JPS58500431A - High efficiency organosolv saccharification method - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] High efficiency organosolv saccharification method Background of the invention 1. Prior art The organosolv hydrolysis method uses certain woodcutter type cells. We have achieved great results with loin materials, especially lignocellulose materials. organoso The wood most easily delignified in Luso solution is cottonwood; Do conifers like Douglas fir and pines provide substantial resistance? Indicated. Sugar cane shell is It was found that it is relatively easy to hydrolyze. Essentially cellulose, especially crystalline fluorine Codon linters are extremely difficult to hydrolyze using conventional techniques. there were.

Differences in hydrolysis are related to variations and heterogeneities in the structure and chemical composition of cellulosic materials. I have to work on it. Therefore, the conventional organonorbe method is not suitable for delignification or for treating cellulose products. Mainly applied to quality. Codon linters are especially avoided in terms of glycation manipulation. The reason for this is that codon linters are highly resistant to hydrolysis. and hydrolysis to rapidly convert polymeric glucans to monomeric sugars. This is due to the harsh process conditions required.

The prior art involves delignification and/or saccharification of cellulosic materials and vegetable crops. Rudame's various organosolder methods are described. Generally this kind of method is a combination of water and a solvent, such as an alcohol or ketone, and sometimes other non-polar solvents. Mixtures include use with acidic compounds that promote hydrolysis. usually In this case, the treatment required to achieve delignification and additional hydrolytic The processing time depends on the hydrolysis power of the solvent system and the deligninization of the individual lignocellulosic materials. It can last several hours depending on their ability. Conventional methods have poor delignification ability and require hydration. The decomposition rate is slow, and the conversion of sugars to non-organic substances, mainly furfural and organic acids, is slow. It is a sign that the change is severe. Therefore, the recovery rate of sugar is low, and this food is Law? It lacked the appeal of developing it on a commercial scale. To the best of the inventor's knowledge However, all prior art saccharification methods have some of these drawbacks. There is. This is especially true when using the organosolder method, especially for soldering, ton linter, and softwood soldering. This is originally attached to the organosolder method for materials that are difficult to hydrolyze, such as It was thought for a long time that there was.

Therefore, Dreyfus, U.S. Pat. No. 1,919,623 (1) (933) pre-prepared wood with concentrated acid in an acetone-water carrier solvent mixture. After pretreatment and removal of organic solvents, acid-containing wood can be heated for several hours at low temperatures. And lignin? It states that they should occur at the same time. Reportedly, processed The lignocellulose is virtually insoluble in acetone-ether water mixtures. , treatment of the prehydrolyzed material with the same solvent removes only the excess acid and allows for another treatment. It is said that he used it for good reason. Minutes of pre-hydrolyzed cellulose material into the harpoon The solution was carried out by boiling in a weak acid aqueous solution. As expected, the light is on Doylefus. Issued U.S. Patent No. 2,022,654 describes a method for producing cellulose pulp. A similar attempt was also described in which the method involved aqueous 8D% 1 in water. Use concentrated mineral acid dissolved in setone to pre-treat the wood to soften it. After substantially removing the acid, add 50-80% acetone water in a pressure vessel. Or, using a mixture of acetone and a non-polar organic solvent at 170° to 20°C and 9 to 1 Process the chips for 2 hours. According to Schlaepfer et al. U.S. Patent No. 2,959.500 is non-reactive with alcohols. alcohol and in the presence of a small amount of acidic compound, which is a requirement of the patent claim. water and, if necessary, a non-polar solvent at 1200-200°C The hydrolysis method used in ℃ is described. Conceivably, this method Relatively slow and with limited saccharification power, sugar yields are much inferior to quantitative yields. Ru. U.S. Patent No. 1,964.646 to Oxley et al. (1934) discloses slow saccharification with strong acids. Kleiner) (Kle inert) and Tayenthal, U.S. Patent No. No. 1,856,567 (1932) uses a small amount of shun or The base is used at elevated temperatures to produce cellulose pulp in a pressure vessel. It discloses the use of hydroalcohol. Processed in 6-hour steps each Then it is written. Other prior art is U.S. Pat. No. 2,951,775, the method involves heating at temperatures between 25°C and 00C. The wood is saccharified by multiple applications of concentrated hydrochloric acid.

2. Purpose of the invention The main objective of the present invention is to rapidly and quantitatively solubilize and The goal is to collect and recover the waste.

Another object of the present invention is to shorten the hydrolysis time in the hydrolysis of cellulose materials. and substantially increase the rate of sugar formation.

Yet another object of the present invention is that sugars are separated into non-sugars during high temperature hydrolysis of cellulosic materials. The goal is to reduce the amount of time it takes to understand the situation.

Yet another object of the invention is that if the cellulosic material is lignocellulose, Its chemical components are simultaneously dissolved and then recovered separately, mainly xylose and hexylose. The source is to obtain sugar and lignin.

Yet another object of the invention is to simply The released pentoses and hexoses are converted to their respective dehydration products, e.g. It is converted into monomeric furfural and hydroxymethylfurfural and levulin. Fural, resolinic acid? It is to collect.

Another object of the present invention is to evaporate organic volatiles from the hydrolyzate and If lignin is contained, when it is separated from the aqueous solution, an amount of 10i or more Quantitative hydrolysis of cellulosic materials at a rate such that sugar solids are obtained from solution It is to be.

Another objective of the present invention is to maintain and adjust the acid concentration required to maintain a constant hydrolysis rate. the catalytic effect of acids on sugar decomposition at high temperatures. Effect? This is to substantially reduce the amount.

In another aspect, an object of the invention is to achieve certain desired reactions in the hydrolysis process. Maximize sugar recovery by lowering the reaction temperature required to obtain the speed. Is Rukoto.

