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    • 专利摘要:
    Single Step Hydrolytic Process and Process for Converting Lignocellulose to Value-Added Chemicals The present invention relates to a single step hydrolytic process for converting lignocellulose to value-added chemicals in which said process is catalyzed by at least one heterogeneous solid acid catalysts selected from a group comprising zeolites, zeolites with si / metal, mesoporous silica, oxides and phosphates, clays, ion exchange resins, heteropoly acids, various sulfates, phosphates, selenates, crystalline materials and materials. Amorphous.
    公开号:BR112012017478B1
    申请号:R112012017478-9
    申请日:2010-01-27
    公开日:2018-08-14
    发明作者:Laxmikant Dhepe Paresh；Sahu Ramakanta
    申请人:Council Of Scientific & Industrial Research；
    IPC主号:
    专利说明:

    (54) Title: HYDROLYTIC PROCESS OF SINGLE REACTOR AND SINGLE STEP FOR THE CONVERSION OF XYLANE TO XYLOSE AND ARABINOSIS (51) Int.CI .: C08B 1/00; C13K 13/00 (73) Holder (s): COUNCIL OF SCIENTIFIC & INDUSTRIAL RESEARCH (72) Inventor (s): PARESH LAXMIKANT DHEPE; RAMAKANTA SAHU (85) National Phase Start Date: 07/13/2012
    1/29
    Invention Patent Descriptive Report for
    HYDROLYTIC PROCESS OF SINGLE REACTOR AND SINGLE STEP FOR THE CONVERSION OF XYLAN IN XYLOSIS AND ARABINOSIS
    Field of the Invention:
    [001] The present invention relates to a single-step hydrolytic process for converting lignocellulose into chemical compounds of added value. More particularly, the present invention relates to a one-step hydrolytic process for converting an inedible source such as hemicellulose into value-added chemical compounds such as arabinose and xylose catalyzed by a heterogeneous catalyst.
    Background of the Invention:
    [002] Lignocelluloses are available in abundance and are a renewable source consisting of approximately 40-50% cellulose, 25-30% hemicellulose and 20-25% lignin. Technologies exist to separate cellulose, hemicellulose and lignin from each other and, therefore, raw material, hemicellulose is easily obtainable.
    [003] Hemicellulose, a carbohydrate that is cheap and abundantly available across the globe and is the main factor that many countries will be independent about their chemical needs. Hemicellulose, which is basically derived from the inedible source, will have an advantage over edible sources for its conversion into chemical compounds insofar as it is independent of geopolitical and food crisis factors.
    [004] Conversion of fossil food supplies (crude oil, natural gas, coal, etc.) into chemical compounds and energy produces a significant amount of carbon dioxide that causes global warming. The recent exponential rise in the price of crude oil against the backdrop of a mismatch in growing demand and limited supply has pushed the world economy into bad luck. Besides that,
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    2/29 geopolitical factors and finite reserves available only in selective areas on land are also held responsible for the present situation. In order to maintain fuel prices and maintain carbon dioxide at constant levels, efforts are being made in the field of producing biomass-based fuels (bioethanol and biodiesel) and this in turn has made the situation more complex. As these fuels are mainly sought after from increasing uses of edible sources such as starch (corn, rice, etc.) and vegetable oils (seed oils), it has also attracted a lot of criticism across the globe in a note of rising oil prices. foods. Thus, ways to overcome limitations arising from the use of fossil feed stock and edible sources for the synthesis of chemical compounds are being sought through the use of an inedible biomass source under the title biorefinery. Biomass during its growth captures light energy, water and carbon dioxide to form carbohydrates in a process of photosynthesis. The integral part of CO 2 fixation during carbohydrate synthesis makes the use of plant-derived biomass a totally carbon neutral process. The net annual yield of photosynthesis is about 1.3 trillion tonnes, thus making it the largest renewable source available and a portion of these renewable inedible sources are lignocellulosic materials such as wood and agricultural waste.
    β- link (1 -> 4)
    Cellulose structure [005] Although the main wood component is cellulose,
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    3/29 which constitutes almost 40-50% of wood material, the other main constituent (approximately 25-30%) of wood and the second largest plant-derived renewable food stock is hemicellulose. Cellulose consists of C6 glucose units (hexoses) and is a highly crystalline material. On the other hand, hemicelluloses are complex heterogeneous polymers composed of C5 (D-pentoses) and C6 (D-hexoses) monosaccharides such as xylose, mannose, arabinose, glucose, galactose, glucuronic acid, uronic acid, etc. depending on the source, as shown in the figure below. Softwood hemicellulose mainly consists of xylose, arabinose, mannose, galactose, glucuronic acid, etc. and hardwood hemicellulose is mainly made up of xylose and glucuronic acid. Concluding from the discussion above, there are 4 main factors, for example: food security, cost efficiency, climate change and localized industry independent of geopolitical scenarios, which are directing the global research community to work on non-edible renewable sources for production chemical and fuel compounds.
    Hemicellulose derived from soft wood
    4-O-Methyl-D-glucuronic acid L-arabinose
    Connections a- (1 - ^ 2) connections to (1 -> 3)
    Hemicellulose derived from hard wood
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    4/29
    4-O-Methyl-D-glucuronic acid Bonds a- (1 2) [006] To convert lignocellulosic material (cellulose, hemicellulose, and lignin) into chemical and fuel compounds, these polysaccharides must be selectively broken down into corresponding monosaccharides. Currently, much research is devoted to the hydrolysis (or decomposition) of lignocellulosic materials into chemical compounds of added value. Known technologies for biomass hydrolysis include: diluted acid hydrolysis, concentrated acid hydrolysis, alkaline hydrolysis, and enzymatic hydrolysis. In the hydrolysis process, in the presence of excess water, the ketal function of the polysaccharides can be hydrolyzed to form hemiacetals and this can release the sugar monomer form via oligomer formation. Being insoluble in water, cellulose and hemicellulose hydrolysis is a difficult task and therefore requires specific reaction conditions.
    [007] Acid hydrolysis (HCl, H 2 SO 4 both diluted and concentrated) of hemicellulose has been known for a long time, but due to the difficulty in inhibiting xylose degradation, danger of corrosion, problems in handling and, storage of acids and generation of neutralization dumping, its industrial use is prevented. In the past, concentrated inorganic acids (H2SO4) under mild conditions (100-150 o C) were used, but acid recovery was very difficult and expensive. To overcome this, a further diluted acid pathway was established, but it required severe conditions such as 150-200 o C and positive pressure.
