pressure. A supercritical fluid exists at or above its "critical point," the point of greatest temperature and pressure at which the liquid and vapor (gas) phases can exist in equilibrium with one another. Above the critical pressure and critical temperature, the distinction between the liquid and gas phases disappears. A supercritical fluid has approximately the penetration properties of a gas simultaneously with the solvent properties of a liquid. Consequently, the extraction of supercritical fluid has the benefit of high penetrability and good solvation.
[0035] Reported critical temperatures and pressures include: for pure water, a critical temperature of about 374.2 ° C, and a critical pressure of about 22.1 mPa (221 bar). Carbon dioxide has a critical point of about 31 ° C and about 72.9 atmospheres (about 1072 psig). Ethanol has a critical point of about 243 ° C and about 63 atmospheres. Methanol has a critical point of about 239 ° C (512.8 K) and about 1174.0 psia (80.9 bar). The critical point for other alcohols can be verified from the literature or experimentally.
[0036] Almost critical water has a temperature at or above about 300 ° C and below the critical water temperature (374.2 ° C), and a pressure high enough to ensure that all the fluid is in the liquid phase. Subcritical water has a temperature of less than about 300 ° C and a pressure high enough to ensure that all of the fluid is in the liquid phase. The temperature of subcritical water can be greater than about 250 ° C and less than about 300 ° C, and in many cases subcritical water has a temperature between about 250 ° C and about 280 ° C. The term "compressed hot water" is used interchangeably here for water that is at or above its critical state, or defined here as almost critical or subcritical, or any other temperature above about 50 ° C but, lower than that subcritical and at pressures such that the water is in a liquid state.
[0037] As used here, a fluid that is "supercritical" (for example, supercritical water, supercritical ethanol, supercritical CO2, etc.) indicates a fluid that would be supercritical if present in pure form under a given set of temperature conditions and pressure. For example, "supercritical water" indicates water present at a temperature of at least about 374.2 ° C and a pressure of at least about 22.1 mPa (221 bar), whether the water is pure water, or present as a mixture (eg water and ethanol, water and CO2, etc.). So, for example, "a mixture of subcritical water and supercritical carbon dioxide" indicates a mixture of water and carbon dioxide at a temperature and pressure above that critical point for carbon dioxide, but below the critical point for water, regardless of whether the supercritical phase contains water and regardless of whether the aqueous phase contains any carbon dioxide. For example, a mixture of subcritical water and supercritical CO2 can have a temperature of about 250 ° C to about 280 ° C and a pressure of at least about 22.5 mPa (225 bar).
[0038] As used here, "C1-C5 alcohol" indicates an alcohol comprising 1 to 5 carbon atoms. Examples of C1-C5 alcohols include, but are not limited to, methanol, ethanol, n-propanol, isopropanol, n-butanol, s-butanol, t-butanol, i-butanol, n-pentanol, 2-pentanol, 3- pentanol, 2-methyl-1-butanol, 2-methyl-2-butanol, 3-methyl 1-1-butanol, 3-methyl-2-butanol, and 2,2-dimethyl-1-propanol. Mixtures of one or more of these alcohols can be used.
[0039] As used here, "solid matrix" indicates a composition comprising a solid or particulate component.
[0040] As used here, "liquid fraction" indicates a liquid comprising at least one component of which is a product of a reaction or treatment step. For example, and without limitation, a liquid fraction after a hydrolysis step may include a product from the hydrolysis step with unreacted components and / or one or more additional products or by-products from the hydrolysis step and / or one or more products from a previous treatment stage.
[0041] As used here, "continuous" indicates a process in which it is uninterrupted for its duration, or interrupted, paused or suspended only momentarily in relation to the duration of the process. Biomass treatment is "continuous" when the biomass is fed into the apparatus without interruption or without substantial interruption, or processing of said biomass is not done in a batch process.
[0042] As used here, "lies" indicates the length of time for which a given portion or cake of material is within a reaction zone or reaction vessel. The "residence time" as used here, including examples and data, is reported under ambient conditions and is not necessarily the current elapsed time.
[0043] Figure 1 shows a schematic of an embodiment of a method of the invention of converting lignocellulosic biomass 102 into xylose (solution form) 107, glucose (solution form 115), and lignin (solid form) 116. Lignocellulosic biomass 102 is pretreated in a pretreatment reactor 101 using compressed hot water (HCW) 103 (where compressed hot water is under subcritical conditions) and, optionally, supercritical CO2 104 by hydrolyzing hemicellulose to hemicellulose sugars, for example, xylose and xylooligosaccharides. The resulting slurry 105 is subjected to solid / liquid (S / L) separation 106; the liquid phase contains hemicellulosic sugars and the solid phase contains most of glucan and lignin. Optionally, acid 108, preferably an inorganic acid (such as sulfuric acid), can be added separately or as part of the cooling fluid, not shown. The yields of hemicellulosic sugars in the solution and of glucan and lignin in the solid phase are typically> 80%,> 90%, and> 90% (of theory), respectively. This solid matrix 109 is mixed with water, and optionally preheated, then subjected to hydrolysis in a hydrolysis reactor 110 using supercritical and quasi-critical fluids. Supercritical water (SCW) 111 and supercritical CO2 112 (and optionally acid 113) act as glucan by selectively hydrolyzing it while most of the lignin remains insoluble. After solid / liquid separation 114, the liquid phase containing the hexose sugars 115 and the solid phase containing most of the lignin 116 are obtained. Optionally, an acid 113, preferably an inorganic acid (such as sulfuric acid), can be added as well as increasing the hydrolysis of the cellulose while slowing the solubilization of the lignin. Lignin serves as fuel 117 (as used in a boiler, not shown) while hexose and pentose sugars are raw materials for fermentations and in the derivation of high-value intermediates and chemicals. Pre-treatment of Biomass
[0044] In one embodiment of a method of the present invention, the biomass is subjected to continuous treatment comprising a pre-treatment step, in which said biomass is contacted with a first supercritical, almost critical or subcritical fluid to form a solid matrix and the first net fraction. In another embodiment, the supercritical or quasi-critical fluid comprises water and, optionally, carbon dioxide, and is substantially free of C1-C5 alcohols. In another embodiment, the supercritical or quasi-critical fluid comprises water and carbon dioxide. In the embodiments of the present invention where the supercritical or quasi-critical fluid comprises carbon dioxide, the amount of carbon dioxide present can be less than about 10%, less than about 9%, less than about 8%, less than about 7%, less than about 6%, less than about 5%, less than about 4%, less than about 3%, less than about 2%, or less than about 1%. In another embodiment, the supercritical or quasi-critical fluid does not include carbon dioxide. In another embodiment, the supercritical or quasi-critical fluid does not include an alcohol.
[0045] In another embodiment, the pre-treatment step occurs at a temperature and pressure above the critical point of at least one component of a fluid. In another embodiment, the pre-treatment step occurs at a temperature and pressure above the critical point for all components of the fluid. In another embodiment, the pretreatment step occurs at a temperature of about 180 ° C to about 260 ° C, for example, from about 185 ° C to about 255 ° C, from about 190 ° C to about 250 ° C, about 195 ° C to about 245 ° C, about 200 ° C to about 240 ° C, about 205 ° C to about 235 ° C, about 210 ° About 230 ° C, about 215 ° C to about 225 ° C, about 180 ° C, about 185 ° C, about 190 ° C, about 195 ° C, about 200 ° C , about 205 ° C, about 210 ° C, about 215 ° C, about 220 ° C, about 225 ° C, about 230 ° C, about 235 ° C, about 240 ° C, about 245 ° C, about 250 ° C, about 255 ° C, or about 260 ° C.
[0046] In another embodiment, the pretreatment step occurs at a pressure of about 5 mPa (50 bar) to about 11 mPa (110 bar), for example, from about 5 mPa (50 bar) to about 11 mPa (110 bar), about 6 mPa (60 bar) to about 10.5 mPa (105 bar), about 7 mPa (70 bar) to about 10 mPa (100 bar), about from 8 mPa (80 bar) to about 9.5 mPa (95 bar), about 5 mPa (50 bar), about 5.5 mPa (55 bar), about 6 mPa (60 bar), about 6.5 mPa (65 bar), about 7 mPa (70 bar), about 7.5 mPa (75 bar), about 8 mPa (80 bar), about 8.5 mPa (85 bar), about of 9 mPa (90 bar), about 9.5 mPa (95 bar), about 10 mPa (100 bar), about 10.5 mPa (105 bar), or about 11 mPa (110 bar).
[0047] In another embodiment, the pretreatment step occurs at a temperature of about 180 ° C to about 260 ° C and at a pressure of about 5 mPa (50 bar) to about 11 mPa (110 bar ). In another embodiment, the pre-treatment step occurs at a temperature of about 230 ° C to about 240 ° C and a pressure of about 5 mPa (50 bar).
[0048] In another embodiment, the biomass resides in the pre-treatment stage or about 1 to about 5 minutes, for example, about 1 minute, about 1.1 minutes, about 1.2 minutes, about 1.3 minutes, about 1.4 minutes, about 1.5 minutes, about 1.6 minutes, about 1.7 minutes, about 1.8 minutes, about 1.9 minutes, about 2 minutes, about 2.1 minutes, about 2.2 minutes, about 2.3 minutes, about 2.4 minutes, about 2.5 minutes, about 2.6 minutes, about 2.7 minutes , about 2.8 minutes, about 2.9 minutes, about 3 minutes, about 3.1 minutes, about 3.2 minutes, about 3.3 minutes, about 3.4 minutes, about 3.5 minutes, about 3.6 minutes, about 3.7 minutes, about 3.8 minutes, about 3.9 minutes, about 4 minutes, about 4.1 minutes, about 4.2 minutes, about 4.3 minutes, about 4.4 minutes, about 4.5 minutes, about 4.6 minutes, about 4.7 minutes, about 4.8 minutes, about 4.9 minutes , or about 5 m innutes.
[0049] In one embodiment, the products from the pre-treatment stage are cooled after the completion of the pre-treatment stage. Cooling can be accomplished by any means known in the art including, without limitation, direct cooling, indirect cooling, passive cooling, etc. The term "direct cooling" as used here indicates that a cooling fluid is contacted or mixed with the products of the pre-treatment step, where the cooling fluid has a lower temperature than the products of the pre-treatment step. For example, and without limitation, direct cooling can be accomplished by contacting the products of the pre-treatment step with a cooling fluid comprising water, where the cooling fluid has a lower temperature than the products of the pre-treatment step . In the direct cooling modes, the cooling fluid is in direct contact with and can mix with the products of the pretreatment stage. On the contrary, the term "indirect cooling" as used here indicates that cooling is carried out by means in which the products of the pre-treatment step are not contacted with or mixed with a cooling fluid. For example, and without limitation, indirect cooling can be performed by cooling at least a portion of the vessel in which the products of the pre-treatment step are located. In the indirect cooling modalities, the products of the pretreatment stage are not directly in contact with, and therefore, do not mix with the cooling fluid. The term "passive cooling" as used here indicates that the temperature of a pre-treated biomass is reduced without contacting a pre-treated biomass with a cooling fluid. For example, and without limitation, pre-treated biomass can be passively cooled by storing a pre-treated biomass in a holding tank or reservoir for a period of time during which the temperature of a pre-treated biomass decreases in response to ambient temperature conditions. Alternatively, the pre-treated biomass can be passively cooled by passing a pre-treated biomass through a tube or other means of conversion on the way to a second treatment reactor in which the tube or other means of transport is not cooled by contact with a cooling fluid. The term "cooling fluid" as used herein includes solids, liquids, gases, and combinations thereof. In cooling modes, whether direct or indirect, cooling can be carried out by means other than the use of a cooling fluid, for example, by induction. The term "heat exchange" as used here includes direct cooling, indirect cooling, passive cooling, and combinations thereof. Solid-liquid separation of pre-treated biomass
[0050] In one embodiment, a pre-treated biomass comprises a solid matrix and a liquid fraction. The solid fraction can comprise, for example, cellulose and lignin, while the liquid fraction can comprise, for example, xylooligosaccharides. In one embodiment, the solid fraction and the liquid fraction are separated. Separation can occur, for example, by filtration, centrifugation, extrusion, etc.
[0051] In one embodiment, the solid fraction and the liquid fraction are separated by extrusion. This is generally shown in figure 6, where a motor 602 is used to drive the threads of extruder 601 into a barrel of extruder 603 to move the pretreatment hydrolysis slurry or cellulose 604 into the extruder. A dynamic plug 605 of the extruded material is formed, creating a low pressure zone prior to the plug and a high pressure zone in addition to the plug in the extruder barrel. The liquid fraction is compressed from the wet extruded material 606 before the dynamic buffer 605. The solid fraction 607 (for example, in -45% solids) exits through the extruder. The thread pitch is defined as the distance between a top of the thread to the next top of the thread. The term "variable pitch thread" indicates a threaded thread having more than one pitch along the axis. Therefore, according to one embodiment, an extruder for the separation of the solid matrix and the liquid fraction comprises a plurality of variable pitch threads. In one embodiment, the thread (s) of the extruder is (are) driven by one or more motors. Pre-treated Solid Matrix Hydrolysis
[0052] In one embodiment, the solid matrix formed during the pre-treatment is subjected to further processing. In one embodiment, the solid matrix is contacted with a second supercritical or quasi-critical fluid. In a related modality, the second supercritical or quasi-critical fluid is the same as the first supercritical, quasi-critical or subcritical fluid used during the pre-treatment step. In another embodiment, the second supercritical or quasi-critical fluid is different from the first supercritical, quasi-critical or subcritical fluid used during the pre-treatment step. For example, and without limitation, the second supercritical or quasi-critical fluid may comprise one or more additional components or one or more components compared to the first supercritical, quasi-critical or subcritical fluid. Alternatively, the second supercritical or quasi-critical fluid may comprise the same components as the first supercritical, quasi-critical or subcritical fluid, but at a different rate than the first supercritical, quasi-critical or subcritical fluid. In another embodiment, the second supercritical or quasi-critical fluid has the same components as the first supercritical, quasi-critical or subcritical fluid, optionally for the same reasons, but is used at a different temperature and / or pressure than the first supercritical, quasi-critical fluid or subcritical. In a related embodiment, the temperature and pressure of the second supercritical or quasi-critical fluid differs from that of the first supercritical, quasi-critical or subcritical fluid such that one or more components of the second supercritical or quasi-critical fluid are in a different state than they are in when in the first supercritical, almost critical or subcritical fluid. For example, and without limitation, the first and second supercritical or quasi-critical fluids may each comprise water and carbon dioxide, but the temperature and pressure of the first supercritical, quasi-critical or subcritical fluid is such that both components are in the supercritical state , while the temperature and pressure of the second supercritical or quasi-critical fluid is such that the water is in an almost critical or subcritical state.
