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    • 专利摘要:
    process for the continuous hydrolysis of cellulosic biomass and process for the production of monosaccharides, sugar-based chemicals, biofuels or materials together with sulfonated alignine of lingnocellulosic biomass. The present invention relates to a continuous process for enzymatic hydrolysis of cellulosic biomass and an apparatus for carrying out such process. According to the present invention, a steady state is reached in a reactor with respect to the hydrolysis reaction. in this sense, the total high solids cellulosic biomass (preferably 10% or greater, even more preferably between 15 and 30%) is continuously added to said reactor, while at least partially hydrolyzed cellulosic biomass is continuously removed from said reactor. reactor. the steady state is adjusted, ie the amount of cellulosic biomass added and the amount of at least partially hydrolyzed cellulosic biomass removed are adjusted so that the retention time of a portion of the cellulosic biomass added in the reactor is longer than than its "liquefaction time", ie the time required to transform a solid suspension to the time required to transform a solid suspension into pumpable liquid during hydrolysis, ie the time required to reduce the viscosity of the solid. mud to a value that is acceptable for further processing.
    公开号:BR112012032212B1
    申请号:R112012032212-5
    申请日:2011-06-16
    公开日:2019-09-24
    发明作者:Anders Sjoede；Anders Froelander；Martin Lersch；Gudbrand Roedsrud；Kristin Hals；Anne Mari Kloeften；Lennart Delin；Mats H. Johansson
    申请人:Borregaard As；
    IPC主号:
    专利说明:

    PROCESS FOR THE CONTINUOUS HYDROLYSIS OF CELLULOSIC BIOMASS AND ITS USE AND PROCESS FOR THE PRODUCTION OF MONOSACARIDES, SUGAR-BASED CHEMICALS, BIOFUELS OR MATERIALS ALONG WITH THE SULPHONATED LIGNINE OF LIGNOCELLOUS BIOMASS
    Summary of the Invention [0001] The present invention relates to a continuous process for the enzymatic hydrolysis of cellulosic biomass. The improved hydrolysis according to the present invention is of particular use in converting biomass in general to cellulose, that is, the process of converting cellulosic biomass into useful chemicals or commodities, for example, biofuel.
    [0002] In one embodiment, the present invention relates to a process for the continuous hydrolysis of cellulosic biomass comprising at least the following steps:
    P) supply of at least one reactor, which can be operated at steady state;
    (A) adding a predetermined amount of cellulosic biomass to said reactor, wherein said cellulosic biomass has a solids content of at least 10%, preferably at least 15%, preferably at least 20%, preferably at least minus 25%, even more preferably at least 30%; even more preferably from 10% to 45%, even more preferably from 15% to 45%, even more preferably from 20% to 40% or 15% to 30%;
    A ') adding a predetermined amount of enzymes to said reactor;
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    2/31 (E) carrying out at least a partial enzymatic hydrolysis of the cellulosic biomass in said reactor.
    [0003] In said process, the steady state is reached, in which cellulosic biomass is continuously added to said reactor, while at least partially hydrolyzed cellulosic biomass is continuously removed from said reactor, in which said cellulosic biomass is less partially hydrolyzed, which is continuously removed, has a viscosity, as measured on a Physica MCR 101 rheometer in a beaker with a stirrer (FL 100 / 6W), of no more than 25 Pa-s (Pascal-second), preferably not more than 10 Pa-s, preferably not more than 5 Pa-s, more preferably not more than 3 Pa-s, more preferably not more than 1 Pa-s.
    [0004] Viscosity is measured under standard conditions (20 ° C, 1 bar). The person skilled in the art will have information on how to measure said viscosity in the example given in the present patent application.
    [0005] Preferably, in said steady state, said viscosity remains essentially constant or remains essentially below any of the values
    above described for viscosity to long on one period in time prolonged, for example, over of 2 hours, 4 hours, 6 hours, 12 hours or more. [0006] The purpose to establish a stationary state at the
    said reactor is to allow the hydrolysis of cellulosic biomass with a comparatively high solids content. It is desirable to carry out enzymatic hydrolysis with high loads
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    3/31 solids, preferably 10% total solids content (ST) or more, particularly from an environmental and economic point of view, as it reduces water and energy consumption, as well as the investment costs of the equipment. However, one of the challenges of hydrolysis of cellulosic biomass with a high solids content is to achieve sufficient mixing due to the high viscosity of the mud with the high solids content. Conventionally, particularly in batch processes known to the art, mixing is only possible using energy-demanding machines with a complex design.
    [0007] In accordance with the present invention, in said reactor, a hydrolysis reaction in steady state is achieved. In this sense, cellulosic biomass with a high content of total solids (preferably 10% or more, even more preferably between 15 and 40%) is continuously added to the said reactor, while the cellulosic biomass at least partially hydrolyzed is continuously removed from the reactor. said reactor. The steady state is adjusted, that is, the amount of cellulosic biomass added and the amount of cellulosic biomass that is at least partially hydrolyzed removed is adjusted, so that the average retention time of cellulosic biomass in the reactor is longer than the respective liquefaction time. medium, that is, the period of time required to transform a solid sludge into a pumpable liquid during hydrolysis, that is, the time required to lower the sludge viscosity to an acceptable value for further processing.
    [0008] According to the present invention, this liquefaction time is adequately described by the viscosity of the
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    4/31 cellulosic biomass at least partially hydrolyzed which is continuously removed from the reactor. Said viscosity, measured on a Physica MCR 101 rheometer in a beaker with a stirrer (FL 100 / 6W), is not more than 25 Pa-s (Pascal-second), preferably no more than 10 Pa-s, preferably not more than 5 Pa-s, more preferably not more than 3 Pa-s, more preferably not more than 1 Pa-s.
    [0009] In a preferred embodiment, as the glucose yield of the overall process is increased, the process for the continuous hydrolysis of cellulosic biomass is implemented in a cascade of at least two reactors, that is, step (P) is :
    (P) supply of a cascade of at least two reactors, which can be operated at steady state.