    [008] The other method widely studied for hydrolysis of lignocellulosic materials is reactions catalyzed with enzymes. For the hydrolysis of hemicellulose, a mixture of endo- and exo-xylanase and betaxylosidase are additionally used with alpha-arabine furanosidase and some other enzymes. Enzymatic hydrolysis that is very specific
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    5/29 in the direction of product formation is usually done at lower temperatures (50-80 o C) but at a defined (acidic) pH. The known disadvantages of this method are low activity, use of buffers to maintain a specific pH at which enzymes work and make the system corrosive and the high cost of enzymes that hinder cost efficiency and also, product-enzyme separation is difficult when both , product and catalyst are soluble in water.
    [009] Thermochemically (> 700 o C) also, degradation of lignocellulosic materials is possible. In the gasification process, lignocellulosic material is decomposed at high temperatures under restricted oxygen to yield valuable synthesis gas (CO + H 2 ). Several such processes are known. In the pyrolysis method, lignocellulosic material is heated at high temperatures without oxygen to yield a mixture of oils, tar and coal. In these processes it is difficult to obtain high selectivity for any compound due to the very high temperatures employed under which normal sugars are unstable and still undergo decomposition. The other disadvantage is the formation of coal, tar and oils. These compounds do not have much market value due to their complex structures and can therefore be considered unnecessary. Finally, these methods require very high energy input and are therefore not cost effective.
    [0010] Hydrolysis of lignocellulosic materials using compressed hot water (sub and supercritical waters) is also reported. In this technique, in the absence of a catalyst at 200-380 o C and about 22 MPa, lignocellulosic material is subjected to the condition of critical water for a short period of time to form hydrolysis products. Lack of high selectivity for any product due to the additional reaction (in the direction of decomposition) and high energy input requirement restrict its use. Additionally, under these conditions, water becomes petition 870180018454, from 03/07/2018, p. 8/39
    6/29 if super acidic and therefore can corrode the reactor material which increases the capital cost of the entire process.
    [0011] A research paper published in Energy and Fuels 2005, entitled Plug-Flow reactor for continuous hydrolysis of Glucans and Xylans from pretreated corn fiber by Young Mi Kim, Nathan Mosier, Rick Hendrickson and Michael R. Ladisch; Vol. 19, pages 2189-2200 shows the use of a strong solid acid catalyst in the form of solid ion exchange resins (Amberlyst 35W type micro reticular resin; Dowex 50WX2, SK104, SK110 gel type packaged in fixed beds at 130 o C for continuous hydrolysis of soluble glycans and xylans. It is also shown that the first insoluble hemicelluloses are under 160 o C, and pH 4-7 are converted to a solid form (oligosaccharides) and then these dissolved oligosaccharides are separated by centrifugation and are further exposed to resins ion exchange. The reaction is a two-step process.
    [0012] Another research publication published in Angewandte Chemie Int. Ed. Entitled Catalytic conversion of cellulose into sugar alcohols by Atsushi Fukuoka and Paresh L. Dhepe; 2006, 45, 5161-5163; related to glucose cellulose hydrolysis and glucose reduction to sorbitol and mannitol through the use of metallic catalyst supported on material selected from the gamma groupAl 2 O 3 , HY (2.6), HUSY (15), HUSY (20), HUSY (40), HZSM-5 SiO 2 Al2O3, SiO2, TiO2, ZrO2, FSM-16, H-BeH-Beta, HMOR, or active carbon. [0013] WO2007 / 100052 A1 entitled Catalyst for hydrolysis of cellulose and / or reduction of its hydrolysis product; and method for producing sugar alcohol from cellulose shows hydrolysis of a cellulose and / or reduction of its hydrolysis product, in the presence of a catalyst, selected from the periodic transition metal group 8-11 (Pt, Ru, Pd , Rh, Ni, Ir).
    [0014] Still, EP0329923 shows production of polyhydric alcohol at
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    7/29 from polysaccharide (starch) using metal supported on silica alumina or solid acid catalyst from the acid zeolite group (Faujasite type zeolite, HZSM-5, H-Beta, H-Modernite).
    [0015] US4075406 entitled Process for making xylose describes a method for recovering xylose from pentosan, preferably raw materials containing xylan, including the steps of hydrolysis with sulfuric acid from the crude material, purification of hydrolyzate through ion exclusion and removal color and then subjecting the purified solution to chromatographic fractionation on an ion exchange column to provide a solution containing a high level of xylose.
    [0016] Following the technologies discussed above and their limitations, a study on hemicellulose hydrolysis catalyzed by solid acids was undertaken. The main advantages of using solid acids are, easy to separate catalyst (solid) and product (soluble in water) through simple filtration and operation under neutral conditions without any corrosion (as acidic sites are bound to solid and not are released into the reaction media) in a totally green environment (as no waste can be generated and water is used as the reaction medium).
    [0017] None of the previous techniques shown above teach or explain a cost effective, anti-corrosion hemicellulose hydrolysis reaction of a reactor.
    Objects of the Invention [0018] The main objective of the present invention is to provide a one-step process for converting an inedible source such as lignocellulose to a value-added material such as xylose, arabinose, glucose, mannose, glucuronic acid, furaldehyde, etc. [0019] Yet another objective of the invention is to provide a single step hydrolysis of lignocellulose for xylose and arabinose catalyzed by
    Petition 870180018454, of March 7, 2018, p. 10/39
    8/29 solid heterogeneous acid catalyst.
    Summary of the Invention:
    [0020] According to the present invention which provides a hydrolytic process of a reactor and a single step for the conversion of lignocellulose into chemical compounds of added value, said process comprising the steps of:
    The. loading of lignocellulose in the reactor followed by loading of a solvent and at least one heterogeneous solid acid catalyst;
    B. optionally, reactor washing with inert gas or air;
    ç. adjustment of pressure to 100-7,000KPa (1-70 bar) and temperature of 50-250 o C of the reactor, under agitation;
    d. elevation of agitation speed to 10-2000 rpm after required temperature stabilization;
    and. conducting said reaction above for a period of 0.1 to 96 hours to obtain the desired value-added product.
    [0021] In one embodiment of the present invention the heterogeneous solid acid catalyst used is selected from the group comprising zeolites, zeolites with Si / metal, mesoporous silica, oxides and phosphates, clays, ion exchange resins, heteropoly acids, various sulfates, phosphates, selenates, crystalline materials and amorphous materials.
    [0022] In yet another modality, the catalyst used is a zeolite catalyst with Si / Al = 1-100 with regular pore structure and pore diameter in the range of 0.3-1.5 nm, zeolites such as ZSM-5 , Y, X, Beta and MOR, zeolites in their H, Na or NH 4 forms, but are converted to H form for the generation of acidic sites.
