EP0093088B1 - Procédé pour hydrolyser de la cellulose en glucose - Google Patents

Procédé pour hydrolyser de la cellulose en glucose Download PDF

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Publication number
EP0093088B1
EP0093088B1 EP83810172A EP83810172A EP0093088B1 EP 0093088 B1 EP0093088 B1 EP 0093088B1 EP 83810172 A EP83810172 A EP 83810172A EP 83810172 A EP83810172 A EP 83810172A EP 0093088 B1 EP0093088 B1 EP 0093088B1
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EP
European Patent Office
Prior art keywords
solution
cellulose
hci
water
glucose
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP83810172A
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German (de)
English (en)
French (fr)
Other versions
EP0093088A1 (fr
EP0093088A2 (fr
Inventor
Ake Allan Johansson
Alain Roman
Jean-Michel Armanet
Jean-Pierre Sachetto
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
HYDROCEL Srl
Battelle Memorial Institute Inc
Original Assignee
HYDROCEL Srl
Battelle Memorial Institute Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by HYDROCEL Srl, Battelle Memorial Institute Inc filed Critical HYDROCEL Srl
Priority to AT83810172T priority Critical patent/ATE16510T1/de
Publication of EP0093088A1 publication Critical patent/EP0093088A1/fr
Publication of EP0093088A2 publication Critical patent/EP0093088A2/fr
Application granted granted Critical
Publication of EP0093088B1 publication Critical patent/EP0093088B1/fr
Expired legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C13—SUGAR INDUSTRY
    • C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
    • C13K1/00—Glucose; Glucose-containing syrups
    • C13K1/02—Glucose; Glucose-containing syrups obtained by saccharification of cellulosic materials