[0053] In one embodiment, the second supercritical or quasi-critical fluid comprises water and, optionally, carbon dioxide, and is substantially free of C1-C5 alcohols. In another embodiment, the second supercritical or quasi-critical fluid comprises water and carbon dioxide. In the embodiments of the present invention where the second supercritical or quasi-critical fluid comprises carbon dioxide, the amount of carbon dioxide present can be less than about 10%, less than about 9%, less than about 8% less than about 7%, less than about 6%, less than about 5%, less than about 4%, less than about 3%, less than about 2%, or less than about 1%. In another embodiment, the second supercritical or quasi-critical fluid does not include carbon dioxide.
[0054] In one embodiment, the solid matrix has a residence time in the hydrolysis step of about 1 second to about 30 seconds. In another embodiment, the solid matrix has a residence time in the hydrolysis step of about 1 second to about 30 seconds. In another embodiment, the solid matrix has a residence time in the hydrolysis step of about 1 second to about 20 seconds. In another embodiment, the solid matrix has a residence time in the hydrolysis step of about 1 second to about 15 seconds. In another embodiment, the solid matrix has a residence time in the hydrolysis step of about 1 second to about 10 seconds. In another embodiment, the solid matrix has a residence time in the hydrolysis step of about 1 second to about 5 seconds. In another embodiment, the solid matrix has a residence time in the hydrolysis step of about 1 second to about 4 seconds. In another embodiment, the solid matrix has a residence time in the hydrolysis step of about 1 second to about 3 seconds. In another embodiment, the solid matrix has a residence time in the hydrolysis step of about 1 second to about 2 seconds. In another embodiment, the solid matrix has a residence time in the hydrolysis step of less than about 1 second. In another embodiment, the solid matrix has a residence time in the hydrolysis step of about 1 second, about 1.1 seconds, about 1.2 seconds, about 1.3 seconds, about 1.4 seconds, about 1.5 seconds, about 1.6 seconds, about 1.7 seconds, about 1.8 seconds, about 1.9 seconds, or about 2 seconds.
[0055] In one embodiment, the hydrolysis step occurs at a temperature above the critical temperature of one or more components of the second supercritical or quasi-critical fluid. In another embodiment, the hydrolysis step occurs at a temperature of about 275 ° C to about 450 ° C. In another embodiment, the hydrolysis step occurs at a temperature of about 300 ° C to about 440 ° C. In another embodiment, the hydrolysis step occurs at a temperature of about 320 ° C to about 420 ° C. In another embodiment, the hydrolysis step occurs at a temperature of about 340 ° C to about 400 ° C. In another embodiment, the hydrolysis step occurs at a temperature of about 350 ° C to about 390 ° C. In another embodiment, the hydrolysis step occurs at a temperature of about 360 ° C to about 380 ° C. In another embodiment, the hydrolysis step occurs at a temperature of about 370 ° C to about 380 ° C. In another embodiment, the hydrolysis step occurs at a temperature of about 377 ° C.
[0056] In one embodiment, the hydrolysis step occurs at a pressure above the critical pressure of one or more components of the second supercritical or quasi-critical fluid. In another embodiment, the hydrolysis step occurs at a pressure of about 20 mPa (200 bar) to about 25 mPa (250 bar). In another embodiment, the hydrolysis step occurs at a pressure of about 21 mPa (210 bar) to about 24 mPa (240 bar). In another embodiment, the hydrolysis step occurs at a pressure of about 22 mPa (220 bar) to about 23 mPa (230 bar). In another embodiment, the hydrolysis step occurs at a pressure of about 20 mPa (200 bar), about 20.5 mPa (205 bar), about 21 mPa (210 bar), about 21.5 mPa (215 bar), about 22 mPa (220 bar), about 22.5 mPa (225 bar), about 23 mPa (230 bar), about 23.5 mPa (235 bar), about 24 mPa (240 bar) )), about 24.5 mPa (245 bar), or about 25 mPa (250 bar).
[0057] In one embodiment, the hydrolysis step occurs at a temperature and pressure above the critical temperature and critical pressure, respectively, of one or more components of the second supercritical or quasi-critical fluid. In another embodiment, the hydrolysis step occurs at a temperature of about 300 ° C to about 440 ° C and a pressure of about 20 mPa (200 bar) to about 25 mPa (250 bar).
[0058] In one embodiment, the solid matrix is fed into a hydrolysis or treatment reactor by an extruder. In a related embodiment, the extruder comprises one to a plurality of threads. In a related embodiment, the extruder consists of two threads (the "twin screw extruder"). In another embodiment, the extruder comprises a plurality of variable pitch threads.
[0059] In one embodiment, the solid matrix is fed into a hydrolysis reactor (not shown) by an eductor associated with the hydrolysis reactor. In one embodiment, steam 803 is used to propel or drag a solid matrix 801 through eductor 802 and into the hydrolysis reactor (not shown), as shown, for example, in figure 8, using an extruder 805 to move the solids fed 804 into the 802 eductor.
[0060] In one embodiment, hydrolysis occurs in a hydrolysis reactor. In one embodiment, the hydrolysis reactor comprises a 901 conical reactor, as shown in figure 9. In another embodiment, the hydrolysis reactor comprises a tank reactor. In one embodiment, the contents of the hydrolysis reactor are agitated during hydrolysis. In a related embodiment, the contents of the hydrolysis reactor are continuously agitated. The term "continuously stirred" or alternatively "continuously stirred" as used here indicates that the contents of the reactor are stirred, mixed, etc. during most of the hydrolysis step, during substantially the entire hydrolysis step, or during the entire hydrolysis step. Brief or intermittent periods of time during which the contents of the reactor are not agitated are within the meaning of "continuously agitated" and "continuously agitated" as used here. Agitation or movement can be carried out by any means known in the art including, without limitation, agitation or mechanical movement, by vibrations, or by non-uniform injection of the supercritical fluid into the hydrolysis reactor. In one embodiment, agitation is performed by an impeller associated with a 903 motor. In a related embodiment, the impeller is associated with a 904 shaft which in turn is associated with a 903 motor. In a related embodiment, the impeller is helically associated with the axis. In another embodiment, the impeller is associated circumferentially with the shaft. In a related embodiment, the impeller comprises a helical impeller 1001, as shown, for example, in figure 10. In another embodiment, the impeller comprises flexible blades 1002. In another embodiment, the impeller comprises a plurality of blades, as shown, for example. example, in figure 11 with impeller blades 1101a, 1101b, 1101c, 1101 d, and 110le. In another embodiment, the impeller comprises a plurality of helical blades.
[0061] In one embodiment, the hydrolysis reactor comprises a tube (that is, a tubular hydrolysis reactor). In a related embodiment, the tubular hydrolysis reactor is an extruder. In a related embodiment, the extruder comprises a screw. In another embodiment, the extruder comprises a plurality of threads. In another embodiment, one or more threads of the extruder are threads of variable pitch. In another embodiment, one or more extruder threads are associated with one or more motors. In an embodiment in which the extruder comprises two or more threads, said threads rotate together. In an embodiment in which the extruder includes two threads (a "twin screw extruder"), said threads 601 rotate together, as shown in figure 6. In an embodiment in which the extruder is a twin thread extruder, said threads turn in reverse.
[0062] In one embodiment, the solid matrix is maintained at a temperature of at least about 175 ° C, at least about 180 ° C, at least about 185 ° C, at least about 190 ° C, at least about 195 ° C, or at least about 200 ° C from the start of the pre-treatment step to at least the end of the hydrolysis step. The term "kept at a temperature of at least" as used here indicates that the temperature of a solid matrix does not fall significantly below the specified temperature.
[0063] In one embodiment, hydrolysis of a solid matrix according to a process of the present invention produces at least an insoluble fraction of lignin and a second liquid fraction (including soluble sugars and soluble lignin, if present). In one embodiment, the second liquid fraction comprises glucose, cell-oligosaccharides, and soluble lignin, if present. In one embodiment, the insoluble fraction of lignin comprises insoluble lignin. In another embodiment, the second liquid fraction comprises glucose and cell oligosaccharides and the insoluble fraction of lignin comprises insoluble lignin.
[0064] In one embodiment, at least one of the insoluble fraction of lignin and the second liquid fraction is cooled after a hydrolysis step. In one embodiment, cooling occurs before the insoluble fraction of lignin and the second liquid fraction are separated. In another mode, cooling occurs after the insoluble fraction of lignin and the second liquid fraction are separated. In another embodiment, at least a portion of the cooling step occurs concurrently with the separation of the insoluble fraction of lignin and the second liquid fraction. In one embodiment, one or more of the insoluble fraction of lignin and the second liquid fraction are cooled to a temperature of about 180 ° C to about 240 ° C, about 185 ° C to about 235 ° C, about 190 ° C to about 230 ° C, about 195 ° C to about 225 ° C, about 200 ° C to about 220 ° C, about 205 ° C to about 215 ° C, about 180 ° C, about 185 ° C, about 190 ° C, about 195 ° C, about 200 ° C, about 205 ° C, about 210 ° C, about 215 ° C, about 220 ° C, about 225 ° C, about 230 ° C, about 235 ° C, or about 240 ° C.
[0065] In one modality, one or more of the insoluble fraction of lignin and the second liquid fraction are suddenly cooled. In another embodiment, one or more of the insoluble fraction of lignin and the second liquid fraction are quenched to a temperature of about 20 ° C to about 90 ° C, about 25 ° C to about 85 ° C, about from 30 ° C to about 80 ° C, about 35 ° C to about 75 ° C, about 40 ° C to about 70 ° C, about 45 ° C to about 65 ° C, about 50 ° C to about 60 ° C, about 20 ° C, about 25 ° C, about 30 ° C, about 35 ° C, about 40 ° C, about 45 ° C, about 50 ° C , about 55 ° C, about 60 ° C, about 65 ° C, about 70 ° C, about 75 ° C, about 80 ° C, about 85 ° C, or about 90 ° C. In one embodiment, one or more of the insoluble fraction of lignin and the second liquid fraction are quenched after a hydrolysis step, but before any separation step. In a related modality, one or more of the insoluble fraction of lignin and the second liquid fraction are quenched without any initial cooling after hydrolysis. In another embodiment, one or more of the insoluble lignin fraction and the second liquid fraction are cooled down sharply after the first separation of the insoluble lignin fraction from the second liquid fraction. In another embodiment, at least a portion of the sudden cooling step occurs concurrently with a separation step. In another embodiment, one or more of the insoluble fraction of lignin and the second liquid fraction are quenched after the first cooling to a temperature of about 180 ° C to about 240 ° C, about 185 ° C to about 235 ° C, about 190 ° C to about 230 ° C, about 195 ° C to about 225 ° C, about 200 ° C to about 220 ° C, about 205 ° C to about 215 ° C , about 180 ° C, about 185 ° C, about 190 ° C, about 195 ° C, about 200 ° C, about 205 ° C, about 210 ° C, about 215 ° C, about 220 ° C, about 225 ° C, about 230 ° C, about 235 ° C, or about 240 ° C.
[0066] Cooling and / or rough cooling can be performed by any means known in the art including, without limitation, the extraction or removal of water from the mixture, quickly reducing the pressure exerted on the mixture, contacting the mixture with a relatively refrigerant gas , liquid or other material, etc. Separation of the Hydrolyzed Mixture
[0067] In one embodiment, the insoluble fraction of lignin and the second liquid fraction are separated by extrusion. In a related embodiment, extrusion takes place in an extruder. In a related embodiment, an extruder used to separate the insoluble fraction of lignin and the second liquid fraction comprises one of a plurality of threads. In a related embodiment, the extruder includes two threads. This is generally shown in figure 6, where a motor 602 is used to drive the threads of extruder 601 into a barrel of extruder 603 to move the pretreatment hydrolysis slurry or cellulose 604 into the extruder. A dynamic plug 605 of the extruded material is formed, creating a low pressure zone prior to the plug and a high pressure zone in addition to the plug in the extruder barrel. The liquid fraction is compressed from the wet extruded material 606 before the dynamic buffer 605. The solid fraction 606 (for example, -45% solids) exits through the extruder. In one embodiment, an extruder for separating a solid matrix and the liquid fraction can comprise one of a plurality of variable pitch threads. In one embodiment, the thread (s) of the extruder is (are) rotationally associated with, or driven by, one or more motors.
[0068] In one embodiment, the pre-treated biomass temperature is maintained above about 185 ° C through a hydrolysis step, and thereafter the temperature is reduced to about 220 ° C before the slurry is suddenly cooled. hydrolyzed by rapidly reducing pressure to about atmospheric pressure. In a related modality, the separation of the insoluble fraction of lignin from the second liquid fraction is achieved by skimming or filtration. In a related embodiment, the temperature of the hydrolyzed slurry is reduced such that the lignin precipitates. In a related embodiment, lignin precipitates without the addition of a precipitating or flocculating agent. In another embodiment, the pressure exerted on the products of the hydrolysis step is reduced to about 105 kPa or less, or about 101,325 kPa or less after the hydrolysis step. Hydrolysis of Celo-oligosaccharides
[0069] One embodiment includes a second hydrolysis step in which the second liquid fraction is contacted with a third quasi-critical or subcritical fluid to produce a third liquid fraction comprising glucose monomers.
[0070] In one embodiment, a second hydrolysis step occurs at a temperature that is greater than the critical temperature of at least one component of the fluid. In another embodiment, a second hydrolysis step occurs at a temperature of about 220 ° C to about 320 ° C, about 230 ° C to about 310 ° C, about 240 ° C to about 300 ° C, about 250 ° C to about 290 ° C, about 260 ° C to about 280 ° C, about 220 ° C, about 230 ° C, about 240 ° C, about 250 ° C, about 260 ° C, about 270 ° C, about 280 ° C, about 290 ° C, about 300 ° C, about 310 ° C, or about 320 ° C.