    [0023] In yet another modality, the z / zeolite catalysts with Si / Metal used are zeolites with a Si to metal ratio = 1-100 (metal silicates), where the metal is Ga, Ti, Fe, Cr, Zn, P , B, or Zr. [0024] In yet another modality, the catalyst used is
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    9/29 mesoporous silica catalyst selected from MCM-41, FSM-16, SBA15, HMM with regular pore structure and> 2 nm pore diameter and silicas with linked functional groups such as carboxylic acid, thiol, SO 3 H.
    [0025] In yet another modality, the mesoporous silica catalysts used are optionally incorporated with metal selected from Ga, Al, Sb, In, Fe, Ti, and P.
    [0026] In yet another modality, the mesoporous silica catalyst used is selected from Al-MCM-41, Al-SBA-15 and GaMCM-41.
    [0027] In yet another modality, the oxide and phosphate catalysts used are selected from the group consisting of niobic acid (Nb 2 O 5 ), MoO 3 / ZrO 2 , WO 3 / ZrO 2 , zirconium phosphates, lanthanum phosphates, phosphates of niobium, and Mo, W, Nb, P, V, Si, Al supported on or mixed with SiO2, Al2O3, SiO2-Al2O3, TiO2, C, metal oxides, polymers, and supports both alone and in combination thereof.
    [0028] In yet another modality, the clay catalyst used is selected from the group consisting of aluminum silicates, phyllo silicates, pillar clays, exchanged cation clays and acid-treated clays, preferably Montmorillonite type (K10).
    [0029] In yet another embodiment, the ion exchange resin catalyst is preferably a cation exchanger selected from the group consisting of Amberlyst-15, Amberlyst-35, Amberlite, Amberjet, Aowex, Auolite, Nafion pearls (type NR50) and composites of silica naphion (type SAC-13).
    [0030] In yet another modality, the hetero polyacid catalyst used is selected from the group consisting of Keggin type, Dawson type, Waugh type, Anderson type and Silverton type.
    [0031] In yet another modality, the heteropoly acid catalyst
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    10/29 used is optionally heteropoly acids of phosphotungstic acid, phosphomolybdic acid, silicotungstic and molybdovanadophosphoric acid or anions thereof, supported on the group comprising metal oxides, carbon, resins, polymers and / or the metal replacing H + such as Cs x H 3 -x PW 12 O 40 , where x = 0-3 and Cs x H 4-x SiW 12 O 40 , where x = 0-4, the substitution metals can be: Cs, Pd and Rh and the like. [0032] In yet another modality, the heterogeneous catalyst used is selected from sulfates, phosphates and selenates.
    [0033] In yet another modality, the supports used are optionally crystalline or amorphous selected from the group consisting of Al2O3, ZrO2, SiO2, TiO2, organo silicates, carbon, polymers, oxides as such or modified with acid treatment or functionalized to yield acid properties .
    [0034] In yet another modality, the inert gas used in step b is selected from nitrogen, argon, helium and hydrogen.
    [0035] In yet another modality, the ratio of substrate to solvent used is in the range of 0.001-0.5 weight / weight.
    [0036] In yet another modality, the substrate to catalyst ratio is in the range of 0.2-500 weight / weight.
    [0037] In yet another embodiment, the solvent used in the reaction is organic solvent or a mixture of water and organic solvent in a ratio of 1:99 to 99: 1 and organic solvent is selected from the group consisting of alcohols, ethers, esters, hexane, toluene acids, and xylene.
    [0038] In yet another modality, the catalyst used is recyclable and reusable.
    [0039] In yet another modality, the source of hemicellulose used is selected from the group consisting of softwood, hardwood, lignocelluloses, grasses, crops, spent crops, trees, plants, wood waste, agricultural waste, forest waste,
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    11/29 pulp, paper, pulp and paper dumping, municipal dumping, food processing dumping and its by-products.
    The present invention relates to a one-step process of hydrolysis of lignocellulose to xylose and arabinose catalyzed by solid heterogeneous acid catalyst. Hemicellulose (Xylan substrate model) is derived from spelled oats or birch that is loaded into a reactor. Water and catalyst are also charged and then the reactor is flushed with nitrogen and the final pressure of 100-7,000KPa (1-70 bar) is maintained at room temperature. The reactor is heated to the desired temperature (50-250 o C) under slow stirring. Once the desired temperature is achieved, agitation is increased to 500 rpm. Reactions are made for varying periods of time from 0.1 to 96 hours.
    Brief Description of Drawings:
    [0041] Figure 1 illustrates catalyst effect on hemicellulose hydrolysis: Xylan (oat spelled), 0.6 g; catalyst, 0.3 g; water, 60 g; pressure of N 2 , 5,000KPa (50 bar) at room temperature; temperature, 130 o C; reaction time, 48 h; agitation, 500 rpm.
    [0042] Figure 2 illustrates hydrolysis catalyzed with solid hemicellulose acid: Xylan (oat spelled), 0.6 g; catalyst, 0.3 g; water, 60 g; pressure of N 2 , 5,000KPa (50 bar) at room temperature; temperature, 130 o C; reaction time, 48 h; agitation, 500 rpm.
    [0043] Figure 3 illustrates the temperature effect on hemicellulose hydrolysis: Xylan (oat spelled), 0.6 g; HUSY (Si / Al = 15), 0.3g; water, 60 g; pressure of N 2 , 5,000KPa (50 bar) at room temperature; temperature, 130 o C; reaction time, 48 h; agitation, 500 rpm.
    [0044] Figure 4 illustrates the pressure effect on hemicellulose hydrolysis: Xylan (oat spelled), 0.6 g; HUSY (Si / Al = 15), 0.3g; water, 60 g; temperature, 130 ° C; reaction time, 24 h; shake, 500
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    12/29 rpm.
    [0045] Figure 5 illustrates the effect of a source of hemicellulose on hydrolysis: Xylan (oat spelled), 0.6 g; HUSY (Si / Al = 15), 0.3g; water, 60 g; N2 pressure, 5,000KPa (50 bar) at room temperature; temperature, 130 o C; reaction time, 48 h; agitation, 500 rpm.
    Detailed Description of the Invention [0046] The present invention shown here describes an environmentally benign one-step process, for conversion through hydrolysis of an inedible material, such as lignocellulose into value-added materials such as xylose, arabinose, glucose, mannose, galactose, glucuronic acid and the like in which the hydrolysis process is catalyzed by a solid, heterogeneous acid catalyst. Lignocellulosic or lignocellulose material of the invention is cellulose, hemicellulose and lignin.
    [0047] The substrate for the reaction is hemicellulose embedded in the cell walls of any plant, and can be derived from any source of softwood or hardwood and is insoluble in water. Softwood hemicelluloses are derived from plants such as pine, spruce, cedar, larch, douglas-spruce, tsuga, cypress, redwood, yew, red deal, yellow deal, western red and the like. Hardwood hemicelluloses are derived from plants such as English oak, beech, ash, elm, sycamore, birch, walnut and the like. Other sources of hemicelluloses can be selected from lignocelluloses and grasses, crops, spent crops, trees, wood waste (including sawdust), agricultural waste (including corn straw, bagasse), forest waste, pulp and paper and their evictions, municipal eviction, eviction from food processing and by-products, etc.
