• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    CONTINUOUS OR SEMICONTINUOUS PROCESS FOR TREATING BIOMASS. Fermentable sugar useful for the production of biofuels is produced from biomass in a continuous or semi-continuous manner providing biomass that can be pumped.
    公开号:BR112014027355B1
    申请号:R112014027355-3
    申请日:2013-05-07
    公开日:2020-12-29
    发明作者:Paul Richard Weider；Robert Lawrence Blackbourn；David Matthew Brown
    申请人:Shell Internationale Research Maatschappij B.V.；
    IPC主号:
    专利说明:

    Field of the Invention
    [0001] The invention relates to a process for treating biomass, and more specifically to a pre-treatment of biomass for the production of sugars from materials containing polysaccharides and compositions, for use in biofuel or other products with value high. Background of the Invention
    [0002] Lignocellulosic biomass is seen as an abundant renewable resource for fuels and chemicals due to the presence of sugars in the cell walls of plants. More than 50% of the organic carbon on the earth's surface is contained in plants. This lignocellulosic biomass is comprised of hemicelluloses, cellulose and smaller portions of lignin and protein. These structural components are comprised primarily of monomers of pentose and hexose sugars. Cellulose is a polymer comprised mostly of glucose polymerized by condensation and hemicellulose is a precursor to pentose sugars, mostly xylose. These sugars can be easily converted into fuels and valuable components, provided they can be released from the cell walls and polymers that contain them. However, plant cell walls have evolved considerably in resistance to microbes, chemical or mechanical disruption to produce component sugars. In order to overcome the biomass recalcitrance of soil it is altered by a chemical process known as pre-treatment. The purpose of the pre-treatment is to hydrolyze the hemicellulose, break the protective lignin structure and break the crystalline structure of the cellulose. All of these steps improve the enzymatic access capacity for cellulose during the subsequent hydrolysis step (saccharification).
    [0003] Pretreatment is seen as one of the primary cost drivers in lignocellulosic ethanol and as a consequence a number of pretreatment approaches have been investigated in a wide variety of types of feed loads. Cellulose saccharification enzymatically holds the promise of higher sugar yields under milder conditions and is therefore considered by many to be more economically attractive. The recalcitrance of crude biomass for enzymatic hydrolysis requires a pretreatment to improve the susceptibility of cellulose to hydrolytic enzymes. A number of pretreatment methods, as described in Nathan Mosier, Charles Wyman, Bruce Dale, Richard Elander, YY Lee, Mark Holtzapple, Michael Ladisch 'Features of promising technologies for pretreating of lignocellulosic biomass "Bioresource Technology 96 (2005) pp.673-686, were developed to alter the structural and chemical composition of biomass to enhance enzymatic conversion.A very recent comparison of "leading pretreatment" technologies was achieved by a Biomass Refining Consortium for Applied Innovation and Rationale (CAFI) and reported in a Bioresource Technology journal in December 2011. Such methods include the diluted acid vapor burst treatment described in U.S. Patent No. 4,461,648, hydrothermal pretreatment without the addition of chemicals described in WO 2007/009463 A2, ammonia freeze explosion described in AFEX; Holtzapple, MT, Jun, J., Ashok, G., Patibandla, SL, Dale, BE, 1991, The ammonia fre eze explosion (AFEX) process - a practical ligno cellulose pretreating, Applied Biochemistry and Biotechnology 28/29, pp. 59-74, and extraction of organosolve described in U.S. Patent No. 4,409,032. Despite this, pretreatment was cited as the most expensive process for converting biomass into fuels ("Methods for Pretreating of Biomass ligno cellulose for Efficient Hydrolysis and Biofuel Production" Ind. Eng. Chem. Res., 2009, 48 (8 ), 3713-3729.)
    [0004] A pretreatment that has been extensively explored is a diluted sulfuric acid (H2SO4) process at high temperature, which effectively hydrolyzes the hemicellulose portion of the biomass to soluble sugars and exposes cellulose so that enzymatic saccharification is Of success. The parameters that can be used to control the conditions and the effectiveness of the pre-treatment are time, temperature, and acid loading. These are usually combined in a mathematical equation called the combined severity factor. In general, the higher the loading of acid used, the lower the temperature that can be used; this comes at a cost of acid and its subsequent neutralization. Conversely, the lower the temperature, the greater the pre-treatment process; this comes at the cost of volumetric productivity. It is desirable to lower the temperature since the pentose sugars readily decompose to form furfural and other species which represent a loss of yield and these compounds are poisons for downstream fermentation. However, the use of higher concentrations of acid necessary to lower pretreatment temperatures below those where furfural formation becomes easy (BP Lavarack, GJ Griffin, D. Rodman "The acid hydrolysis of sugarcane bagasse hemicelluloses to product xylose, arabinose, glucose and other products. "Biomass and Bioenergy 23 (2002) pp.367-380) requires sufficient amounts of acid that strong acid recovery is an economic imperative. If diluted acid streams and higher temperatures are employed for the pretreatment reaction it produces increased amounts of furfural and the acid that passes downstream must be neutralized resulting in inorganic salts which complicates downstream processing and requires water treatment systems. more expensive residual.
    [0005] The amount of water used in the pre-treatment additionally impacts the energy balance downstream and the overall economy of the fuel ethanol process. Additionally, there has been a recent review article that studies the economic impact of total solids shipments on the enzymatic hydrolysis of pre-treated corn straw produced by pretreatment of diluted sulfuric acid (Humbird, D., Mohagheghi, A., Dowe , N., Schell DJ "Economic Impact of Total Solids Loading on enzimatic hydrolysis of diluted acid pretreated with stover" Biotechnol. Prog., 2010, Vol. 26, No. 5, 1245 - 1251. (Published on the network on May 26 2010. It is thought that in a commercially relevant cellulosic ethanol process at scale, it will be necessary to carry out hydrolysis of enzymatic cellulose in the total pretreated slurry in a higher total solids loading, while it is mentioned in the article that it may be economically necessary , performing enzymatic hydrolysis at a high total solids load remains challenging with reduced enzymatic yields, that is, in part due to an increase in toxic impurities generated in the p more concentrated re-treatment. Summary of the Invention
    [0006] Given the above information it is desirable to provide a biomass pretreatment process to provide high total solids loading for the enzymatic cellulose hydrolysis which can provide better enzymatic yields. In addition, it is desirable to provide a biomass pretreatment process that can be operated in a continuous or semi-continuous manner instead of batch processes.
    [0007] In one embodiment of the present invention a continuous or semi-continuous process for treating biomass comprises: (a) providing a biomass containing polysaccharides; (b) contact the biomass with a solution containing at least one a-hydroxysulfonic acid at a temperature within the range of 50 ° C to 150 ° C and a pressure within the range of 1 barg (0.1 mPa man.) at 10 barg (1 mPa man.) to provide a biomass solution, in which said biomass solution contains in the range of 1% by weight to 25 by weight of biomass based on the solution, and thus hydrolyzing the biomass to produce at least a product that contains fermentable sugar; (c) removing a-hydroxysulfonic acid in its component form from the product by heating and / or reducing pressure to produce an acid-removed product containing at least one fermentable sugar substantially free of a-hydroxysulfonic acid; (d) separating a high solid / liquid mixture from said acid-removed product to form a stream of wet solids containing at least 12% by weight of undissolved solids based on the stream of wet solids, and a stream of bulk liquid containing at least one fermentable sugar; (e) recycling said removed a-hydroxysulfonic acid to step (b) as components or in its recombined form; and (f) recycling at least a portion of the bulk liquid stream from (d) to step (b); wherein the bulk liquid stream comprises more than 2% by weight of the fermentable sugar based on the bulk liquid stream.
    [0008] In yet another embodiment, a process further comprises hydrolyzing the stream of wet solids.
    [0009] The functionalities and advantages of the invention will be apparent to those skilled in the art. While various changes can be made by those skilled in the art, such changes are within the spirit of the invention. Brief Description of Drawings
    [00010] These drawings illustrate certain aspects of some of the modalities of the invention, and should not be used to limit or define the invention.
    [00011] Fig. 1 schematically illustrates a block flow diagram of lignocellulose pretreatments.
    [00012] Fig. 2 schematically illustrates a block flow diagram of a biomass treatment process modality of the invention. Detailed Description of the Invention
    [00013] While reducing the amount of water for biomass, additional complications occur. In the weight ratios of biomass to water, typically known as consistency, 12% to 15% of the mixture is no longer a solution that can be pumped, but instead behaves like a wet solid. The equipment needed to process these moist solids or mixtures with high consistency (moving, mixing and heat transfer) becomes more expensive, inefficient in energy and inconvenience. Knowledge of how to scale up these new untested pieces of equipment further complicates the development of new fuel production processes.
    [00014] It has been found that the present invention provides an improved method for pretreating commercial-scale biomass in a process to produce sugars and biofuels. The process of the invention incorporates a recyclable acid that can be recovered in a pre-treatment process that can be pumped which results in a pre-treated mixture with low water content, high content of biomass solids, high content of sugar with a lot of low residual acidity (lower salts) and low levels of toxins produced in the pre-treatment (such as furfural).
    [00015] The low temperature pretreatment process makes a liquid / solid substrate (stream of wet solids) that hydrolyzes the same as or better in the presence of pretreatment liquids than if the pretreated solids are rinsed free of pretreatment liquors in contrast to the process reported in the article by Humbird, D. et al.
