JPS59500648A - Method for hydrolyzing cellulose to glucose - Google Patents

Abstract

Wet cellulose is treated by gaseous HCl without cooling, which results in a preliminary degradation of the material and deformation of an aqueous acid solution of oligomer sugars. This solution is then supersaturated by HCl in order to complete the hydrolysis, resulting in the formation of reversion oligomers and, after degasing, recovery of a portion of HCl and addition of water, said oligomers are transformed into glucose by boiling in a diluted acid medium.

Description

[Detailed description of the invention] cellulose to glucose Hydrolysis method The present invention involves dissolving chlorinated hydrogen gas into the water that is impregnated into cellulose. Hydrolyze the wet cellulose using the resulting supersaturated aqueous solution of hydrochloric acid to The purpose is to provide a way to transform into a course.

“Supersaturation” or “overconcentration” means that the weight concentration of HCt relative to water in the solution is Saturation of pure water to its equilibrium point with gaseous HC1 at a temperature and pressure of This means that the concentration is higher than that normally obtained. In this way, the surrounding The maximum solubility by weight of HCt in aqueous HCL solution under pressure is as shown in °C. It is known that for various temperatures it corresponds to the following value: 10°/44.0 4; 20°/4202; 30°/40.22; 40°/38.68; 5 0°/37.34; 60°/35.94 (e.g. Kirk and Osmer (KIRK & OTHMER), Encyclopedia of Chemical Technology (195o) 12, 9187). pure water Alternatively, an aqueous solution of an organic substance, such as alcohol, dimethylformamide or other By using water-compatible solvents, these solubility values can be substantially increased. can.

For this purpose, sugar can be used.

In fact, this goal is to calculate the saturation concentration in pure water (under the same temperature and pressure conditions). A sugar solution containing a concentration of HCl (obtained by dissolving gaseous HCl) exceeding describes the effective dissolution of cellulose in According to this literature, this method Therefore, by using not more than 80 parts by weight of HCt, 100 parts by weight of cellulose It was possible to convert sugar into glucose.

However, to achieve such an effect, a hydrolyzed base material (cellulose Preparation (at 10% moisture content) should be done without excessive water dilution (using water that passes through the bath). It is necessary to use dried cellulose. As is now known, wood Delignification of lignocellulosic materials (moisture content approximately 30-50%) such as The evaporation of water present in cellulose derived from need to consume.

Therefore, concentrated aqueous hydrochloric acid solution, which enables the conversion of cellulose into sugars, is Directly saturate the wet cellulose with gaseous HCt for in situ delivery. Attempts to improve this disadvantage by and until now, this heat has not been considered detrimental with respect to the stability of the reaction products. Attempts were made to improve this problem using other methods. In this way, Yo Patent Application No. 81201182.3 and other texts cited in this application According to the literature, it is generated by the dissolution of gaseous HCl in water that permeates through cellulose. the heat generated by the system is absorbed by a cooling method that does not involve any substantial temperature increase. , which accomplishes this addition of gaseous HC7 at relatively low temperatures. eye Due to its fluffy structure at the bottom, there is good contact between the cellulose and the cooling surface. and normal cooling equipment is inefficient at maintaining that temperature at a low level. .

Other documents, namely Swiss Patent No. 97.623 and Y, K. Ce1lulosesaccharificatio by USAMA) n Process with HCl Gas”, Chemi cal Economy and Engineering Review 11 (6) (1979), p. 32-36, first concentrated hydrochloric acid Impregnating the cellulose with water and then dissolving it in this acid (with a concentration of about 40%) Sometimes gaseous HCl is added which produces little heat. However, this Also, if you want to limit the amount of gaseous HCl used as much as possible, , pre-dried cellulose containing 5 to 10 drops of water, which is uneconomical, as mentioned above. It is preferable to use a base.