Yet another object of the invention is to have a much lower heat capacity and heat of vaporization than water. Therefore, a large proportion of acetone can be easily vaporized to cool the hydrolyzate. By using 70% or more, the energy required for hydrolysis can be reduced. Is Rukoto.

Yet another object of the present invention is the selective desorption of cellulosic materials in a very short period of time. By applying lignin and hydrolysis, it can be used for animal feed, food additives and industrial purposes. Substantially pure, poorly polymerized cellulose filtrate useful as a filler or adsorbent That is.

The above purposes and other purposes can be achieved one by one by reading the explanation below. It will become clear.

The present invention uses a solvent mixture of acetone and water containing small amounts of acidic compounds to What crushed cellulose material may contain? Processed at elevated temperatures in a pressure trough sugar-like carbon from the cellulosic material by forming reducing sugars in the liquid. This invention relates to an improvement in a method for producing a hydrolysis product of a hydrate, and the improvement Good is (a) in a pressure vessel at an elevated temperature, together with the cellulosic material, the solvent mixture; a mixture of acetone and water containing at least 70 volumes of acetone and a catalytic Acidic compound of? ! l Get ready, (b) Until the cellulosic material is at least partially dissolved.

and that the solubilized sugars from cellulosic materials do not decompose into non-saccharides in the liquid. Cellulosic material is placed in a solvent mixture such that at least 90% is recovered. Process at elevated temperatures for a limited time.

and (C) Cool the liquid as soon as it is removed from the pressure vessel.

It is characterized by this.

The present invention also uses a solvent mixture of acetone and water containing small amounts of acidic compounds to A crushed cellulosic material that may contain gunins is heated at an elevated temperature in a pressure vessel. treatment to solubilize all lignin and form reducing sugars in the liquid. hydrolysis products of carbohydrates such as sugars and lignin from said cellulosic materials; This invention relates to an improvement in the method of manufacturing (a) Solvent mixture with cellulosic material in a pressure vessel at elevated temperature. A mixture of acetone and water containing as a mixture at least 70 volumes of acetone and Prepare a catalytic acidic compound, (b) 1 in which the cellulose material is at least partially dissolved, and the cellulose material At least 90% of the soluble sugars are recovered without decomposition into non-saccharides. The cellulosic material is prepared in one step at elevated temperature in a solvent mixture as follows. treatment for a time sufficient to dissolve not more than 50% of the cellulose, thereby Most of the carbohydrates contained in cellulosic materials are completely dissolved and hydrated. (C) Continuously remove the liquid from the pressure vessel; (d) Controlled acetone extraction. The liquid is rapidly cooled by flash evaporation of , leaving an aqueous solution, and (θ) 　Recover sugar and all lignin from the residual aqueous solution This is a distinctive feature.

Acetone having a volumetric concentration f’r in water of 70% or more and a catalytic amount of acid are used together. In case of hydrolysis under elevated saccharification temperatures, the residence time in the pressure vessel must be limited. Acetone forms a stable complex with the sugar produced in the solution, significantly accelerating the rate of hydrolysis2. It was inadvertently discovered that it could be advanced. of polymeric carbohydrates through the formation of sugar complexes. The phenomenon of accelerated decomposition is not well documented in the prior art literature, and is not predicted from the prior art literature. It is also impossible to see.

Typically, such complexes exist in aqueous acetone solutions, especially at such high temperatures. It was believed that it could not exist. The results of the present invention show that under selective conditions , decomposition of sugar during the saccharification process does not substantially occur, but It is roughly 500 times faster than the alkyl gelconds and polyglucan The reason is that the ton complex was observed to be hydrolyzed. There is a complex between acetone and acetone. Another advantage is that it is based on simple methods such as evaporation, selective hydrolysis and liquid-liquid extraction. It is easy to separate into individual sugars. Nanatsuma in the presence of mineral acids at room temperature Regarding the formation of complexes of sugars in anhydrous acetone, -Bohydrate Chemistry (Methods 1nCarbohydra) te Chemistry), volume 2, page 618.

The term "cellulosic material" refers to plant and wood products, generally in pulverized form. Includes source material.

The acidic compound may be of inorganic origin or of organic origin. , must be inert to solvents. Inorganic acids such as sulfuric acid, hydrochloric acid and phosphoric acid Strong acids are preferred, such as aluminum chloride, 1aW1 aluminum, ferric chloride. Acidic salts and organic acids such as trifluoroacetic acid can also be used.

The elevated temperature is between 145° and 260°C, and between 160° and 210°C. The most favorable case.

The catalytic amount of acidic compound is between 0.05 and 0.5% based on the weight of the solvent mixture. is preferred. When choosing a high temperature, what is the amount? It is particularly effective to reduce the amount.

The reaction time for one treatment is the solid residue at a specific acid concentration and reaction temperature. The time required to dissolve 50% of the Reducing sugars in dissolved form can be obtained with a high yield that can be used. High temperature and sugar heat Rating time regulates the amount of solvent fed to the reactor, the concentration of acid used, the amount of acetone Generally depends on quantity and elevated temperature. Therefore, very quick hydration To achieve the decomposition time, an acid concentration of 0.04 to 0.06N and an acetone concentration of about 80% are required. degrees and temperatures of 200°C or higher are used. However, 2. - close to the theoretical value To improve the yield of sugar, low acid 111j (0.02N and below), high acetic acid Tons! ji (180% or higher) and high temperature (200°C or higher) is most preferable. Ru.