    [00016] α-hydroxysulfonic acid is effective for treating biomass by hydrolyzing biomass to fermentable sugars such as pentose such as xylose at a lower temperature, (eg 100 ° C for a-hydroxyethane sulfonic acid or a-hydroxyethane sulfonic acid) producing little furfural in the process. A portion of the cellulose has also been shown to hydrolyze under these comparatively mild conditions. It has been found that other polysaccharides such as starch are also readily hydrolyzed to component sugars by α-hydroxy sulfonic acids. In addition, a-hydroxysulfonic acid is reversible for recyclable and readily removable materials unlike mineral acids such as sulfuric, phosphoric, or hydrochloric acid. The lower temperatures and pressures used in the treatment of biomass lead to lower equipment costs. The ability to recycle fragile pentose sugars from the end of pre-treatment to the entry of pre-treatment, without their subsequent conversion to undesirable materials such as furfural, allows to decrease the consistencies in the pre-treatment reaction itself, which still passes a mixture of solids with high consistency containing highly soluble sugars outside the pre-treatment. Biomass pretreated in this way has been shown to be quite susceptible to additional saccharification, especially enzyme-mediated saccharification.
    [00017] Using pretreatment at high temperatures and dilute acid, free xylose is readily dehydrated to form a toxic, furfural by-product. Thus, in high temperature diluted acid processes, it is desirable to finish the pre-treatment reaction as soon as most of the xylan has been hydrolyzed in order to minimize the decomposition of xylose. Any free sugars recycled to the front end of a diluted acid process at an elevated temperature can decompose immediately and result in very high levels of furfuras without a real increase in sugars. This can prevent any attempt to recycle pretreatment liquids to accumulate soluble sugar levels. Thus, at a higher temperature, once the pretreatments have passed, the amount of acid solution for "dry weight" of biomass introduced in the pretreatment determines the last concentration of fermentable sugar obtained. This is balanced by the absorptive nature of biomass with the mixing, transport and heat transfer that become more and more difficult as the relative amount of biomass solids to liquid is increased. The process of the invention uses conditions of low severity (e.g. low temperature) that are possible with the pretreatment using higher concentrations of α-hydroxysulfonic acids, which allow the recycling and accumulation of sugars in the pretreatment reactor stage. The lower temperature process dramatically reduces the rate of decomposition of C5 and C6 sugars for other species such as furfural. Thus, free sugars can be introduced (through recycling) to the front end of a low temperature process and they will pass through the pretreatment unchanged. This allows to accumulate high concentrations of sugar at steady state while dealing with the least consistency in the pretreatment process. The lower temperature has other advantages as if the temperatures were below the reported melting point of lignin, the lignin in the biomass is quite unchanged in texture which results in a pre-treated material that flows free without fouling. This allows for easy liquid / solid separation at the pre-treatment end. Using this invention results in a biomass slurry with high consistency with high concentrations of soluble sugars and low inhibitors such as furfural. The last concentration of undissolved solids passed from the pre-treatment is thus determined by the ratio of fresh water and biomass placed at the front of the process.
    [00018] α-hydroxysulfonic acids of the general formula
    where R] and R2 are individually hydrogen or hydrocarbyl with up to 9 carbon atoms that may or may not contain oxygen can be used in the treatment of the present invention. Α-hydroxysulfonic acid can be a mixture of the acids mentioned above. The acid in general can be prepared by reacting at least one carbonyl compound or carbonyl compound precursor (eg, trioxane and paraformaldehyde) with sulfur dioxide or sulfur dioxide precursor (eg, sulfur and oxidizer, or sulfur trioxide and agent reducer) and water according to the following general equation 1.
    where Ri and R2 are individually hydrogen or hydrocarbyl with up to 9 carbon atoms or a mixture of them.
    [00019] Illustrative examples of the carbonyl compounds useful for preparing the α-hydroxysulfonic acids used in this invention are found where RI = R2 = H (formaldehyde) Ri = H, R2 = CHJ (acetaldehyde) Ri = H, R2 = CH2CH3 (propionaldehyde) Ri = H, R2 = CH2CH2CH3 (n-butyraldehyde) Ri = H, R2 = CH (CH3) 2 (i-butyraldehyde) Ri = H, R2 = CH2OH (glycolaldehyde) Ri = H, R2 = CHOHCH2OH (glyceraldehyde) Ri = H, R2 = C (= 0) H (glyoxal)
    R] = R2 = CH (acetone) R, = CH2OH, R2 = CH3 (acetol) RI = CH3, R2 = CH2CH3 (methyl ethyl ketone) RI = CH3, R2 = CHC (CH3) 2 (mesityl oxide) RI = CH3, R2 = CH2CH (CH3) 2 (methyl i-butyl ketone) R1, R2 = (CH2) 5 (cyclohexanone) or RI = CH3, R2 = CH2C1 (chloroacetone)
    [00020] The carbonyl compounds and their precursors can be a mixture of compounds described above. For example, the mixture can be a carbonyl compound or a precursor such as, for example, trioxane which is known to thermally revert to formaldehyde at high temperatures, metaldehyde which is known to revert thermally to acetaldehyde at high temperatures, or an alcohol which can be converted to the aldehyde by dehydrogenating the alcohol to an aldehyde by any known methods. An example of such a conversion to aldehyde from alcohol is described below. An example of a source of carbonyl compounds may be a mixture of hydroxyacetaldehyde and other aldehydes and ketones produced from rapid pyrolysis oil as described in "Fast Pyrolysis and Bio-oil Upgrading, Biomass-to-Diesel Workshop", Pacific Northwest National Laboratory, Richland, Washington, September 5 and 6, 2006. Carbonyl compounds and their precursors can also be a mixture of ketones and / or aldehydes with or without alcohols that can be converted to ketones and / or aldehydes, preferably in the range from 1 to 7 carbon atoms.
    [00021] The preparation of a-hydroxysulfonic acids by combining an organic carbonyl compound, SO2 and water is a general reaction and is illustrated in equation 2 for acetone.

    [00022] α-hydroxysulfonic acids appear to be as strong as, if not stronger, HC1 since an aqueous solution of the adduct has been reported to react with NaCl releasing the weaker acid, HC1 (see US 3,549,319). The reaction in equation 1 is a real equilibrium, which results in simple acid reversibility. That is, when heated, the balance shifts to the initial carbonyl, sulfur dioxide, and water (component form). If the volatile components (for example, sulfur dioxide) are allowed to escape from the reaction mixture through vaporization or other methods, the acid reaction is completely reversed and the solution becomes effectively neutral. Thus, by increasing the temperature and / or lowering the pressure, sulfur dioxide can be removed and the reaction completely reverses due to the Le Chatelier principle, the destination of the carbonyl compound is dependent on the nature of the material used. If carbonyl is also volatile (for example, acetaldehyde), this material is also easily removed in the vapor phase. Carbonyl compounds such as benzaldehyde, which are moderately soluble in water, can form a second organic phase and be separated by organic means. Thus, the carbonyl can be removed by conventional means, for example, the continued application of heat and / or vacuum, steam and nitrogen extraction, solvent washing, centrifugation, etc. Therefore, the formation of these acids is reversible due to the fact that the temperature is high, sulfur dioxide and / or aldehyde and / or ketone can flash from the mixture and be condensed or absorbed in another place in order to be recycled. . These reversible acids, which are almost as strong as strong mineral acids, have been found to be effective in biomass treatment reactions. These treatment reactions have been found to produce very little of the unwanted furfural by-products produced by other conventional mineral acids. In addition, as acids are effectively removed from the reaction mixture following treatment, neutralization with base and formation of salts to complicate downstream processing is substantially avoided. The ability to reverse and recycle these acids also allows for the use of higher concentrations than would otherwise be economically and environmentally practical. As a direct result, the temperature employed in the treatment of biomass can be reduced to decrease the formation of by-products such as furfural or hydroxymethylfurfural.
    [00023] It was found that the position of the balance given in equation 1 at any given temperature and pressure is greatly influenced by the nature of the carbonyl compound used, steric and electronic effects that have a strong influence on the thermal stability of the acid. More steric volume around the carbonyl, which tends to favor less thermal stability of the acid form. Thus, the acid resistance and the simple decomposition temperature can be adjusted by selecting the appropriate carbonyl compound.
    [00024] In one embodiment, the acetaldehyde starting material to produce α-hydroxysulfonic acids can be provided by converting ethanol, produced from the biomass fermentation process of the invention, to acetaldehyde by dehydrogenation or oxidation. Dehydrogenation can typically be performed in the presence of copper catalysts activated with zinc, cobalt, or chromium. At reaction temperatures of 260 to 290 ° C, the ethanol conversion per pass is 30 to 50% and the selectivity for acetaldehyde is between 90 and 95 mol%. By-products include crotonaldehyde, ethyl acetate, and higher alcohols. Acetaldehyde and unconverted ethanol are separated from the hydrogen-rich exhaust gas by washing with ethanol and water. Pure acetaldehyde is recovered by distillation, and an additional column is used to separate ethanol for recycling products with a higher boiling point. It may not be necessary to supply pure aldehyde for the a-hydroxysulfonic acid process above and the raw stream may be sufficient. Hydrogen-rich purge gas is suitable for hydrogenation reactions or can be used as a fuel to provide some endothermic heat from the ethanol dehydrogenation reaction. The copper-based catalyst has a life of several years but requires periodic regeneration. In an oxidation process, ethanol can be converted to acetaldehyde in the presence of air or oxygen and using a silver catalyst in the form of bulk crystals or wire mesh. Typically, the reaction is carried out at temperatures between 500 ° and 600 ° C, depending on the ratio of ethanol to air. Part of the acetaldehyde is also formed by dehydrogenation, with additional combustion of hydrogen to produce water. At a given reaction temperature, the endothermic heat from dehydrogenation partially displaces the exothermic heat from oxidation. The ethanol conversion per pass is typically between 50 and 70%, and selectivity for acetaldehyde is in the range of 95 to 97% by mol. By-products include acetic acid, CO and CO2. The separation steps are similar to those in the dehydrogenation process, except that the current is generated by the heat recovery from the reactor effluent stream. The purge gas stream consists of nitrogen containing some methane, hydrogen, carbon monoxide and carbon dioxide; can be used as a poor fuel with low calorific value. An alternative method to produce acetaldehyde by air oxidation of ethanol in the presence of a Fe-Mo catalyst. The reaction can be carried out at 180 to 240 ° C and at atmospheric pressure using a multitubular reactor. According to patent examples, selectivities for acetaldehyde between 95 and 99 mol% can be obtained with ethanol conversion levels above 80%.
