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    • 专利摘要:
    This invention relates to the hydrolysis industry, and specifically to methods for producing sugars from cellulosic material. The purpose of the invention is to accelerate the process and increase the yield of sugars. The crushed cellulosic material and cooking liquor are introduced into the reaction tank. In the reaction vessel, the crushed material is hydrolyzed under elevated pressure and 145-230 ° C. The cooking liquor contains acetone, water, and 0.001-0.1 normal sulfuric or hydrochloric acid. Acetone concentration of 70-90%. The sugar solution obtained as a result of the hydrolysis of the cellulose-containing material is cooled to 100 ° C. The cooking liquid and the crushed material are introduced into the reaction tank at such a rate that the flow time between feeding the material and withdrawing the resulting sugar solution does not exceed the time previously determined to hydrolyze 50% of the solids of the hydrolyzable material and release without splitting at least 90% of the dissolved sugars . The method allows to speed up the hydrolysis process and increase the yield of sugars. 5 tab. (Ls
    公开号:SU1701115A3
    申请号:SU823526203
    申请日:1982-06-24
    公开日:1991-12-23
    发明作者:Паснер Ласло；Чанг Пей-Чинг
    申请人:Бау-Унд Форшунгсгезельшафт Термоформ Аг (Инопредприятие)；
    IPC主号:
    专利说明:

    N o
    This invention relates to the hydrolysis industry, and specifically to methods for producing sugars from cellulosic material.
    The aim of the invention is to accelerate the process and increase the yield of sugars,
    In tab. Figure 1 shows the dependence of the rate of direct reaction at 180 ° C and the steady hydrolysis of cotton fibers on the concentration of acetone; the ratio of solution / wood is 10/1, the catalyst is 0.04 normal H2S04. In tab. 2 shows the effect of acid concentration on the rate of direct hydrolysis during stationary hydrolysis of cotton fibers; the reaction temperature is 180 ° C, the solvent is acetone / water in a 80/20 ratio, the solution / wood ratio is 10/1.
    In tab. 3 shows the effect of temperature on the rate of hydrolysis of cotton fibers and sugar resistance in an acidified cooking liquid containing acetone and water at a ratio of 80:20; Catalyst-0, 04 is normal H2S04, solution / wood ratio is 10/1.
    In tab. 4 reflects the effect of high hydrolysis temperature and low concentration of acid catalyst on the stability of sugars in the hydrolysis of cotton fibers using cooking liquid

    with
    containing acetone and water at a ratio of 80:20 and a solution / wood ratio of 10/1.
    In tab. 5 reflects the hydrolysis rates of selected types of wood at a hydrolysis temperature of 180 ° C and using a cooking liquid containing acetone and water at a ratio of 80:20 and in the presence of 0.04 normal sulfuric acid.
    Example 1. The degree of saccharification and the time of existence of sugar are compared for the three systems, namely: acidified water (weak aqueous acid solution), acidified aqueous solution of ethanol and acidified aqueous solution of acetone in the following example,
    In each case, purified cotton fibers are used, having a TAPPI of 0.5%, a viscosity of 35 gpm and 73 a crystallinity index at 7% moisture. Acidification is carried out with sulfuric acid using solutions of various dissolving systems, each of which was 0.04 normal with respect to the acid. The conditions for hydrolysis are as follows.
    In a series of experiments, one g of cotton fiber samples after kiln drying was placed in a 20 ml stainless steel vessel lined with glass together with 10 ml of dissolving mixture and heated at 180 ° C for various periods of time, and the residual solids and fixed sugars in solution, applied to graph paper. The time required to obtain approximately 99%, 75%, 50% and 25% dissolution of the substrate is taken from the graphs and is summarized in table. 1. At the end of the reaction periods, the heating is interrupted, the vessel is cooled and its cold contents are filtered through a medium-porosity glass filter, the undissolved residue is first washed with warm water, followed by washing with several 5 ml portions of acetone, and finally with warm water. After drying at 105 ° C, the weight of the residue is determined gravimetrically.
    For comparative analytical purposes, the combined filtrates are diluted to 100 ml with water, half-milliliter aliquot is sent to the test tube with 3 ml of 2.0 normal sulfuric acid added and subjected to secondary hydrolysis at 100 ° C with heating in a boiling salt bath for 40 minutes . The solution is neutralized with cooling, and the sugars present in the solution are determined by their reducing effect. The results are therefore unambiguously based on the reaction product, monosaccharides, released during hydrolysis. The theoretical percentage of reducing sugars that are available after substrate hydrolysis is determined by the difference between the known chemical composition of the starting material and the weight loss resulting from hydrolysis. To calculate the increase in weight of the carbohydrate fraction due to the hydration of the polymer with
    0 decomposition into monomeric sugars, the weight loss is usually multiplied by 1.1111, the weight percentage (11.11%) of added water s cellulose during hydrolysis to monomeric sugars.