In addition, in actual industrial practice, the information disclosed in the first document cited above is Extremely dry and pure cellulose suitable for ideal embodiments is rarely processed. However, wet cellulosic products such as wood corrugations and wood pulp or other Gnocellulosic materials are very frequently processed. Moisture level of such materials The water content is often on the order of 30-41 and even 50 parts. disassembled This water present in the cellulose naturally dilutes the acid and reduces the solubility of the solution. Reduces acid grade at the cost of power. As an illustration, 100g of 40% hydrochloric acid When dissolving cellulose with a water weight of 40 parts in solution, the starting acid After adding only 5g of this wet cellulose (2g of water), the acid titer was added. It is found that the amount of acid is about 40-39%; Since the solving ability has already been significantly reduced, in order to recover it, It may be necessary to add HCl. Therefore, in reality, wet cellulose If hydrolytic degradation is desired, add additional gaseous HCl regularly. 5 for water in cellulose. It can be seen that the droplets of HCt titer will be advantageously regularly supplemented. Furthermore, this In terms of (other oligomers) to give a solution of about 22°C of dry cellulose. I admit that it's not too much.

Now, when gaseous HCl is bubbled in this solution at 40°C, the latter becomes voluminous. It is easy for the HCt titer of the solution to reach values on the order of 48% at 40°C. solution (as mentioned above, at equilibrium, 38% in pure water at 40°C). Additional 15-16. Absorbs 9 HCt. Such solutions work wonders against dry cellulose. has a strong dissolving power; in fact, it can be dissolved and then hydrolytically (glucose and other oligomers), the solution concentration of the degraded product is on the order of 84% by weight. 580 g of it will be gradually dissolved giving a solution of 40°C. In this example, approximately 600 g of dry Using dried cellulose and 60 g of water (actually, 100 g of 40% HCt ). And the weight of water associated with this total amount of dry cellulose is , corresponds to a potential moisture content of the order of 10% for the latter. Therefore, the moisture level When processing cellulose products containing more than 10% The amount of water present is already sufficient to form the acidic solution for treatment together with the hydrochloric acid gas. Yes, and in principle there is no need to try to add more water. of course , converting cellulose to be hydrolyzed into glucose to save HCA. operate in the presence of the minimum amount of water necessary to The lower the concentration, the smaller the amount of HCl0 required to obtain a solution with a predetermined concentration) is preferable. Although it seems, it is not advantageous to dry wet cellulose and Very often cellulose containing more than 10% moisture (usually 30-40%) is The work is done using Incidentally, excess water can be added to the reaction mixture by dilution. It is noteworthy that the fluidity of materials is definitely improved.

The method according to the invention thus requires working with relatively moist cellulose. and yet with substantial savings in HCt compared to known methods. It is possible to achieve this. As you will see later, this method still uses energy Save money. This method uses gaseous HCL without temperature control through cooling methods. Pre-impregnation of effectively moist cellulose may be carried out using Based on the surprising discovery that it does not have any detrimental effect on the solution progress or reaction yield. It's a spider. In fact, in this first step, gaseous substances enter the water passing through the fibers. The action of hydrochloric acid, which is formed by dissolving HCt of This causes degradation of the chain into shorter chains, but the amount of glucose liberated at this stage is Despite the relatively high temperatures achieved in the stage, still relative to the amount of possible decomposition of it It is believed that this amount is too small to cause substantial yield reduction. In contrast, this As a result of the preliminary hydrolysis of It becomes a combination.

Such a semi-liquid aggregate moistens the walls of the container in which it is contained and is then subjected to conventional methods. Therefore, it can be effectively cooled.