    [0048] The reaction is conducted in a type of reactor that is
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    13/29 selected from autoclave, stainless steel vessel or teflon vessels or glass reactor or plate plasma reactor with variable capacity.
    [0049] The reaction is carried out at a temperature ranging from 50 o C to 250 o C, under inert gas (nitrogen, helium, argon, etc.) or hydrogen or air pressure of 100-7,000KPa (1-70 bar) . The reaction time varies from 0.1-96 hours at 10-2000 rpm speed with optional washing.
    [0050] The solvent for the reaction is selected from the group comprising combinations of water and organic solvents in the ratio of 1:99 to 99: 1. The organic solvent comprises the group of alcohols, ethers, hexane, toluene, xylene and the like.
    [0051] The substrate: solvent ratio varies in the range of 0.001-0.5 weight / weight.
    [0052] The concentration of substrate: catalyst of the invention is in the range of 0.2-500 weight / weight.
    [0053] In one embodiment of the invention, hemicellulose, xylan model substrate derived from oat or birch spelled is loaded into the reactor. Water and catalyst are charged and the reactor is flushed with nitrogen and the final pressure of 100-7,000KPa (1-70 bar) is maintained at room temperature. The reactor is heated to the desired temperature (50-250 o C) under slow stirring. Stirring is increased to 500 rpm and reaction is carried out for 0.1-96 hours to obtain xylose, arabinose and glucose and xylitol. The reaction mixture is further analyzed by HPLC / LC-MS and yield is determined.
    [0054] The heterogeneous catalysts of the present invention are selected from the group of solid acid catalysts comprising zeolites, Si / metal zeolites (metallo silicates), mesoporous silica, modified mesoprorous silicas, oxides and phosphates, clays, ion exchange resins, heteropoly acids , various sulfates,
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    14/29 phosphates, selenates, crystalline materials, amorphous materials and the like. Catalyst can be of rare earth element and its compounds either supported as acid or neutral support or are in combination with sulfates or their precursor. Catalysts are optionally activated at 150 o C or 550 o C for 1-16 hours in air or under vacuum. In addition, the catalyst of the invention can be reused as exemplified here below.
    [0055] Zeolites with Si / Al = 1-100 with regular pore structure and pore diameter in the range of 0.3-1.5 nm including zeolites such as ZSM-5, Y, X, Beta, MOR and the like , in their H form or in Na or NH4 forms, but before reaction they are converted to H form to generate acidic sites, are the catalyst zeolite class of the present invention.
    [0056] Zeolites with Si / Metal = 1-100 (metallo silicates), where the metal is Ga, Ti, Fe, Cr, Zn, P, B, or Zr can also catalyze the hydrolytic conversion of hemicellulose. Metal can also be rare earth metal.
    [0057] Solid acids can also be selected from various mixed metals such as silica aluminum phosphates (SAPO), ALPO and the like.
    [0058] The mesoporous silica catalysts are MCM-41, FSM16, SBA-15, type HMM with regular pore structure and> 2 nm pore diameter, including said silicas with linked functional groups such as carboxylic acid, thiol, -SO3H and the like.
    [0059] Mesoporous silicas with incorporated metal to increase acidity are such as Al-MCM-41, Ga-MCM-41, Al-SBA-15 and the like. The oxide and phosphate catalysts that catalyze hydrolysis of hemicelluloses are niobic acid (Nb2O5), MoO3 / ZrO2, WO3 / ZrO2, zirconium phosphates, lanthanum phosphates, niobium phosphates, and Mo, W, Nb oxides, supported on SiO2 Al2O3, SiO2-Al2O3, and
    Petition 870180018454, of March 7, 2018, p. 17/39
    15/29 similar. The clay catalysts of the invention are selected from aluminum silicates, phylo silicates, pillar clays, clay with exchanged cations, clays treated with acid, preferably montmorillonite type (K10).
    [0060] Ion exchange resins, preferably cation exchangers selected from Amberlyst-15, Amberlyst-35, Amberlite, Amberjet, Dowex, Duolite, Nafion pearls (type NR50) and Nafion-silica composites (type SAC-13) can catalyze reaction of the present invention.
    [0061] The heteropoly acids are selected from Keggin type, Dawson type, Waugh type, Anderson type or Silverton type. Heteropolyacid is optionally phosphotungstic acid, phosphomolybdic acid, tungstic silic acid or phosphoric vanished molybdenized heteropoly acids or their anions. They are supported catalysts in which said support is selected from the group consisting of oxides of metals, carbon, resins and polymers. The metal replacing H + is also included such as C x H 3-x PW 12 O 40 , where x = 0-3.
    [0062] Other catalysts of the invention are various sulfates, phosphates, selenates, and various supports which are optionally crystalline or amorphous selected from Al2O3, ZrO2, SiO2, TiO2, organo silicates, carbon, sulfated zirconia, polymers, oxides as such or modified with acid treatment. Mixed metal oxides such as Cu / ZnO / Al2O3 and the like.
    [0063] In one embodiment of the invention, the single-step hydrolytic process as described herein comprised the conversion of cellulose to value-added derivatives selected from xylose, arabinose, xylitol, arabitol, furfural, xylaric acid, glycols and hydroxy furans. The step of converting cellulose to value-added derivatives is catalyzed by solid acid catalysts and supported metal catalysts. Conversion processes
    Petition 870180018454, of March 7, 2018, p. 18/39
    16/29 hemicellulose and cellulose for value-added derivatives are single reactor processes.
    [0064] As seen in figure 1, formation of xylose from hemicellulose requires a catalyst, with more than 90% conversion and 51% xylose yield is obtained over HBeta catalyst (Si / Al = 19) with reaction conditions mentioned in figure 1. In addition to xylose formation, oligomers such as xylopentose (5 xylose units linked together), xylotriose (3 xylose units linked together) and xylobiosis (2 xylose units linked together) they are also obtained with yields of 6, 10 and 14%, respectively. Without catalyst only 50% xylopentose and 10% xylthetraose (4 xylose units linked together) yield is observed and no xylose formation was possible. This clearly emphasizes the fact that the hemicellulose hydrolysis reaction is a catalytic reaction, that is, the reaction requires an acid catalyst. Glucose formation is not observed due to the superposition of glucose and xylose peaks in the analysis. However, calculations for the formation of xylose are based on the combined area (glucose + xylose) and xylose and total glucose present in the substrate (that is, in spelled oat model substrate,> 70% xylose and <15% glucose are present).