    5 As can be seen from the table. 1, the hydrolysis rate increased continuously with increasing acetone concentration to 50%. However, significant increases were observed only when the acetone concentration
    0 was increased to over 70% by volume of the acidified solvent mixture. Very fast hydrolysis rates were achieved when the acetone solutions were almost anhydrous. It turned out that dissolved
    The 5 sugars are most stable when using a solvent mixture with an acetone concentration of 80-90%, although the relative half-lives were relatively short. Sakharov sustainability achieved
    0 more than 90% when the reaction time at the temperature is less than that required for the hydrolysis of 50% of the substrate to dissolved products. The time required for hydrolysis of 50% of the substrate to the dissolved pro duct is called the half-life of sugar resistance. This criterion takes place despite what stage of hydrolysis is meant. The effect of solvent on the rate of hydrolysis and sugar resistance in
    For a limited time of hydrolysis, it is a substance of the invention, in accordance with which the maximum values of acetone concentration in the reaction mixture were determined to be 80-90%. We believe that at higher concentrations of acetone, the dependence of the rate of hydrolysis on increasing temperature and acid concentration corresponds to the known kinetic principles in contrast to
    0 from acid diluted with water and acidified water-ethanol systems, in which the balance of increasing higher hydrolysis and degradation rates of sugar does not improve with the increase in these parameters,
    5 Especially temperatures. Improving sugar resistance with an increase in the concentration of acetone is associated with the formation of acetone-sugar complexes, which improve stability at high temperatures. Complexes are easily guided by
    free sugars when heated with dilute acid at 100 ° C for a limited period of time.
    With identical stationary acidified ethanol-water cooking, when the concentration of ethanol is above 80%, neither delignification nor hydrolysis was obtained due to the fact that the acid catalyst was quickly spent on the reaction with alcohol to form ethyl hydrogen sulfate (C2H2-0-S02-OH) and the formation of simple diethyl ether by condensation of two ethanol molecules. Under these conditions, the formation of ether was essential. Alkyl glucosides, which are formed in solutions of high concentration alcohols, are essentially hydrolyzed also with great difficulty to free sugars than the corresponding acetone complexes, and alcoholysis gives oligomeric sugars rather than monomers, as in the case of water-acetone solutions. Consequently, alcohols are mostly not suitable as a hydrolysis medium due to undesirable loss of solvent and the danger that ether represents from the point of view of the possibility of an explosion. The ability to delignify acidified alcohol solutions with lignified materials is low, which is also a disadvantage.
    In cooking with a mixture of 80:20 ethanol / water in the presence of 0.190% (0.04 normal) sulfuric acid at 180 ° C, the hydrolysis rate was 5.47 x 103 min 1, and the half-life of decomposition of cotton fibers was 126.8 minutes. A maximum of 76% was dissolved within 254 minutes, and the crystalline residue showed resistance to hydrolysis in an alcohol solvent. It turned out that the residual acid concentration was 1/4 of the initial one, i.e. 0.01 normal, and it is possible that the balance was spent in various adverse reactions.
    The data show that under identical hydrolysis conditions, an extremely long hydrolysis time is required to completely dissolve the cotton fibers in acidified water and acidified aqueous ethanol medium. Increasing the concentration of ethanol from 50 to 80% does not increase the rate of hydrolysis or, in particular, does not increase the sugar resistance. The rate of hydrolysis in ethnolic water was slightly higher than in diluted water and acid.
    From the example it follows that a high concentration of acetone (more than 70%) is necessary for a high rate of hydrolysis and high sugar resistance. Under conditions designed to extract sugar with a yield of more than 90%, the reaction time or time
    High-temperature exposure is preferable to choose less time for half-lives. Thus, in accordance with the data, the generalization of saccharification and the quantitative extraction of sugar would require percolation or a process in which the residence time of the solution would not exceed 10 minutes when the mixture of acetone: water in a ratio of 80:20 with 0, 04
    0 normal sulfuric acid is used as a dissolving mixture at 180 ° C.