The conventional aqueous weak acid and alcoholic organosolv method has been used for cottonwood spp. For use with hydrolyzed lignocellulosic materials such as sugar cane husks (bagasse) Even if it does, it is relatively slow and has limited hydrolysis power. Sugar production in a single process When hydrolyzed, it usually takes 60 minutes to 60 minutes for these woods to be hydrolyzed. It takes time. Lignin is a dark, fire-resistant substance that is insoluble in alkalis and most organic solvents. It is turned into resin in chunks. The continuous Percollet-Nyon method takes a relatively long time of 60 to 90 minutes. Although short hydrolysis times have been identified, the sugar yield obtained with this type of method is 45-50% of the theoretical value? It almost never goes over. The high yield of sugar is due to the addition of enzymes. Although it is said to be achieved by the water splitting method, the only thing that can be hydrolyzed by enzymes is dehydration. Limited to lignified cellulose and continuous fermentation for 4 hours, batch fermentation The disadvantage of this method is that it requires a hydrolysis time of 24 hours or more. this However, even materials that are difficult to hydrolyze, such as codon linters and Douglas fir wood, are Can be easily processed by the invention and dissolves within 40 minutes and 20 minutes respectively be done. The yield of reducing sugar and lignin according to the present invention is 95% of the theoretically obtained amount. %, and they are obtained in high purity and highly reactive form.

Components of metal reactor walls, piping and other control equipment that come into contact with heated liquids. by transition metal ions such as N1, co, Or, Fθ and CU, which may be included as To eliminate the catalytic effects associated with sugar decomposition, a reactor with an inert lining is used. used.

When using the method of the invention, the selected prevailing temperature and acid concentration in the reaction vessel are In any case, from the time required to hydrolyze 50% of the remaining solid residue. Continuous percolation at a predetermined speed with short residence times ion is desired and, depending on the degree of hydrolysis to be tolerated, the material may be partially or completely removed. Total lysis is obtained. In multi-step patch processing, the initial delignification Partial hydrolysis with oxidation yields relatively pure cellulose. Same or different Continuous hydrolysis using a solvent mixture of The material components can be separated step by step to achieve pure agriculture and high yield.

Regardless of these process choices, it is common to recover pentose from the reaction mixture. The method first involves distillation under reduced pressure with flash evaporation of most of the acetone. Either continue, or perform steam distillation to obtain the pentose sugar complex in the distillate. It is. Pentose and hexose can be separated using such a simple method. This is because there is a large difference in boiling point between these acetone-sugar complexes. these When the concentration of acetone is 70 volumes or more, the complex can be treated by high temperature hydrolysis of the present invention. During the process, it will form even if water is present.

The lignin dissolved in the remaining aqueous sugar solution has a relatively low molecular weight (MWW = 3200) as granules. R filtered or centrifuged and washed with cold water. Afterwards, these granules can be dried into powders with a spherical particle size of 2 to 600μ. Ru. To purify the crude lignin, it is repeatedly redissolved in acetate/filtered and dissolved. Any remaining residue is spray dried with a highly concentrated acetone solution.

The residual aqueous solution after separating the lignin precipitation is a clear solution with a concentration of 10% or so. It consists primarily of hexose sugars and also contains one or more water-soluble components.

pent when hydrolyzed by acidification and boiled for at least 20 minutes The main fractions from the hexose distillate and hexose syrup are in the form of monosaccharides and Obtained in purity. If desired, the separated sugar fraction may be boiled in the presence of an acid. By carrying out for a long time under It is known in the art that sugars can be selectively converted to dehydrated products.

After hydrolyzing the cellulosic material for a limited time under elevated temperature, the sugar The temperature of the reaction mixture was rapidly lowered below 100°C to prevent undesirable decomposition of T1. It is very important to Even if a dilute acid exists, below the boiling point of water, Since it was observed that no significant degradation of sugars occurred, volatiles were removed by controlled flashing. Cooling is best achieved by removal with a flash treatment. Usually fermented and other Continue to cool the liquid to ambient temperature or below (25°C) before entraining. I can do it.

The above method can be operated in continuous or semi-continuous mode, in the latter case The principle of steaming is used. In the semi-continuous saccharification process, one set of pressures is applied at each of the various stages. By using a container, it can be compared to a continuous method.

In continuous operation, all stages of hydrolysis are carried out in a single pressure vessel, with individual Always measure the product mix by the saccharification program set. crushed wood solids and cooking liquid are constantly fed into the pressure vessel. The supply ratio is based on raw material supply and production The time between material removal is fixed at any one possible stage of the process. Exceeding the predetermined time required to hydrolyze 50% of the residue make sure it doesn't happen. Therefore, the residence time is always adapted to the most sensitive stage and Therefore, the sugar recovery rate at the specific stage is set to exceed 90%. Conceivable The three major saccharification stages are:

(a) Bulk delignification and prehydrolysis; up to 75% of the ligation during this stage Kinloth and 95% of the major hemicelluloses (Kinloth in hardwoods and 1 in soft woods) , mannose can be completely removed from wood. Solid residue yield is always 50% of starting material That's all.

(b) Continuous delignification and cellulose purification stage; during this stage delignification is almost complete, and the remainder of the hemicellulose sugars and some of the amorphous glucans are removed. At this stage, the solid residue is generally less than 35% and is mainly composed of solids. It is crystalline.

(C) Complete saccharification progresses, and the residual cellulose in step (b) breaks down into heptameric sugars. It will be solved. In order to achieve a good circulation recovery rate of 90%, it is necessary to Exchanges must be made more than once.

In continuous operation, the liquid recovered from the various hydrolysis stages is It may contain sugars derived from cloves.

This means that together with the chips, C (preliminary hydrolysis at the top of the column from the remaining liquid pumped) This is a necessary aspect for devices that are not equipped with means for separating. According to the present invention When the sugar is purified, this kind of separation operation is not necessary to purify the sugar. The reason is a misunderstanding. This is because sugar is obtained as a body, and pentose and hexose have different volatilities. .