    [00025] As used here, the term "biomass" means organic materials produced by plants (for example, leaves, roots, seeds and branches). Common sources of biomass include: agricultural waste (for example, corn husks, straw, seed husks, sugar cane remains, bagasse, nut shells, and cattle manure, poultry, and pigs); wood materials (for example, wood or bark, sawdust, wooden bar, and mill scrap); municipal waste (for example, waste paper and yard waste); and energy crops (for example, poplars, willows, grass, alfalfa, prairie bluestream, corn, soybeans, seaweed and seaweed). The term "biomass" also refers to the primary building blocks of all of the above, including, but not limited to, saccharides, lignins, celluloses, hemicelluloses, and starches. The term "polysaccharides" refers to structures of polymeric carbohydrates, of repeating units (either mono- or di-saccharides) joined by glycosidic bonds. These structures are generally linear, but can contain varying degrees of branching. Examples include storage polysaccharides such as starch and glycogen, and structural polysaccharides such as cellulose and chitin. Biomass is typically pre-processed to suitable particle size, which can include milling. Not having the intention to restrict the scope of the invention, it is typically found that it is easier to process smaller biomass particles. Biomass that is small in size to facilitate handling (for example, less than 1.3 cm) are particularly susceptible materials.
    [00026] Several factors affect the conversion of the biomass feed load in the hydrolysis reaction. The carbonyl compound or the incipient carbonyl compound (such as trioxane) with sulfur dioxide and water must be added in an amount and under effective conditions to form α-hydroxysulfonic acids. The temperature and pressure of the hydrolysis reaction must be in the range to form α-hydroxysulfonic acids and to hydrolyze biomass to fermentable sugars. The amount of carbonyl compound or its precursor and sulfur dioxide must be to produce a-hydroxysulfonic acids in the range from 1% by weight, preferably from 5% by weight to 55% by weight, preferably to 40% by weight , more preferably to 20% by weight, based on the total solution. For the reaction, excess sulfur dioxide is not necessary, but any excess sulfur dioxide can be used to direct the equilibrium in the eq. 1 to favor the acid form at elevated temperatures. The contact conditions of the hydrolysis reaction can be conducted at temperatures preferably at least from 50 ° C depending on the a-hydroxysulfonic acid used, although such temperature can be as low as the ambient temperature depending on the acid and pressure used. The contact condition of the hydrolysis reaction can vary preferably up to and including 150 ° C depending on the α-hydroxysulfonic acid used. In a more preferred condition the temperature is at least from 80 ° C, even more preferably at least 100 ° C. In a more preferred condition the temperature range up to and including 90 ° C to 120 ° C. The reaction is preferably conducted as low as pressure is possible, given the requirement to contain excess sulfur dioxide. The reaction can also be conducted at a pressure as low as 1 barg (0.1 mPa man.), Preferably 4 barg (0.4 mPa man.), For a pressure as high as 10 barg (1 mPa man.). The temperature and pressure to be used optimally will depend on the particular a-hydroxysulfonic acid chosen and optimized based on the economic considerations of metallurgy and containment vessels as practiced by those skilled in the art.
    [00027] Various methods have been used by those skilled in the art to circumvent such obstacles for mixing, transporting and transferring heat. Thus the percentage of total solids to liquids by weight of the biomass (consistency) can be as low as 1% or greater depending on the chosen device and the nature of the biomass (even as high as 33% if specialized equipment is developed or used). The percentage of solids is a percentage by weight of dry solids base and the% by weight of liquids contains water in the biomass. In the preferred embodiment, where more conventional equipment is desired, then the consistency is from at least 1% by weight, preferably at least 2% by weight, more preferably at least 8% by weight to 25% by weight, preferably for 20% by weight, more preferably up to 15% by weight.
    [00028] The temperature of the hydrolysis reaction can be chosen so that the maximum amount of carbohydrates that can be extracted is hydrolyzed and extracted as fermentable sugar (more preferably pentose and / or hexose) from the biomass feed load while limits the formation of degradation products. The temperatures required for successful pretreatment are controlled by the reaction time, the pH of the solution (acid concentration), and the reaction temperature. So when the acid concentration is high, the temperature can be reduced and / or the reaction time extended to achieve the same goal. The advantages of lowering the reaction temperature are that fragile monomeric sugars are protected from degradation for dehydrated species such as furfural and that the lignin shield is not dissolved or fused and redeposited in the biomass. If high enough levels of acid are employed, temperatures can be reduced below the point at which sugar degradation or lignin deposition is problematic; this in turn is made possible through the use of reversible α-hydroxysulfonic acids. In such a low temperature process it becomes possible to recycle a mixture of sugars from the end of a pre-treatment process to a pre-treatment process. This allows the sugars to accumulate to a high steady state value while still dealing with a slurry that can be pumped through the pretreatment process. Such a process is highlighted in the diagram below. In this process, biomass, water, and a-hydroxysulfonic acid are combined in the acid hydrolysis stage and reacted to perform the pre-treatment of the biomass. The acids are separated from the reaction mixture as described above and recycled to the pretreatment reactor. Then a mixture with a high solid / concentrated liquid content (wet solid stream) is separated from the bulk liquid, which is also recycled to the reactor. In this way the ratio of biomass to liquids is defined by the ratio of feeding of these components and the optimized target of wet biomass to move towards enzymatic hydrolysis.
    [00029] In some embodiments, a plurality of reactor vessels can be used to carry out the hydrolysis reaction. These vessels can have any design capable of carrying out a hydrolysis reaction. Suitable reactor vessel designs may include, but are not limited to, batch reactors, porous bed, co-current, counter-current, agitated tank, downflow, or fluidized bed. Staged reactors can be employed to find the most economical solution. The solids from the remaining biomass feed charge can then optionally be separated from the liquid stream to allow more severe processing of the recalcitrant solids or to pass directly into the liquid stream for further processing which may include enzymatic hydrolysis, fermentation, extraction, distillation and / or hydrogenation. In another embodiment, a series of reactor vessels can be used with an increasing temperature profile so that a desired sugar fraction is extracted into the vessel. The outlet of each vessel can then be cooled before combining the currents, or the currents can be fed individually for the next reaction for conversion.
    [00030] Suitable reactor designs may include, but are not limited to, a backmixed reactor (eg, a stirred tank, a bubble column, and / or a mixed jet reactor) can be employed if viscosity and characteristics of partially digested biocomposite based feed charge and liquid reaction media is sufficient to operate in a regime where biocomposite based feed charge solids are suspended in an excess liquid phase (as opposed to a stacked pile digester). It is also conceivable that a porous bed reactor can be used with the biomass present as the stationary phase and an a-hydroxysulfonic acid solution that passes over the material.
    [00031] In some embodiments, the reactions described below are performed on any suitable design system, including systems comprising continuous flow reactors and vessels (such as CSTR and plug flow reactors), batch, semi-stacked or multiple systems and flow reactors through packaged bed. For reasons of economic feasibility only, it is preferable that the invention be practiced using a steady-state steady-flow system. In an advantage of the process in contrast to the pretreatment reactions of the diluted acids where residual acid is left in the reaction mixture (<1% by weight of sulfuric acid), the lower temperatures employed using these acids (5 to 20% in weight) result in substantially lower reactor pressures that result in potentially less expensive processing systems such as plastic-lined reactors, duplex stainless steel reactors, for example, such as type 2205 reactors.
    [00032] Figure 1 shows an embodiment of the present invention for converting biomass to sugars. In this embodiment, a biomass feed charge 112 is introduced to a hydrolysis reaction system 114 along with a recycle stream 118. The hydrolysis reaction system 114 can comprise a number of components including a-hydroxysulfonic acid generated on site. The term "in situ" as used here refers to a component that is produced within the general process; it is not limited to a particular reactor for production or use and is therefore synonymous with a component generated in the process. The hydrolysis reaction system 114 may contain one or more reactors and optionally extractors of solids or slurry. The reacted product stream 116 from 114 is introduced into the acid removal system 120 where the acid is removed in its component form then it is recovered 122 (and optionally washed 124) and recycled through the recycle stream 118 to 114 and product stream 126 containing at least one fermentable sugar (e.g., pentose and optionally hexose) substantially without a-hydroxysulfonic acids is produced. Optionally, at least a portion of the liquid in the product stream 116 containing a-hydroxysulfonic acid can be recycled to the hydrolysis reaction system 114. The product stream 126 is provided for a separation system 200 where a mixture with a high solid content / liquid is separated from the acid-removed product stream to form a wet solids stream 220 containing at least 12% by weight of undissolved solids containing cellulose, preferably in the range of 15% by weight to 35% by weight of undissolved solids , and more preferably in the range of 20 to 25% by weight of undissolved solids, based on the wet solids stream, and a bulk liquid stream 210 that can be made up of 20 to 80% by weight of liquid from of the product stream removed by acid containing fermentable sugar (eg, pentose and optionally hexose). At least a portion of the bulk liquid stream 210 is recycled to the hydrolysis reaction system where the bulk liquid stream comprises more than 2% by weight, preferably 5% by weight or more, more preferably 8% by weight or more of fermentable sugar based on the bulk liquid stream. The bulk liquid stream is recycled in such a way as to maintain the hydrolysis reaction and can be pumped, preferably 15% by weight or less of solids content in the hydrolysis reactor. As a modality, a portion of the bulk liquid recycle stream 210 can be used to dilute the hydrolysis reaction system 114 for the entry of biomass into the hydrolysis reactor in the system, and / or to facilitate the extraction of solids at the bottom. reactor (or reactor system output) or can be added to an extractor or to the reactor product stream 116 for dilution. A portion of the bulk liquid stream 210 that optionally contains fermentable sugar can be removed, 250, and further processed to produce biofuel components or other chemicals. The required composition water can be introduced into the primary pretreatment system 114 or in several other locations to achieve the desired results. For example, water of required composition can be introduced for the solids / liquid separation step 200 in a way to produce a rinsed biomass, allowing the predominant pentose stream to be processed as a separate stream 250.