    The residence time should be significantly shorter when higher temperatures and concentrations are used.
    5 acids as shown in the following examples.
    Solid residues with a yield of less than 50% show a high degree of crystallinity of 87%, have a pure white color, and have a degree of polymerization (SP) of 130-350.
    Example 2. The effect of temperature on the hydrolysis of cotton Linger in acidified aqueous solutions containing 0.04 normal sulfuric acid in a mixture of acetone: water in a ratio of 80:20 at different periods of hydrolysis was studied so that weight loss can be determined at 25 , 50.75 and 99%, as in example 1. All cooking
    0 were preheated by ds 35 ° C before being placed in an oil bath in order to minimize the effect of the time to temperature rise at the various temperature levels studied. The processing of the products and the analysis corresponded to the same procedures as in Example 1, and the results are summarized in Table. 3
    As can be seen from the data in Table 3, an increase in temperature effectively affects the rate of hydrolysis, at such one stage, the reaction time during cooking, exceeding the half-life of sugar when dissolved at any stage of hydrolysis, increases to some extent the rate of sugar splitting at use of higher temperature conditions. However, it was found that hydrolysis at high temperature makes it possible to carry out
    0 almost continuous hydrolysis with a high yield even with a substrate that is difficult to hydrolyze, such as cotton linters. The sugar breakdown rate can be shifted to some extent by reducing the acid concentration and increasing the solution / wood ratio, whereby the rate of the direct reaction (Ki) during hydrolysis remains unchanged, but the sugar breakdown rate (K2) decreases. Thus, the sugar resistance, which depends on the Ki / K2 ratio, is greatly improved, especially if high concentrations of acetone are used,
    Example 3. In the cooking described in this example, the hitherto unknown dependence of the increase in sugar resistance is investigated with a reduced acid concentration and an increase in reaction temperatures without any decrease in the high hydrolysis rates disclosed here (see Table 4).
    The effect of a reduced concentration of acid, but high temperature demonstrates cooking one gram of cotton linter samples (weight after kiln drying) in glass-lined stainless steel vessels, together with 10 ml of an acetone mixture; water in a ratio of 80:20 cooking solution containing 0 , 01 and 0.005 normal H2 SO4 relative to the dissolving mixture, and were heated until 50 and 75% of the susbrate was dissolved at the reaction temperature of 190 ° C - 220 ° C.
    Cooling and processing of the reaction products to determine the sugar resistance and reaction rate were carried out as in Example 1,
    The data indicates that it is possible to successfully reduce and change the acid concentration by increasing the reaction temperature without losing the reaction rate with an increase in the concomitant sugar yield (stability) when using hydrolysis solutions containing at least 80% acetone.
    Example 4 One g of samples of several types of wood is hydrolyzed in a mixture of acetone: water in a ratio of 80:20, containing 0.04 normal sulfuric acid npit 180 ° C. The hydrolysis rates are calculated only for crystalline cellulose fractions in order to avoid distorting the results from easily hydrolyzing lignin and hemicelluloses,
    In tab. Table 4 shows the mass loss times of 25%, 50%, 75, and 99% of the Initial mass after kiln drying, together with the calculated reaction rates.
    The processing of the products corresponded to Example 1, except that after the removal of volatile substances by distillation, it was necessary to remove the precipitated lignins by filtration or centrifugation.
    It is obvious that, under identical conditions, the hydrolysis rate for wood is about twice the hydrolysis rate for cotton fibers.
    The rate of hydrolysis of Douglassei wood was slightly lower than the rate of hydrolysis of aspen and sugarcane bark. When carrying out hydrolysis in pure water
    system under other selected conditions (the same temperature and the same content of acid catalyst) obtained a hydrolysis rate of 0.5x103, and recorded only 6% loss in weight for cooking
    0 with a duration of 280 minutes at 180 ° C - the usual temperature of hydrolysis in dilute acid. Thus, the hydrolysis solution with a high content of acetone accelerates at least 100 times the hydrolysis
    5 Douglas and simultaneous dissolution of lignin compared to what is possible in a pure acetone system.
    Among the products of partial sacchariva-nm wood are solid residues with the yield
    0 approximately 30 to 35% are pure white, lacking residual lignin. This cellulose fraction has a crystallinity index of 80% of aspen wood and SP 80-280. Similar results were obtained with other types of wood.