In summary, the process of the invention is characterized as follows: The cellulosic material is subjected to degradation comprising two separate steps (the two steps being , which can be executed sequentially without clear transitions). No cooling in the first step Cellulose fibers are impregnated with gaseous HCt. This gaseous HCt is It quickly dissolves in the available water (cellulose water) which is absorbed onto the fibers of A solution is formed whose titer approximately corresponds to the saturation concentration of HCt in pure water. child increases to a value of the order of magnitude. Under these conditions, a quick Pre-degradation of cellulose occurs in the acid formed in this way in cellulose fibers. Occurs with dissolution of predegradation products. Therefore, this solution is As mentioned above, it is possible to dissolve additional amounts of HCL and in this way "superconcentrate" Form a solution. The current state of the technology (e.g. European e-patent application no. 81) 201182.3), such high temperatures cause cellulose be harmful to hydrolysis reaction products (e.g. decomposition of liberated hexoses) It is generally accepted that to minimize these disadvantages and impregnation at low temperatures (0 and 1 Efforts have been made to achieve temperatures between 0° C. or even lower. However, as already pointed out As previously mentioned, such temperature control is due to the fuzzy nature of cellulose and its cooling properties. This is difficult to achieve in practice due to ineffective contact with surfaces. And now, The following was discovered. i.e. wet cellulose with gaseous HCA This continuous temperature increase for the phenomenon of impregnation of cellulose may be due to the hydrolytic degradation of cellulose. Not only is it harmless to the product obtained from the very significantly beneficial to crops and increases the final yield of glucose; therefore, this Step 9 It even becomes undesirable. In the following description, gaseous This step of impregnation with HCA is defined by the term "adiabatic absorption". .

Once this preliminary adiabatic absorption has taken place, the cellulose is concentrated and predegraded. The product partially dissolves on contact with acid solution. and the walls of the reaction vessel and For example, external cooling mats that are moved together with the cooling liquid temperature control is relatively easy to establish.

Continuation of the reaction can therefore occur under temperature controlled conditions. Then after the adiabatic absorption stage cells that are partially degraded at temperatures that favor this absorption (relatively low temperatures). A step will follow involving additional dissolution of gaseous HCt in the solution surrounding the loin.

This stage involves almost complete liquefaction of the fiber mass subjected to the reaction, which occurs after a heating period. Ends with complete dissolution occurring. Only such liquefaction removes sugars and other predegradants. Due to the preliminary formation (in the adiabatic stage) of the acidic solution of the product (for the reasons mentioned above) This interpretation is based on supersaturation using additional amounts of HCl. After such addition, which is possible due to the presence of dissolved products, residual cells Work on the loin and bring this even at low temperature, then under full heat, until done. 10 7 Tawara 59-500648 (4) It is possible to completely dissolve Is Umono.

This second step is defined as “isothermal absorption” and therefore the cellulose in supersaturated HCl. leads to the formation of a thick liquid consisting of almost complete dissolution of the base. After this dissolution has occurred (this can be done within a very short time or at 30-40°C). (can occur within 3 hours), removing the main part of the HCl (e.g. by degassing) and dilution with water, and finally this diluted solution (that HCt Quieter (on the order of 1 to 5 parts) is brought to a boil, and in most cases it is on the order of 100 parts. Achieving its complete transformation into glucose (by a post-hydrolysis step) with close yields If we consider that it is sufficient to cormorant. To avoid confusion in this description, the level of the aqueous solution of this acid, or other HCt concentration values that may be dissolved in this solution. given by the weight of HCt divided by the weight of acid and water, ignoring You will remember that.

We provide the following general information regarding the operating conditions associated with this various reaction steps. Possible: rapid impregnation with relatively high temperature rise to carry out an adiabatic absorption step Advantageously, a gas flow of HCl is used at a velocity sufficient to allow. 40~100℃ 1st Temperatures of about 100° C. are advantageous, with a range of 70 to 100° C. being preferred. In fact, the temperature Within this range, the preliminary degradation rate of cellulose fibers is It's good enough. The concentration of hydrolysis products in such an acidic solution is determined in the next isothermal step. The amount of HCl to be absorbed by the lever solution was determined using pure water under the same conditions. be sufficient to give a supersaturation level that significantly exceeds the corresponding value obtained. appropriate to enable. Of course, the amount of HCl used in the first step Moisture level of cellulose (as a general rule, this moisture varies from 10 to 50% by weight) The higher this level is, the more likely it is to supply the desired concentration of acid. It is understood that a large amount of HCl is added to achieve this.