    [00033] Figure 2 shows an embodiment of the present invention for converting biomass to alcohols. In this embodiment, a biomass feed charge 112 is introduced to a hydrolysis reaction system 114 along with a recycle stream 118. The hydrolysis reaction system 114 can comprise a number of components including a-hydroxysulfonic acid generated on site. The term "on site" as used here refers to a component that is produced within the general process; it is not limited to a particular reactor for production or use and is therefore synonymous with a component generated in the process. The hydrolysis reaction system 114 may contain one or more reactors and optionally solid or slurry extractors. The stream of reacted product 116 from 114 is introduced into the acid removal system 120 where the acid is removed in its component form then it is recovered 122 (and optionally washed 124) and recycled through recycle stream 118 to 114 and product stream 126 containing at least one fermentable sugar (e.g., pentose and optionally hexose) substantially without a-hydroxysulfonic acids is produced. The acid removed as components is recycled to 114 as components and / or in its recombined form. Optionally, at least a portion of the liquid in the product stream 116 containing a-hydroxysulfonic acid can be recycled to the hydrolysis reaction system 114. The product stream 126 is provided for a separation system 200 where a mixture with a high solid content / liquid is separated from the acid-removed product stream to form a wet solids stream 220 containing at least 12% by weight of undissolved solids containing cellulose, preferably in the range of 15% by weight to 35% by weight of undissolved solids , more preferably in the range of 20% by weight to 25% by weight of undissolved solids, based on the wet solids stream, and a bulk liquid stream 210 which can make up to 20 to 80% by weight of the stream liquid of product removed from acid containing fermentable sugar (eg pentose and optionally hexose). At least a portion of the bulk liquid stream 210 is recycled to the hydrolysis reaction where the bulk liquid stream comprises more than 2% by weight, preferably 5% by weight or more, more preferably 8% by weight or more , fermentable sugar based on the bulk liquid stream. The stream of bulk liquid is recycled in such a way as to maintain the hydrolysis reaction that can be pumped, preferably 15% by weight or less of solids content in the hydrolysis reactor. As a modality, a portion of the bulk liquid recycling stream 210 can be used to dilute the hydrolysis reaction system 114 towards the entry of biomass into the hydrolysis reactor in the system, and / or for the ease of extracting solids in the bottom products of the reactor (or reactor system outlet) or can be added to an extractor or towards the product stream of reactor 116 for dilution. At least a portion of the wet solids stream 220 can optionally be provided for a washing system that can have one or more water washing steps. It is one of the features of the invention that the washing step may not be necessary due to the composition of the product stream and the wet solids stream produced by the continuous or semi-continuous process of the invention. If the wash step is employed, a liquid wash stream (not shown in the figure) can pass back to the pretreatment reactor 114 as a portion of the water inlet stream, and / or be supplied to the system separator 200. At least a portion of the bulk liquid stream 210 can optionally be processed to remove and recover any acetic acid present. At least a portion of the bulk liquid stream 210, comprised primarily of pentose sugars in water, can be processed independently of the products or recombined with hydrolyzate 310 as a feed for the fermentation system 400. The (optionally washed) stream of solids 220 is provided for the enzymatic hydrolysis system 300 as a high solids feed load for the enzymatic hydrolysis system. In the enzymatic hydrolysis system 300, pre-treated biomass, and optionally hemicelluloses from a portion of the bulk solution stream, is hydrolyzed with an enzyme solution, while the hydrolyzate (aqueous sugar stream) 310 is produced and fermented in the fermentation system 400 in the presence of a microorganism to produce a stream of fermented product containing at least one alcohol (alcohol stream 410). Alcohol 510 can then be recovered in a recovery system 500 from the alcohol stream 410 which also produces the aqueous effluent stream 520. Lignin can optionally be removed (not shown) after the enzyme hydrolysis system, after the system fermentation or after the recovery system by the lignin separation system. The aqueous effluent stream after the removal of lignin can optionally be recycled as an aqueous effluent recycle stream for the hydrolysis reaction thereby reducing the intake of fresh water in the overall process.
    [00034] The treatment reaction product contains fermentable sugar or monosaccharides, such as pentose and / or hexose which is suitable for further processing. Optionally, at least a portion of the liquid stream containing the residual α-hydroxysulfonic acid of the product containing the fermentable sugar stream can be recycled for the treatment reaction. Residual a-hydroxysulfonic acid can be removed by applying heat and / or vacuum from the product stream containing fermentable sugar to reverse the formation of a-hydroxysulfonic acid to your starting material to produce a stream containing fermentable sugar substantially free of α-hydroxysulfonic acid. In particular, the product stream is substantially free of α-hydroxysulfonic acid, which means that no more than 2% by weight is present in the product stream, preferably not more than 1% by weight, more preferably not more than 0.2% by weight, even more preferably not more than 0.1% by weight present in the product stream. The temperature and pressure will depend on the particular a-hydroxysulfonic acid used and minimizing the temperatures employed is desirable to preserve the sugars obtained in the treatment reactions. Typically the removal can be conducted at temperatures in the range of from 50 ° C, preferably from 80 ° C, more preferably from 90 ° C to 110 ° C to 150 ° C. The pressure can range from 0.5 bara (0.05 mPa abs.) To 2 barg (0.2 mPa man.), More preferably from 0.1 barg (0.01 mPa man. ) at 1 barg (0.1 mPa man.). It can be seen by one skilled in the art that treatment reaction 114 and removal of acid 120 may occur in the same vessel or in a different vessel or in a number of different types of vessels depending on the reactor configuration and the stage provided the system is designed so that the reaction is conducted under favorable conditions for the formation and maintenance of a-hydroxysulfonic acid and the favorable removal for the reverse reaction (as components). As an example, the reaction in reactor vessel 114 can be operated at approximately 100 ° C and a pressure of 4 barg (0.4 mPa man.) In the presence of alpha-hydroxyethane sulfonic acid and removal of vessel 120 can be operated in approximately 110 ° C and a pressure of 0.5 barg (0.05 mPa man.). It is further contemplated that the reversal can be favored by the reactive distillation of the formed a-hydroxysulfonic acid. In recycling the removed acid, optionally additional carbonyl compounds, SO2, and water can be added as needed. The removed starting material and / or a-hydroxysulfonic acid can be condensed and / or washed by contact with water and recycled to the reaction system 114 as components or in its recombined form.
    [00035] The preferable residence time of the biomass to contact a-hydroxysulfonic acid in the hydrolysis reaction system can be in the range of 5 minutes to 4 hours, even more preferably 15 minutes to 1 hour.
    [00036] Thus, a typical hydrolysis reaction mixture contains (a) biomass containing polysaccharides, (b) at least one a-hydroxysulfonic acid, (c) water, and (d) at least one fermentable sugar. It has been found that a ketone or beta-sulfo aldehyde compound forms in the reaction mixture with time and acid concentration. It will accumulate to steady state with liquid recycling in a continuous or semi-continuous process of the invention. After a-hydroxysulfonic acid is removed, the bulk liquid stream is removed, the wet solid stream may contain (a) biomass containing polysaccharides (undissolved solids), (b) water, and (c) at least one compound ketone or beta-sulfo aldehyde. Without the intention of being bound in theory, it is thought that the very low acidity (lower salts) and low levels of toxins produced in the pre-treatment (such as furfural) allow the wet solids to be additionally hydrolyzed by enzyme without previous washing steps as required for conventional biomass pretreatment processes. Additionally, without intending to be bound by theory, it is thought that the presence of a ketone or beta-sulfo aldehyde compound that is present in a concentration of at least 0.01% by weight, preferably at least 0.03% by weight , more preferably at least 0.5% by weight to 5% by weight, more preferably up to 2% by weight, based on the wet solids stream, can help facilitate the hydrolysis of the enzyme.
    [00037] It is thought that the ketone or beta-sulfo aldehyde compound has the following general formula:
    where R1 and R2 are individually hydrogen or hydrocarbyl with up to 9 carbon atoms.
    [00038] Sulphonated crotonaldehyde where R1 is a methyl group and R2 is hydrogen is preferred.
    [00039] The separation system can be carried out using any separation method to separate wet and liquid solids. Examples of suitable separation methods, for example, can include centrifugal force, filtration, decantation, and other similar methods.
    [00040] In one embodiment, the product stream containing cellulose can be further hydrolyzed by other methods, for example, by enzymes to further hydrolyze biomass to sugar products containing pentose and hexose (eg, glucose) and fermented to produce alcohols as described in US Publication No. 2009/0061490 and US Patent No. 7,781,191.
    [00041] In yet another modality, fermentable sugar can be converted to furfurral or hydroxymethylfurfüral (HMF) or additionally fermented to alcohols. Although in some embodiments it is desirable to minimize furfural formation, if furfural formation is desired, the acid-containing solution from step (b) can be further heated to a temperature in the range of from 110 to 160 ° C, more preferably in the range of from 120 to 150 ° C to form at least one product stream containing furfural. In one embodiment, the temperature of step (b) is maintained at a temperature of 100 ° C or less if it is desirable to obtain minimal furfural in the product stream.