Based on its insolubility in water, lignin is separated and removed outside the reactor. The organic volatiles are recovered by flash evaporation.

Separating the first and second stage liquors from the remaining hydrolyzate products continues to separate the liquors from the remaining hydrolysis products. The dehydration of pentose sugars can be caused by heating, and the corresponding furfura It has particular significance in the production of alcohol and levulinic acid. In this case, Only a small proportion of the source sugars should be saccharified. Furfura from pentose sugar A good idea for producing mol is to heat the flash evaporation stage. Alternatively, Good results have also been obtained using the steam strip method, with relatively pure pentose solutions. Liquid is obtained almost stationarily. This distillate is acidified and processed under highly controlled conditions. It can be reheated under low temperature, producing highly pure furfural with a yield of over 95%. be done.

When carrying out hydrolysis in a semi-continuous manner, complete saccharification and dissolution are achieved; To achieve a material recovery of 95% or more, it is necessary to perform five liquid exchanges. preferred liquid The wood to wood ratio is between 7:1 and 10:1. mass ped (mass ’bea) ) at a steady liquid-to-wood ratio of 7.1. The total amount of liquid required for OKY’V hydrolysis is a total of 13.56:1. For a liquid to wood ratio of 1356 to 9. Under these conditions - The average sugar concentration in the residual aqueous phase (271 kg) was 30% (recovered sugar 8 2.5 to 9).

In the continuous percolation method, the liquid to wood ratio can always be kept at 10.1, For example, when necessary, both wood and liquid are added continuously, and the amount of water present in the reactor is added continuously. The hydrolyzed products can be sequentially extracted. This also flattens volatile matter. A concentration of about 67-40% of sugar in the liquid after removal of sugar has been established. reactor. Such a high concentration of sugar solids requires conventional methods to use a hydrolysis system using strong acids. Is it possible only when using dilute acid hydrolysis? Hopefully it will be achieved This is something that could not have happened.

The discussion of liquid-to-wood ratios is particularly important for organosolves and acid hydrolysis. It is important. After all, the liquid-to-wood ratio is important in the hydrolysis and solvent recovery process. In addition to human power, water is used after fermenting sugar into ethanol and other organic solvents. The energy involved in the process of recovering alcohol from solution is directly related to human power. It is. Therefore, the liquid-to-wood ratio is important when converting biomass to liquid chemicals. economics as well as energy efficiency of the process (energy consumed during conversion) The effect on the energy gain (gained energy) is significant.

Steaming the ground cellulosic material with steam before mixing with the hydrolyzate is a It is advantageous for expelling the air that is present. Such treatment allows for rapid liquid removal. Transparency is aided. Such operations are well known in the art.

In this example, six competing systems are used: acidified water (aqueous weak acid); Saccharifying power and sugar survival for acidified aqueous ethanol and acidified aqueous acetone compared.

In either case, Tarabee (TAPP) 0.5% viscosity is 35 cP. A purified codon linter having a crystal layer index of 76% at a water content of 7% was used.

Acidification is carried out using sulfuric acid 2 to prepare raw material solutions in various solvents, and in each case The acid was 0.04N. The hydrolysis conditions were as follows.

- In a series of experiments, 1 g of codon linter was added with 10 ml of solvent mixture. sample (oven dry weight)? In a 20m1 stainless steel container lined with glass. and heated at 1-80°C for various lengths of time to remove any remaining solids and detectable substances in the solution. The resulting sugars were plotted on graph paper.

From this graph, the time required to obtain approximately 99.75.50% and 25% dissolution of the substrate can be read. The results are shown in Table 1.

Heating at the end of the reaction period? Suspended and quenched in a container, with moderate porosity The entire contents of the container were passed through a glass crucible. Any undissolved residue should be washed with warm water first. Wash with water, rinse several times with 5ml of acetone, and finally rinse with warm water. Ta. After drying at 105°C, the weight of the residue was determined by the superposition measurement method. It was measured.

Comparative analysis? For the purpose, dilute the combined r solution with water to 10021, and make 0.5ml. An aliquot of Kaoru was placed in a test tube.

2. Add 3 ml of ON sulfuric acid and heat in a boiling water bath to 10' 0℃ for 40 minutes. Secondary hydrolysis was carried out. After cooling, the solution is neutralized and the reducing power of the sugar present in the solution is Measured by. Essentially based on the monosaccharides liberated during hydrolysis, the results are uniform. It was one. The theoretical % of reducing sugar obtained after hydrolyzing the substrate, starting material measured by the difference between the known chemical composition of the material and the weight loss due to hydrolysis. Established. Carbohydrate fractionation due to hydration of the polymer as it breaks down into monomeric sugars To compensate for the weight gain of the action, the weight loss is usually multiplied by 1.1111'&. child This is the weight percent of water added to cellulose during hydrolysis to monomeric sugars (1 1.11%).

As is clear from Table 1, as the acetone concentration increases to 50%, the hydrolysis rate gets better. However, significant improvements were made when acetone mu was added to the acidified solvent mixture. It can only be observed when the compound has a capacity of 70 or more. Mostly anhydrous acetate when using a solution.