[0071] In one embodiment, the second hydrolysis step occurs at a pressure greater than the critical pressure of at least one component of the fluid. In another embodiment, a second hydrolysis step occurs at a pressure of about 3 mPa (30 bar) to about 9 mPa (90 bar), about 3.5 mPa (35 bar) to about 8.5 mPa ( 85 bar), about 4 mPa (40 bar) to about 8 mPa (80 bar), about 4.5 mPa (45 bar) to about 7.5 mPa (75 bar), about 5 mPa (50 bar) at about 7 mPa (70 bar), about 5.5 mPa (55 bar) at about 6.5 mPa (65 bar), about 3 mPa (30 bar), about 3.5 mPa ( 35 bar), about 4 mPa (40 bar), about 4.5 mPa (45 bar), about 5 mPa (50 bar), about 5.5 mPa (55 bar), about 6 mPa (60 bar), about 6.5 mPa (65 bar), about 7 mPa (70 bar), about 7.5 mPa (75 bar), about 8 mPa (80 bar), about 8.5 mPa ( 85 bar), or about 9 mPa (90 bar).
[0072] In one embodiment, a second hydrolysis step occurs at a temperature and pressure greater than the critical temperature and critical pressure, respectively, of one or more components of the fluid. In another embodiment, a second hydrolysis step occurs at a temperature of about 220 ° C to about 320 ° C, about 230 ° C to about 310 ° C, about 240 ° C to about 300 ° C, about 250 ° C to about 290 ° C, about 260 ° C to about 280 ° C, about 220 ° C, about 230 ° C, about 240 ° C, about 250 ° C, about 260 ° C, about 270 ° C, about 280 ° C, about 290 ° C, about 300 ° C, about 310 ° C, or about 320 ° C, and the pressure is about 3 mPa ( 30 bar) to about 9 mPa (90 bar), about 3.5 mPa (35 bar) to about 8.5 mPa (85 bar), about 4 mPa (40 bar) to about 8 mPa (80 bar), about 4.5 mPa (45 bar) to about 7.5 mPa (75 bar), about 5 mPa (50 bar) to about 7 mPa (70 bar), about 5.5 mPa ( 55 bar) at about 6.5 mPa (65 bar), about 3 mPa (30 bar), about 3.5 mPa (35 bar), about 4 mPa (40 bar), about 4.5 mPa (45 bar), about 5 mPa (50 bar), about 5.5 mPa (55 bar), about 6 mPa (60 bar), about 6.5 mPa (65 bar), about 7 mP a (70 bar), about 7.5 mPa (75 bar), about 8 mPa (80 bar), about 8.5 mPa (85 bar), or about 9 mPa (90 bar).
[0073] In one embodiment, the third almost critical or subcritical fluid comprises water. In another embodiment, the third quasi-critical or subcritical fluid still comprises acid (either an inorganic acid or an organic acid). In another embodiment, the third quasi-critical or subcritical fluid still comprises carbon dioxide. In another embodiment, the third quasi-critical or subcritical fluid comprises water and acid. In another embodiment, the third quasi-critical or subcritical fluid comprises an alcohol. In another embodiment, the third quasi-critical or subcritical fluid does not include an alcohol. In another embodiment, the third quasi-critical or subcritical fluid comprises water, carbon dioxide, and an acid.
[0074] In embodiments where the third quasi-critical or subcritical fluid comprises an acid, the amount of acid may be present in an amount of about 0.1% to about 2%, about 0.1% to about 1 , 5%, about 0.1% to about 1%, about 0.1% to about 0.5%, about 0.1% to about 0.4%, about 0.1% about 0.3%, about 0.1% to about 0.2%, about 0.5% to about 2%, about 0.5% to about 1.5%, about 0.5% to about 1%, less than about 2%, less than about 1.5%, less than about 1%, less than about 0.5%, less than about 0.4%, less than about 0.3%, less than about 0.2%, or less than about 0.1%. In another embodiment, the third quasi-critical or subcritical fluid comprises a catalytic amount of acid. In modalities where the third quasi-critical or subcritical fluid comprises an acid (either an inorganic acid or an organic acid). Suitable inorganic acids include, but are not limited to: sulfuric acid, sulfonic acid, phosphoric acid, phosphonic acid, nitric acid, nitrous acid, hydrochloric acid, hydrofluoric acid, hydrobromic acid, hydroiodic acid. Suitable organic acids include, but are not limited to, aliphatic carboxylic acids (such as acetic acid and formic acid), aromatic carboxylic acids (such as benzoic acid and salicylic acid), dicarboxylic acids (such as oxalic acid, phthalic acid, sebacic acid , and adipic acid), aliphatic fatty acids (such as oleic acid, palmitic acid, and stearic acid), aromatic fatty acids (such as phenyl stearic acid), and amino acids. The acid can be selected from the group consisting of hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, sulfonic acid, phosphoric acid, phosphonic acid, nitric acid, nitrous acid, and combinations thereof.
[0075] In embodiments where the third almost critical or subcritical fluid comprises carbon dioxide, the amount of carbon dioxide present can be less than about 10%, less than about 9%, less than about 8% less than about 7%, less than about 6%, less than about 5%, less than about 4%, less than about 3%, less than about 2%, or less than about 1% by weight based on the weight of the third quasi-critical or subcritical fluid. In another embodiment, the third quasi-critical or subcritical fluid does not include carbon dioxide.
[0076] In one embodiment, the second liquid fraction has a residence time in a second hydrolysis step of about 1 second to about 30 seconds, about 1 second to about 25 seconds, about 1 second to about 20 seconds, about 1 second to about 15 seconds, about 1 second to about 10 seconds, about 1 second to about 5 seconds, about 5 seconds to about 30 seconds, about 5 seconds to about 25 seconds, about 5 seconds to about 20 seconds, about 5 seconds to about 15 seconds, about 5 seconds to about 10 seconds, about 1 second, about 1.1 seconds, about 1.2 second, about 1.3 seconds, about 1.4 seconds, about 1.5 seconds, about 1.6 seconds, about 1.7 seconds, about 1.8 seconds, about 1.9 seconds , about 2 seconds, about 2.1 seconds, about 2.2 seconds, about 2.3 seconds, about 2.4 seconds, about 2.5 seconds, about 2.6 seconds, about 2.7 seconds, about 2.8 seconds, about 2.9 seconds, about 3 seconds, about 4 seconds, about 5 seconds, about 6 seconds, about 7 seconds, about 8 seconds, about 9 seconds, about 10 seconds, about 15 seconds, about 20 seconds, about 25 seconds, or about 30 seconds.
[0077] In one embodiment, the products of a second hydrolysis stage are cooled after the completion of the hydrolysis stage. Cooling can be performed by any means known in the art including, without limitation, direct cooling, indirect cooling, passive cooling, etc. The term "direct cooling" as used here indicates that a cooling fluid is contacted or mixed with the products of a second hydrolysis step, where the cooling fluid has a lower temperature than the products of a second hydrolysis step. For example, and without limitation, direct cooling can be accomplished by contacting the products of a second hydrolysis step with a cooling fluid comprising water, where the cooling fluid has a lower temperature than the products of a second hydrolysis step. hydrolysis. In the direct cooling modes, the cooling fluid is in direct contact with and can be mixed with the products of the second hydrolysis step. On the contrary, the term "indirect cooling" as used here indicates that cooling is carried out by means in which the products of a second hydrolysis step are not contacted with or mixed with a cooling fluid. For example, and without limitation, indirect cooling can be performed by cooling at least a portion of the vessel in which the products of a second hydrolysis step are located. In the indirect cooling modalities, the products of a second hydrolysis stage are not directly in contact with, and, therefore, do not mix with the cooling fluid. The term "passive cooling" as used here indicates that the temperature of pre-treated biomass is reduced without contacting a pre-treated biomass with a cooling fluid. For example, and without limitation, products from a second hydrolysis step can be passively cooled by storing the products in a storage tank or reservoir for a period of time during which the temperature of the products decreases in response to ambient temperature conditions. . Alternatively, the products of a second hydrolysis step can be passively cooled by passing the products through a tube or other carrier where the tube or other carrier is not cooled by contact with a cooling fluid. The term "coolant" used here includes solids, liquids, gases, and combinations thereof. In both direct and indirect cooling modes, cooling can be carried out by means other than the use of a cooling fluid, for example, by induction. The term "heat exchange" as used here includes direct cooling, indirect cooling, and combinations thereof.
[0078] In one embodiment, the third liquid fraction comprises glucose. In one embodiment, the third liquid fraction comprises glycolaldehyde. In a related embodiment, glycolaldehyde is present in the third liquid fraction in an amount of at least about 5%, at least about 10%, at least about 12%, at least about 15%, at least about 20% at least about 25%, at least about 30%, at least about 35%, at least about 40%, at least about 45%, at least about 50%, at least about 55%, at least about 60%, at least about 65%, at least about 70%, at least about 75%, at least about 80%, at least about 85%, at least about 90%, at least minus about 95%, or about 100% of the maximum theoretical glycolaldehyde yield. In one embodiment, glycolaldehyde is present in the third liquid fraction in an amount less than the amount of glucose present in the third liquid fraction. In one embodiment, glycolaldehyde is present in the third liquid fraction in an amount greater than the amount of glucose present in the third liquid fraction. Xyloligosaccharide hydrolysis
[0079] In one embodiment, the first liquid fraction formed by the pre-treatment of biomass is contacted with a fourth quasi-critical or subcritical fluid to produce a fourth liquid fraction comprising xylose monomers.
[0080] In one embodiment, the fourth almost critical or subcritical fluid comprises water. In another embodiment, the fourth quasi-critical or subcritical fluid comprises carbon dioxide. In another embodiment, the fourth quasi-critical or subcritical fluid comprises water and carbon dioxide. In another embodiment, the fourth quasi-critical or subcritical fluid comprises an alcohol. In another embodiment, the fourth quasi-critical or subcritical fluid does not include an alcohol. In another embodiment, the fourth quasi-critical or subcritical fluid comprises an acid.
[0081] In another embodiment, the fourth quasi-critical or subcritical fluid comprises water, carbon dioxide, and an acid.
[0082] In embodiments where the fourth almost critical or subcritical fluid comprises carbon dioxide, an amount of carbon dioxide present can be less than about 10%, less than about 9%, less than about 8% less than about 7%, less than about 6%, less than about 5%, less than about 4%, less than about 3%, less than about 2%, or less than about 1%. In another embodiment, the fourth quasi-critical or subcritical fluid does not include carbon dioxide.
[0083] In embodiments where the fourth quasi-critical or subcritical fluid comprises an acid, the amount of acid may be present in an amount of about 0.1% to about 2%, about 0.1% to about 1 , 5%, about 0.1% to about 1%, about 0.1% to about 0.5%, about 0.1% to about 0.4%, about 0.1% about 0.3%, about 0.1% to about 0.2%, about 0.5% to about 2%, about 0.5% to about 1.5%, about 0.5% to about 1%, less than about 2%, less than about 1.5%, less than about 1%, less than about 0.5%, less than about 0.4%, less than about 0.3%, less than about 0.2%, or less than about 0.1%. In another embodiment, the quasi-critical or subcritical fluid comprises a catalytic amount of acid. In modalities where the fourth quasi-critical or subcritical fluid comprises an acid (either an inorganic acid or an organic acid). Suitable inorganic acids include, but are not limited to: sulfuric acid, sulfonic acid, phosphoric acid, phosphonic acid, nitric acid, nitrous acid, hydrochloric acid, hydrofluoric acid, hydrobromic acid, hydroiodic acid. Suitable organic acids include, but are not limited to, aliphatic carboxylic acids (such as acetic acid and formic acid), aromatic carboxylic acids (such as benzoic acid and salicylic acid), dicarboxylic acids (such as oxalic acid, phthalic acid, sebacic acid , and adipic acid), aliphatic fatty acids (such as oleic acid, palmitic acid, and stearic acid), aromatic fatty acids (such as phenyl stearic acid), and amino acids. The acid can be selected from the group consisting of hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, sulfonic acid, phosphoric acid, phosphonic acid, nitric acid, nitrous acid, and combinations thereof.
[0084] In one embodiment, the first liquid fraction has a residence time in the xylooligosaccharide hydrolysis step of about 1 second to about 30 seconds, about 1 second to about 25 seconds, about 1 second to about 20 seconds, about 1 second to about 15 seconds, about 1 second to about 10 seconds, about 1 second to about 5 seconds, about 5 seconds to about 30 seconds, about 2 seconds to about 25 seconds, about 5 seconds to about 25 seconds, about 5 seconds to about 20 seconds, about 5 seconds to about 15 seconds, about 5 seconds to about 10 seconds, about 10 seconds to about 15 seconds, about 1 second, about 1.1 seconds, about 1.2 seconds, about 1.3 seconds, about 1.4 seconds, about 1.5 seconds, about 1.6 second, about 1.7 seconds, about 1.8 seconds, about 1.9 seconds, about 2 seconds, about 2.1 seconds, about 2.2 seconds, about 2.3 seconds , about 2.4 seconds, about 2.5 seconds, about 2.6 seconds, about 2.7 seconds, about 2.8 seconds, about 2.9 seconds, about 3 seconds, about 4 seconds, about 5 seconds, about 6 seconds, about 7 seconds, about 8 seconds, about 9 seconds, about 10 seconds, about 15 seconds, about 20 seconds, about 25 seconds, or about 30 seconds.
[0085] In one embodiment, the xylooligosaccharide hydrolysis step occurs at a temperature that is greater than the critical temperature of at least one component of the fourth fluid. In another embodiment, a second hydrolysis step occurs at a temperature of about 220 ° C to about 320 ° C, about 230 ° C to about 310 ° C, about 240 ° C to about 300 ° C, about 250 ° C to about 290 ° C, about 260 ° C to about 280 ° C, about 220 ° C, about 230 ° C, about 240 ° C, about 250 ° C, about 260 ° C, about 270 ° C, about 280 ° C, about 290 ° C, about 300 ° C, about 310 ° C, or about 320 ° C.
[0086] In one embodiment, the xylooligosaccharide hydrolysis step occurs at a pressure greater than the critical pressure of at least one component of the fourth fluid. In another embodiment, the second hydrolysis step occurs at a pressure of about 3 mPa (30 bar) to about 9 mPa (90 bar), about 3.5 mPa (35 bar) to about 8.5 mPa ( 85 bar), about 4 mPa (40 bar) to about 8 mPa (80 bar), about 4.5 mPa (45 bar) to about 7.5 mPa (75 bar), about 5 mPa (50 bar) at about 7 mPa (70 bar), about 5.5 mPa (55 bar) at about 6.5 mPa (65 bar), about 3 mPa (30 bar), about 3.5 mPa ( 35 bar), about 4 mPa (40 bar), about 4.5 mPa (45 bar), about 5 mPa (50 bar), about 5.5 mPa (55 bar), about 6 mPa (60 bar), about 6.5 mPa (65 bar), about 7 mPa (70 bar), about 7.5 mPa (75 bar), about 8 mPa (80 bar), about 8.5 mPa ( 85 bar), or about 9 mPa (90 bar).
[0087] In one embodiment, the xylooligosaccharide hydrolysis step occurs at a temperature and pressure greater than the critical temperature and critical pressure, respectively, of one or more components of the fourth fluid. In another embodiment, the xylooligosaccharide hydrolysis step occurs at a temperature of about 220 ° C to about 320 ° C, about 230 ° C to about 310 ° C, about 240 ° C to about 300 ° C, about 250 ° C to about 290 ° C, about 260 ° C to about 280 ° C, about 220 ° C, about 230 ° C, about 240 ° C, about 250 ° C , about 260 ° C, about 270 ° C, about 280 ° C, about 290 ° C, about 300 ° C, about 310 ° C, or about 320 ° C, and the pressure of about 3 mPa (30 bar) to about 9 mPa (90 bar), about 3.5 mPa (35 bar) to about 8.5 mPa (85 bar), about 4 mPa (40 bar) to about 8 mPa (80 bar), about 4.5 mPa (45 bar) to about 7.5 mPa (75 bar), about 5 mPa (50 bar) to about 7 mPa (70 bar), about 5, 5 mPa (55 bar) to about 6.5 mPa (65 bar), about 3 mPa (30 bar), about 3.5 mPa (35 bar), about 4 mPa (40 bar), about 4 , 5 mPa (45 bar), about 5 mPa (50 bar), about 5.5 mPa (55 bar), about 6 mPa (60 bar), about 6.5 mPa (65 bar), about 7 mPa (70 bar), about 7.5 mPa (75 bar), about 8 mPa (80 bar), about 8.5 mPa (85 bar), or about 9 mPa (90 bar).