    [00042] In yet another embodiment, fermentable sugars can be converted to higher hydrocarbons as a biofuel component using catalytic hydrogenation and condensation techniques instead of additional enzyme and fermentation hydrolysis. Typically the product containing fermentable sugar is contacted with hydrogen in the presence of a hydrogenolysis catalyst to form a plurality of oxygenated intermediates, and then further processing the oxygenated intermediates to produce a fuel mixture in one or more processing reactions. In one embodiment, a condensation reaction can be used in conjunction with other reactions to generate a fuel mixture and can be catalyzed by a catalyst comprising functional acid or base sites, or both to produce a liquid fuel. As used herein, the term "higher hydrocarbons" refers to hydrocarbons having an oxygen to carbon ratio of less than at least one component of the biomass feed load. As used herein the term "hydrocarbon" refers to an organic compound comprising primarily hydrogen and carbon atoms, which is also an unsubstituted hydrocarbon. In certain embodiments, the hydrocarbons of the invention also comprise heteroatoms (for example, oxygen or sulfur) and thus the term "hydrocarbon" can also include substituted hydrocarbons.
    [00043] In such an example, the product stream containing fermentable sugar can be further processed to produce mixtures of C4 + compounds useful for biofuels as described in US Publication Nos. US2011 / 0154721 and US2011 / 0282115. As another example, the product stream containing fermentable sugar can be further processed to produce mixtures of C4 + compounds useful for biofuels as described in U.S. Publication No. 20080216391. The solid feed may also be suitable for use in reactions of rapid pyrolysis leading to fuels and chemicals.
    [00044] The term "fermentable sugar" refers to oligosaccharides and monosaccharides that can be used as a carbon source (for example, pentoses and hexoses) by a microorganism in a fermentation process. It is contemplated that fermentable sugar can be fermented as described above, but it can also be processed by other methods without fermentation to produce fuels as described above. The term "pentose" refers to monosaccharides with five carbon atoms. The term "hexose" refers to monosaccharides with six carbon atoms.
    [00045] In enzymatic hydrolysis - fermentation processes, the pH of the pre-treated feed charge for enzymatic hydrolysis is typically adjusted so that it is within a range which is optimal for the cellulase enzymes used. In general, the pH of the pre-treated feed load is adjusted to within a range of 3.0 to 7.0, or any pH in between.
    [00046] The temperature of the treated feed load is adjusted so that it is within the optimum range for cellulase enzyme activity. In general, a temperature of 15 ° C to 100 ° C, 20 ° C to 85 ° C, preferably 30 ° C to 70 ° C or any temperature between them, is suitable for most cellulase enzymes. Cellulases, β-glucosidase and other auxiliary enzymes required for cellulose hydrolysis are added to the pre-treated feed charge, before, during, or after adjusting the temperature and pH of the aqueous slurry after pre-treatment. Preferably the enzymes are added to the pre-treated lignocellulosic feed charge after adjusting the temperature and pH of the slurry.
    [00047] By the term "cellulase enzymes" or "cellulases," is meant a mixture of enzymes that hydrolyze cellulose. The mixture can include cellobiohydrolases (CBH), glucobiohydrolases (GBH), endoglucanases (EG), proteins of the glycosyl hydrolysis family 62 (GH61) and β-glucosidase. By the term "β-glucosidase", is meant any enzyme that hydrolyzes the glucose dimer, cellobiose, to glucose. In a non-limiting example, a cellulase mixture can include EG, CBH, GH61 and β-glucosidase enzymes.
    [00048] Enzymatic hydrolysis can also be performed in the presence of one or more xylanase enzymes. Examples of xylanase enzymes that can also be used for this purpose and include, for example, xylanase 1, 2 (Xynl and Xyn2) and β-xylosidase, which are typically present in cellulase mixtures.
    [00049] The process can be carried out with any type of cellulase enzymes, regardless of their source. Non-limiting examples of cellulases that can be used include those obtained from fungi of the genera Aspergillus, Humicola, and Trichoderma, Myceliophthora, Chrysosporium and bacteria of the genera Bacillus, Thermobifida and Thermotoga. In some embodiments, the host cell of the filamentous fungus is an Acremonium cell, Aspergillus, Aureobasidium, Bjerkandera, Ceriporiopsis, Chrysosporium, Coprinus, Coriolus, Cryptococcus, Filibasidium, Fusarium, Humicola, Magnaporthe, Mucor, Necelecore, Myceliopor Penicillium, Phanerochaete, Phlebia, Piromyces, Pleurotus, Schizophyllum, Talaromyces, Thermoascus, Thielavia, Tolypocladium, Trametes, or Trichoderma.
    [00050] The cellulase enzyme dosage is chosen to convert the cellulose from the pre-treated feed load to glucose. For example, an appropriate cellulase dosage can be 1 to 100 mg of enzyme (dry weight) per gram of cellulose.
    [00051] In practice, hydrolysis can be carried out in a hydrolysis system, which can include a series of hydrolysis reactors. The number of hydrolysis reactors in the system depends on the cost of the reactors, the volume of the aqueous slurry, and other factors. Enzymatic hydrolysis with cellulase enzymes produces an aqueous (hydrolyzate) sugar stream comprising glucose, unconverted cellulose, lignin and other sugar components. Hydrolysis can be performed in two stages (see U.S. Patent No. 5,536,325), or it can be performed in a single stage.
    [00052] In the fermentation system, the aqueous sugar stream then fermented by one or more fermentation microorganisms to produce a fermentation wort comprising the alcohol fermentation product useful as biofuels. In the fermentation system, any one of a number of known microorganisms (for example, yeast or bacteria) can be used to convert sugar into ethanol or other alcohol fermentation products. Microorganisms convert sugars, including, but not limited to, glucose, mannose and galactose present in the clarified sugar solution to a fermentation product.
    [00053] Many known microorganisms can be used in the present process to produce the desired alcohol for use in biofuels. Clostridia, Escherichia coli (E. coli) and recombinant strains of E. coli, generically modified strain of Zymomonas mobilis as described in US2003 / 0162271, U.S. Patent No. 7,741,119 and U.S. Patent No. 7,741,084 are some examples of such bacteria. The microorganisms may additionally be a yeast or a filamentous fungus of the genus Saccharomyces, Kluyveromyces, Candida, Pichia, Schizosaccharomyces, Hansenula, Kloeckera, Schwanniomyces, Yarrowia, Aspergillus, Trichoderma, Humicola, Acremonium, Fusarium, and Penicillium. Fermentation can also be carried out with recombinant yeast modified to ferment both hexose and pentose sugars to ethanol.
    [00054] Recombinant yeasts that can ferment one or both of the sugars of pentose xylose and arabinose to ethanol are described in U.S. Patent No. 5,789,210, U.S. Patent No. 6,475,768, European Patent EP 1,727,890, European Patent EPI 863,901 and WO 2006/096130. The use of xylose can be mediated by the xylose reductase / xylitol dehydrogenase route (for example, WO9742307 Al 19971113 and W09513362 Al 19950518) or the xylose isomerase route (for example, W02007028811 or W02009109631). It is also contemplated that the fermentation organism can also produce fatty alcohols, for example, as described in WO 2008/119082 and PCT / US 07/011923. In another modality, fermentation can be carried out by yeast capable of predominantly fermenting C6 sugars, for example, through the use of commercially available strains such as Thermosacc and Super start.
    [00055] Preferably, the fermentation is carried out at or near the optimum temperature and pH of the fermentation of the microorganism. For example, the temperature can be from 25 ° C to 55 ° C, or any amount in between. The fermentation dose of the microorganism will depend on other factors, such as the activity of the fermentation microorganism, the desired fermentation time, the reactor volume and other parameters. It will be appreciated that these parameters can be adjusted as desired by a person skilled in the art to achieve optimal fermentation conditions.
    [00056] Fermentation can be carried out in batch, continuous fermentation or fed batch modes, with or without stirring. The fermentation system can employ a series of fermentation reactors.
    [00057] In some embodiments, the hydrolysis system and the fermentation system can be conducted in the same vessel. In one embodiment, hydrolysis can be partially completed and the partially hydrolyzed stream can be fermented. In one embodiment, a simultaneous saccharification and fermentation (SSF) process where the hydrolysis system can be run until the final percentage solid target is satisfied and then the hydrolyzed biomass can be transferred to a fermentation system.
    [00058] The fermentation system produces an alcohol stream preferably containing at least one alcohol having 2 to 18 carbon atoms. In a recovery system, when the product to be recovered in the alcohol stream is a distilled alcohol, such as ethanol, the alcohol can be recovered by distillation in a manner known to separate such alcohol from an aqueous stream. If the product is to be recovered in the alcohol stream it is not an alcohol that can be distilled, such as fatty alcohols, the alcohol can be recovered by removing alcohols as solids or oils from the fermentation vessel, thus separating it from the fermentation stream. aqueous effluent.
    [00059] While the invention is susceptible to the various forms of modifications and alternatives, specific modalities of the same are shown by means of examples described here in detail. It will be understood that the detailed description of the same is not intended to limit the invention to the particular form described, but on the contrary, the intention is to cover all modifications, equivalents and alternatives that are within the spirit and scope of the present invention as defined by the attached claims. The present invention will be illustrated by the following illustrative embodiment, which is provided for the illustration only and should not be construed as limiting the claimed invention in any way. ILLUSTRATIVE MODALITIES
    [00060] General Methods and Materials
    [00061] In the examples, the aldehyde or aldehyde precursors were obtained from Sigma-Aldrich Co.
    [00062] Whole wheat straw having the following components analyzed using standard TAPPI methods (T-249, T-222, T-211) and had the following average composition on a dry basis: Glucan 38.8% by weight Xylan 23 % by weight Lignin 22% by weight Gray 5.9% by weight Others 10.3% by weight Analytical methods Determination of oxygenated components in the aqueous layer.