    [0010] In a preferred embodiment, said process for the continuous hydrolysis of cellulosic biomass comprises at least the following steps:
    P) supply of a cascade of at least two reactors, which can be operated in steady state;
    (A) adding a predetermined amount of cellulosic biomass in a first reactor, wherein said cellulosic biomass has a solids content of at least 10%, preferably at least 15%, preferably at least 20%, preferably at least minus 25%, even more preferably minus 30%, more preferably 10% to 45%, even more preferably 15% to 45%, even more preferably 20% to 40% or 15% to 30%;
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    5/31 (A ') adding a predetermined amount of enzymes to said first reactor;
    (E) carrying out partial enzymatic hydrolysis of cellulosic biomass in said first reactor;
    (T) continuous removal of partially hydrolyzed cellulose biomass from step (E1), which has a viscosity, measured on a Physica MCR 101 rheometer in a beaker with a stirrer (FL
    100 / 6W), of no more than 25 Pan - s (Pascal-second), in preferably no more than 10 Pan s, in preference no more than 5 Pa-s, more preferably no greater than 3 Pa s, more preferably not more in 1 Pa-s and transfer gives
    same for a second reactor, which can be operated in steady state;
    (E ') carrying out the additional enzymatic hydrolysis in the partially hydrolyzed cellulosic biomass obtained in step (E) in said second reactor.
    Background to the Invention [0011] As is generally accepted, resources for petroleum-based chemicals and for oil used as (fossil) fuel are limited. An alternative resource currently used is biofuel as obtained from biomass. Various sources of biomass can be used.
    [0012] The first generation of biofuels are biofuels made from sugar, starch, vegetable oil or animal fat using conventional technology. An example of basic raw material for the production of the first generation of biofuels are seeds or grains, such as wheat, which
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    6/31 produce starch that is hydrolyzed and fermented in bioethanol, or sunflower seeds, which are pressed to produce vegetable oil that can be transformed into biodiesel. However, these raw materials can also enter the animal or human food chain. Therefore, first generation biofuels have been criticized for diverting food from the human food chain, leading to food shortages and price increases.
    [0013] On the other hand, second generation biofuel can be produced sustainably using biomass made up of residual non-food parts (that is, not digestible) from current crops, such as stems, leaves, bagasse (residue from cane fiber) , bark, etc., which are left behind, once the food crop has been extracted, as well as other raw materials, which are not used for food purposes (non-food crops), such as wood, annual plants and cereals that they comprise small grains as well as industrial residues, such as sawdust, peels and fruit pulp, wine processing, etc.
    [0014] An important step in the general conversion of biomass for this second generation of biofuels is the hydrolysis of pre-treated or untreated cellulosic biomass in smaller units. In said hydrolysis step, the cellulose chains are broken by breaking at least one β-Ι-4-glycosidic bond.
    [0015] More specifically, cellulose is a linear insoluble polymer of repetitive units of glucan linked by e-1-4-glycosidic bonds. In water, cellulose is typically hydrolyzed by attack by the electrophilic hydrogen of the molecule
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    7/31 water in the glycosidic bond. In cellulose chains, each unit of glucose has the potential to form three hydrogen bonds with the monomers in adjacent chains, resulting in a stable crystalline structure, which is not easily hydrolyzed. The rate of the hydrolysis reaction can be increased using high temperatures and pressures or it can be catalyzed by a diluted or concentrated acid or by enzymes (as is the case in the present invention).
    [0016] On an industrial scale, it is of particular interest to hydrolyze cellulosic biomass with a high solids content. Conventionally, cellulosic biomass with a high solids content is hydrolyzed using excess hydrolysis times, usually between days 5 to 7, sometimes using combined configurations, where hydrolysis and fermentation are carried out simultaneously.
    [0017] US 2009/0209009 refers to the enzymatic hydrolysis of cellulose and reports that the cost of enzymes can be reduced by introducing a cellulose binding domain over one of the enzyme components necessary for cellulose degradation, called beta -glucosidase. To achieve this, specific binding agents are required. This binding agent allows the enzyme to bind to cellulose for convenient recycling. In addition, the hydrolysis reaction is carried out in dedicated solids retention reactors, where the solids have a retention time that is longer than that of the liquid.
    [0018] WO 2009/14067 describes a batch feeding process with the separation of solids and dilution of the substrate
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    8/31 capable of handling large amounts of total suspended solids (TSS) in the reactor.
    [0019] An article by Brethauer, S .; Wyman, C.E. Review: Contínuous hydrolysis and fermentation for cellulosic ethanol productíon Biores. Technol. 2010, 4862 discusses batch versus continuous hydrolysis and the fermentation process, in general terms, but with an emphasis on fermentation. The mentioned advantages include reduced cleaning and filling time of the vessel, which translates into an increase in volumetric productivity, smaller reactors, smaller capital investments and ease of control in steady state. The data presented in the article are from continuous fermentation experiments.
    [0020] An article by Fan, Z.L .; South, C .; Lyford, K .; Munsie, J .; van Walsum, P .; Lynd, L.R. “Conversion of paper sludge to ethanol in a semi continuous solid-fed reactor” Bioprocess Biosyst. Eng. 2003, 93 describes a semi-continuous reactor, in which a paper slurry is fed at determined intervals in a reactor operating with an SFS (= simultaneous saccharification and fermentation). The authors noted that by decreasing the frequency of feeding (feeding additions by residence time), cellulase feeding can be decreased.
    [0021] In light of the prior art as discussed above, an object of the present invention is to provide a process for the enzymatic hydrolysis of cellulosic biomass, in which a cellulosic biomass of comparatively high solids content can be hydrolyzed under industrial scale conditions , minimizing costs (investment and operation).