[0088] In one embodiment, the products of the xylooligosaccharide hydrolysis step are cooled after the completion of the xylooligosaccharide hydrolysis step. Cooling can be carried out by any means known in the art including, without limitation, direct cooling or indirect cooling. The term "direct cooling" as used here indicates that a cooling fluid is contacted or mixed with the products of the xylooligosaccharide hydrolysis step, where the cooling fluid has a lower temperature than the products of the hydrolysis step of xylooligosaccharide. For example, and without limitation, direct cooling can be accomplished by contacting the products of the xylooligosaccharide hydrolysis step with a cooling fluid comprising water, where the cooling fluid has a lower temperature than the products of the xylooligosaccharide hydrolysis. In direct cooling modes, the cooling fluid is in direct contact with and can be mixed with the products of the xylooligosaccharide hydrolysis step. On the contrary, the term "indirect cooling" as used here indicates that cooling is carried out by means in which the products of the xylooligosaccharide hydrolysis step are not contacted with or mixed with a cooling fluid. For example, and without limitation, indirect cooling can be performed by cooling at least a portion of the vessel in which the products of the xylooligosaccharide hydrolysis step are located. In indirect cooling modes, the products of the xylooligosaccharide hydrolysis step are not directly in contact with, and therefore do not mix with, the cooling fluid. The term "cooling fluid" as used herein includes solids, liquid gases, and combinations thereof. In the modes of direct or indirect cooling, cooling can be performed by means other than the use of a cooling fluid, for example, by induction. The term "heat exchange" as used here includes direct cooling, indirect cooling, and combinations thereof. Additional Modalities
[0089] In one embodiment, the biomass treatment method comprises: a pre-treatment step, in which said biomass is contacted with a first supercritical, almost critical or subcritical fluid to form a pre-treated slurry comprising a matrix solid and a first liquid fraction comprising xylooligosaccharides; wherein said first supercritical, almost critical or subcritical fluid comprises water and, optionally, CO2; and wherein said first supercritical, almost critical or subcritical fluid is substantially free of C1-C5 alcohol; a first separation step, wherein said solid matrix and said first liquid fraction are separated; a first hydrolysis step, wherein said solid matrix is contacted with a second supercritical or quasi-critical fluid to form a fraction containing insoluble lignin and a second liquid fraction comprising cell oligosaccharides; wherein said second supercritical or quasi-critical fluid comprises water and, optionally, CO2; and wherein said second supercritical or quasi-critical fluid is substantially free of C1-C5 alcohol; a second separation step, wherein said fraction containing insoluble lignin and said second liquid fraction are separated; and a second hydrolysis step, wherein said second liquid fraction is contacted with a third quasi-critical or subcritical fluid to form a product comprising glucose monomers; wherein said third quasi-critical or subcritical fluid comprises water and, optionally, acid, preferably an inorganic acid.
[0090] In another embodiment, the biomass treatment method comprises: a pre-treatment step, in which said biomass is contacted with a first supercritical, almost critical or subcritical fluid to form a pre-treated slurry comprising a matrix solid and a first liquid fraction comprising xylooligosaccharides; wherein said first supercritical, almost critical or subcritical fluid comprises water and, optionally, CO2; and wherein said first supercritical, almost critical or subcritical fluid is substantially free of C1-C5 alcohol; a first separation step, wherein said solid matrix and said first liquid fraction are separated; a first hydrolysis step, wherein said solid matrix is contacted with a second supercritical or quasi-critical fluid to form a fraction containing insoluble lignin and a second liquid fraction comprising cell oligosaccharides; wherein said second supercritical or quasi-critical fluid comprises water and, optionally, CO2; and wherein said second supercritical or quasi-critical fluid is substantially free of C1-C5 alcohol; a second separation step, wherein said fraction containing insoluble lignin and said second liquid fraction are separated; and a second hydrolysis step, wherein said second liquid fraction is contacted with a third quasi-critical or subcritical fluid to form a product comprising glucose monomers; wherein said third quasi-critical or subcritical fluid comprises water and, optionally, CO2. a third hydrolysis step, wherein said first liquid fraction is contacted with a fourth quasi-critical or subcritical fluid to form a second product comprising xylose monomers; wherein said fourth quasi-critical or subcritical fluid comprises water and, optionally, acid, preferably inorganic acid.
[0091] In yet other embodiments, the invention is directed to methods of increasing the level of xylose produced from biomass, comprising: fractionation of said biomass to form: a solid fraction comprising: cellulose; and insoluble lignin; and a first liquid fraction at a first temperature and at a first pressure comprising: a soluble C5 saccharide selected from the group consisting of xylooligosaccharides, xylose, and mixtures thereof; separating said solid fraction from said first liquid fraction at a second pressure; wherein said first pressure and said second pressure are substantially the same (preferably, said second temperature is less than said first temperature); adding to said first liquid fraction an aqueous acid to increase the level of said soluble C5 saccharide in said liquid fraction to form a second liquid fraction at a second temperature; and optionally, hydrolysis of said second liquid fraction to form xylose. In certain embodiments, said xylooligosaccharides in said first liquid fraction have about 2 mer units to about 25 mer units; and said xylooligosaccharides in said second liquid fraction have about 2 mer units to about 15 mer units. In certain preferred embodiments, the yield of said xylose is at least 70% of the theoretical yield. In certain embodiments, said aqueous acid is selected from the group consisting of an organic acid and an inorganic acid. Suitable inorganic acids include, but are not limited to: sulfuric acid, sulfonic acid, phosphoric acid, phosphonic acid, nitric acid, nitrous acid, hydrochloric acid, hydrofluoric acid, hydrobromic acid, hydroiodic acid. Suitable organic acids include, but are not limited to, aliphatic carboxylic acids (such as acetic acid and formic acid), aromatic carboxylic acids (such as benzoic acid and salicylic acid), dicarboxylic acids (such as oxalic acid, phthalic acid, sebacic acid , and adipic acid), aliphatic fatty acids (such as oleic acid, palmitic acid, and stearic acid), aromatic fatty acids (such as phenyl stearic acid), and amino acids. The acid can be selected from the group consisting of hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, sulfonic acid, phosphoric acid, phosphonic acid, nitric acid, nitrous acid, and combinations thereof. Preferably, said inorganic acid is diluted sulfuric acid. The amount of acid can be present in an amount of about 0.1% to about 2%, about 0.1% to about 1.5%, about 0.1% to about 1%, about from 0.1% to about 0.5%, about 0.1% to about 0.4%, about 0.1% to about 0.3%, about 0.1% to about 0.2%, about 0.5% to about 2%, about 0.5% to about 1.5%, about 0.5% to about 1%, less than about 2% >, less than about 1.5%, less than about 1%, less than about 0.5%, less than about 0.4%, less than about 0.3%, less than about 0.2%, or less than about 0.1%,
[0092] In still other modalities, the invention is directed to methods of increasing the level of glucose produced from lignocellulosic biomass, comprising:
[0093] The provision of a fractionated biomass (preferably, under pressure greater than ambient), comprising: a first solid fraction comprising: cellulose; and insoluble lignin; e is a first liquid fraction; mixing said solid fraction with water to form a slurry; preheating said slurry to a temperature lower than the critical water point; contacting said slurry with a second reaction fluid to form: a second solid fraction comprising: insoluble lignin; and a second liquid fraction comprising: a saccharide selected from the group consisting of cell oligosaccharides, glucose, and mixtures thereof; wherein said second reaction fluid comprises water and, optionally, carbon dioxide, said second reaction fluid having a temperature and pressure above the critical point of water and carbon dioxide; and reducing the temperature of said reaction mixture to a temperature below the critical water point; and optionally, the hydrolysis of said second liquid fraction to form glucose.
[0094] Preferably, the method is continuous. In certain embodiments, reducing the temperature of said reaction mixture to a temperature below the critical water point comprises contacting said reaction mixture with a composition comprising water. In other embodiments, the temperature of said reaction mixture at a temperature below the critical point of water comprises contacting said reaction mixture with a composition comprising water and acid at a level of less than about 10%, preferably less than about 5%, more preferably less than about 2%, and even more preferably, less than about 1% by weight, based on the total weight of said composition. In certain embodiments, said fractioned biomass is prepared by contacting said biomass with a first reaction fluid, comprising water and, optionally, carbon dioxide, said first reaction fluid having a temperature and pressure above the critical point of carbon dioxide, and at least one of said temperature and said pressure of said first reaction fluid being below the critical temperature and the critical water temperature. In certain embodiments, said preheating is carried out at a temperature of about 245 ° C to about 255 ° C and a pressure of about 20 mPa (200 bar) to about 26 mPa (260 bar). In certain embodiments, said contact of said slurry with a second reaction fluid is carried out at a temperature of about 358 ° C to about 380 ° C and a pressure of about 20 mPa (200 bar) at about 26 mPa (260 bar). In certain embodiments, said temperature reduction of said reaction mixture is carried out at a temperature of about 260 ° C to about 280 ° C and a pressure of about 20 mPa (200 bar) to about 26 mPa (260 Pub). In certain preferred embodiments, the yield of said glucose is at least about 63% of the theoretical yield. In certain aspects, the method yields a composition, comprising: glucose of at least about 63% by weight, based on the total weight of the composition; Water; less than about 13.0% glycolaldehyde, by weight, based on the total weight of the composition; less than about 2.0% glycolic acid, by weight, based on the total weight of the composition; and wherein said glucose is extracted from biomass using extraction of supercritical fluid.
[0095] In one embodiment, an extruder is used by one or more of: a conveyor, a reactor, and a heat exchange for one or more of a biomass pretreatment and hydrolysis steps. In one embodiment, an extruder is used as a conveyor, a reactor, and a heat exchange. In one embodiment, a first extruder is used as a conveyor, reactor, and / or a heat exchange for the pre-treatment of biomass, and a second extruder is used as a conveyor, reactor, and / or a heat exchange for a hydrolysis step. In a related embodiment, a third extruder is used as a carrier, reactor, and / or a heat exchange for a second hydrolysis step.
[0096] In one embodiment, an extruder comprises one or more threads. In another embodiment, an extruder comprises two threads. In another embodiment, an extruder comprises more than two threads. In another embodiment, two or more threads of an extruder rotate together. In a related mode, the two or more threads turn in reverse. Device
[0097] FIGURE 1 shows a scheme of a modality of the apparatus of the invention to convert lignocellulosic biomass 102 to xylose (solution form) 107, glucose (solution form 115), and lignin (solid form) 116. Lignocellulosic biomass 102 is pretreated in a pretreatment reactor 101 using compressed hot water (HCW) 103 (where compressed hot water is under subcritical conditions) and, optionally, supercritical CO2 104 to hydrolyze hemicellulose into hemicellulose sugars, for example, xylose and xylooligosaccharides. The resulting slurry 105 is subjected to solid / liquid (S / L) separation 106; the liquid phase contains hemicellulosic sugars and the solid phase contains mainly glucan and insoluble lignin. Optionally, acid 108, preferably inorganic acid (such as sulfuric acid), can be added separately or as part of the cooling fluid, not shown. The yields of hemicellulosic sugars in the solution and of glucan and lignin in the solid phase are typically> 80%,> 90%, and> 90% (of theory), respectively. This solid matrix 109 is mixed with water and, optionally, preheated, then subjected to hydrolysis in a hydrolysis reactor 110 using supercritical and quasi-critical fluids. Supercritical water (SCW) 111 and supercritical CO2 112 (and, optionally, acid 113) act on the glucan to selectively hydrolyze it while most of the lignin remains insoluble. After solid / liquid separation 114, liquid phase containing hexose sugars 115 and solid phase containing mainly lignin 116 are obtained. Optionally, an acid 113, preferably an inorganic acid (such as sulfuric acid), can be added, as it increases the hydrolysis of cellulose, while slowing the solubilization of lignin. Lignin serves as fuel 117 (as used in a boiler, not shown), while hexose and pentose sugars are fermentations of raw materials and derived from high intermediate and chemical values.
[0098] In one embodiment, an apparatus for converting biomass comprises (a) a pretreatment reactor and (b) a hydrolysis reactor. In a related embodiment, the hydrolysis reactor is associated with the pretreatment reactor. In a related embodiment, the hydrolysis reactor is associated with the pretreatment reactor and is adapted so that the pretreated biomass is transported from the pretreatment reactor to the hydrolysis reactor. In a related embodiment, the biomass is transported from the pretreatment reactor to the hydrolysis reactor using an extruder, an eductor, or a pump. In one embodiment, an extruder distributes the pre-treated biomass from the pre-treatment reactor to the hydrolysis reactor. In a related embodiment, the extruder comprises a thread rotatably associated with a motor. In another related embodiment, the extruder comprises two threads (a "twin screw extruder"). In one embodiment, the extruder has a variable pitch thread.