    [00063] A sample or standard is analyzed by injection into a current of a mobile phase that follows through a Bio-rad column (Aminex HPX-87H, 300 mm x 7.8 mm). The reverse phase HPLC system (Shimadzu) equipped with both IR and UV detectors and the signals are recorded as peaks in a data acquisition and data processing system. Components are quantified using external calibration through calibration curves based on injection of known concentrations of the target components. Some of the components were calculated using a single pattern point. The reference samples contain 0.5% by weight of Glucose, Xylose and Sorbitol in water. HPLC instrument conditions: Column: Bio-Rad Aminex HPX-87H (300 mm x 7.8 mm) Flow rate: 0.6 ml / minute Column oven: 30 ° C Injection volume: 10 μL UV detector : @ 320 NM IR detector: mode - A; track - 100 Running time: 70 minutes Mobile phase: 5 mM sulfuric acid in water
    [00064] The sample is injected either directly or diluted with water first, but it ensures that there are no particulars. Pass through a 0.2 μm syringe filter if there is precipitation in the sample or diluted sample. The samples were analyzed for Glucose, Xylose, Formic acid, Acetic acid, Arabinose, hydroxymethyl furfural, and Furfural content. Examples General procedure for the formation of α-hydroxysulfonic acids.
    [00065] Aldehydes and ketones will readily react with sulfur dioxide in water to form α-hydroxy sulfonic acids according to equation 1 above. These reactions are generally quick and somewhat exothermic. The order of addition (SO2 for carbonyl or carbonyl for SO2) does not appear to affect the reaction result. If carbonyl is capable of aldol reactions, preparation of concentrated mixtures (> 30% by weight) is best conducted at temperatures below room temperature to minimize side reactions. It has been found to be beneficial to trace the course of the reaction using probes that employ Infrared Spectroscopy in place (ISIR) capable of being inserted into pressure reaction vessels or systems. There are several manufacturers of such systems such as the Mettler Toledo Autochem's Sentinal probe. In addition to being able to see the starting materials: water (1640 cm'1), carbonyl (from approximately 1750 cm'1 to 1650 cm'1 depending on the organic carbon structure) and SO2 (1331 cm'1) , the formation of a-hydroxysulfonic acid is accompanied by the formation of characteristic bands of the SCh 'group (broad band around 1200 cm'1) and the extensions of the a-hydroxy group (single to multiple bands around 1125 cm'1 ). In addition to monitoring the formation of a-hydroxy sulfonic acid, the relative position of the balance at any temperature and pressure can be readily assessed by the relative peak heights of the starting components and the acid complex. The definitive presence of a-hydroxy sulfonic acid under biomass hydrolysis conditions can also be confirmed with ISIR and it is possible to monitor the growth of sugars in the reaction mixture by monitoring the appropriate IR bands. Example 1 Formation of 40% by weight q-hydroxyethanesulfonic acid from metaldehyde.
    [00066] A sealed 2L Parr autoclave equipped with a DiComp IR probe was charged with 999.98 grams of nitrogen washed with deionized water and 212.02 grams of metaldehyde. Two Hoke vessels containing 171.19 and 167 grams, 338.19 grams total, of sulfur dioxide are attached to the reactor as a "blow chamber injector". The reactor is closed and the pressure tested with nitrogen gas. The stirrer starts at 1000 rpm and the IR acquisition starts. Sulfur dioxide is injected into the reactor through a ball valve and its accumulation in the reaction mixture noted in the IR spectrum with strong absorption at 1331 cm'1. Due to the solubility of metaldehyde wash water, no absorption bands due to this material are noticed. The formation of a-hydroxysulfonic acid was monitored by an IR at the site. After the addition of sulfur dioxide, the reactor was warmed up slowly and at approximately 50 ° C the formation of a-hydroxyethane sulfonic acid guarantees, with bands for this species, a wide centralized band 1175 cm'1 and two sharp bands at 1038 cm'1 and 1015 cm'1, increasing as the sulfur dioxide bands fall and the temperature rises to a maximum of 68 ° C due to the exothermic reaction. The reaction was stirred for one hour after the end with no further changes in the IR spectrum. The reaction mixture was cooled to room temperature and the residual pressure vented through a caustic scrubber, purging the gas cap several times with nitrogen to remove any free sulfur dioxide. The light yellow acid solution was transferred to a tared bottle, recovering 1468.74 g of a-hydroxyethane sulfonic acid solution. The proton NMR analysis revealed this to be 36.7% by weight of α-hydroxyethane sulfonic acid. Example 2 Formation of 40% by weight q-hydroxyethanesulfonic acid from acetaldehyde
    [00067] Approximately 245 grams of ice-cooled acetaldehyde is transferred to 1107 grams of cold degassed nitrogen (<5 ° C) water in a 2 liter conical flask. The flask was gently shaken to dissolve the acetaldehyde in the water. The solution was warmed to room temperature and 1340.68 grams of aqueous solution containing 242.77 grams of acetaldehyde were transferred to a 2000 ml Parr autoclave adjusted with IR optics. The reactor and the contents are then cooled so that the temperature of the liquid is below 5 ° C. Two single-ended Hoke vessels containing a total of 361.07 grams of sulfur dioxide are connected to the inlet of the reaction vessel as the blow chamber injector. The mixture was stirred at 1000 rpm and the acquisition of IR data is started. Sulfur dioxide is injected into the acetaldehyde / water solution and a quick exothermic reaction takes place, the temperature of the reaction mixture rises to 39 ° C. The IR bands of sulfur dioxide and acetaldehyde drop and those for a-hydroxyethane sulfonic acid rise rapidly, indicating the conversion of reagents to product acid. The reaction mixture is allowed to cool to room temperature, vented through a caustic scrubber and the gas cap purged with nitrogen for a few minutes to remove any residual SO2 or acetaldehyde. The reactor contents are transferred to a tared glass bottle. A total of 1691.41 grams is recovered. The analysis of proton NMR shows that it should be 40.01% by weight of a-hydroxyethane sulfonic acid in water without discernible by-products. Examples 3-7 Pre-treatment reaction with recycle; 120 ° C, 15 minutes, 1500 rpm stirring
    [00068] For a 2 liter Parr C276 reactor adjusted with IR optics on site, approximately 120 grams of wheat straw with a characterized composition was added [dry base: xylan 23% by weight; glucan 38.8% by weight] cut to nominal 0.5 cm particles. The exact dry weight of biomass is given in column b. To this was added approximately 1000 grams of 5% by weight of a-hydroxyethane sulfonic acid (HESA) prepared by diluting a 40% by weight loading solution of the acid or recycled acid from the vaporization of components at the end of a reaction cycle with deionized water. The target acid concentration was confirmed by the proton NMR of the starting mixture that it integrates over the peaks for water and acid. The top of the reactor with an impeller with 4 blades downwards was positioned on top of a reaction vessel and the reactor sealed. The pressure integrity of the reactor system and the replacement of air atmosphere was achieved by pressurizing with nitrogen to 100 psig (689.4 kPa man.) Where the sealed reactor was maintained for 15 minutes without loss of pressure followed by ventilation for the atmospheric pressure. The acquisition of IR was initiated and the reaction mixture stirred at 1500 rpm. The reactor was then heated to 120 ° C and maintained at the target temperature for 15 minutes. During this period of time the IR on the spot reveals the presence of HESA, SO2, and acetaldehyde in an equilibrium mixture. An increase in sugars is evident in the IR spectra, with an increase in the typical xylose and glucose band height being apparent. At the end of the reaction period, the acid reversion was achieved by opening the reactor gas cap to an overhead condensation system to recover the acid and simultaneously adjusting the reactor temperature set point to 100 ° C. Vaporization from the reactor quickly cools the reactor contents to the 100 ° C set point. The aerial condensation system was comprised of a flask with a 1 liter jacket fitted with an optical fiber based on an IR probe in place, a dry ice acetone condenser at the outlet and the gas inlet coming through a condenser of 18 "long steel made from a C-276 diameter 'A' tubing core fitted inside the stainless steel tube with appropriate connections to reach a hull condenser and tube that drains down into a recovery vial A recovery flask was loaded with approximately 400 grams of Dl water and the condenser and jacket flask cooled with a circulating fluid maintained at 1 ° C. The progress of acid reversal was monitored through the use of IR on the spot both in the Parr reactor as well as in the overhead condensation flask. During the reversal of the first component to leave the Parr reactor it was SO2 followed quickly by a decrease in the bands for HESA. pour into the recovery bottle and then fall off quickly as HESA was formed from the combination of vaporized acetaldehyde with this component. The reversal was continued until the IR at the Parr reactor site showed no remaining trace of a-hydroxyethane sulfonic acid. The IR of the light parts revealed that the concentration of HESA at this point reached a maximum and then started to decrease due to dilution with condensed water, free of components of a-hydroxyethane sulfonic acid, accumulating in a recovery bottle. The total mass of light condensed material in column c. The condensate is analyzed using proton NMR to determine the recovery of the used α-hydroxyethane sulfonic acid, this value is given in column d. The reaction mixture was then cooled to room temperature, opened and the contents filtered through the Buchner funnel with medium filter paper using a vacuum cleaner to remove the liquid through the funnel. The wet solids are transferred from the Buchner funnel and placed in a filter press where an additional portion is pressed from the solids to create a biomass mixture with high consistency for enzymatic hydrolysis and further analysis. The dry weight is determined by washing a portion of the solids with water and then drying in the oven to a constant weight, then the amount of biomass removed in the pre-treatment cycle given in column e. A small portion of the combined and pressed liquid filtrate (total mass given in column f) is removed for analysis for HPLC, NMR, and elemental analysis by XRF; the rest is reverted to the next cycle with fresh biomass. A recycling experiment is achieved by combining the primary filtrate and the pressed liquids with a sufficient amount of HESA, both recycled from the light from the previous run or fresh acid from a 40% by weight loading solution, and water to produce 1000 grams of a 5% by weight acid solution that are taken up to a 2 liter Parr C276 reactor where it is mixed with another 120 gram portion of fresh biomass. The pretreatment cycle, ventilation and recovery, and filtration are repeated a number of times to demonstrate the development of significant soluble sugars. The analytical results per cycle are given in Table 1 where the growth in sugars xylose, glucose, and arabinose (as the monomer) as well as the concentration of acetic acid in the filtrate is readily observed (columns f, g, h, and i respectively). The amount of furfural remains very low through all the recycles as given in column j. The overall growth in xylose and glucose per pass (columns k and 1 respectively) remains essentially constant with a slight decrease in monomer due to the increased presence of oligomers (not shown). Table 1 Pre-treatment with Recycles - 0.25 hours; 120 ° C, 1500 RPM
    Examples 8 to 12 Pre-treatment reaction with recycle; 120 ° C, 60 minutes, 1500 rpm stirring.