As a practical matter, at temperatures in the range 70-100°C, the acid Levels should be between about 39 and 45 by weight of HC7 for this solution. It was confirmed that it is preferable to add a certain amount of HCl. cellulose assembly An increase in temperature within the body will affect the rate of HCt absorption (i.e., the aggregates of cellulose being processed). depending on the flow rate of the gas used) as well as its moisture content. Also, during the absorption phenomenon, the temperature values measured at various points of this aggregate are not very different. and this means that the heat of reaction is easily transferred into or within the fibers of the aggregate. It is also worth noting that the That's an interesting thing to do. The only significant variables observed are at a particular time, i.e. This maximum temperature is related to the time it takes for high temperatures to be achieved at various points within the assembly. The location of the degree is naturally that aggregate under processing as the front of the absorbing gas progresses through the aggregate. A body that moves over time from one end of the body to the other (e.g., from the bottom to the top) It is. Low moisture level in cellulose (10-20% by weight for temperature The increase value corresponds to the lower part of the above range (40-60℃ or even lower). On the contrary, for high moisture levels (ao-sos) the temperature rise value is even more important. Yes, above the range mentioned above (70-100℃ or even higher in special cases) It is also worth noting that it is getting closer. Generally near the top of the aforementioned range. Using lower temperatures favors higher yields of glucose at the end of the hydrolysis operation. However, due to the force, these temperatures may cause thermal decomposition of the desired product. Note that it should not be too high to prevent (formation of cool-like residue). I was noticed. Therefore, the temperature rises rapidly at each point of the fiber mass under treatment, then ensure that the temperature drops quickly due to rapid dissipation of the released heat This is especially important. Then, the quality of this operation depends on the concentration of cellulose fibers. To some extent, the steepness J of the temperature peak corresponding to the adiabatic impregnation process at each point of coalescence It will depend on the degree. This peak can be achieved by appropriately adjusting the flow rate of gaseous HCt. This adjusts the steepness of the arc.

After the temperature of this aggregate has fallen as a result of internal dissipation of the released heat, the second operation Adiabatic absorption is followed by an isothermal absorption phase. This isothermal absorption is derived The temperature in the vicinity will depend somewhat on the prevailing conditions at the initial stage. one In general, if the adiabatic step is achieved at a temperature on the higher end of the aforementioned range, the fibers will be transparent. The solution is saturated with a relatively high concentration of dissolved degradation products, and as a result , its HCt absorption capacity to achieve a significant degree of supersaturation (at relatively high temperatures) even if the Second stage HCA absorption is achieved Temperature (as can be seen here, the lower the temperature of the aqueous solution, the greater its HCA absorption capacity. (increasing amount) is therefore related to the desired level for such supersaturation. It is rather unimportant that the temperature is, for example, between 10 and 40°C. obtain. In contrast, if the first stage is carried out at a temperature in the rather lower part of the range mentioned above, , the HC1 absorption capacity of the permeating solution is much smaller, and as a result , rather, to achieve the desired high HCl supersaturation level, e.g. The second stage is carried out at a low temperature on the order of 10°C, preferably in the interval 10-20°C. It would be preferable to Regardless of the method, the key criteria in this case are , the final acid level of the aqueous solution obtained at the end of the first stage. The maximum saturation level obtained using pure water under the same conditions is at least 5 times 1 It is something that can be overcome. This level can stay between 43 and 60 weight class. , the preferred interval is 48 to 52 strokes (as can be seen here, the The acid level is the value of this solution, ignoring sugars and other oligomers dissolved in it. Also given by the weight of HCt divided by the total weight of HCt and water ). At the end of the second stage, this operation was carried out between 5 and 20 °C. In some cases, cellulose aggregates generally exist in the form of a rather fluid paste. . In contrast, this second stage is performed at relatively high temperatures (e.g. between 20 and 40°C). When carried out, almost all the cellulose is dissolved and this aggregate is It is a viscous liquid.

The third step of this process is that the solution is already dissolved in an acidic solution during the second step or almost completely 5 Concerning the completion of hydrolytic degradation of dissolved cellulose. Therefore, this stage In the process, glucobylanose monomers remain until the decomposition into the corresponding glucose molecules is completed. (Of course, as will be seen later, there is a risk of a moist phase or liquid that is substantially homogeneous (except for soluble impurities) phase is obtained, followed by partial repolymerization to a reversion polymer (e.g. , K.