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    9/31 [0022] This object (and others) is / are solved through the following process for the continuous hydrolysis of cellulosic biomass comprising at least the following steps:
    (P) supply of at least one reactor, which can be operated at steady state;
    (A) adding a predetermined amount of cellulosic biomass to said reactor, wherein said cellulosic biomass has a solids content of at least 10%, preferably at least 15%, preferably at least 20%, preferably at least minus 25%, even more preferably at least 30%; even more preferably from 10% to 45%, even more preferably from 15% to 45%, even more preferably from 20% to 40% or 15% to 30%;
    A ') adding a predetermined amount of enzymes to said reactor;
    (E) carrying out at least a partial enzymatic hydrolysis of the cellulosic biomass in said reactor, in which, a steady state is reached, in which the cellulosic biomass is continuously added to said reactor, while the cellulosic biomass at least partially hydrolyzed is continuously removed from said reactor, in which said at least partially hydrolyzed cellulosic biomass, which is continuously removed, has a viscosity, measured on a Physica MCR 101 rheometer in a beaker with a stirrer (FL 100 / 6W), of no more than 25 Pa-s (Pascal-second), preferably no more than 10 Pa-s, preferably no more than 5 Pa-s, more preferably
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    10/31 not more than 3 Pa-s, more preferably not more than 1
    Pa-s.
    [0023] In this sense and throughout the entire description of the present invention, the term solids content (also known to the person skilled in the art as ST or total solids) indicates the ratio between the weight of a sample after drying at 105 ° C for 16h and the weight of the same sample before said drying.
    [0024] Correspondingly, the term SDT or Total Dissolved Solids, as used throughout the present patent application, means the ratio between the weight of the dry filtrate (105 ° C for 16h) resulting from a sample after being filtered and the weight of the same sample before said filtration and drying.
    [0025] The term SST or Total Suspended Solids represents the ratio of the weight of the dry filtered cake (105 ° C for 16h) resulting from a sample after it has been filtered
    and the weight of the same sample before gives referred filtration and drying. So the connection between these measures is ST = SDT + SST. [0026] When implementing the process continuous, from wake up with The gift invention, that is, through of establishment in one state and stationary and a regime of viscosity defined, the
    problems based on the high initial viscosity and complex design of the reactor are solved. In particular, the present invention solves the problem of carrying out a commercially viable enzymatic hydrolysis at a high solids load, keeping the viscosity in the reactor low. This
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    11/31 invention allows the enzymatic hydrolysis of a high total solids content and a low total suspended solids (SST) content to be carried out as a continuous process, with or without enzyme recycling.
    [0027] No special stirring is required in the reactor as there is no problem with elevated SST. As a consequence, conventional CSTRs (continuous agitated tank reactors) can be used in the process of the present invention. Therefore, preferably, the reactor (at least one) used in the process according to the present invention is a continuous agitated reactor, even more preferably a continuous agitated tank reactor.
    [0028] An additional embodiment that resolves the object (s) recited above also increases the glucose yield of the overall process. In this sense, the process for the continuous hydrolysis of cellulosic biomass according to the present invention, in particular in step (P) is carried out in a cascade of at least two reactors.
    [0029] There is no limit to the maximum number of reactors. The number of reactors operated in cascade (i.e., operated sequentially) depends, essentially, on the desired glucose yield.
    [0030] In a preferred aspect of the present invention, the amount of enzymes required in the overall process is reduced by at least 30%, preferably at least 40%, through the inclusion of a recycling circuit, in which the enzymes are recycled . In this sense, the hydrolyzate, that is, the liquid phase that comprises hydrolyzed cellulose and
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    12/31 enzymes, from the (last) reactor is subjected to a separation step, in which the non-hydrolyzed solids are separated from the hydrolyzate still containing enzymes. The said hydrolyzate liquid is then mixed with the non-hydrolyzed (fresh) cellulosic biomass, which is then introduced into the (first) hydrolysis reactor.
    Brief description of the Figures [0031] Figure 1 shows a continuous reactor operated according to the process of the present invention with an optional subsequent cascade of additional reactors;
    [0032] Figure 2 shows a flow diagram of the continuous enzymatic hydrolysis of cellulosic biomass in a cascade of at least two reactors, in which at least a part of the enzymes added to the reactor are recycled;
    [0033] Figure 3 shows a flow diagram of the continuous enzymatic hydrolysis of cellulosic biomass in a cascade of at least two reactors, in which the inhibition of hydrolysis by a high sugar load is minimized in a reactor cascade, which sequentially decreases in volume;
    [0034] Figure 4 represents the evolution of the viscosity of cellulosic biomass submitted to enzymatic hydrolysis over time, providing information on the minimum expected retention time at steady state;
    [0035] Figure 5 is a flow chart of a concept of global biorefinery, according to an embodiment of the present invention;
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    13/31 [0036] Figure 6 shows a flow diagram of the continuous enzymatic hydrolysis of cellulosic biomass in a cascade of three reactors according to Examples 2 and 3;
    Detailed Description of the Invention [0037] The present invention relates to the hydrolysis of cellulosic biomass. There is no restriction with regard to the type or composition of cellulosic biomass other than biomass comprising cellulose. According to an appropriate definition, biomass is the total mass of (formerly) living matter, in particular organic matter, within a given unit of environmental area, preferably plant material, vegetation or agricultural waste used as a source of fuel or energy. The fact that the previously living biomass is also included as cellulosic biomass implies that recycled cellulosic materials, in particular recycled cotton materials and / or products based on recycled paper or other conceived recycled materials based on cellulose, are also included. Any mix of recycled cellulosic materials, such as recycled paper products with any other type of cellulosic biomass is also included.
    [0038] According to a preferred embodiment, said cellulosic biomass comprises more than 30% cellulose (% by weight, based on the total mass), preferably more than 50% cellulose, preferably greater than 70% of cellulose. In this sense, the term cellulose also includes the term hemicellulose. Preferred cellulosic biomass, according to the present invention, comprises cotton, cotton fibers and lignocellulosic biomass, that is, biomass
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    14/31 comprising both the lignin components and cellulosic and / or hemicellulosic components.
    [0039] Preferred cellulosic biomass, which is particularly suitable for the process according to the present invention, is based on energy crops, annual plants, agricultural residues and wood.