    [0065] As seen in the figure. 2, it is observed that during the course of the reaction, first hemicellulose is thermally decomposed into oligomers, which in turn are still converted into monomers (xylose). It is also interesting to note that after activation of the HUSY catalyst (Ai / Al = 15), xylose yield (40%) increases compared to non-activated catalyst (26%). Arabinose formation was also seen with a yield of approximately 70%. Formation of furaldehyde derived from xylose and / or arabinose dehydrocyclization was also observed with 14% yield over
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    17/29 SO 4 2 7ZrO 2 catalyst.
    [0066] The effect of temperature on the catalytic reaction of the present invention is seen in figure 3. It is clearly seen that the reaction is very dependent on temperature. At 100 o C, about no xylose formation is observed but when the temperature increases from 100 to 200 o C, xylose formation increases with a decrease in time. At 120 o C, 13% xylose formation is observed after 72 hours of reaction time, while at 130 and 140 o C, 40 and 47% xylose formation is observed after 48 and 22 hours of reaction time, respectively . If the temperature is still raised to 150 o C, 160 o C and 170 o C, xylose formation is 45, 41, 43% after 10, 6 and
    2.5 hours of reaction time, respectively. Still the increase in temperature to 200 o C, yielded 45% of xylose within 30 minutes of reaction time.
    [0067] It is observed from figure 4 that in 1 atm of pressure, after 24 hours of reaction with HUSY catalyst (Si / Al = 15), 18% of xylose are formed. When pressure increased to 500KPa (5 bar) and above, the formation of xylose almost remains constant (approximately 30-40%).
    [0068] It is well known that hemicelluloses derived from softwood and hardwood have different morphologies and that the degree of polymerization (DP), that is, total units of xylose linked together to form a polymer are different. In the case of softwood hemicellulose, it is reported that DP is approximately 100 while for hardwood hemicellulose it is around 200. This makes hardwood hemicellulose difficult to degrade or the reaction rate may be lower. Considering this, a study on the source of hemicellulose was carried out and the results are shown in figure 5 where it is observed that almost the same formation of xylose is possible with any hemicellulose substrate.
    Petition 870180018454, of March 7, 2018, p. 20/39
    18/29 [0069] It is observed that with solid acid catalysts, hemicellulose is hydrolyzed to monosaccharides such as xylose, glucose, arabinose, mannose, oligomers such as xylopentose, xylotetraose, xylotriose, xylobiosis, and is also still being converted to furaldehyde and 5- hydroxy methyl furfuraldehyde (HMF). Derived xylose can be widely used as a raw material for the synthesis of a variety of chemical compounds both chemically and biochemically. Xylitol production after hydrogenation of the -CHO group from xylose is well reported. In addition, xylitol is used extensively in food, pharmaceutical and thin coating applications. The most important use of xylitol is as a sweetener and is used in sugar-free candies; that can be consumed by diabetic patients. Xylose can also be converted to glycols (ethylene, propylene), etc.) and can also act as a hydrogen source as shown for sorbitol substrate. Xylose can also be converted to ethanol, 2,3-butanediol, lactic acid and many other chemical compounds.
    [0070] The process of the invention has the following advantages over conventional processes catalyzed with enzyme and catalyzed with mineral acid (HCl, H 2 SO 4 ):
    1. It is a non-corrosive system.
    2. The process does not generate any neutralization discharge when the system operates at neutral pH due to the solid acid catalyst and water is used as a reaction medium.
    3. The separation of catalyst and product is easy, as the catalyst is solid and insoluble in the reaction medium while the products (xyloxe, arabinose, glucose, furaldehyde, oligomers, etc.) formed are soluble in water. Therefore the expensive total process of separating catalyst from reaction media / product is avoided and just a simple filtration step can be employed.
    Petition 870180018454, of March 7, 2018, p. 21/39
    19/29
    4. The handling of catalyst is very easy and does not require any special precautions as required for handling mineral acids.
    5. The reaction is industrially applicable.
    [0071] The process of the present invention is described below with reference to the following examples, which are illustrative only and should not be construed to limit the scope of the invention in any way.
    Example: 1 [0072] In an autoclave 0.6 g of xylan (hemicellulose derived from soft spelled oat wood), 0.3 g HUSY (Si / Al = 15) and 60 g of water are loaded. Reactor is washed 3 times with nitrogen gas. [0073] After that, 5,000KPa (50 bar) of nitrogen is charged into the reactor. The reactor is heated to 130 o C under low agitation (100 rpm). With the desired temperature of 130 o C, agitation was increased to 500 rpm. Periodic sampling was done and the reaction was stopped after 48 hours.
    Reaction mixture analysis:
    [0074] Reaction mixture is analyzed by HPLC (Shimadzu Co., Japan). Water is used as an elution solvent. Refractive index detector (RID) and UV-vis are used for the detection of compounds. Calibration of all compounds (xylose, arabinose, glucose, 5-hydroxy methyl furfural (HMF) and furaldehyde) was performed before analysis. Confirmation of products was also done by LCMS analysis.
    Example 2:
    [0075] In an autoclave (batch reactor), 0.6 g of xylan (hemicelluloses derived from soft wood, spelled oats), 0.3 g of Cs2.5H0.5PW12O40 and 60 g of water are loaded. The reactor is washed 3 times with nitrogen gas. After that, 5,000KPa (50 bar) of nitrogen
    Petition 870180018454, of March 7, 2018, p. 22/39
    20/29 are loaded into the reactor. The reactor is heated to 130 o C under low agitation (100 rpm). At the desired temperature of 130 o C the agitation was increased to 500 rpm. Periodic sampling was done and the reactions were stopped after 24 hours to yield 40% xylose. Example 3 [0076] In an autoclave, 0.6 g of xylan (hemicelluloses derived from soft wood, spelled oats), 0.3 g of HUSY (Si / Al = 15) and 60 g of water are loaded. The reactor is washed 3 times with helium gas. After that, 5,000KPa (50 bar) of helium is charged to the reactor. The reactor is heated to 130 o C under low agitation (100 rpm). At the desired temperature of 130 o C the agitation was increased to 500 rpm. Periodic sampling was done and the reactions were stopped after 48 hours to yield 38% xylose.
    Example 4 [0077] In an autoclave, 0.6 g of xylan (hemicelluloses derived from soft wood, spelled oats), 0.3 g of Nb2O5 and 60 g of water are loaded. The reactor is washed 3 times with nitrogen gas. After that, 5,000KPa (50 bar) of nitrogen is charged to the reactor. The reactor is heated to 170 o C under low agitation (100 rpm). At the desired temperature of 170 o C the agitation was increased to 500 rpm. Periodic sampling was done and the reactions were stopped after 3 hours to yield 19% xylose.