    Example 5. An advantage of the present invention is that a high concentration of acetone contributes to
    Formation of relatively stable acetone-sugar complexes despite the presence of water. The greater stability of sugar complexes at high temperature fundamentally affects the stability of the dissolved sugars (see Table 1). Further, due to the differences in volatility and solubility of the various sugar complexes, the invention allows for easy segregation and almost quantitative
    0 extraction of pt of basic wood sugars, if necessary. However, as a result of the mixed nature of sugar derivatives in aqueous hydrolysates, if such a complete and thorough separation is necessary. it is always necessary to neutralize the separated aqueous sugar wort after removing the volatile substances and concentrate the wort to a syrup. The syrup is then re-dissolved in anhydrous acetone, containing 3% acid, and held for at least 6 hours until all sugars form their diecetone complexes, respectively, before starting a thorough separation, as described below.
    5 The separated sugar complexes readily hydrolyze in dilute acid at boiling for at least 20-40 minutes. Thus, 10 g of large aspen sawdust {passed through a 5-mesh sieve.) Was loaded with 100 ml of a shredding solution consisting of a mixture of acetone: water in a ratio of 80:20 and 0.04 of normal sulfuric acid as a catalyst. In a pressure vessel, a temperature of 180 ° C was created by immersing it in a hot glycerol bath for 9 minutes, and heating was continued for the required reaction time.
    In another large pressure vessel, a 450 ml hydrolysis solution containing an acetone: water mixture in the ratio of 80:20 and 0.04 normal sulfuric acid was also preheated and connected to the reaction vessel via a siphon tube and a shut-off valve. After three minutes (12 minutes in general) at the reaction temperature, the reaction solution was poured into a small chemical beaker containing 75 g of crushed ice. The reaction vessel was immediately loaded again with a hot solution from the storage vessel and the reaction was continued for an additional 3 minutes until the contents were reloaded. reactor, as described above. A total of five changes were made to the solution, and the solutions were collected for analysis. The cooled contents of the reactor were analyzed as follows.
    Hydrolysates Nos. 1 and 2 were combined with each other before evaporation of low boiling volatile substances. Rapid evaporation of acetone at low temperature (50 ° C) and reduced pressure leads to precipitation of flocculent lignin, which, when peeled off, coalesces into small granule clusters. The lignin is thoroughly filtered from the mother liquor, washed with two parts of water and dried in vacuo until a constant weight is obtained in the form of a powder. 1.67 g of lignin powder with an average molecular weight of 2800 were obtained.
    The mixed filtrate (127 ml) was neutralized and subjected to distillation with water vapor in an all-glass apparatus and about 35 ml of distillate was collected. Both the distillate and the residual solution were brought to 100 ml and 0.5 ml portions of each, acidified with sulfuric acid to obtain 3% acid and boiled for 40 minutes in a water bath. The solutions were neutralized, and the reducing force of sugar was determined by the method of Somogi. The yield of sugars in distillate equals 1.89 g from a residual solution of 1.96 g.
    Gas chromatographic determination of alditol acetate of sugars in steam distillate indicated mainly xylose and. arabinose, while in residual solution for glucose, mannose and galactose with small traces of xylose.
    Hydrolyzate No. 3 contained only traces of lignin after acetone evaporation, was too small to be collected and determined gravimetrically. It was removed by centrifugation. The aqueous residue (97 ml) was acidified to 3% acid with sulfuric acid, boiled for 40 minutes and, after neutralization, filtered and brought to 100 ml. The content of reducing sugar in the filtrate, determined by the Somogi method, was equal to 1.83 g. Gas chromatographic analysis of alditol acetate, determined in the sample aliquot, indicated mainly glucose with traces of mannose and galactose.
    Ms 4 and 5 hydrolyzates were treated and analyzed in the same way as N 3. Hydrolyzate No. 4 yielded 1.73 g of reducing sugars, and hydroisat No. 5 gave 1.40 g of sugars, and in both cases only glucose was contained, indicated Gas chromatographic analysis of aliquots of samples.
    The undissolved residue was 0.12 g after 2 hours of drying in an oven at 105 ° C.
    The total yield of products is as follows, g:
    Powdered lignin
    The total number of pentose
    Sakharov
    Total Hexose
    Sakharov
    Undissolved residue
    (99% glucose)


    Mass balance,% Lignin98.2
    Sugar37,8
    Example 6. Under the same conditions of hydrolysis as in example 5, 10 g of PS (furnace drying of Douglasi sawdust passed through a 10 mesh sieve) was pre-extracted with dichloromethane and dried in air in a room with controlled humidity to 8% moisture, hydrolyzed with a solvent mixture of acetone: water in a ratio of 80:20, containing 0.05 normal hydrochloric acid, for five consecutive stages. Each reaction step lasted 3 minutes at 200 ° C. The warm-up time was t min. Again, hydrolysates Nos. 1 and 2 were combined, while the subsequent fractions were analyzed separately.