MTJELLER, K. et al., Lebensmittel, Z. nters, u, Forsch, 100, 437-441 (1955 ). At the end of the second stage of this process, the solution is added to the supersaturated acid solution. The conditions to stop the depolymerization of cellodextrin, which exists in the exposed state, are critical. The solution is held at a given temperature for a sufficient period of time to achieve complete depolymerization. It is enough to have it. The following approximate conditions are suitable: 30℃/2-3 Time: 40℃/1 hour; 50℃/30 minutes; 60℃/15 minutes; 70℃/710 minutes Time: 80°C for 15 minutes. During this operation, some gaseous HCl is generally released, albeit in a small proportion.

As a practical matter, the acid solution to be removed from the reactor used in the second stage is placed It is possible to carry out this transformation in a closed or other temperature controlled vessel.

This vessel may be a tank connected directly to the outlet of the reactor; The solution is kept in the container long enough to ensure that the reaction proceeds to completion. The resulting solution is then degassed.

This degassing, which constitutes the fourth stage of any process, is a normal condition for those skilled in the art. It can be carried out by heating under reduced pressure, ie under reduced pressure. Generally, 40-100℃ Pressures at temperatures of the order of 20 to 600 Torr are advantageous. in general , the acid solution reaching this degassing stage has the following HCt content: 47-50%/30℃: 43-45%/40℃; 42-43% 150℃; 40. ~43°/60°C; 39~40%770°C, and these values are generally completely exceeds the value corresponding to a HC1-saturated solution of . During degassing, Hct level A significant decrease in the amount of water is observed. -As an example, you may cite the following figures: : That is, at 80℃/2oo~25oTorr, this acid level is 28 Go down to the turret. Sugars and other oligomers present in the solution before degassing (leverage) The concentration of oligomers) can be varied within wide limits and In the case of implementation with lurose (e.g. 10chi), values of 80-88chi can be reached. Ru. When using cellulose with a moisture content of 40-50%, the sugar level is typically 35-50%. on the order of 50% by weight (these contents are based on the proportion of these sugars present in the solution). , calculated as the weight of potential sugar divided by the weight of water and HCA added. (including calculation). After removing both parts of HCt by degassing, these levels Naturally, the acid titer will increase to about 0.5 to 5 g. The solution is diluted with water and this value is converted to glucose which is available by refluxing. Suitable for enabling post-hydrolysis of Noshi/S-john oligomers.

For example, 23 t HCl and 90 t potential glucose (90 t) 1 kg degassing containing 0.011 of sugar, 23 g of HCl and 77.9 of water) If you start with a solution of It is easy to calculate that an approximately 1% HC1 solution with 8% sugar is obtained. It can be done. Post-hydrolysis operations are common (e.g. European A' Patent Application No. 812 01182.3) and the sugars formed are then separated. and used in the same manner as described in this document.

The process of the present invention is effective in treating wastes containing impurities such as minerals (ash) and lignin. Suitable for degrading lulose and cellulose products. For such products is a de-gunin protein disclosed in European Patent Application No. 81810276.9. 7Xlll of wood obtained from cess, as well as newspaper and pulp from wastewater from paper mills. Waste pulp and other slurry wastes may be cited. In such a case, try resetting the Gunin and mineral impurities are not affected by the hydrolysis solution and are ultimately diluted. After it is dissolved, it remains either in the form of a dispersion of insoluble material in the hydrolysis solution or as a solution. child These insoluble particles may then be removed by filtration by conventional methods. this Regarding this, the fluidity of the aggregate resulting from the second step of the hydrolysis process makes it It is noted that dependence on the presence of lignin and mineral salts tends to reduce Will.

The following examples further illustrate the invention by reporting experimental details. It is. To illustrate some examples, a sample embodying the process of the invention will be described. Reference is made to the attached drawing which represents the test equipment.