    Example 5 [0078] In an autoclave, 0.6 g of xylan (hemicelluloses derived from soft wood, spelled oats), 0.3 g of Al2O3 and 60 g of water are loaded. The reactor is washed 3 times with nitrogen gas. After that, 5,000KPa (50 bar) of nitrogen is charged to the reactor. The reactor is heated to 170 o C under low agitation (100 rpm). At the desired temperature of 170 o C the agitation was increased to 500 rpm. Periodic sampling was done and the reaction was stopped
    Petition 870180018454, of March 7, 2018, p. 23/39
    21/29 after 3 hours to yield 20% xylose.
    Example 6 [0079] In an autoclave, 0.6 g of xylan (hemicelluloses derived from soft wood, spelled oats), 0.3 g of SO 4 2- / ZrO 2 and 60 g of water and 5,000 kPa (50 bar) argon are charged. The reactor is heated to 170 o C under low agitation (100 rpm). At the desired temperature of 170 o C the agitation was increased to 500 rpm. The reaction was stopped after 3 hours (no washing is done) to yield 11% xylose.
    Example 7 [0080] In an autoclave, 0.6 g of xylan (hemicelluloses derived from soft wood, spelled oats), 0.3 g of MCM-41 (Si / Al = 50) and 60 g of water are loaded. The reactor is washed 3 times with nitrogen gas. After that, 5,000KPa (50 bar) of nitrogen is charged to the reactor. The reactor is heated to 170 o C under low agitation (100 rpm). At the desired temperature of 170 o C the agitation was increased to 500 rpm. Periodic sampling was done and the reaction was stopped after 3 hours to yield 14% xylose.
    Example 8 [0081] In an autoclave, 0.6 g of xylan (hemicelluloses derived from soft wood, spelled oats), 0.3 g of Al-SBA-15 (Si / Al = 10) and 60 g of water are loaded . The reactor is washed 3 times with nitrogen gas. After that, 5,000KPa (50 bar) of nitrogen is charged to the reactor. The reactor is heated to 170 o C under low agitation (100 rpm). At the desired temperature of 170 o C the agitation was increased to 500 rpm. Periodic sampling was done and the reaction was stopped after 3 hours to yield 4% xylose.
    Example 9 [0082] In an autoclave, 0.6 g of xylan (hemicelluloses derived from soft wood, spelled oats), 0.3 g of Amberlyst-15
    Petition 870180018454, of March 7, 2018, p. 24/39
    22/29 (catalyst is refluxed in water and washed with hot water before use) and 60 g of water is loaded. The reactor is washed 3 times with nitrogen gas. After that, 5,000KPa (50 bar) of nitrogen is charged to the reactor. The reactor is heated to 130 o C under low agitation (100 rpm). At the desired temperature of 130 o C the agitation was increased to 500 rpm. Periodic sampling was done and the reaction was stopped after 48 hours to yield 7% xylose.
    Example 10 [0083] In an autoclave, 0.6 g of xylan (hemicelluloses derived from soft wood, spelled oats), 0.3 g of SiO2-Al2O3 (Si / Al = 15) and 60 g of water are loaded. The reactor is washed 3 times with nitrogen gas. After that, 5,000KPa (50 bar) of nitrogen is charged to the reactor. The reactor is heated to 130 o C under low agitation (100 rpm). At the desired temperature of 130 o C the agitation was increased to 500 rpm. Periodic sampling was done and the reaction was stopped after 24 hours to yield 5% xylose.
    Example 11 [0084] In an autoclave, 0.6 g of xylan (hemicelluloses derived from soft wood, spelled oats), 0.3 g of Ga-MCM-41 (Si / Ga = 10) and 60 g of water are loaded . The reactor is washed 3 times with nitrogen gas. After that, 5,000KPa (50 bar) of nitrogen is charged to the reactor. The reactor is heated to 170 o C under low agitation (100 rpm). At the desired temperature of 170 o C the agitation was increased to 500 rpm. Periodic sampling was done and the reaction was stopped after 3 hours to yield 9% xylose.
    Example 12 [0085] In an autoclave, 0.6 g of xylan (hemicelluloses derived from soft wood, spelled oats), 0.01 g of HUSY (Si / Al = 15) and 60 g of water are loaded. The reactor is washed 3 times with nitrogen gas. After that, 5,000KPa (50 bar) of nitrogen is
    Petition 870180018454, of March 7, 2018, p. 25/39
    23/29 loaded into the reactor. The reactor is heated to 130 o C under low agitation (100 rpm). At the desired temperature of 130 o C the agitation was increased to 500 rpm. Periodic sampling was done and the reaction was stopped after 48 hours to yield 34% xylose.
    Example 13 [0086] In an autoclave, 0.6 g of xylan (hemicelluloses derived from soft wood, spelled oats), 0.3 g of HUSY (Si / Al = 15) and 20 g of water are loaded. The reactor is washed 3 times with nitrogen gas. After that, 5,000KPa (50 bar) of nitrogen is charged to the reactor. The reactor is heated to 130 o C under low agitation (100 rpm). At the desired temperature of 130 o C the agitation was increased to 500 rpm. Periodic sampling was done and the reaction was stopped after 24 hours to yield 36% xylose.
    Example 14 [0087] In an autoclave, 0.6 g of xylan (hemicelluloses derived from soft wood, spelled oats), 0.3 g of HUSY (Si / Al = 15) and 60 g of solvent (40 g of toluene and 20 g of water) are loaded. The reactor is washed 3 times with nitrogen gas. After that, 5,000KPa (50 bar) of nitrogen is charged to the reactor. The reactor is heated to 120 o C under low agitation (100 rpm). At the desired temperature of 120 o C the agitation was increased to 1000 rpm. Periodic sampling was done and the reaction was stopped after 48 hours to yield 8% xylose.
    Example 15 [0088] In an autoclave, 0.6 g of xylan (hemicelluloses derived from soft wood, spelled oats), 0.3 g of HUSY (Si / Al = 15) and 60 g of water are loaded. The reactor is washed 3 times with nitrogen gas. After that, 5,000KPa (50 bar) of nitrogen is charged to the reactor. The reactor is heated to 130 o C under low agitation (100 rpm). With the desired temperature of 130 o C the agitation was increased
    Petition 870180018454, of March 7, 2018, p. 26/39
    24/29 to 1000 rpm. Periodic sampling was done and the reaction was stopped after 48 hours to yield 42% xylose.
    Example 16 [0089] In an autoclave (batch reactor), 0.6 g of xylan (hemicelluloses derived from soft wood, spelled oats), 0.3 g of HUSY (Si / Al = 15) and 60 g of water are loaded. The reactor is heated to 130 o C under low agitation (100 rpm). At the desired temperature of 130 o C the agitation was increased to 500 rpm. Periodic sampling was done and the reaction was stopped after 48 hours. In this reaction, no inert gas is used and it yielded 38% xylose.