Very rapid hydrolysis rates were obtained. Solvent mixture containing 80-90% acetone It was found that the stability of the melt was the highest when combined use was used, but the relative His life was relatively short. Sugar survival above 90% means that 50% of the substrate is produced obtained when the reaction time at each temperature is kept below the time required to hydrolyze the It will be done. The time required to hydrolyze 50% of the substrate to dissolved products is the sugar survival factor. It is called life. This criterion concerns which steps of hydrolysis are considered. It holds true regardless. Both hydrolysis rate and sugar survival for limited hydrolysis time The effect of solvents on the reaction mixture is the most surprising discovery of the present invention. It was found that the maximum effect was achieved when the concentration of acetone was around 80-90%. It was done. At acetone concentrations higher than this, the temperature and acid #! rises beyond expectations once It was observed that the hydrolysis rate response followed well-known kinetic principles. This is a high The balance between the rate of hydrolysis and the increase in glycolysis is the increase in these parameters, Aqueous dilute acid systems and acidified aqueous systems, especially those that were not improved by increasing temperature The results were in contrast compared to the two ethanol-based cases. With increasing degree of acetone complexation, The improved survival of sugars indicates that sugars have improved stability at high temperatures. This is the key to the formation of sugar complexes. These complexes can be used for a limited time 10 Extremely easy and safe hydrolysis by heating with dilute acid to 0°C It is broken down into free sugar.

Same constant acidified ethanol-water steaming with ethanol concentration above 80% In Ni(・, neither delignification nor hydrolysis was observed. Ta. The cause of this is that the acid catalyst reacts with the alcohol, resulting in hydrogen sulfate x chill (C2H5- 0-8O2-OH) by Ik shadow formation and condensation of two ethanol molecules. This is because it is immediately consumed in forming diethyl ether.

Under these conditions, ether formation was substantial. 1.ta Alkylgelcots, which are formed in highly concentrated alcohol solutions, are Hydrolysis to free sugars is difficult compared to the It is an oligomeric sugar, and it is not as strong as in the case of an acetone-aqueous solution. There isn't. Alcohols therefore lead to undesirable solvent loss and explosive ethers. It is unsuitable as a medium for hydrolysis due to the general dangers caused by Lifchinin For chemical substances, the low delignification power of acidified alcohol solutions is decisive. This is a disadvantage. 180°C in the presence of 0.190% (0.04N) sulfuric acid In 80:20 ethanol:water steaming, the hydrolysis rate is 5.47 X 103 min-1, and the half-life of codon linter degradation is 126. It was 8 minutes. Maximum 76% dissolved in 254 minutes, crystalline residue dissolved in alcohol showed substantial resistance to hydrolysis ((residual The acid concentration was found to be the original concentration of 0.01N. remainder The acid was probably consumed in various side reactions.

Under the same hydrolysis conditions, acidified water medium and acidified water medium Ethanol medium VCx: For complete dissolution of 1 ton linter, an excessively long time is required. Hydrolysis time? It is clear from the data that this is necessary.

Increasing the ethanol concentration from 50% to 80% did not improve the hydrolysis rate. However, the percent sugar survival was not improved either. Hydrolysis rate in ethanol water is just barely better than the hydrolysis rate in dilute aqueous solution. It was.

These examples include high acetylation rates of over 70% for high rates of hydrolysis and high sugar survival. This clearly indicates that ton concentration is essential. Obtain a circulation recovery rate of over 90% Under the conditions shown in , a shorter reaction than that shown for (or heating time at high temperature) is preferable. Therefore, according to these data, Q, 80:20 acetone with 04N sulfuric acid: 1 as a solvent mixture When used at a temperature of 80°C, complete saccharification and quantitative sugar recovery are achieved by the residence time of the liquid. percolation method or bus-through method (pass thr It should be according to the process). As shown in the example below When using high temperatures and concentrated acid concentrations, the residence time can be substantially reduced. There must be a point.

The solid residue with a yield of less than 50% shows a high degree of crystallinity (87%) and is a pure white product. It has a DP (degree of polymerization) of 130 to 150.

Table 1. In the steady-state hydrolysis of codon linters as a function of acetone concentration forward reaction rate.

25 49 95 Recovery rate Excellent 9978ro 27 Defective 255 99# Excellent 99 87 58 /l Defective 253　99/／Good 99 41 56 II Defective Example　■ in 80:20 acetone:water using codon linters as substrates. Investigating the effect of acid concentration on hydrolysis rate and sugar survival at a temperature of 180°C Ta.

In constant cooking, codon linters are added with 10 ml of suitable hydrolyzate. 1 g sample (oven dried) was hydrolyzed in a glass-lined stainless steel pressure vessel. , and heated until the original matrix mass was hydrolyzed and dissolved.

Draw a graph as in Example 1, with 25, 50, 75 and 99% hydrolysis. The level was measured.

The reaction product was worked up in the same manner as in Example I. The results are shown in Table 2. .

Within the range of experiments, higher concentrations of acid lead to higher rates of hydrolysis and less solid residue. Regarding...-7.The time indicated as life exceeds the single-step hydrolysis time. As a result, the speed at which the shield decomposed became somewhat faster. Sulfuric acid and hydrochloric acid of the same concentration are almost mutually exclusive. It was observed that the result was a corner. When the concentration of acid is increased, the life of No.-7. As is clear from the fact that it is shortened to , it has a substantial effect of promoting hydrolysis was recognized. Therefore, if all other conditions are held constant, the concentration of acid should be limited. The rate of hydrolysis can be easily controlled by

Table 2 Effect of acid on forward hydrolysis rate in steady hydrolysis of codon linters The effect of the concentration of.

Temperature = 180°C1 Solvent: Acetone/Water - 80/20, L/W = 10/1°25 ro 2.5 99 50 77.9 90 0.01 0.047 75 155.8 8.9 1 6799 517.0 57 99 195.0 67 99 87.7 58 99 56.2 52 99 37.5 50 25 12.8 98 99 204.5 60 Example　■ 80: 20 acetone: acidified water containing 0.04 N sulfuric acid in water Hydrolysis of codon linters using aqueous acetone solutions at various hydrolysis times Examining the effect of temperature on the solution, as in Example 1, 25°50.75 and 9 A weight loss of 9% was measured. For all steaming, boil at 35°C before placing in the oil bath. The effect of heating time at various temperature levels investigated I tried to remove Hibiki.