    [00069] This series of recycling experiments was conducted as described by examples 3 to 7 with the results given in Table 2. These results show that in the longer time of the reaction results in a slight increase in sugars, most of the dissolution of the biomass occurs quickly and a-hydroxysulfonic acid recoveries are generally improved with shorter reaction times. Table 2 Pretreatment with Recycles - 1 hour; 120 ° C, 1500 rpm

    [00070] Examples 13-17
    [00071] Pre-treatment reaction with recycle; 120 ° C, 120 minutes, 1500 rpm stirring.
    [00072] This series of recycling experiments was described by examples 3 to 7 with the results given in Table 3. These results show that in an extended reaction time it still results in high sugar yield with low degradation and low furfural production. Table 3 Pre-treatment with Recycles - 2 hours; 120 ° C, 1500 rpm

    [00073] The existence of what is thought to be a kind of surfactant has also been analyzed for the composition by a combination of techniques including proton NMR, 2d NMR, mass spectroscopy, separation techniques, to be sulfonated crotonaldehyde and quantified by NMR .
    [00074] The surfactant species was present in Example 11 in an amount of approximately 0.2% by weight. Examples 18 Enzymatic hydrolysis of biomass treated with g-hydroxysulfonic acids.
    [00075] This example demonstrates the ability of the described pretreatment process to produce substrate that is susceptible to enzymatic hydrolysis.
    [00076] A proportion of the pretreated slurry of Example 11 was used as a substrate for enzymatic hydrolysis. The degree of hydrolysis was determined by the amount of glucose released. Experiments were carried out in triplicate.
    [00077] Enzymatic hydrolysis was performed in a sealed 125 ml flask with 5.0% cellulose (not washed) (grams of cellulose per 100 ml of slurry) in 50 mM sodium acetate buffer at pH = 5 The enzyme used was Novozymes Cellic CTec2 ™, at a concentration of 15.0 mg of enzyme (in dry weight) per gram of cellulose. The reaction was initiated by mixing the enzyme, preheated to 50 ° C, the pre-treated solid biomass substrate that was also preheated to 50 ° C. The reaction mixture was incubated at 50 ° C for up to 96 hours in a shaker-type incubator (Infors HT Multitron ™) at 250 rpm.
    [00078] In the case of unwashed pre-treated samples, the pH of the hydrolysis reaction was closely monitored and maintained in a pH range of 4.9 to 5.1 using a 5M sodium hydroxide solution (NaOH).
    [00079] Glucose concentrations were determined by high performance liquid chromatography (HPLC) from 0.5 ml aliquots taken from the reaction mixture at appropriate time points during or after hydrolysis. The aliquots were centrifuged at 13000 g for 1 minute, immediately after removing the reaction mixture. 100 of the resulting supernatant was then diluted in 900 μE of 10 mM sulfuric acid to stop hydrolysis, followed by HPLC analysis using a Bio-Rad Aminex ™ HPX-87P column. the cellulose conversion percentages were calculated from the measured glucose levels and the cellulose content of the original substrate, the latter being determined from the maximum amount of glucose that can be released by completely hydrolyzing the cellulose.
    [00080] The results are shown in Table 4 below. Table 4 Hydrolysis of the enzyme

    [00081] The data demonstrate that the substrate produced by treatment with lignocellulose α-hydroxysulfonic acid is readily hydrolyzed by cellulose hydrolysis enzymes. As is typical with enzymatic lignocellulose hydrolysis, the conversion rate of cellulose produced by a-hydroxysulfonic acid treatment starts high and then gradually decreases as cellulase activity decreases over time. Similar trends were observed with many other pretreated lignocellulose substrates. In addition, the data indicate almost complete conversion of cellulose to glucose. Taken together, these data suggest that a-hydroxysulfonic acid treatment may create material susceptible to cellulase.
    权利要求:
    Claims (10)
    [0001]
    1. Continuous or semi-continuous process to treat biomass, characterized by the fact that it comprises: (a) providing a biomass containing polysaccharides; (b) contact the biomass with a solution containing at least one a-hydroxysulfonic acid at a temperature within the range of 50 ° C to 150 ° C and a pressure gauge within the range of 1 bar (0.1 mPa) at 10 bar (1 mPa) to provide a biomass solution, where the biomass solution contains in the range of 1% by weight to 25% by weight of biomass based on the solution, and thus hydrolyzes the biomass to produce at least one product containing fermentable sugar; (c) removing a-hydroxysulfonic acid in its component form from the product by heating and / or reducing the pressure to produce an acid-removed product containing at least one fermentable sugar substantially free of a-hydroxysulfonic acid; (d) separating a high solid / liquid mixture from the acid-removed product to form a stream of wet solids containing at least 12% by weight of undissolved solids based on the stream of wet solids, and a stream of bulk liquid containing fermentable sugar; (e) recycling the removed a-hydroxysulfonic acid for step (b) as components or in its recombined form; and, (f) recycling at least a portion of the bulk liquid stream to step (b); wherein the bulk liquid stream comprises more than 2% by weight of fermentable sugar based on the bulk liquid stream.
    [0002]
    2. Process according to claim 1, characterized by the fact that a-hydroxysulfonic acid is present in an amount of 1% by weight to 55% by weight, based on the solution.
    [0003]
    Process according to either of Claims 1 or 2, characterized in that the biomass solution contains more than 5% by weight of fermentable sugar.
    [0004]
    Process according to any one of claims 1 to 3, characterized in that the biomass content in the biomass solution is less than 20% by weight, preferably less than 15% by weight, more preferably 10% by weight. weight or less.
    [0005]
    Process according to any one of claims 1 to 4, characterized in that it further separates a stream of C5 from the liquid stream.
    [0006]
    Process according to any one of claims 1 to 5, characterized in that the hexose content of the wet solid stream is greater than 0.5% by weight based on the wet solid stream.
    [0007]
    Process according to any one of claims 1 to 6, characterized in that the a-hydroxysulfonic acid is produced from (a) a carbonyl compound or a precursor to a carbonyl compound with (b) sulfur dioxide or a precursor to sulfur dioxide and (c) water.
    [0008]
    Process according to any one of claims 1 to 7, characterized in that the biomass is contacted with α-hydroxysulfonic acid at a temperature of 120 ° C or less.
    [0009]
    Process according to any one of claims 1 to 8, characterized in that it additionally comprises (g) hydrolyzing the liquid / solid mixture thereby producing a stream of sugar.
    [0010]
    Process according to claim 9, characterized in that it additionally comprises (h) fermenting the sugar stream thereby producing fermented products.