[0099] In one embodiment, a first reactor is adapted to feed one or more products from a first reaction to a second reactor. For example, and without limitation, a pretreatment reactor is adapted to feed a solid matrix into a hydrolysis reactor. In one embodiment, the first reactor is adapted in such a way that one or more reacted products is continuously fed into a second reactor. In a related embodiment, an extruder is associated with the first reactor, said extruder adapted to feed one or more products reacted in a second reactor. In a related embodiment, the extruder is a twin screw extruder. In another embodiment, the first reactor comprises an extruder. In a related embodiment, at least a portion of the extruder is adapted to separate two or more reacted products. For example, and without limitation, a pretreatment reactor comprising an extruder is adapted such that at least a portion of the extruder separates pretreated biomass into a first liquid fraction and a solid matrix; and said extruder is further adapted to feed said solid matrix to a hydrolysis reactor. In another embodiment, an eductor is associated with the pretreatment reactor and is adapted to feed one or more reaction products from a first reactor to a second reactor. In a related embodiment, steam is used to force said one or more reaction products from the first reactor to the second reactor. In a related embodiment, the eductor comprises a vapor inlet through which a relatively high vapor pressure is introduced, and in which one or more reaction products from the first reactor is transferred to the second reactor in response to an elevated vapor pressure in the eductor.
[00100] In one embodiment, a reactor comprises an extruder in which at least a portion of a reaction occurs. In a related embodiment, the extruder is a twin-screw extruder, optionally with variable pitch threads.
[00101] In one embodiment, a reactor is adapted to separate the products from the reaction that occurs in the reactor. For example, and without limitation, a hydrolysis reactor is adapted to separate a second liquid fraction and an insoluble fraction containing lignin after the solid matrix hydrolysis occurs in the hydrolysis reactor. In a related embodiment, a reactor comprises an extruder, in which at least a portion of a reaction occurs and in which at least a portion of the reacted products is separated into its component parts. This is generally shown in FIGURE 3, where a motor 301 is used to drive a screw extruder 303 within an extruder drum 305 to move the biomass (not shown) that is fed through the biomass feed 307. A dynamic plug 311 of the biomass extruder is formed, creating a low pressure zone 315, before the plug and a high pressure zone 317 in addition to the plug in the extruder drum. Wet fluid 309, in this case water, is added to the extruder drum. The liquid fraction is compressed from extruded wet biomass (compressed solution 313) before the dynamic buffer. The solid fraction 323 (for example, in 45-50% solids) exits through the discharge valve 319 in a reactor 321 for further treatment. In a related embodiment, extrusion takes place in an extruder. In a related embodiment, an extruder used to separate the solid fraction and liquid fraction comprises one for a plurality of threads. In a related embodiment, the extruder comprises two threads (a "twin screw extruder"), as shown in Figure 4 with an extruder-type reactor 402 with double threads 404a and 404b that move the biomass that is introduced through the biomass feed 406 through the extruder, process it before it leaves the extruder, and is controlled by a pressure control valve 405. In another embodiment, the reactor comprises a drain through which a liquid fraction leaves the reactor.
[00102] In one embodiment, a reactor comprises a water inlet that is adapted to allow water to be introduced or injected into the reactor. The reactor can be used for pre-treatment of biomass, the hydrolysis of a solid matrix, the hydrolysis of a liquid fraction, etc. In a related embodiment, water is introduced into the reactor through the water inlet to extinguish a pre-treatment or hydrolysis reaction. In a related embodiment, water is introduced through a water inlet after at least a portion of the content has been reacted (for example, pre-treated or hydrolyzed). In an embodiment in which the reactor comprises an extruder, said reactor has a reaction zone defined as the portion of the length of the extruder in which the pretreatment or hydrolysis reaction occurs. In such an embodiment, biomass, solid matrix, or a liquid fraction enters the reaction zone at a first end and pre-treatment or hydrolysis occurs while the material is forced through the reaction zone towards a second end. In another embodiment, a water inlet is positioned in an extruder-type reactor at least halfway between said first end and said second end, at least 5/8 of the way between said first end and said second end, at least 2/3 of the shape between said first end and said second end, at least 3/4 of the path between said first end and said second end, or at least 7/8 of the path between said first end and said second end.
[00103] In one embodiment, a reactor comprises a plurality of units 401a, 401b, 401c, and 401 d, adapted to allow water to be introduced or injected into the reactor, for example, as shown in FIGURE 4. The reactor can be used for pre-treatment of biomass, hydrolysis of a solid matrix, hydrolysis of a fraction of liquid, etc. In a related embodiment, water is introduced into the reactor through at least one of the plurality of water injection units to adjust at least one of the reactor's temperature and pressure. In a related embodiment, said water injection units are associated along the length of an extruder-type reactor 402, as shown in FIGURE 4. In another related embodiment, a fluid comprising water and at least one other component is introduced in the reactor through at least one of the plurality of water injection units. In another embodiment, the fluid comprising water has at least one of a known temperature and a known pressure.
[00104] In one embodiment, a reactor comprises one or more temperature control units 403a, 403b, 403c and 403d adapted to monitor the temperature of a reaction occurring in the reactor, for example, as shown in FIGURE 4. The reactor can be used for pre-treatment of biomass, hydrolysis of a solid matrix, hydrolysis of a fraction of liquid, etc. In a related embodiment, said temperature control units are associated with one or more water injection units. In a related embodiment, the temperature control units are adapted in such a way that when the reaction temperature falls outside a predetermined temperature range, said temperature control units cause one or more water injection units to allow the introduction of a fluid. In a related embodiment, the temperature and / or pressure of the fluid to be injected into the reactor is known. In another related embodiment, any one of a plurality of temperature control units is associated with a single water injection unit. In another related embodiment, any one of a plurality of water injection units is associated with a single temperature control unit. In another embodiment, any one of a plurality of temperature control units is associated with one of a plurality of water injection units and vice versa.
[00105] In one embodiment, a pretreatment reactor comprises a 901 conical reactor, as shown in FIGURE 9. In addition, to use as a pretreatment reactor, the reactor can alternatively be used for hydrolysis of a solid matrix, hydrolysis of a liquid fraction, etc. In a related embodiment, the conical reactor comprises a reaction vessel with a conical shape defined by an axis, a radius, and an internal periphery; and a mixing mechanism (for example, impeller 902 and motor 903). In a related embodiment, the mixing mechanism comprises an arm that rotates about the axis of the conical reactor and substantially parallel with the radius of the conical reactor, a first motor operatively associated with said arm, an impeller defined by an impeller shaft associated with said arm and with a second motor, through which the impeller rotates about its impeller axis and substantially parallel to the inner periphery of the conical reactor. In a related mode, the first and second engines comprise a single engine. In another related embodiment, the impeller further comprises an impeller shaft that extends substantially along the impeller shaft and at least one impeller blade circumferentially associated with said impeller shaft. In a related embodiment, the impeller comprises an impeller blade. In a related embodiment, said impeller blade is helically associated with the impeller shaft.
[00106] In one embodiment, the apparatus for converting biomass comprises:
[00107] a pretreatment reactor adapted for pretreated biomass;
[00108] a first hydrolysis reactor associated with said pretreatment reactor and adapted to hydrolyze a solid matrix formed in the pretreatment reactor;
[00109] a second hydrolysis reactor associated with said pretreatment reactor and adapted to hydrolyze a first liquid fraction formed in the pretreatment reactor; and
[00110] optionally, a third hydrolysis reactor associated with said first hydrolysis reactor and adapted to hydrolyze a second liquid fraction formed in said first hydrolysis reactor.
[00111] The present invention is further defined in the following Examples, in which all parts and percentages are by weight, unless otherwise specified. It should be understood that these examples, while indicating preferred embodiments of the invention, are given by way of illustration only and are not to be construed as limiting in any way. From the above discussion and these examples, one skilled in the art can determine the essential features of the present invention, and without departing from its spirit and scope, can make various changes and modifications of the invention to adapt it to the various uses and conditions. EXAMPLES Example 1: Continuous pretreatment of biomass
[00112] A continuous pilot scale system with a capacity of 100 kg / d (dry basis) was used. A schematic of the pretreatment facility is shown in FIGURE 2. The biomass slurry in water 201 is fed into an oven 203 and heated. Optionally, carbon dioxide 205 is introduced as a supercritical fluid with supercritical CO2, being a catalyst for the 207 pretreatment reactor. After pretreatment, the fractionated biomass is cooled by introducing the cooling fluid 209, such as water (with or without acid, preferably an inorganic acid). The liquid fraction 215 containing the xylose is separated using a solid / liquid separator 211 from the solid fraction 213 containing cellulose and lignin. The experiments were carried out in the temperature range of 220-250 ° C, pressure of 10 mPa (100 bar) and residence times of 1-1.6 minutes. FIGURE 14 shows the yields in the input feed base, the feed containing ~ 35% glucan, ~ 18% xylan and ~ 30% lignin (mixed hardwoods). Example 2: Hydrolysis of continuous cellulose using supercritical and quasi-critical water
[00113] A continuous pilot scale system with a capacity of 100 kg / d (dry basis) was used. The scheme of the cellulose hydrolysis installation is shown in Figure 7. The pre-treated biomass slurry 701 is first preheated in an oven 702, then directly subjected to hydrolysis in a 707 hydrolysis reactor using supercritical fluids and almost critical. Supercritical water (SCW) 705 (prepared by heating a stream of water 703 in a 704 oven under pressure) and supercritical CO2 706 (and, optionally, acid, not shown) act on the glucan to selectively hydrolyze it while most of the lignin remains insoluble. The hydrolyzed slurry is cooled and with, for example, 708 chilled water (with or without a diluted acid, preferably an inorganic acid, such as sulfuric acid) to delay the hydrolysis reaction and prevent the formation of degradation products. The use of acid in cooling also hydrolyzes cell-oligosaccharides to glucose monomers. The hydrolyzed slurry is further cooled with cooling fluid, such as water 709. After the solid / liquid separation 710, the liquid phase containing hexose sugars 711 and the solid phase containing mostly lignin 712 are obtained. The experiments were carried out in the temperature range of 360-374 ° C, pressure of 22.5 mPa (225 bar) and residence time of 1s. CO2 was introduced into the slurry (4% by weight), supercritical CO2 being a catalyst. The temperature is maintained for a desired residence time by directly extinguishing the reaction by injecting cold water. Table 1 and Table 2 show the yields in the input feed base, the feed containing ~ 55% glucan and ~ 40% lignin (pre-treated solids), for residence times of 1s and 1.2s, respectively. All yields are% of the theoretical value and refer to those in the solution except for the lignin that is in the solid phase. Cellulose hydrolysis and lignin solubilization are inversely correlated. Glycoaldehyde and glycolic acid are also produced in significant quantities and can be separated as valuable products.
Example 3: Continuous conversion of xylooligosaccharides (XOS) - to xylose monomers using acid and compressed hot water
[00114] A continuous system with a capacity of 10 kg / d (dry basis) was used. A scheme of the installation was similar to that shown in FIGURE 2. The xylose solution produced from a pretreatment operation similar to that of Example 1 was used as a starting material. The experiments were carried out in the temperature range of 180-240 ° C, pressure of 10 mPa (100 bar) and residence time of 1-3s. H2SO4 at 0.1% - 0.2% (pH = 1.7-2.0) was introduced into the solution as a catalyst. The results show that ~ 90% monomeric xylose yield can be achieved in 1s using 0.2% (Figure 15). Example 4: Continuous conversion of cell oligosaccharides (COS) to glucose monomers using acid and compressed hot water
[00115] A continuous system with a capacity of 10 kg / d (dry basis) was used. A scheme of the installation was similar to that shown in FIGURE 2. The slurry produced from a cellulose hydrolysis operation similar to that of Example 2 was filtered and the resulting solution was used as a starting material. The experiments were carried out in the temperature range of 200-260 ° C, pressure of 10 mPa (100 bar) and residence time of 1-3 s. 0.2% H2SO4 or 0.25% oxalic acid was introduced into the solution as a catalyst. The results show that the yield of - 90% monomeric glucose can be achieved in 1s using 0.1% sulfuric acid, as shown in FIGURE 13. Example 5: Effect of cellulose hydrolysis residence time on the production of glucose and its derivatives
[00116] The hydrolysis of the continuous cellulose was carried out at 377 ° C on the solid matrix prepared by the pretreatment step described above at different residence times (1.6 s, 5 s, 7 S, and 10 s). Yields (as a percentage of the theoretical maximum for each component) were measured for certain components (glucose, post-hydrolysis of glucose (PH), glycoaldehyde (GLA), and the sum of glucose (PH) and GLA. shown in FIGURE 12, where glucose is shown as a diamond, the PH of glucose is shown as a triangle, the glycoaldehyde (GLA) is shown as a square, and the sum of glucose (PH) and GLA is shown as an X. As the residence time increases the level of total glucose (PH of glucose) decreases and the level of glycoaldehyde increases, so it is possible to adjust the process to produce more sugar (glucose) or to produce more by-products (such as glycoaldehyde) .
[00117] The glycoaldehyde can be easily hydrogenated to monoethylene glycol (MEG), using Raney nickel catalyst, for example. In addition, glycolic acid, glyceroaldehyde, lactic acid, and acetic acid are generated, which can be isolated using, for example, liquid-liquid extraction.
[00118] Ethanol fermentation was carried out using glucose solution produced from the residence time of 1.6 s. The solution, after treatment with activated carbon and excess treatments, was fermentable at high yields. The results are shown in Table 2. Table 2: Ethanol fermented using glucose solution
Example 6: Effect of CO2 on the production of glucose and its derivatives
[00119] The continuous cellulose hydrolysis with and without CO2 was carried out at 377 ° C with a residence time of 1.6 s on the solid matrix prepared by the pretreatment step described above. The results are shown in Table 3. Table 3: CO2 effect