The principal elements of the depicted apparatus include: In other words, Immersion (zone la) and isothermal absorption (zone 1b subjected to cooling means) are carried out. Scree conveyor reactor 1, hydrolysis reaction to complete hydrolytic degradation vessel 2 , a degassing vessel or “stripper” 3 and a post-hydrolysis reactor 4 . child The operation of this device, as is clear from the drawings, is as follows. wet cellulose The base is introduced into the loading chamber (see arrow) and airtight with rotating pulp. After passing through a non-returning device 6, it enters the reactor 1. Next, this is impregnated in zone 1b with gaseous HCt coming from line 7; The zone is kneaded by screw 8 which moves all of it into zone 1b. Isothermal absorption takes place in line 1b with HCl introduced from line 9. of reactor 1 From the outlet, this aggregate is transferred by a duct 10 into the hydrolyzer 2, during which H The CtO fraction is removed and recycled by pump 11. Complete degradation of cellulose This is accomplished in the hydrolyzer 2 with the formation of a The temperature of the reactor is controlled by the action of a heat exchanger 120. Then this liquid The mass passes to a degassing reactor 3, from where it is pumped by a pump 13. Post-hydrolysis tank 4, during which the acid from the degassing is partially transferred into tank 15. (see condenser 14) (aqueous hydrochloric acid) and this gaseous fraction is passed through line 1 6. In reactor 4, this mass is mixed with water (see line 17) The resulting solution is diluted and hydrolyzed to glucose using Cooled and neutralized in tank 20 using CaC03 (see line 19) .

Example 1 6.92% pure (impurities consist of lignin, residual bentosan and ash). 44.9 cellulose pulp (378 g dry matter containing 2.66 F water, 4 1.28% moisture) in a fruit approximately 6 crn in diameter with a mantle to circulate the liquid. The pulp was then heated to 10 g/hr of H (by 4 streams). Saturated (during 15 minutes). very rapidly up to about 80°C in the first few minutes of absorption A temperature increase of 3 is observed, after which the temperature increases towards the end of the absorption period C The temperature gradually decreased to 0°C. After weighing, an increase in the weight of HCl of 2.159 was observed, The concentration of the acid thus formed in the water contained in the nokulp was then 44,7 tsp. Met. After this initial absorption period, Gurg becomes a relatively light and bubbly body. The materials were used. And in this state it is circulated into the external mantle. The coolant liquid in contact with the flask wall is sufficiently dense to allow for multiple temperature control. Gave.

Therefore, by circulating water at 10°C in this mantle, the pre-degraded When the sample reaches this temperature, add an additional 0.45% using gaseous HCl. It was processed again for 10 minutes to allow addition. This stage (thermal expansion) During this period, the titer of this acid solution reached an HCl value of 49.43% by weight. HCt After this supersaturation using Rapid and complete liquefaction of this aggregate (5-10 minutes) is achieved by heating to 40°C. ) and during the next hour (still at a temperature of 40°C) about 0.6 F HCL. The removal of gas was caused. Therefore, the titer of this solution is (acid present and (based on the weight of acid present relative to the total amount of water). melt Regarding the concentration of the dissolved product (glucose precursor), we calculated that 37% value was obtained. The solution thus obtained has a density of 1.4 and flows freely.

It can be easily circulated through the pipe and by the usual methods It can be sucked out. The weight ratio of HCI used/hydrolyzed cellulose is: 2.673.78 = 0.38.

Example 2 With the same equipment used in the experiment of Example 1, except for the larger volume, 35. A 148y pulp with 8% moisture was treated in exactly the same way. This Kurureso is 53 g of water and 95 g of pure cellulose, which theoretically corresponds to 1051 g of glucose. It contained a

The total uptake of HCl (during the adiabatic and isothermal stages) was 46 g. Then, The thus treated aggregate (total −i 1.94 g) was analyzed for its three components. Usually water is extracted by the Nokal Fischer method and HCl is extracted by titration. The amount of solids was determined by the difference), which gave the following results: solid glucose Precursor: 100g (total 516 parts), water: 48g (24,7 parts) and HC l: 46 g (23,7 section). Therefore, the acid titer is 46/(46+ 48) = 49% by weight.