    [0040] Commercial energy crops are normally densely planted, high-yielding crop species that are preferably of no or limited value as food. For example, wood crops such as willow, Miscanthus, Willow or Poplar are preferred energy crops.
    [0041] As preferred examples of annual plants are straw, sugar cane and cassava.
    [0042] Agricultural residues include parts of arable crops that should not be used for the main purpose of producing food, fodder or fiber, for example, used animal fodder and feathers. These residues are exemplified by sugarcane bagasse and corn stalk.
    [0043] The particularly preferred starting material for sugar cane can be divided into bagasse, sugar and straw. Bagasse is a fibrous material consisting of cellulose, hemicellulose, lignin, extracts, inorganic salts and other organic substances such as proteins and organic acids.
    [0044] Bagasse and hardwood have many similarities, that is, high xylan content, short fiber length and lower lignin and cellulose content compared to soft wood. However, the bagasse has a slightly ash content
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    Higher 15/31. The ash content can be explained by the differences in plant morphology and the method of exploration. The length of the short fiber in the bagasse is mainly due to its high sap content (~ 30%).
    [0045] In general, based on the fact that mechanical size reduction may not be necessary and that the highest yields of hydrolysis are obtained, it is particularly preferred to conduct the process according to the present invention with non-agricultural waste - woodworkers, in particular, bagasse, as cellulosic biomass.
    [0046] Wood is also a suitable material for the present process. In that sense, all types of wood are suitable.
    [0047] According to the present process, the pulp of the cellulosic biomass is enzymatically hydrolyzed. Cellulose is a linear insoluble polymer of repetitive units of glucan linked by e-1-4-glycosidic bonds. In water, cellulose is hydrolyzed by attack by the electrophilic hydrogen of the water molecule at the glycosidic bond. In cellulose chains, each unit of glucose has the potential to form three hydrogen bonds with the monomers in adjacent chains, resulting in a stable crystalline structure, which is not easily hydrolyzed. The rate of the hydrolysis reaction can be increased by using high temperatures and pressures or it can be catalyzed by a diluted or concentrated acid or by enzymes, preferably, as is the case in the present invention by enzymes.
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    In accordance with a preferred embodiment of the present invention, enzyme complexes associated with the extracellular or cellular membrane (cellulases) that can specifically hydrolyze the cellulose polymer to soluble glucose monomers are used in the hydrolysis step. Cellulases are complexes of muiltiproteins that consist of synergistic enzymes with different specific activities that can be divided into exo- and endo-cellulases (glucanase) and β-glucosidase (cellobiose). In addition, there are enzymes (hemicellulases, laccases, lignolytic peroxidases, etc.) that can break down the other main components of cellulosic biomass. All of these enzymes and their combinations are preferred enzymes that can be used in the enzymatic hydrolysis of the present invention.
    [0049] Cellobiose is a known inhibitor of glucanases and β-glucosidase end product is known to alleviate this inhibition by converting cellobiose into glucose (limiting step). In industrial processes, for example, yeast ethanol fermentation, cellulase saccharification efficiency can be improved by simultaneous saccharification and fermentation (SSF). The biggest challenge with SSF concerns the different optimal temperature for common hydrolytic enzymes and fermentation organisms. In addition to inhibiting the final product, lignin is known to reduce the performance of the enzyme by not specifically binding to cellulases.
    [0050] It is preferred that the cellulosic biomass be subjected to at least one type of pre-treatment before hydrolysis, which confers at least some lignin from the cellulosic biomass
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    17/31 in a water-soluble form, making it particularly suitable for the hydrolysis step of the present invention.
    [0051] Therefore, according to a preferred embodiment, the cellulose pretreatment is carried out to increase the specific cellulose surface area. The correct pretreatment has the advantages of increasing the rate of enzymatic hydrolysis, due to the more accessible substrate and also through the removal of potentially inhibitory substances.
    [0052] Although the process according to the present invention is applicable to all types of cellulosic materials, it is preferable that the material is pre-treated in a separate step that precedes the hydrolysis step. It was found that said pre-treatment step increases the efficiency of enzymatic hydrolysis.
    [0053] Said pre-treatment is mechanical or chemical, preferably chemical.
    [0054] In mechanical (pre) treatment, force or energy is transferred to cellulosic biomass, for example, by dividing or cutting or beating the biomass into smaller particles. Then, no chemical reagents are added and the chemical structure of the material components remains essentially unchanged.
    [0055] In the chemical (pre) treatment, at least one chemical reagent is added and the chemical structure of at least one component of the component in the biomass is changed. As will be discussed in more detail below, cooking of the sulfite is
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    18/31 is a chemical pretreatment and is actually the preferred type of pretreatment.
    [0056] In a preferred embodiment, cellulosic biomass is used in the present process, in particular lignocellulosic biomass, which does not require mechanical (pre) treatment and in which the cooking of the sulphite is the only (pre) treatment. Sulfite cooking can be divided into four main groups: acid, bisulfite, weak alkaline acid and alkaline sulfite pulping.
    [0057] In the preferred pretreatment according to the present invention, the cellulosic biomass is cooked with a sulfite, preferably sodium, calcium, ammonium or magnesium sulfite under acidic, neutral or basic conditions. This pretreatment step dissolves most of the lignin as sulfonated lignin (lignosulfonate), along with the parts of the hemicellulose.
    [0058] Surprisingly, in the present process, it has been found that the use of sulfite cooking as a pre-treatment step in the production of fuels or chemicals from fermentable sugars is very efficient, since it leads to higher overall yields of Chemicals. In essence, a higher output (> 80%) of useful chemicals is achieved than in any other known sugar platform biorefinery technology.
    [0059] The fact that the cellulose pulp resulting from the pre-treatment of a single stage is particularly low in impurity, in particular lignin, makes it easier to develop or adapt the enzymes for hydrolysis.