    Example 17 [0090] In an autoclave (batch reactor), 0.6 g of xylan (hemicelluloses derived from soft wood, spelled oats), 0.3 g of sulfonated MCM-41 (MCM-41 with -SO 3 H group on) and 60 g of water are loaded. The reactor is flushed 3 times with nitrogen gas and 5,000KPa (50 bar) of nitrogen is charged to the reactor. The reactor is heated to 120 o C under low agitation (100 rpm). With the desired temperature of 120 o C the agitation was increased to 500 rpm. Periodic sampling was done and the reaction was stopped after 48 hours to yield 10% xylose.
    Example 18 [0091] In an autoclave, 0.6 g of xylan (hemicelluloses derived from soft wood, spelled oats), 0.3 g of montmorillonite K10 (clay) and 60 g of water are loaded. The reactor is flushed 3 times with nitrogen gas and 5,000KPa (50 bar) of nitrogen is charged to the reactor. The reactor is heated to 170 o C under low agitation (100 rpm). At the desired temperature of 170 o C the agitation was increased to 500 rpm. Periodic sampling was done and the reaction was stopped after 3 hours. This resulted in 29%
    Petition 870180018454, of March 7, 2018, p. 27/39
    25/29 xylose.
    Example 19 [0092] In an autoclave (batch reactor |), 0.6 g of xylan (hemicelluloses derived from soft wood, spelled oats), 0.6 g of HUSY (Si / Al = 15) and 60 g of water are loaded. The reactor is flushed 3 times with nitrogen gas and 5,000KPa (50 bar) of nitrogen is charged to the reactor. The reactor is heated to 170 o C under low agitation (100 rpm). With the desired temperature of 170 ° C Agitation was increased to 500 rpm. Periodic sampling was done and the reaction was stopped after 3 hours.
    [0093] After removing the reaction mixture from the autoclave, it is centrifuged and wet sprayed (containing catalyst and unreacted hemicellulose) is removed. This wet spray is washed 3 times with cold distilled water. Then, the powder is used for the next reaction with loading as follows, 0.6 g xylan, HUSY catalyst (Si / Al = 15) recovered with unreacted hemicellulose (wet spray) and 60 g of water. The reaction conditions for the recycling experiment are the same as above. Periodic sampling is done and the reaction was stopped after 3 hours, resulting in 36% xylose yield.
    Example 20 [0094] In a teflon reactor (batch reactor), 0.4 g of xylan (hemicelluloses derived from oat spelled softwood), 0.2 g of HUSY (Si / Al = 15) and 40 g of water are loaded. The reactor is heated to 130 o C with agitation (rpm is not measured). The reaction is stopped after 24 hours, to yield 30% xylose.
    Example 21 [0095] In an autoclave (batch reactor), 0.6 g of xylan (hemicelluloses derived from soft wood, spelled oats), 0.24 g of HUSY (Si / Al = 15) and 0.06 g of SO 4 2- / ZrO 2 (total amount of
    Petition 870180018454, of March 7, 2018, p. 28/39
    26/29 catalyst, 0.3 g) and 60 g of water are loaded. The reactor is washed 3 times with nitrogen gas. After that, 5,000KPa (50 bar) of nitrogen is charged to the reactor. The reactor is heated to 170 o C under low agitation (100 rpm). At the desired temperature of 170 o C the agitation was increased to 500 rpm. Periodic sampling was done and the reaction was stopped after 3 hours to obtain 33% xylose yield.
    Example 22 [0096] In an autoclave (batch reactor), 0.6 g of xylan (hemicelluloses derived from soft wood, spelled oats), 0.3 g of HUSY (Si / Al = 15) and 60 g of water are loaded. The reactor is washed 3 times with nitrogen gas. After that, 5,000KPa (50 bar) of nitrogen is charged to the reactor. The reactor is heated to 130 o C under low agitation (100 rpm). At the desired temperature of 130 o C agitation was increased to 500 rpm. Periodic sampling was done and the reaction was stopped after 48 hours. The result of the reaction is 36% xylose yield.
    Example 23 [0097] In an autoclave, 0.6 g of bagasse, 0.3 g of HUSY (Si / Al = 15) and 60 g of water are loaded. The reactor is washed 3 times with nitrogen gas. After that, 5,000KPa (50 bar) of nitrogen is charged to the reactor. The reactor is heated to 170 o C under low agitation (100 rpm). At the desired temperature of 170 o C the agitation was increased to 500 rpm. Periodic sampling was done and the reaction was stopped after 1.5 hours to yield 0.09 g of xylose. Example 24 [0098] In an autoclave, 0.6 g of bagasse, 0.3 g of montmorillonite K10 (clay) and 60 g of water are loaded. The reactor is washed 3 times with nitrogen gas. After that, 5,000KPa (50 bar) of nitrogen is charged to the reactor. The reactor is heated to
    Petition 870180018454, of March 7, 2018, p. 29/39
    27/29
    170 o C under low agitation (100 rpm). At the desired temperature of 170 o C the agitation was increased to 500 rpm. Periodic sampling was done and the reaction was stopped after 1.5 hours to yield 0.08 g of xylose.