The mixture was kept at 40°C for 1 hour (while the 10,9 gaseous I (CA evaporated)). , and this mixture was reanalyzed as described above. Then the following results were obtained: solid : 100g (54%); Water: 48g (26, 1 section): HCt: 36g (19.6%). The titer of this acid was then 429 Ti.

The liquid thus obtained is transferred into a thin layer nick volator (evaporator Wall temperature 80℃ 1 pressure 200-250 Torr) and 177g H (J gas) It was possible to recover it. After condensation, H 21 g of liquid ζ with CL i.e. 5.88. ! Hct of 9) remained.

Thus, in this mixture there are approximately 12.44 g of HCl, 32S of water and 10 0 g of solid glucose precursor (reversion oligomer) remained. residual The concentration of acid remaining in the water is 12.44/44.44=28% HCL. release The mixture, which solidifies on standing, was heated to give a solution of 15% solids and 2% Hct. was dissolved in 525 g of water and the solution was boiled under reflux for 1 hour. This solution After filtration and bleaching, 100 g of glucose (yield 95 g. ), HCl/glucose weight ratio=0-48 was obtained.

Example 3 Obtained by the method disclosed in European Patent Application No. 81810246.9 3. 10.97N Cellulose/NO Lupe (Red Oak) with 4.15% water Then, the operation was carried out in exactly the same manner as disclosed in Example 1. This no4rupu , total 6.739 cellulose, 3.49. ! 9 water and 075g lignin , bentosan and residual ash. Gaseous form used in the adiabatic absorption stage The Hct flow is about 16.9 HCt/hr, and the absorption amount is 3.0 after 15 minutes. 5,17, which is 4664%, which corresponds to the formation of an acid solution of Hct. It was. During this predegradation phase, carefully note the temperature changes within the fiber assembly and The value of was recorded.

15 36 In addition, 0.749 Hct (corresponding to 3,79 & total amount) is absorbed. The isothermal absorption operation was carried out at 10°C for 10 minutes using a gas flow rate of (Final solution titer: 52.06 based on total amount of water and HCt present) wt% acid).

Heat the mixture to 40°C and bring it to this temperature for 1 hour to complete the hydrolysis. Holds time. During this operation, 1.1 A decrease in 59 HCA was observed. Then, perform the degassing operation disclosed in Example 3. (temperature 80°C, pressure 200 Torr). Weigh after degassing for 15 minutes Measure the weight loss of 2.419c water + HCA), and after 30 minutes, further 0. A reduction of 99.9 was measured (1.27 g of gaseous HCt and 217 g of 286 The total amount including the thiic acid solution is 3.449, i.e. 55.4 of the water and acid initially present. 6% decrease).

After degassing, the composition of the residue was as follows; namely, sugar 71011; HCA 0.769: H2o 1.95I, and when expressed in chi, each 72%: 8cm; 20cm.

This residue was diluted with water and subjected to subsequent hydrolysis treatment as in the previous example. A yield of 94% glucose was obtained. The weight ratio of HCt/glucose is 05 It was 6.

Example 4゜ 3 3.1 #glucose giving a solution of 59% by weight glucose in 27.4% acid 32% of -sulphate (30,55,9 pure glucose) and 18.11F Aqueous HCt was mixed under stirring at 40°C. Then, at 40°C, the gas The solution was saturated using gaseous HCl. When 6.2g of this gaseous HC1 is a bar After a while, 8.38 g had dissolved after 1 hour. Therefore, 50.84% by weight of glucose course, 60.1 g of solution containing 247% water and 239% acid by weight. I got the liquid. The HCt titer of the aqueous part of this solution (defined as solution A) is It was 48.8%.

Furthermore, in the same impregnated tube as used in Examples 1 and 2, the A total amount of 7.739 HCt was prepared using the gaseous HCA described in the examples (in the adiabatic phase). 5.159 during and 2.69 during the 10 °C isothermal phase) , 19.03F cellulose noggle f (11,2:M dry hardness) containing 41cm humidity. body and 7.89 water) were treated. Therefore, the maximum of the acid solution obtained in this way is The final concentration is 49.4q6. Therefore, within the margin of error, prehydrolyzed The acid titer of the solution in contact with the fibers is close to that of the acid glucose determination (g). I can recognize that.