[00120] As can be seen, the difference in the various levels of products and derivatives produced by the continuous hydrolysis of cellulose with and without CO2 was statistically insignificant. Thus, it appears that there is no beneficial effect on glucose yield, derivative yield, or lignin recovery. Therefore, it would be beneficial to avoid the cost of pumping CO2, CO2 compression for recycling, and the added complexity of including CO2 under supercritical conditions. Example 7: Effect of CO2 in the pre-treatment step
[00121] The pre-treatment of biomass with CO2 was carried out at about 230 ° C to 240 ° C, with about 1.5 minutes of residence time. The results are shown in Figure 5. These data show that there was good xylose recovery in the solution and glucan recovery in the solids.
[00122] Although the preferred forms of the invention have been described, it will be apparent to those skilled in the art that various changes and modifications can be made which will achieve some of the advantages of the invention without departing from the spirit and scope of the invention. Therefore, the scope of the invention is to be determined solely by the claims to be attached.
[00123] When ranges are used here for physical properties, such as molecular weight, or chemical properties, such as chemical formulas, all combinations, and subcombination of ranges of specific modalities in them are intended to be included.
[00124] The descriptions of each patent, patent application, and publication cited or described in this document are hereby incorporated by reference, in their entirety.
[00125] Those skilled in the art will appreciate that numerous changes and modifications can be made to the preferred embodiments of the invention and that such changes and modifications can be made without departing from the spirit of the invention. It is therefore intended that the appended claims cover all such equivalent variations as they fall within the true spirit and scope of the invention.