    The combined solution of hydrolyzate No. 1 and hydrolyzate No. 2 gave 2.39 g of lignin upon low-temperature evaporation of volatile substances, and 135 ml of an aqueous solution was collected by filtering powdered lignin. The dried lignin had an average molecular weight of 3200. The filtrate was neutralized to pH 8 and distilled.
    water vapor in the all-glass unit. Collected in an amount of 28 ml of distillate contained 0.62 g of pentose, which, after passing through the cation exchange resin as an acid and re-distilling with filtrate steam, produced 0.58 g of xylose as determined by gas chromatography.
    The residue after the above steam distillation (128 ml) was neutralized in an ion exchange column, the filtrate was centrifuged to a syrup, seeded with some crystalline mannose and left overnight. The crystalline material was separated by filtration and recrystallized from ethanol ether. The crystals were redissolved in water, acidified to 3% acid and boiled for 40 minutes to isolate the sugars in the free state. After neutralization with silver carbonate, the solution was analyzed by gas chromatography with alditol acetates to determine the sugar concentration. The only type of sugar determined by chromatography was mannose with a calculated yield of 1.00 g.
    The ethanol electrofluoric efcra solution was extracted with 5 ml portions of water, and the collected aqueous layers were combined with the syrup isolated from the crystalline product described above. The solution was briefly heated to remove the alcohol, brought to 3% hydrochloric acid, boiled AO min, neutralized with silver carbonate, and alditol acetates were prepared for chromatographic analysis. The combined syrup and filtrate contained a total of 58 grams of sugars, of which 0.29 grams was galactose, 0.25 grams glucose and 0.04 grams mannose.
    Hydrolyzate No. 3 yielded 1.89 g of pure glucose with 0.4 g of lignin precipitate upon removal of the fluids,
    Hydrolyzate No. 4 yielded 1.66 g of pure glucose with very small traces of lignin, while hydrolyzate No. 5 yielded 1.85 g of glucose without lignin. The undissolved residue was 0.18 g consisted of 99% glucose,
    The total yield of products is as follows, g:
    Hydrolyzate Ns 1-3: LMgnin 2.79
    0 5 0 5
    0 5
    0
    five
    Xylose 0.58
    Arabinose (by difference) 0.04
    Mannose1,00
    Hexose 0.58
    Hydrolyzate Mg 3: Hexose 1.89
    Hydrolyzate number 4: Hexose 1.66
    Hydrolyzate number 5: Hexose 1.85
    Unhydrolyzed residue 0.18
    10.57
    Total sugar yield 7.60 g 95.95% (theoretical) lignin yield: 98%.
    On a large industrial scale, cooling of the isolated sugar solutions is best achieved by controlling the rapid evaporation of the volatile fractions. The cooling of liquid samples outside the pressure vessel in examples 5 and 6 with crushed ice is convenient for small scale treatments.
    权利要求:
    Claims (1)
    [1]
    Claims method for producing sugars from a cellulose-containing material, including grinding cella (tin-containing material, introducing a cooking liquid containing acetone, water and 0.001-0.1 normal sulfuric or hydrochloric acid into the reaction tank, hydrolysis of the material at elevated pressure and temperature to obtain a solution of sugars and the selection of the resulting solution of sugars, characterized in that, in order to speed up the process and increase the yield of sugars, a cooking liquid with an acetone concentration of 70-90% is used, and The temperature of hydrolysis is 145–230 ° C, while the resulting sugar solution is rapidly cooled to 100 ° C, and the cooking liquid and pulverized cellulose-containing material are introduced into the reaction tank at such a rate that the time between feeding the material and extracting the resulting sugar solution does not exceed the time required for hydrolysis of 50% of the solids of the hydrolyzable material and separation without splitting at least 90% of the dissolved sugars isolated from cellulosic material.
    0.01
    0.047
    0.02
    0.095
    0.0
    0.190
    Table 2
    23.6
    2.65
    52.7
    5.92
    15
    Note, Acetone / water 90: 10t 0.10 normal
    water 1.0 (K 2.1, table 1)
    1701115
    16 Continuation of table 2
    Table3
    Table 5
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
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