Final treatment and analysis of the product was carried out according to Example I and the results are summarized in Table 5.

Increasing the temperature has a pronounced effect on accelerating the rate of hydrolysis, and in general In such single-step batch cooking, the sugar content at any stage of hydrolysis is Decomposition...The reaction time exceeding -7.life is the sugar decomposition rate under the high temperature conditions used. From these data, it can be seen that the However, such high temperatures In fact, hydrolysis is difficult for substrates that are difficult to hydrolyze, such as codon linters. However, it was found that it could be immediately hydrolyzed in high yield. The decomposition rate of sugar is This is offset to some extent by lowering the acid concentration and increasing the liquid-sealed wood ratio. , in which case the forward reaction rate in hydrolysis (forward react, i onrate) (kl) is not affected, and the rate of glycolysis (k2) decreases.

Thereby, the survival of sugars, which depends on the ratio of k/2 to If used, it will be significantly improved.

Table 6. Acidified 80: Codon linters in acetone water of 20 Effect of temperature on hydrolysis rate and survival of sugars.

Catalyst: 0.04N H2SO4, L/W=10/1゜99　640　40 99 87.7 58 99 15.2, 63 25 0.59 99 99 6.17 58 Appetizer Acetone/Water-90/10.0.10N H2SO4゜Rok Water-1.0 (k, = 2.1; Table 1) Example ■ The steaming experiments reported in this example were performed by lowering the acid concentration and increasing the reaction temperature. So far, we have been trying to increase sugar survival without reducing the high hydrolysis rate. This explains a relationship that has never been observed before.

This unique finding is illustrated by the data in Table 4.

Although the concentration of acid is reduced, the effect of increasing the reaction temperature is -19 samples (Osin dry weight) of 0.01 to 0.0 to the solvent mixture 80:20 acetone containing 05N H2SO: glass with 10ml of steaming liquid. Steamed in a stainless steel pressure vessel lined with steam at a reaction temperature of 190-220°C. This is demonstrated by heating this until 50% and 75% dissolution of the substrate is obtained. It was.

The reaction product was cooled and worked up as outlined in Example I to ensure survival of the sugars. and the reaction rate was measured.

If you use a hydrolyzate with an acetone content of 80% or more, it will work even if the acid concentration is lowered. Good results were obtained by increasing the reaction temperature, the reaction rate did not decrease, but Data show that sugar yield (survival) also increases. This trend is Increasing the rate of hydrolysis and survival of sugars can be achieved by increasing the concentration of acid and increasing the temperature. This is contrary to the results of all previously published scientific literature, which appears to be a function of Seamen, J, F, AC8゜Honolulu 1979; B IO-Energy, Atlanta 1980).

The surprising solvent effect of acetone water systems has never been observed in the scientific literature or in the prior art. It has never happened or been reported.

Table 4. 80:20 acetone: for hydrolysis of codon linters in aqueous solvents The effect of high reaction temperatures and very low acid catalyst concentrations on the survival of sugars.

9 0.01 normal (H2so, ] 490 ppm 0.005 normal [H2SO, 11245ppm example ■ A 1 g sample of some wood species was mixed with 0.04 N H2SO, containing 8 Hydrolyzed in 0:20 acetone:water at 180°C. Hydrolysis rate is easy The purpose is to prevent confusion caused by the effects of hydrolyzable lignin and hemicellulose. was calculated only for the crystalline cellulose fraction. original open dry goods 25°50.75 of quality and time to 99% material loss and calculated reaction rate are shown in Table 4.

The product was worked up in the manner described in Example I, and the volatile components were removed by distillation. After removing the precipitated lignin, remove the precipitated lignin by the 6 separation method; It was.

Under the same conditions, the hydrolysis rate of wood t codon linter hydrolysis rate It is clear that the amount is roughly twice that of the average. Circulation due to increased forward reaction rate The yield was truly impressive.

The speed of Douglas fir was slightly slower than that of I. spp. and cane husk. Shika in a purely aqueous system, with identical pond conditions (same temperature and acid catalyst content). When hydrolysis was attempted, the result was 280 minutes at 180°C, the normal dilute acid hydrolysis temperature. A hydrolysis rate of 0.5 x 103 min-1 was obtained by long-term steaming for 1 weight loss. & Only 6% were recorded. Therefore, hydrolysis with high acetone content By using a solution, the hydrolysis rate of Douglas fir is faster than that possible in a purely aqueous system. The hydrolysis is more than 100 times faster than the previous one, and lignin is dissolved at the same time. .

The solid residue of 60-35% yield of the product of partial wood evaporation is pure white. It is a colored substance and does not contain residual lignin. This cellulose fraction is , when cottonwood is used as raw material, crystallinity index of 80% and weight of 80-2800 It has a degree of accuracy (DP).

Similar results can be obtained for other types of wood.

Table 5 80:20 acetone:water mixture in the presence of 0.04N sulfuric acid as catalyst Typical wood-like hydrolysis rate at 180°C in compound.

(liquid/wood = 10/1) 99 ro 4.5 92. 99 46.1 86 Example　■ Despite the presence of water, the high acetone concentration makes the acetate relatively stable. It is recognized that it is another advantage of the present invention that a ton-sugar complex is formed. . The excellent stability of sugar complexes at high temperatures has favorable consequences for the survival of dissolved sugars. give. The data in Table 1 clearly shows the improvements.

In addition, due to the difference in volatility and solubility of various complexes, the present invention (in the present invention, five types It is possible to easily separate the main wood rods of the class, and if desired, they can be separated into most It can be isolated quantitatively. However, sugar derivatization in aqueous hydrolysis products Due to the miscibility of the body, if complete and precise separation is desired, removal of volatiles is necessary. The aqueous sugar juice recovered after fermentation is neutralized and the juice is concentrated.