权利要求:
Claims (19)
[0001]
1. Method for the continuous treatment of biomass characterized by the fact that it comprises: a pre-treatment step, in which said biomass is contacted with a first supercritical, almost critical, or subcritical fluid to form a solid matrix and a first fraction liquid; wherein said first supercritical, quasi-critical, or subcritical fluid comprises water and, optionally, CO2; and wherein said first supercritical, almost critical, or subcritical fluid is free of C1-C5 alcohol; and a hydrolysis step, wherein said solid matrix is contacted with a second supercritical or quasi-critical fluid to produce a second liquid fraction and an insoluble fraction containing lignin; wherein said second supercritical or quasi-critical fluid comprises water and, optionally, CO2; and wherein said second supercritical or quasi-critical fluid is free of C1-C5 alcohols.
[0002]
2. Method according to claim 1, characterized in that said first supercritical, quasi-critical, or subcritical fluid and said second supercritical or quasi-critical fluid comprises less than 10% carbon dioxide.
[0003]
3. Method, according to claim 1, characterized by the fact that said pre-treatment step occurs at a temperature and pressure below the critical point of at least one component of said first supercritical, almost critical, or subcritical fluid.
[0004]
4. Method according to claim 1, characterized by the fact that said pre-treatment step is carried out at a temperature of 150 ° C to 300 ° C.
[0005]
5. Method, according to claim 1, characterized by the fact that said pretreatment step is carried out at a pressure of 5 MPa (50 bar) to 11.5 MPa (115 bar).
[0006]
6. Method, according to claim 1, characterized by the fact that said biomass has a residence time of 1 minute to 5 minutes in said pre-treatment step.
[0007]
7. Method according to claim 1, characterized by the fact that said first liquid fraction comprises xylooligosaccharides.
[0008]
8. Method according to claim 1, characterized in that said second supercritical or quasi-critical fluid includes 0% acid.
[0009]
9. Method according to claim 1, characterized by the fact that said solid matrix has a residence time of 1 second to 30 seconds in said hydrolysis step.
[0010]
10. Method according to claim 1, characterized by the fact that said hydrolysis step occurs at a temperature and pressure above the critical point of at least one component of said second supercritical or quasi-critical fluid.
[0011]
11. Method according to claim 1, characterized by the fact that said hydrolysis step occurs at a temperature of 275 ° C to 450 ° C.
[0012]
12. Method, according to claim 1, characterized by the fact that said hydrolysis step occurs at a pressure of 20 MPa (200 bar) to 25 MPa (250 bar).
[0013]
13. Method, according to claim 1, characterized by the fact that said solid matrix is maintained at a temperature of 185 ° C or higher from the beginning of said pre-treatment step, until at least the end of said hydrolysis step.
[0014]
14. Method according to claim 1, characterized in that it further comprises: a second hydrolysis step in which said second liquid fraction is contacted with a third quasi-critical fluid, or a third subcritical fluid, to produce a third fraction liquid comprising glucose monomers; wherein said third quasi-critical fluid, or said third subcritical fluid comprises water, and optionally, acid.
[0015]
15. Method according to claim 14, characterized in that said second hydrolysis step occurs at a temperature of 220 ° C to 320 ° C.
[0016]
16. Method according to claim 14, characterized by the fact that said acid is present in an amount less than 1%.
[0017]
17. Method, according to claim 14, characterized by the fact that said acid is selected from the group consisting of hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, sulfonic acid, phosphoric acid, phosphonic acid , nitric acid, nitrous acid, and combinations thereof.
[0018]
18. Method according to claim 14, characterized by the fact that said second liquid fraction has a residence time of 1 second to 30 seconds in said second hydrolysis step.
[0019]
19. Method, according to claim 1, characterized by the fact that it further comprises: a xylooligosaccharide hydrolysis step, in which said first liquid fraction is contacted with a fourth quasi-critical fluid, or a fourth subcritical fluid for producing a fourth liquid fraction comprising xylose monomers; wherein said quasi-critical fourth fluid or subcritical fourth fluid comprises water, and optionally, acid.