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    19/31 [0060] Pre-treatment with sulfite is preferably carried out according to one of the following achievements. In the same and throughout the present description, pretreatment with sulfite is also referred to as cooking:
    • acid cooking (preferably SO2 with a hydroxide, even more preferably with Ca (OH) 2, NaOH, NH4OH or Mg (OH) 2), • bisulfite cooking (preferably SO2 with a hydroxide, even more preferably with NaOH, NH4OH or
    Mg (OH) 2), • alkaline weak cooking (preferably Na2SO3, even more preferably with Na2CO3) and • alkaline cooking (preferably with Na2SO3 hydroxide, even more preferably with NaOH).
    [0061] With respect to the sulfite pretreatment step (sulfite cooking), which is a preferred pretreatment to be implemented before the enzymatic hydrolysis according to the present invention, the respective disclosure of WO 2010/078930 , with the title Lignocellulosic biomass conversion as it was deposited on December 16, 2009 is incorporated by reference into the present description.
    [0062] The present invention also relates to an integrated process for the production of monosaccharides, sugar-based chemicals, biofuels or materials together with the sulfonated lignin of the lignocellulosic biomass that comprises at least the following steps:
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    20/31 (i) pre-treatment of lignocellulosic biomass, preferably in a sulphite cooking step;
    (ii) separation of the pre-treated lignocellulosic biomass from step (i) to:
    (a) a liquid liquefied sulfite phase, which preferably comprises 50% or more of lignin from the lignocellulosic biomass in the form of sulfonated lignin, and in (b) a pulp, which preferably comprises 70% or more of the cellulose of the lignocellulosic biomass;
    (iii) hydrolysis of the pulp (b) of step (ii) in a chemical sugar platform comprising monosaccharides, wherein said hydrolysis step is the process for the continuous hydrolysis of the lignocellulosic biomass as described above.
    (iv) optionally, additional treatment of the monosaccharides from step (iii) resulting in useful chemical products, biofuels and / or proteins, and (v) direct conversion or further processing of the sulfonated lignin from the liquid phase (a) in step (ii) in useful chemicals, biofuels and / or materials.
    [0063] This general process is schematically represented in Figure 5.
    [0064] Step (iv) of said process relates to the fermentation of monosaccharides, in particular hexoses and pentoses in ethanol or other sugar-based chemicals or for the production of biomass proteins.
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    21/31 [0065] Fermentation involves microorganisms that break down sugars by releasing energy, while the process results in products like an alcohol or an acid. Saccharomyces cerevisiae (baker's yeast) is most often used to ferment hexoses to ethanol. One mole of glucose will stoichiometrically produce 2 moles of ethanol plus 2 moles of carbon dioxide. Bagasse pulp contains relatively large amounts of pentose. These sugars can either be fermented or metabolized to produce biomass proteins.
    [0066] With or without reference to the integrated process described above for the production of monosaccharides, the present invention relates to the hydrolysis of cellulosic biomass as described above. With regard to said hydrolysis, the following embodiments are preferred.
    [0067] In a preferred embodiment, in the continuous process of the present invention, the entire sludge of liquid and solid components moves through the reactors at the same rate, that is, non-hydrolyzed fiber solids and the aqueous phase of the sludge is conserved during the same time interval in said reactor.
    [0068] According to a first embodiment, as exemplified in Figure 1, the substrate, that is, cellulosic biomass, is fed to a reactor and enzymes are added. The process is carried out continuously, that is, in a steady state. In said reactor, the substrate, that is, cellulosic biomass, is hydrolyzed. The viscosity of the partially hydrolyzed cellulosic biomass, in a reactor operated in accordance with the present invention, with
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    22/31
    25% ST (composed of 10% SST and 15% SDT), can be approximated by the batch viscosity of the corresponding experiment after a reaction time of 16 hours.
    [0069] There is no restriction with respect to the reactor needed to carry out the process, although a CSTR (continuously agitated tank reactor) is preferred.
    [0070] According to a preferred embodiment, also shown in Figure 1, a cascade of reactors is provided to improve glucose yield. In the additional reactors (after the first reactor described above), the substrate is hydrolyzed again, resulting in a hydrolyzate with a high sugar concentration (= high total dissolved solids, SDT) and a solid residue consisting of a material that cannot be hydrolyzed (lignin, inorganic materials, etc.).
    [0071] Even though the reactor is fed with a substrate that has a high solids content, for example, a ST of 25%, the total suspended levels (SST) in the reactor is only about 10% at steady state ( assuming three reactors in series with a total reaction time of 48 hours, 16 hours in each reactor). The viscosity of the 25% ST solution (composed of 10% SST and 15% SDT) in the steady state reactor of the present invention corresponds to the viscosity in a batch reactor after a reaction time of 16 hours or less.
    [0072] The average retention time in the reactor for cellulosic biomass added to a hydrolysis reactor should be about, preferably slightly longer than the time required
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    23/31 for liquefaction in a batch reactor, with good agitation. Therefore, the average retention time of the first reactor should be chosen so that sufficient liquefaction is achieved for the sludge to be pumpable.
    [0073] According to a second embodiment, the enzyme costs are reduced by employing enzyme recycling. The process is schematically described in Figure 2.
    [0074] In a preferred aspect of the present invention, the amount of enzymes needed in the overall process is reduced by at least 30%, preferably at least 40%, through the inclusion of a recycling circuit, in which the enzymes are recycled .
    [0075] According to this preferred embodiment, the hydrolyzate, that is, the liquid phase comprising the hydrolyzed cellulose and enzymes, from the (last) reactor is subjected to a separation step, in which the non-solid hydrolysates are, at least partially, separated from the hydrolyzate still containing enzymes. Said liquid hydrolyzate is then mixed with the non-hydrolyzed (fresh) cellulosic biomass, which is then introduced into the reactor for hydrolysis.