It is always necessary to flop. then in anhydrous acetone containing 5% acid. Redissolve the flop in until all sugars form their respective diacetone complexes. , for at least 6 hours, after which precision separation is performed as described in section 2 below. separation The resulting sugar complex is easily hydrolyzed by boiling in dilute acid for at least 20 to 40 minutes. Understand.

Smell and add 10 g (OD) of cottonwood coarse sawdust (sifted through a 5 ml sieve). 1 oomt of hydrolyzed solution (containing 0.04N sulfuric acid as a catalyst) (0:20 acetone:water). Heat glycerol in cylinder for 9 minutes 180'C and continue heating until the desired reaction time is reached. Ta.

In a separate large chamber, combine 80:20 acetone:water and 0.04N sulfuric acid. We also preheated 450 ml of hydrolyzed solution containing The tube was connected to the reaction vessel described above. After 5 minutes of reaction temperature (total 9+3=12 minutes) The reaction solution was drained into a small beaker containing 75.9 g of crushed ice. Keep it nearby The hot liquid was immediately reintroduced into the reaction vessel from the container containing the hot liquid, and the reaction was allowed to proceed for an additional 6 minutes. Thereafter, the contents of the reactor were again removed as described above. The liquid was replaced a total of 5 times, These liquids are collected and subjected to analysis. Analysis of the quenched reactor contents was performed as follows. It was; Combine the hydrolysis products*, %, 1 and %, 2 before evaporating the low boiling point volatiles. I made it. Feathers were prepared by flash evaporation of acetone at low temperature (50’O) and reduced pressure. lignin was precipitated. By standing still, this precipitate becomes a small particulate matter. Carefully separate the lumped lignin from the mother liquor and wash it twice with water. After drying in vacuum, a constant weight powder was obtained. The weighing value of recovered lignin powder is 1.6 7.9, and the weight average molecular weight was 2,800.

Combine the F liquids (127+++j), neutralize them, and steam them in a device made entirely of glass. Gaseous distillation was performed and approximately 5 ml of distillate was collected. Both distillate and residual solution 100m/batch each, and acidify each Q, 5m of them with sulfuric acid to 5% acid. The mixture was concentrated and boiled for 40 minutes on a water bath.

The solution was neutralized and the reducing power of sugar was measured by the Somogi method. The yield of 抛 is 1.89 as a distillate. ．． 9. It was 1.969 from the residual liquid.

Gas gas reaction for alcohol acetate obtained from distillate of steam distillation When measured by chromatography, it was found that mainly kinkloose and arabino It was found that it consists of - 10,000, by similar analysis of the residual solution , glucose, mannose and galactose were detected, as well as traces of quinlose. It turned out that they were mixed.

Hydrolysis products%, after evaporating the solvent acetone, traces of lignin However, it was difficult to recover because it contained only a small amount of The measurements were carried out. This material was removed by centrifugation. Aqueous residue (97m/ ) was acidified with sulfuric acid to give an acid concentration of 3%, boiled for 40 minutes, and filtered after neutralization. The area was set to 100m1. When the reduced content of P solution was investigated using the Somogi method, it was 1.859. Met. By GC analysis of sugar alcohol acetate on aliquot samples. The main component is glucose, with trace amounts of mannose and galactose. It was found that it was included.

Hydrolysis products/di, 4 and blades, 5 were treated and analyzed in the same manner as in 466. I went to 1.759 reduction gun is obtained from H-4, 1.40 from H-5 ! 9 sugars were obtained and according to the results of GC analysis on aliquot samples, It was also composed only of glucose.

・The weight of the undissolved residue after drying in Odef at 105°C for 2 hours is 0.12. It was g.

The recoveries are summarized as follows: Powdered lignin 1.67g Total pentose sugar 1.89.9 Total hexose amount 6.92.9 Material balance: 1. Lignin recovery rate: 98.2% 2. Circulation recovery rate: 97.8% Example　■ Pre-extracted with dichloromethane and air-dried to 8% moisture in a temperature-controlled room at 10F. Using OD Douglas fir sawdust (which passes through a 10-mesh sieve) as an example, 80:20 acetone containing 0.05N hydrochloric acid. : Hydrolysis was carried out in 5 sequential steps using a water solvent. Each reaction step consists of 2 It consisted of a 5 minute treatment at a reaction temperature of 00°C. heating to increase temperature The time was 7 minutes. In this case as well, hydrolysis product plates 1 and 2 are combined together. and later fractions were analyzed separately.

From the combined solution of H-1 and H-2, after the volatile components are evaporated at low temperature, 2.59 9 of lignin was obtained and 155 m/a of aqueous was obtained by filtering the lignin powder Fluid was recovered. The weight average molecular weight of the dried lignin was 200. P liquid It was neutralized to pH 8 and subjected to steam distillation using an all-glass apparatus. 28 recovered The mz distillate contained 0.62.9 pentoses.

When this p liquid was passed through an acidic cation exchange resin and steam distillation was repeated, the GC analysis showed that 0.58 & of kinloose was obtained from the pentose of Measured.

The residue (1281117) after the above steam distillation was neutralized with an ion exchange column. , Oki liquid was concentrated to 70 tsuzo, and some crystalline mannose was added as a crystal seed. I left it alone for a while. Collect the crystalline substance by filtration and extract it from ethanol-petroleum ether. It was recrystallized from Dissolve this crystal in water again and acidify it to make rochi acid for 40 minutes. The mixture was boiled for a while to release free shields. Lake Arco by GC after neutralization with silver carbonate An analysis of sugar acetate was performed to determine the concentration of sugar in the solution. Detected by QC The only sugar was mannose and the yield was calculated to be 1.00F.