    Example 25 [0099] In an autoclave, 0.6 g of bagasse, 0.3 g of HBeta (Si / Al = 19) and 60 g of water are loaded. The reactor is washed 3 times with nitrogen gas. After that, 5,000KPa (50 bar) of nitrogen is charged to the reactor. The reactor is heated to 170 o C under low agitation (100 rpm). At the desired temperature of 170 o C the agitation was increased to 500 rpm. Periodic sampling was done and the reaction was stopped after 2 hours to yield 0.09 g of xylose. Example 26 [00100] In an autoclave, 0.6 g of bagasse, 0.3 g of HUSY (Si / Al = 15) and 60 g of water are loaded. The reactor is washed 3 times with nitrogen gas. After that, 5,000KPa (50 bar) of nitrogen is charged to the reactor. The reactor is heated to 120 o C under low agitation (100 rpm). With the desired temperature of 120 o C the agitation was increased to 500 rpm. Periodic sampling was done and the reaction was stopped after 40 hours to yield 0.08 g of xylose. Example 27 [00101] In an autoclave, 0.6 g of bagasse, 0.3 g of HUSY (Si / Al = 15) and 60 g of water are loaded. The reactor is washed 3 times with nitrogen gas. After that, 5,000KPa (50 bar) of nitrogen is charged to the reactor. The reactor is heated to 140 o C under low agitation (100 rpm). With the desired temperature of 140 ° C Agitation was increased to 500 rpm. Periodic sampling was done and the reaction was stopped after 12 hours to yield 0.08 g of xylose. Example 28 [00102] In an autoclave, 0.6 g of bagasse, 0.3 g of HUSY
    Petition 870180018454, of March 7, 2018, p. 30/39
    28/29 (Si / Al = 15) and 60 g of water are loaded. The reactor is washed 3 times with nitrogen gas. After that, 100KPa (1 bar) of nitrogen is charged to the reactor. The reactor is heated to 170 o C under low agitation (100 rpm). At the desired temperature of 170 o C the agitation was increased to 500 rpm. Periodic sampling was done and the reaction was stopped after 1.5 hours to yield 0.08 g of xylose. Example 29 [00103] In an autoclave, 0.6 g of bagasse, 0.3 g of HUSY (Si / Al = 15) and 60 g of water are loaded. The reactor is washed 3 times with nitrogen gas. After that, 500KPa (5 bar) of nitrogen is loaded into the reactor. The reactor is heated to 170 o C under low agitation (100 rpm). At the desired temperature of 170 o C the agitation was increased to 500 rpm. Periodic sampling was done and the reaction was stopped after 1.5 hours to yield 0.09 g of xylose. Example 30 [00104] In an autoclave, 0.6 g of bagasse, 0.3 g of HUSY (Si / Al = 15) and 60 g of water are loaded. The reactor is washed 3 times with nitrogen gas. After that, 5,000KPa (50 bar) of nitrogen is charged to the reactor. The reactor is heated to 170 o C under low agitation (100 rpm). At the desired temperature of 170 o C the agitation was increased to 500 rpm. Periodic sampling was done and the reaction was stopped after 3 hours.
    [00105] After removing the reaction mixture from the autoclave, it is centrifuged and sprayed wet (containing catalyst and unreacted hemicellulose) is removed. This wet spray is washed 3 times with cold distilled water. Then, the spray is used for the next reaction with loading as follows, 0.6 g xylan, HUSY catalyst (Si / Al = 15) recovered with unreacted hemicellulose (wet spray) and 60 g of water. The reaction conditions for the recycling experiment are the same as above. Periodic sampling is done
    Petition 870180018454, of March 7, 2018, p. 31/39
    29/29 and the reaction was stopped after 3 hours, resulting in 36% xylose yield.
    Example 31 [00106] Lignocellulosic material (bagasse) (0.6 g) without any physical and / or chemical pretreatment was mixed with water (30 g), toluene (30 g) and solid acid catalyst, 0.3 g in an autoclave . Reaction temperature of 170 o C was maintained without N 2 pressure. Furfural yield of 40% was observed with HUSY catalyst (Si / Al = 15) after 5 hours of reaction.
    Example 32 [00107] Lignocellulosic material (bagasse) (0.6 g) without any physical and / or chemical pretreatment was mixed with water (30 g), toluene (30 g) and solid acid catalyst, 0.3 g in an autoclave . Reaction temperature of 170 o C was maintained with N2 pressure. 500KPa (5 bar). Furfural yield of 40% was observed with HUSY catalyst (Si / Al = 15) after 5 hours of reaction.
    Petition 870180018454, of March 7, 2018, p. 32/39
    1/2
    权利要求:
    Claims (3)
    [1]
    1. Hydrolytic process of a single reactor and a single step for the conversion of xylan into derived products of added value selected from the group consisting of xylose and arabinose, characterized by the fact that said process comprises:
    The. xylan loading into the reactor followed by a loading of a solvent and at least one heterogeneous solid acid catalyst;
    B. pressure adjustment to 100-7,000KPa (1-70 bar) and reactor temperature of 50-250 o C, under agitation;
    ç. elevation of agitation speed to 10-2000 rpm after required temperature stabilization; and
    d. carrying out said above reaction for a period of 0.1 to 96 hours to obtain said desired value-added product;
    wherein said heterogeneous solid acid catalyst is selected from the group consisting of HUSY (Si / Al = 50), Cs 2 , 5 H 0 , 5 PW 12 O 40 , Nb 2 O 3 , Al 2 O 3 , SO 3 2 - / ZrO 2 , Al-MCM-41 (Si / Al = 50), Al-SBA-15 (Si / Al = 50), Amberlyst-15, SiO 2 -AlO 3 (Si / Al = 15), Ga- MCM41, MCM-41 sulfonated, and montmorillonite K10 (clay).
    [2]
    2. Process according to claim 1, characterized by the fact that:
    The. said process comprises a step of washing the reactor with inert gas or air after step (a) and before step (b), said inert fan selected from the group consisting of nitrogen, argon, helium and hydrogen,
    B. the xylan to solvent ratio is in the range of 0.0010.5 weight / weight; or the xylan to catalyst ratio is in the range of 0.2-500 weight / weight.
    [3]
    3. Process according to claim 1, characterized by the fact that the solvent in the reaction is organic solvent or a
    Petition 870180018454, of March 7, 2018, p. 33/39
    2/2 mixture of water and organic solvent in a ratio of 1:99 to 99: 1 and said organic solvent is selected from the group consisting of alcohols, ethers, esters, hexane, acids, toluene, and xylene.
    Petition 870180018454, of March 7, 2018, p. 34/39
    1/5
    Q Without catalyst «HBeta (SÉ / AÍ-1 &) e
    Yield, %
    40 30 20 § ° 'lL.D &
    -S>
    -2>
    .0
    Compounds
    类似技术:
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    同族专利:
    公开号 | 公开日
    ES2408108R1|2014-01-09|
    JP5750118B2|2015-07-15|
    AU2010344335A1|2012-03-08|
    EP2529036B1|2017-11-22|
    US9267181B2|2016-02-23|
    EP2529036A1|2012-12-05|
    CN102575301A|2012-07-11|
    AU2010344335B2|2014-10-23|
    ES2408108B1|2014-10-21|
    US20120192860A1|2012-08-02|
    JP2013517792A|2013-05-20|
    CN102575301B|2016-03-16|
    WO2011092711A1|2011-08-04|
    ES2408108A2|2013-06-18|
    BR112012017478A2|2015-09-01|
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    法律状态:
    2017-06-27| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2017-09-26| B15K| Others concerning applications: alteration of classification|Ipc: C08B 1/00 (1968.09), C13K 13/00 (1974.07) |
    2017-12-26| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application according art. 36 industrial patent law|
    2018-07-17| B09A| Decision: intention to grant|
    2018-08-14| B16A| Patent or certificate of addition of invention granted|
    优先权:
    申请号 | 申请日 | 专利标题
    PCT/IN2010/000047|WO2011092711A1|2010-01-27|2010-01-27|A one pot and single step hydrolytic process for the conversion of lignocellulose into value added chemicals|
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