    [0076] This is illustrated in Figure 2. In this sense, after hydrolysis of tank 3 of a cascade of three hydrolysis reactors, the hydrolyzate (including enzymes) is separated from the non-hydrolyzed solid residue. Said hydrolyzate is recycled into the system by a mixing tank (leftmost tank in Figure 2). In the said mixing tank, some (residual) hydrolysis may occur, but the said reactor is mainly intended for mixing the
    Petition 870190031533, dated 04/01/2019, p. 30/46
    24/31 recycled hydrolyzate containing enzymes with the added cellulosic biomass (substrate). In an optional separation step after said dedicated mixing tank, part of the hydrolyzate, in particular, part of the final sugar product can be separated for further processing.
    [0077] Therefore, according to a preferred embodiment, at least part of the cellulosic biomass at least partially hydrolyzed, which is continuously removed from the reactor, preferably from the last reactor in a cascade of two or more reactors, is subjected to a separation step, in which the non-hydrolyzed solids are at least partially separated from the hydrolyzate, that is, the liquid phase comprising the hydrolyzed cellulosic biomass and enzymes, in which the said hydrolyzed liquid is then mixed with the cellulosic biomass, preferably in a dedicated reactor or tank, which is then introduced into the process according to the present invention.
    [0078] The added advantage with this process solution is that the hydrolyzate / sugar solution (after the separation of the non-hydrolyzed material) is mixed with the substrate before the (first) reaction tank. This will drastically decrease the amount of enzymes needed by at least 40% (due to the replacement of the liquid phase of the pulp).
    [0079] By mixing the hydrolyzate (after separation of the non-hydrolyzed solids) with fresh substrate (ie cellulosic biomass), enzymes with a carbohydrate binding part can bind to the substrate (cellulose) before being fed to the first hydrolysis reactor. This
    Petition 870190031533, dated 04/01/2019, p. 31/46
    25/31 will allow for a further reduction in enzyme consumption, in addition to the 40% reduction mentioned above.
    [0080] According to an additional preferred embodiment, inhibition of hydrolysis based on the sugar content that is too high (high SDT) is addressed.
    0081] Therefore, any potential sugar inhibition induced from hydrolysis is preferably overcome by sequential separation of sugars.
    [0082] According to this preferred embodiment, as illustrated in Figure 3, the suspended solids are separated from the liquid after the first reactor, in which a hydrolysis reaction occurs.
    [0083] Typically, a conversion of about 60% cellulose / hemicellulose to mono sugars can be achieved in the hydrolysis reactor operated in the steady state according to the present invention. The remaining 40% non-hydrolyzed fibers are then transferred to a second reactor. Enzymes, with a carbohydrate-binding part, are expected to bind to non-hydrolyzed fibers. In addition, enzymes dissolved in the liquid entrained in the fibers will also be transferred to the second reactor. In addition to the enzymes that are recovered from the first reactor, a small amount of enzymes is preferably added to the second reactor.
    [0084] Preferably, the size of the second hydrolysis reactor was reduced in accordance with the amount of non-hydrolyzed fibers in order to achieve the same or, at least, an SST similar to that of the first reactor.
    Petition 870190031533, dated 04/01/2019, p. 32/46
    26/31 [0085] The whole process can be repeated in the same way for any subsequent hydrolysis reactor, which is then reduced proportionally.
    [0086] In general, according to this preferred embodiment, in the process according to the present invention, a cascade of two or more hydrolysis reactors is used, in which at least some hydrolyzate, i.e. the liquid phase comprising the hydrolyzed cellulosic biomass and enzymes of the first reactor, is separated from the solid phase and is subjected to further processing, in any of the subsequent reactors and in which said solid phase is added to a subsequent reactor, preferably being smaller in size and / or volume than the first reactor, wherein an additional predetermined amount of enzyme can be added to said subsequent reactor.
    Examples:
    [0087] The following conventions, as applied throughout the specification, apply for the examples:
    Temperature is given in ° C% denotes weight in% if not specified otherwise
    Equivalent Glucose = The amount of glucose derived from cellulose in the substrate
    Equivalent xylose = The amount of xylose derived from xylan in the substrate
    Example 1 [0088] To determine the approximate average retention time of a first reactor, a sample of bagasse substrate
    Petition 870190031533, dated 04/01/2019, p. 33/46
    27/31 alkaline sulfite stew prepared in a manner similar to the conditions described in Example 1 of WO 2010/078930 was hydrolyzed. Hydrolysis was carried out on a Physica MCR 101 rheometer in a beaker with a shaker (FL 100 / 6W). The rotation speed was 30 rpm and the temperature was 50 ° C. The concentration of cellulosic biomass was 10% and the enzyme addition was 40% V / w of Accellerase Duet (Genencor, CA, USA). Viscosity was monitored continuously and viscosity as a function of time is shown in Figure 4.
    [0089] Hydrolysis results in a rapid initial decrease in viscosity and, after a short time, the viscosity curve begins to flatten and reaches a level where the sample can be seen as a liquid or the like. This viscosity depends on the substrate (in this case: cellulosic biomass) and the experimental conditions, but the hydrolyzed material can be considered liquefied when the viscosity is less than 3 Pa ^ s (Pascal-second), that is, less than 3000 centipoise.
    [0090] The minimum average retention time of the (first) reactor is determined by the liquefaction time, which in turn is dependent on several parameters, such as the substrate, the substrate concentration and quantity and type of enzymes.
    Example 2 [0091] A sample of baked alkaline sulphite bagasse substrate (bagasse pulp) prepared under similar conditions as described in Example 2 of WO 2010/078930 was subjected to hydrolysis in an experimental installation with three reactors in series, as shown in Figure 6. The volume
    Petition 870190031533, dated 04/01/2019, p. 34/46
    The total system 28/31 was measured to be approximately 6.6 liters. The reactors were covered and connected to a water bath for temperature control and the cooling water was circulated in the caps to minimize the evaporation of the reactors.
    [0092] Enzymes (DUET Accellerase from Genencor, CA, USA), buffer (sodium acetate buffer, 50 mM concentration in steady-state reactors) and bagasse pulp were continuously added to reactor 1. The reaction mixture was maintained at 50 ° C in reactors 1 to 3. The hydrolyzate was collected in the product reservoir, which was cooled with water to about 5 ° C.