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同族专利:

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公开号 | 公开日

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BR112012017850A2|2016-04-19|

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US20180355447A1|2018-12-13|

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US20120291774A1|2012-11-22|

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US9359651B2|2016-06-07|

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CA2769746C|2013-10-15|

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CN112159869A|2021-01-01|

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CA2815597C|2016-11-29|

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EP2526225A1|2012-11-28|

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WO2011091044A1|2011-07-28|

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US20160244852A1|2016-08-25|

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CN102859066A|2013-01-02|

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US20130239954A1|2013-09-19|

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US10053745B2|2018-08-21|

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RU2597588C2|2016-09-10|

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CA2945277A1|2011-07-28|

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CA2945277C|2021-01-05|

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US8968479B2|2015-03-03|

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RU2556496C2|2015-07-10|

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RU2015112569A|2015-09-20|

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RU2012135497A|2014-02-27|

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CA2769746A1|2011-07-28|

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EP2526225B1|2019-10-02|

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EP3719145A1|2020-10-07|

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CN102859066B|2016-01-13|

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BR112012017850B8|2020-12-01|

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CN105525043A|2016-04-27|

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US10858712B2|2020-12-08|

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EP2526225A4|2017-07-26|

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CA2815597A1|2011-07-28|

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CN105525043B|2021-03-19|

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法律状态:
2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-02-19| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|

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2019-12-10| B07A| Technical examination (opinion): publication of technical examination (opinion) [chapter 7.1 patent gazette]|

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2020-06-02| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-11-17| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 19/01/2011, OBSERVADAS AS CONDICOES LEGAIS. |

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2020-12-01| B16C| Correction of notification of the grant|Free format text: REF. RPI 2602 DE 17/11/2020 QUANTO AO INVENTOR. |

优先权:

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申请号 | 申请日 | 专利标题

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US29610110P| true| 2010-01-19|2010-01-19|

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US61/296,101|2010-01-19|

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PCT/US2011/021726|WO2011091044A1|2010-01-19|2011-01-19|Production of fermentable sugars and lignin from biomass using supercritical fluids|

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