    类似技术:
    公开号 | 公开日 | 专利标题
    BR112014027355B1|2020-12-29|continuous or semi-continuous process to treat biomass
    US10961595B2|2021-03-30|Treating biomass to produce materials useful for biofuels
    RU2713659C2|2020-02-06|Closed-loop production of furfural from biomass
    BR112016030664B1|2021-06-29|METHOD FOR PRODUCING FURFURAL FROM BIOMASS MATERIAL CONTAINING PENTOSAN
    BR112014013854B1|2021-07-13|METHOD FOR THE TREATMENT OF A BY-PRODUCT OF ETHANOL PRODUCTION
    US20150299739A1|2015-10-22|Processes for producing fermentation products
    BR112017002204B1|2021-01-12|methods to recover a-hydroxysulfonic acid in a biomass treatment process
    同族专利:
    公开号 | 公开日
    IN2014DN09244A|2015-07-10|
    WO2013169706A1|2013-11-14|
    EP2847344A1|2015-03-18|
    PL2847344T3|2020-01-31|
    CA2872456C|2020-07-28|
    US20130295629A1|2013-11-07|
    US9382593B2|2016-07-05|
    AU2013259739A1|2014-12-18|
    AU2013259739B2|2015-08-20|
    CN104395478A|2015-03-04|
    JP6133407B2|2017-05-24|
    EP2847344B1|2019-07-24|
    BR112014027355A2|2020-06-02|
    JP2015523059A|2015-08-13|
    CA2872456A1|2013-11-14|
    CN104395478B|2017-07-28|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2308564A|1938-05-13|1943-01-19|Ralph H Mckee|Recovery of cellulose and lignin from wood|
    US3248278A|1962-02-16|1966-04-26|Pritchard & Co J F|Method of recovering monovalent cations from spent monovalent cation sulfite pulpingliquor|
    US3549319A|1968-05-06|1970-12-22|Fraser Co Ltd|Production of alkali metal sulfites or bisulfites|
    US3821355A|1972-05-08|1974-06-28|Allied Chem|Recovery of sulfur and metal values from sulfur bearing minerals|
    UST962001I4|1976-10-06|1977-09-06|Tennessee Valley Authority|Preparation of dicalcium phosphate from phosphate rock by the use of sulfur dioxide, water, and carbonyl compounds|
    CA1100266A|1977-08-31|1981-05-05|Laszlo Paszner|Organosolv delignification and saccharification process for lignocellulosic plant materials|
    US4238459A|1978-09-11|1980-12-09|Tennessee Valley Authority|Chemical beneficiation of phosphatic limestone and phosphate rock with α-hydroxysulfonic acids|
    US5366558A|1979-03-23|1994-11-22|Brink David L|Method of treating biomass material|
    CA1173380A|1980-02-19|1984-08-28|Michael I. Sherman|Acid hydrolysis of biomass for ethanol production|
    US4461648A|1980-07-11|1984-07-24|Patrick Foody|Method for increasing the accessibility of cellulose in lignocellulosic materials, particularly hardwoods agricultural residues and the like|
    US4306101A|1980-11-05|1981-12-15|Shell Oil Company|Olefin hydration process|
    US4316008A|1980-11-24|1982-02-16|Shell Oil Company|Method for removing catalyst residues from atactic polypropylene|
    US4395356A|1980-11-28|1983-07-26|Shell Oil Company|Method for removing catalyst residues from solutions of poly-1-butene|
    US4396761A|1981-08-21|1983-08-02|Shell Oil Company|Method for removing hydrogenation catalyst residues from hydrogenated conjugated diene polymers|
    US4669545A|1986-05-27|1987-06-02|Shell Oil Company|Well acidization with alpha-hydroxysulfonic acid|
    US5562777A|1993-03-26|1996-10-08|Arkenol, Inc.|Method of producing sugars using strong acid hydrolysis of cellulosic and hemicellulosic materials|
    US5789210A|1993-11-08|1998-08-04|Purdue Research Foundation|Recombinant yeasts for effective fermentation of glucose and xylose|
    IN191596B|1996-05-06|2003-12-06|Purdue Research Foundation|
    SE9901298D0|1999-04-09|1999-04-09|Forskarpatent I Syd Ab|Xylose isomerase with improved kinetic properties|
    US7223575B2|2000-05-01|2007-05-29|Midwest Research Institute|Zymomonas pentose-sugar fermenting strains and uses thereof|
    NO312070B1|2000-07-04|2002-03-11|Karl Weydahl|Process of a process for the production of processable sugar from cellulosic raw materials|
    SE0400816D0|2004-03-26|2004-03-26|Forskarpatent I Syd Ab|Mutated xylose reductase in xylose fermentation in S. cerevisiae|
    US8003352B2|2004-07-16|2011-08-23|Iogen Energy Corporation|Method of obtaining a product sugar stream from cellulosic biomass|
    EP1863901A1|2005-03-11|2007-12-12|Forskarpatent i Syd AB|Arabinose- and xylose-fermenting saccharomyces cerevisiae strains|
    US7781191B2|2005-04-12|2010-08-24|E. I. Du Pont De Nemours And Company|Treatment of biomass to obtain a target chemical|
    CA2959268A1|2005-07-19|2007-01-25|Inbicon A/S|Method and apparatus for conversion of cellulosic material to ethanol|
    WO2007028811A1|2005-09-06|2007-03-15|Cargill, Incorporated|Thermostable xylose isomerase enzymes|
    MY154790A|2007-03-08|2015-07-31|Virent Inc|Synthesis of liquid fuels and chemicals from oxygenated hydrocarbons|
    MX344588B|2006-05-19|2016-12-20|Reg Life Sciences Llc|Production of fatty acids and derivatives thereof.|
    BRPI0809345A2|2007-03-28|2014-10-07|Ls9 Inc|RECOMBINANT CELLS, COMPOSITIONS PRODUCED BY THESE, METHODS FOR PRODUCING FATTY ACID DERIVATIVES IN A RECOMBINANT CELL, FOR INCREASING THE PRODUCTION OF RECOMBINANT DUCTIDOUS CONDUCTIVE PRODUCTS FOR GRADIC ACIDS A PRODUCTION HOST CELL FOR PRODUCING FATTY ACID DERIVATIVES, FATTY ACID DERIVATIVES, BIOFUEL COMPOSITIONS.|
    US7741119B2|2006-09-28|2010-06-22|E. I. Du Pont De Nemours And Company|Xylitol synthesis mutant of xylose-utilizing zymomonas for ethanol production|
    US7741084B2|2006-09-28|2010-06-22|E. I. Du Pont De Nemours And Company|Ethanol production using xylitol synthesis mutant of xylose-utilizing zymomonas|
    CA2697073A1|2007-08-27|2009-03-05|Iogen Energy Corporation|Method for the production of a fermentation product from a pretreated lignocellulosic feedstock|
    WO2009109631A1|2008-03-07|2009-09-11|Dsm Ip Assets B.V.|A pentose sugar fermenting cell|
    WO2010029568A2|2008-07-21|2010-03-18|Praj Industries Limited|A process for production of ethanol from lignocellulosic material|
    EP2321218A1|2008-09-02|2011-05-18|Hcl Cleantech Ltd.|A process for the production of hcl gas from chloride salts and for the production of carbohydrates|
    IT1392910B1|2008-10-21|2012-04-02|Eni Spa|PROCEDURE FOR THE PRODUCTION OF BIOMASS LIPIDS|
    CA2746783A1|2008-12-19|2010-06-24|Mascoma Corporation|Two-stage process for biomass pretreatment|
    CA2747823C|2009-01-14|2015-12-29|Iogen Energy Corporation|Improved method for the production of glucose from lignocellulosic feedstocks|
    US9447347B2|2009-12-31|2016-09-20|Shell Oil Company|Biofuels via hydrogenolysis-condensation|
    CN101787400A|2010-03-31|2010-07-28|华南理工大学|Method for hydrolyzing vegetable fibre by solid acid|
    BR112012028663A2|2010-05-12|2016-08-16|Shell Int Research|method and system|
    ES2484799T3|2010-11-05|2014-08-12|Shell Internationale Research Maatschappij B.V.|Biomass treatment to produce useful materials for biofuels|
    JP2012210160A|2011-03-30|2012-11-01|Nippon Shokubai Co Ltd|Method for producing monosaccharide|
    PL2785194T3|2011-12-01|2016-01-29|Shell Int Research|Method of recovering lipids from microbial biomass|
    PL2791344T3|2011-12-15|2016-08-31|Shell Int Research|Method of treating byproducts from ethanol production|
    CN102559941B|2011-12-21|2014-02-26|中国科学院青岛生物能源与过程研究所|Method for hydrolyzing and saccharifying corncobs|
    US20140024093A1|2012-03-29|2014-01-23|Shell Oil Company|Process for the production of digested biomass useful for chemicals and biofuels|
    WO2013173567A1|2012-05-17|2013-11-21|Shell Oil Company|Methods and systems for processing biomass material|US9260674B2|2012-09-14|2016-02-16|Pedro Manuel Brito da Silva Correia|Biofuel containing furanic compounds and alkoxy benzene compounds and the process for obtaining these compounds from sugar cane by hydrolysis of cellulose, sugars and lignin in ionic liquids|
    US9194012B2|2014-02-02|2015-11-24|Edward Brian HAMRICK|Methods and systems for producing sugars from carbohydrate-rich substrates|
    BR112016023823A2|2014-04-17|2017-08-15|Shell Int Research|method for producing a fermentation product|
    CA2957473A1|2014-08-14|2016-02-18|Shell Internationale Research Maatschappij B.V.|Improved process for treating biomass to produce materials useful for biofuels|
    EP3180297A4|2014-08-14|2018-01-17|Shell Internationale Research Maatschappij B.V.|Process for the manufacture of furural and furfural derivatives|
    EP3180321A4|2014-08-14|2018-04-11|Shell International Research Maatschappij B.V.|Process for preparing furfural from biomass|
    EP3180323B1|2014-08-14|2020-07-22|Shell International Research Maatschappij B.V.|Closed-loop production of furfural from biomass|
    CN106660980A|2014-08-14|2017-05-10|国际壳牌研究有限公司|One-step production of furfural from biomass|
    RU2713660C2|2014-08-14|2020-02-06|Шелл Интернэшнл Рисерч Маатсхаппий Б.В.|Method for producing furfural from biomass|
    EP3141607A1|2015-09-11|2017-03-15|Clariant International Ltd|Process for the purification of biomass hydrolysate|
    WO2017192498A1|2016-05-03|2017-11-09|Shell Oil Company|Lignin-based solvents and methods for their preparation|
    WO2018085176A1|2016-11-01|2018-05-11|Shell Oil Company|Process for the recovery of furfural|
    EP3535248A1|2016-11-01|2019-09-11|Shell Internationale Research Maatschappij B.V.|Process for the recovery of furfural|
    EP3535247B1|2016-11-01|2020-11-25|Shell Internationale Research Maatschappij B.V.|Process for the recovery of furfural|
    RU2019113155A3|2016-11-01|2021-01-19|
    法律状态:
    2018-03-06| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2018-03-13| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2018-03-20| B06I| Publication of requirement cancelled [chapter 6.9 patent gazette]|Free format text: ANULADA A PUBLICACAO CODIGO 6.6.1 NA RPI NO 2462 DE 13/03/2018 POR TER SIDO INDEVIDA. |
    2020-06-23| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-10-20| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-12-29| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 07/05/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201261643633P| true| 2012-05-07|2012-05-07|
    US61/643633|2012-05-07|
    PCT/US2013/039843|WO2013169706A1|2012-05-07|2013-05-07|Continuous or semi-continuous process for treating biomass to produce materials useful for biofuels|
    [返回顶部]