    [0093] The total average input to the system was 144.2 g / h. The average dry substrate concentration at the entrance was 17.1% and the average enzyme load was 0.273 g DUET Accelerase / g dry substrate. The average time (retention) of hydrolysis was calculated to be 46 hours, assuming a reaction mixture density of 1.0 g / mL.
    [0094] The system outlet to the product tank was weighed regularly. The output was, on average, 5.1% lower than the input to the system. The main reason for the loss is considered the evaporation of water from the three reactors and / or the accumulation of material in the reactors. Samples were taken from all three reactors twice a day to measure glucose and xylose production. After 4 to 5 days, the glucose and xylose values in the three reactors stabilized, thus indicating that steady state conditions were achieved. Glucose yield calculated as (g glucose output / h) / (g glucose equivalent / h). The
    Petition 870190031533, dated 04/01/2019, p. 35/46
    29/31 glucose yields in the three reactors calculated as average values over three days at steady state were 24.6% (reactor 1), 40.2% (reactor 2) and 49.6% (reactor 3).
    Xylose yields were calculated as (g xylose output / h) / (g xylose equivalent input / h). The xylose yields in the three reactors calculated as average values over three days at steady state were 33.7% (reactor 1), 56.0% (reactor 2) and 66.0% (reactor 3). Viscosity was measured using a Physica MCR 101 rheometer equipped with a beaker with a stirrer (FL 100 / 6W), the rotation speed was 1 rpm and the temperature was 50 ° C. An average viscosity value in reactor 1, at steady state, was 1.7 Pa-s (Pascal-second) to be compared with the inlet viscosity (a 17.1% substrate suspension), which was measured as 82.2 Pa-s.
    [0095] This example shows that a continuous hydrolysis process with a high solid load at steady state produces a hydrolyzate with high glucose and xylose yield using only conventional stirring. The viscosity in the first reactor was substantially lower than that of the steady state feed.
    Example 3 [0096] A sample of baked alkaline sulfite bagasse substrate (bagasse pulp) prepared under similar conditions as described in Example 1 of WO 2010/078930 was subjected to hydrolysis in an experimental installation with three reactors in series, as shown in Figure 6. The total volume of the system was measured to be approximately 6.6 liters. The reactors were covered and connected to a
    Petition 870190031533, dated 04/01/2019, p. 36/46
    30/31 water for temperature control and cooling water was circulated in the covers to minimize the evaporation of the reactors.
    [0097] Enzymes (DUET Accellerase from Genencor, CA, USA), buffer (sodium acetate buffer, 50 mM concentration in steady-state reactors) and bagasse pulp were continuously added to reactor 1. The reaction mixture was maintained at 50 ° C in reactors 1 to 3. The hydrolyzate was collected in the product reservoir, which was cooled with water to about 5 ° C.
    [0098] The total average input to the system was 144.1 g / h. The average dry substrate concentration at the entrance was 18.8% and the average enzyme load was 0.173 g DUET Accelerase / g dry substrate. The average time (retention) of hydrolysis was calculated to be 46 hours, assuming a reaction mixture density of 1.0 g / mL.
    [0099] The system outlet to the product tank was weighed regularly. The output was, on average, 1% less than the input to the system. The main reason for the loss is considered the evaporation of water from the three reactors and / or the accumulation of material in the reactors. Samples were taken from all three reactors twice a day to measure glucose and xylose production. After 4 to 5 days, the glucose and xylose values in the three reactors stabilized, thus indicating that steady state conditions were achieved. Glucose yield calculated as (g glucose output / h) / (g glucose equivalent / h). Glucose yields in the three reactors calculated as mean values over three days at steady state
    Petition 870190031533, dated 04/01/2019, p. 37/46
    31/31 were 39.8% (reactor 1), 55.0% (reactor 2) and 58.8% (reactor 3).
    Xylose yields were calculated as (g xylose output / h) / (g xylose equivalent input / h). The xylose yields in the three reactors calculated as average values over three days at steady state were 75.0% (reactor 1), 93.2% (reactor 2) and 89.6% (reactor 3). Viscosity was measured using a Physica MCR 101 rheometer equipped with a beaker with a stirrer (FL 100 / 6W), the rotation speed was 30 rpm and the temperature was 50 ° C. An average viscosity value in reactor 1, at steady state, was 1.5 Pa-s (Pascal-second) to be compared with the viscosity of a simulated inlet (a 10% substrate suspension instead of a 18.8% substrate had to be used because of the very high viscosity), which was measured to be 249 Pa-s.
    [0100] This example shows that a continuous hydrolysis process based on a different substrate with a high solid load at steady state produces a hydrolyzate with high glucose and xylose yield using only conventional stirring. The viscosity in the first reactor was substantially lower than that of the steady state feed.
    权利要求:
    Claims (16)
    [1]
    1. Process for the continuous hydrolysis of cellulosic biomass, characterized by comprising at least the following steps:
    (P) supply of at least one reactor, which can be operated at steady state;
    (A) adding a predetermined amount of cellulosic biomass to said reactor, wherein said cellulosic biomass has a solids content of at least 10%;
    (A ') adding a predetermined amount of enzymes to said reactor;
    (E) carrying out at least a partial enzymatic hydrolysis of the cellulosic biomass in said reactor, in which a steady state is achieved in a said process, in which the cellulosic biomass is continuously added to said reactor, while the cellulosic biomass is at least partially hydrolyzate is continuously removed from said reactor, wherein said partially hydrolyzed cellulosic biomass which is continuously removed has a viscosity as measured on a Physica MCR 101 rheometer in a beaker with a stirrer (FL 100 / 6W) of no more than 25 Pa ^ s (Pascal-second) and said viscosity must remain constant for a period of 2 hours or more.