The viscous R-stripe cellulose prepared as described above is soluble (at 40°C). was added to Solution A, whereby it dissolved in 10 minutes. Then this mixture was held at 40° C. for 1 hour, during which time 2.89 gaseous HCt was released. This way The acid content of the sea urchin solution was reduced to 45.2%. Then carry out this solution It was degassed as shown in Example 1 and then mixed until the concentration of dissolved solids was 15 1819 water and 12.59 NaOH to give an acid titer of 4%. diluted using After boiling this solution under reflux for 1 hour, υ Glucose was isolated therefrom and 42.41 g was obtained. This amount is present in solution A Taking into account the amount of I guess. The weight ratio of HC1/cellulose was 0.68.

Examples 5-10 A series of cellulose products with variable glucose content were prepared in Examples 1 and 2. It was attached to the same crop as described in . The properties of these substances (theoretical glucose content) These actual glucose contents (obtained by calculation from the actual glucose content, other possible of glucose compared to the theoretical amount due to the application of a process with Final graphical yields are given in weight percent in the table below. Theory of potential glucose The analytical values for quantity are based on starting in a large excess of 72% H2SO4 (or 40% hydrochloric acid). Dissolution and quantitative hydrolysis of the substance, dilution with a large excess of water, 30 minutes under reflux Post-hydrolysis and HPLC method (high performance liquid chromatography).

Joy, Kay, PALMER.

Analytical Letters (3), 215-224 (19 The apparatus represented in the figure obtained after determination of glucose in solution by (see 75) Crude cell containing 43% water at a rate of 177.02kg/hr Processed the loin. Analysis of this material (in dry form) gave the following values : Cellulose 67.3%; Hemicellulose 14.25%: Lignin 404% ; Impurities 14.41%. To the extent of lines 7 to 415 and lines 9 to 115 A staggered gaseous HCl flow at a rate of 76.32 kg/hr was used.

After post-hydrolysis in reactor 4, 73.5 ki9/hr of glucose and 0. A xylose yield of 95 kg/hr was obtained. Hydrolyzer 2 and ST IJ, J ? The amount of HCl degassed and recycled from No. 3 is 39.87 kl? / in hours This amount corresponds to an effective HC1 consumption of 36.45 kg/hr. Temperature conditions The conditions were essentially the same as those described in the previous examples. Glucose Yutoshi H The consumption of Cl was 9 in 05.

International investigation recipient

Claims (1)

[Claims] 1. A method for hydrolytically converting cellulose into glucose, which involves the following steps: Cheng: a) Draw by dissolving hydrochloric acid gas in the water present in the cellulose fibers. The temperature is increased at such a rate that the temporary temperature increase caused reaches a value of 40-100°C. Moist cellulose containing 30-50% moisture was exposed to hydrochloric acid gas without control. impregnated with, b) The acid level of the resulting solution is at saturation equilibrium under the corresponding conditions of pressure and temperature. Fi to exceed the acid level of the corresponding solution in pure water at at least 5 degrees Impregnation of cellulose by controlling the temperature between 5 and 40℃ until the absorption amount of HC1 is reached. C) The resulting mixture is heated until the hydrolysis of the starting cellulose is completed. heating up to d) subjecting the obtained solution to degassing; e) diluting it with water; Boil the solution until hydrolysis of the dissolved oligomers to glucose is complete. thing A method comprising: 2. At the end of step a), the HCt concentration of the solution passing through the fibers is 39 to 45%. A method according to claim 1, characterized in that: 0 3. The HCL concentration at the end point of step b) is 43-60%. The method according to claim 1. 4. A claim characterized in that the HC1 concentration of the solution after degassing is 20 to 34%. The method described in item 1. 5. Concentration of sugars (glucose and oligomers) dissolved in the solution before degassing The method according to claim 1, characterized in that the weight ratio changes between 38 and 88 weight ratio. Law. 6.H required to hydrolyze 0.1 part of cellulose material (measured in dry state) The method according to claim 1, characterized in that the weight of Ct does not exceed 0.8 parts. . 1