Extract the ethanol-petroleum ether solution with 5 mt of water and collect the aqueous layer. and the syrup from which the crystalline product had been removed were combined. Handle the solution Heat to drive out the alcohol, make 5% acid with hydrochloric acid, boil for 40 minutes, Neutralized with silver carbonate and prepared alcohol acetate for GC analysis. - cord The combined syrup and F solution contain a total of 58g of sugar, of which 0. 29 # is gasictose, 0.25.9 is glucose, and 0. 049 was mannose.

When the volatile components were removed from the hydrolysis product, pure glucose of 1.89.9% was obtained. A precipitate of 0.4 g of lignin was obtained.

Hydrolysis product A4 yields 1.669 pure glucose and a very filtrate. On the other hand, 1.85 g of glucose was obtained from H-5, but Gunin was not obtained. The undissolved residue was 0.18g, and 99% was glucose. It consisted of

The recovery rates are summarized as follows: H-1.2 and 6; lignin 2.79 9 Kinloast 0.58g Mannose 1.00.9 H-4: Hexose '1.661 H-5 = Hexose 1.859 10.5711 Total sugar recovery rate; 7.60 g = 95.95% (relative to theoretical value) lignin times Yield: 98% Under large-scale industrial conditions, quenching of the recovered solution is necessary to control volatile substances. This is best accomplished by controlled evaporation. Implemented with examples ■ and ■ Cooling of liquid samples by crushing ice outside the pressure vessel is convenient for small-scale processing. It was applied because of the fact that

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Claims (1)

[Claims] 1. Using a solvent mixture of acetone and water containing a small amount of acidic compounds, lignin-containing The pulverized cellulose material, which may be Carbohydrates such as sugars from said cellulosic materials by forming reducing sugars within In a method for producing a hydrolysis product of fat In a pressure vessel at elevated temperature, together with the cellulosic material, the solvent mixture and a mixture of acetone and water containing at least 70 volumes of acetone and a catalytic Prepare an acidic compound of +bl until the cellulosic material is at least partially dissolved; At least 90% of the solubilized sugars from the The cellulosic material is restricted in a solvent mixture at elevated temperatures so that the treatment for the specified time, and immediately when the tel liquid is removed from the pressure vessel. A method characterized by cooling it to. 2 Request that the at of acetone in the mixture of acetone and water be 80 to 90% by volume 1. Method for scope 1 of the request. 6. The acidic compound is chonic acid, and the concentration is relative to the weight of the acetone-water mixture. 2. The method according to claim 2, wherein the 4 A method in which the acidic compound is hydrochloric acid and the concentration is acetate. 5. The method of claim 1, wherein the elevated temperature is between 145°C and 260°C. 6) Further hydrolyzing the liquid under theoretically elevated temperature and dilute acid solution 2. The method of claim 1, wherein the method produces an essentially seven-dimensional harpoon. Claim 1: Distilling the Z liquid, thereby vaporizing vents from the liquid. Method. 8 Claim 1.6 or 7, wherein the aqueous solution contains dissolved sugar with a solid content of 15% or more Law. 9. Pressure cellulosic material in at least two stages, the first stage at elevated temperature. After processing in a container and performing each step for a limited time, the cellulosic material The method according to claim 1, for rapidly cooling the. 10. The concentration of acid is changed to 0.1ON and 0.001N by lighting the acetone-water mixture. 4. The method according to claim 6 or 4. 11. Volatile substances contained in the solution are distilled off under reduced pressure, and lignin in the remaining aqueous solution is precipitated. 2. The method of claim 1, further comprising separating the same. 12. Using a solvent mixture of acetone and water containing a small amount of acidic compounds, lignin is treating the ground cellulosic material, which may contain, in a pressure vessel at elevated temperatures; by solubilizing all the lignin and forming reducing sugars in the liquid. Production of hydrolysis products of carbohydrates such as sugars and lignin from cellulosic materials In the method of fa) Solvent mixture with cellulosic material in a pressure vessel at elevated temperature. a mixture of acetone and water containing as a compound an acetone complex of at least 70 volumes; and Prepare a catalytic acidic compound, lbl until the cellulosic material is at least partially dissolved; At least 90% of the sugars solubilized from the This is enough time for less than 50% of the cellulose to dissolve in one step at such a temperature. treatment, thereby partially or substantially removing the carbohydrates contained in the cellulosic material. Completely dissolves and hydrolyzes (Cl: Continuously remove the liquid from the pressure vessel, ldl: 7 cycles of controlled acetone. Liquid by evaporation, i! , upon cooling to form a residual aqueous solution, and (e l A method characterized by recovering all the lignin from the residual aqueous solution. 10. The cellulosic material is lignocellulosic, and the volatile material under reduced pressure is distilled off to obtain a residual aqueous solution and lignin precipitate as a residue, and the sugar is recovered. 13. The method of claim 12, wherein the residual aqueous solution is neutralized prior to washing. 14. The method of claim 12, wherein the concentration of acetone and water is 80-90%. 15 By vaporizing the pentose shield from the residual aqueous solution as an acetone complex 13. The method of claim 12, wherein pentose sugars are separated from hexose sugars. By contacting the 16Wl-acetone complex with aqueous acid at elevated temperature. 16. The method of claim 15, wherein each complex is decomposed. The complex is treated with aqueous acid at elevated temperature until a dehydrated product of 1Z shield is formed. 17. The method of claim 16, which continues processing. 18 Processing cellulosic material in a batch or continuous manner and using the recovered solution According to claim 12, the agent fractions are processed separately or collectively. Method. 19 At the point when essentially pure cellulose is recovered from the reactor as a solid residue, 13. The method of claim 12, wherein hydrolysis of the cellulosic material is conveniently stopped. 20. Claim 1 in which the recovered hydrolyzed liquid is finished by the method described in this specification. Methods 2 and 19.