    [2]
    Process according to claim 1, characterized in that a cascade of at least two reactors is
    Petition 870190031533, dated 04/01/2019, p. 39/46
    2/5 provided in step (P), additionally comprising the next step (T) continuous removal of partially hydrolyzed cellulosic biomass from step (E), which has a viscosity, measured on a Physica MCR 101 rheometer in a beaker with an agitator (FL 100 / 6W), of no more than 25 Pa-s (Pascal-seconds) and transferring it to a subsequent reactor, which can be operated at steady state;
    (E ') carry out the additional enzymatic hydrolysis on the partially hydrolyzed cellulosic biomass obtained in step (E) in said subsequent reactor.
    [3]
    Process according to claim 1 or 2, characterized in that the solids content of the cellulosic biomass, which is added to said reactor, is from 15% to 45%.
    [4]
    Process according to any of claims 1 to 3, characterized in that the viscosity of the partially hydrolyzed cellulosic biomass is continuously removed, as measured on a Physica MCR 101 rheometer in a beaker with an agitator (FL
    100 / 6W), not more than 10 Pa-s.
    [5]
    Process according to any one of claims 1 to 4, characterized in that the cellulosic biomass is lignocellulosic biomass and comprises wood, annual plants, agricultural residues or waste, bagasse or energy crops.
    Petition 870190031533, dated 04/01/2019, p. 40/46
    3/5
    [6]
    Process according to any one of claims 1 to 5, characterized in that the cellulosic biomass comprises more than 20% cellulose.
    [7]
    Process according to any one of claims 1 to 6, characterized in that the cellulosic biomass is subjected to a pretreatment before said hydrolysis, wherein said pretreatment is sulfite cooking and the cellulosic biomass is lignocellulosic biomass. .
    [8]
    Process according to any one of claims 1 to 7, characterized in that the reactor is a CSTR, that is, a continuously stirred tank reactor.
    [9]
    Process according to any one of claims 1 to 8, characterized by enzyme complexes associated with extracellular or cellular membranes, in particular a mixture of cellulases and β-glucosidases, which can specifically hydrolyze the cellulose polymer into soluble glucose monomers, used in said hydrolysis step.
    [10]
    Process according to claim 9, characterized in that the enzymes comprise cellulases, hemicellulases and / or β-glucosidases.
    [11]
    Process according to any one of claims 1 to 10, characterized in that at least some cellulosic biomass at least partially hydrolyzed, which is continuously removed from the reactor, is subjected to a step of
    Petition 870190031533, dated 04/01/2019, p. 41/46
    4/5 separation, in which the non-hydrolyzed solids are at least partially separated from at least part of the hydrolyzate, that is, the liquid phase comprising the hydrolyzed cellulosic biomass and enzymes, in which said hydrolyzate is then mixed with the cellulosic biomass , which is then introduced into a process, in a specific mixing reactor.
    [12]
    Process according to claim 11, characterized in that, after mixing, at least some hydrolyzate is separated from the cellulosic biomass in a separation step.
    [13]
    Process according to any one of claims 2 to 11, characterized in that a cascade of two or more reactors for hydrolysis is used, and in which at least part of the hydrolyzate, that is, the liquid phase comprising hydrolyzed cellulosic biomass and enzymes a from the first reactor is separated from the solid phase and is subjected to further processing, in which said solid phase from said separation is added to a subsequent reactor, smaller in size and / or volume than the first reactor, in which a predetermined amount of additional enzyme is added to said subsequent reactor.
    [14]
    Process according to claim 13, characterized in that it is repeated for all subsequent pairs of adjacent reactors in a cascade of three or more reactors for hydrolysis, where each of the reactors is smaller in size and / or volume than each previous reactor, respectively.
    Petition 870190031533, dated 04/01/2019, p. 42/46
    5/5
    [15]
    15. Process for the production of monosaccharides, sugar-based chemicals, biofuels or materials together with the sulfonated lignin of the lignocellulosic biomass characterized by comprising at least the following steps:
    (i) pre-treatment of lignocellulosic biomass, preferably in a sulfite cooking step;
    (ii) separation of the pre-treated lignocellulosic biomass from step (i) for:
    (a) a liquid liquid phase of sulfite consumed, comprising 50% or more of lignin from the lignocellulosic biomass in the form of sulfonated lignin, and in (b) a pulp, comprising 70% or more of the cellulose of the lignocellulosic biomass;
    (iii) hydrolysis of the pulp (b) of step (ii) on a chemical sugar platform comprising monosaccharides, wherein said hydrolysis step is the process as defined in any of claims 1 to 14;
    (iv) optional additional treatment of the monosaccharides in step (iii) resulting in useful chemicals, biofuels and / or proteins, and (V) direct conversion or further processing of the sulfonated lignin from the liquid phase (a) of step (ii) into products useful chemicals, biofuels and / or materials.
    [16]
    16. Use of the process for continuous hydrolysis of biomass as defined in any one of claims 1 - 14, characterized by being for the production of biodiesel.
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    同族专利:
    公开号 | 公开日
    EP2582820B1|2019-04-10|
    CA2802977C|2019-07-23|
    JP2013531984A|2013-08-15|
    BR112012032212A2|2015-11-24|
    AU2011267415A1|2012-12-06|
    ZA201300451B|2013-08-28|
    MY158552A|2016-10-14|
    JP5926245B2|2016-05-25|
    AU2011267415B2|2014-08-14|
    DK2582820T3|2019-06-24|
    CA2802977A1|2011-12-22|
    CL2012003557A1|2013-08-30|
    EP2582820A1|2013-04-24|
    US20130217074A1|2013-08-22|
    CN103068996A|2013-04-24|
    US9193982B2|2015-11-24|
    RU2013102048A|2014-07-27|
    ES2733218T3|2019-11-28|
    CN103068996B|2016-03-09|
    WO2011157427A1|2011-12-22|
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    法律状态:
    2019-01-02| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|
    2019-08-13| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
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    EP10006308.0|2010-06-17|
    EP10006308|2010-06-17|
    PCT/EP2011/002974|WO2011157427A1|2010-06-17|2011-06-16|Enzymatic hydrolysis of cellulose|
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