Definitions

  • the present invention relates to a process for transforming wet cellulose into glucose by hydrolysis using an aqueous solution of supersaturated hydrochloric acid obtained by dissolving hydrochloric gas in the water impregnating this cellulose.
  • solubility in% by weight of HCl in its aqueous solution at ordinary pressure corresponds, for various temperatures in 'C , to the following values: 10 ° / 44.04; 20 ° / 42.02; 30 ° / 40.22; 40 ° / 38.68; 50 ° / 37.34; 60 ° / 35.94.
  • solubility values can be significantly increased by using, instead of pure water, aqueous solutions of organic substances, for example, alcohols, dimethylformamide or other water-compatible solvents.
  • Sugars can be used for this purpose, in particular as described in Swiss patent No. 228 914.
  • This document indeed mentions the effective dissolution of cellulose in sugar solutions containing a higher concentration of HCI (obtained by supplying gaseous HCI) at the saturation concentration (at the same temperature and pressure conditions) in pure water. According to this document, it was possible, by this means, to carry out the transformation of 100 parts by weight of cellulose into glucose using a weight of HCl not exceeding 80 parts.
  • Such a solution has a surprising dissolving power with respect to dry cellulose; it is indeed possible to gradually add another 580 g at 40 ° C which dissolve little by little, thus providing a solution whose concentration in dissolved products and, subsequently, degraded by hydrolysis (glucose and other oligomers) is of the order of 84% by weight.
  • a total of about 600 g of dry cellulose and 60 g of water were used (in fact, we started with 100 g of 40% HCl) and the weight of water relative to the total of this dry cellulose corresponds to a potential humidity of around 10%.
  • the process according to the invention therefore makes it possible to work with a relatively wet cellulose and, in spite of everything, to achieve a substantial saving in HCl compared to known processes. It is also energy efficient as we will see. It is based on the surprising discovery that it is perfectly possible to pre-impregnate wet cellulose with gaseous HCl without controlling its temperature by cooling and without the release of heat having a harmful influence on the course of hydrolysis and the yield. of the reaction.
  • the adiabatic absorption step will therefore be followed by a stage comprising the additional dissolution of gaseous HCl in the solution surrounding the partially degraded cellulose at a temperature favoring this absorption (relatively low temperatures).
  • This stage results in an almost complete liquefaction of the mass of fibers reacted, complete dissolution occurring subsequently after a heating period. It is obvious that such a liquefaction takes place effectively (by virtue of what has been explained above) only because of the preliminary formation (at the adiabatic stage) of an acid solution of sugars and other products of pre-degradation of cellulose and that it is this solution which, after supersaturation by adding an additional dose of HCI made possible by the presence of the dissolved products, will act on the remaining cellulose and will allow it to dissolve first almost completely, even at low temperature, then complete hot.
  • This second stage called “isothermal absorption” therefore leads to the formation of a thick liquid consisting of an almost complete dissolution of cellulose in supersaturated HCl.
  • the second operation, the isothermal absorption is done following adiabatic absorption, that is to say as soon as the temperature of the mass has dropped by itself by internal dissipation of the heat released.
  • the temperature at which this isothermal absorption is carried out will, in part, depend on the conditions under which the first phase has been carried out. In general, when the adiabatic phase has been carried out at temperatures at the top of the aforementioned range, the acid solution impregnating the fiber will be charged with a relatively high concentration of dissolved degradation products and, consequently, its absorption capacity of the HCI gas (even at relatively high temperatures) to achieve significant supersaturation of this solution will be relatively high.
  • the temperature at which the absorption of the HCI will be carried out in the second stage (it is recalled here that the lower the temperature of an aqueous solution, the higher its capacity for absorbing the HCI) will therefore be rather indifferent relative to the desired rate for such supersaturation and can be understood, for example, between 10 and 40 ° C.
  • the first step was carried out at a temperature fairly close to the bottom of the above-mentioned range, the HCl absorption capacity of the impregnation solution will be less marked and, consequently, it will be advantageous, to achieve the rates high HCI supersaturation, to proceed to the second step at rather low temperatures, for example of the order of 5-30 ° C, the interval of 10 to 20 ° C being preferred.
  • the decisive criterion in this case is the final level of acid in the aqueous solution at the end of the second phase, this rate exceeding by at least 5% the maximum saturation rate that could be obtained with pure water under the same conditions and which may be between 43 and 60% by weight, the preferred range being 48 to 52% (it is recalled here that the acid level of such a solution is indicated in terms of weight of HCI divided by the total weight of HCI and water of the solution, without taking into account sugars and other oligomers also dissolved in it).
  • the cellulosic mass is generally in the form of a fairly fluid paste if the operation has been carried out between 5 and 20 ° C. If, on the other hand, this second stage has been carried out at relatively high temperature higher (for example between 20 and 40 ° C), the cellulose is then almost completely dissolved and the mass is a viscous liquid.
  • the third stage of the process concerns the completion of the hydrolytic degradation of the cellulose which has already completely or almost completely dissolved in the acid solution during the second stage.
  • the conditions for completing the depolymerization of the cellodextrins present, in the dissolved state, in the supersaturated acid solution at the end of the second step of the process are not critical; it suffices to maintain the solution at a given temperature for a sufficient time for this depolymerization to be completed.
  • the following approximate conditions are suitable: 30 ° C / 2-3 h; 40 ° C / 1 h; 50 ° C / 30 min; 60 ° C / 15 min; 70 ° C / 10 min; 80 ° C / 5 min. During this operation, it generally gives off gaseous HCI but in relatively small proportions.
  • this conversion can be carried out in an enclosure or other container at a controlled temperature in which the acid solution withdrawn from the reactor where the second phase took place is placed.
  • This container may be a reservoir connected directly to the outlet of said reactor and in which the solution is kept for sufficient time for the reaction to take place and at the outlet of which the solution is subjected to degassing.
  • This degassing which constitutes the fourth step of the process, can be carried out under the usual conditions of the technique, that is to say by heating under reduced pressure.
  • pressures on the order of 20 to 600 Torr (2.66 to 80 KPa) at temperatures of 40 to 100 ° C are well suited.
  • the acid solutions which reach the degassing compartment have the following HCl contents: 47-50% / 30 ° C; 43-45% / 40 ° C; 42-43% / 50 ° C; 40-43% / 60 ° C; 39-40% / 70 ° C, contents which generally always clearly exceed the values corresponding to saturated solutions of HCl in pure water.
  • HCl contents 47-50% / 30 ° C; 43-45% / 40 ° C; 42-43% / 50 ° C; 40-43% / 60 ° C; 39-40% / 70 ° C, contents which generally always clearly exceed the values corresponding to saturated solutions of HCl in pure water.
  • a significant reduction in the level of HCI
  • the following value may be cited: at 80 ° C / 200-250 Torr (26.6-33.3 KPa), this acid content increases to 28%.
  • the levels of sugars and other oligomers (of reversion) present in the solutions before degassing can vary within wide limits, being able to reach values of 80 to 88% when working on celluloses low in humidity (10% for example).
  • the final sugar levels are generally in the range of 35-50% by weight (these rates are calculated as the weight of potential sugars divided by the total the weight of the water present, that of these sugars and the amount of HCI present). After part of the HCI has left during degassing, these rates of course increase and can reach values of 92 and 56%, respectively.
  • the solution is diluted with water so that the titer of the acid passes to approximately 0.55%, a value which is suitable for the boiling-off oligomers of reversion to be quantitatively post-hydrolyzed to glucose. It is easy to calculate that, for example, starting with 1 kg of degassed solution containing 23% HCI and 90% potential glucose (i.e. 900 g of sugars, 23 g of HCI and 77 g of water) and by diluting this solution with 2.2 liters of water, a solution of approximately 1% HCl and 28% of sugars is obtained.
  • the post-hydrolysis operation is carried out according to the usual means (see for example EP-A-0 052 896), the sugars supplied are then separated and used as also described in this reference.
  • the process of the present invention is suitable for degrading cellulose as well as cellulose products containing impurities such as minerals (ash) and lignin.
  • impurities such as minerals (ash) and lignin.
  • wood pulps obtained according to the delignification process described in patent application EP81 810276.9 as well as newspapers, sugar beet pulp and other paper waste contained in stationery waste water.
  • the mineral or woody impurities are not attacked by the hydrolyzing solutions and are found in solution or in the form of a dispersion of insoluble matter in the final diluted post-hydrolysis solution. These insoluble particles can then be removed by filtration according to the usual means. It will be noted in this regard that the fluidity of the mass resulting from the second step of the hydrolysis process depends on the presence of lignin and mineral salts which tend to decrease it.
  • the main elements of the installation shown include a screw reactor 1 for adiabatic impregnation (zone 1 a) and isothermal absorption (cooled zone 1 b), a hydrolyser reactor 2 to perfect the hydrolytic degradation, a tank 3 of degassing or "stripper" and a post-hydrolysis reactor 4.
  • the operation of the installation which is moreover evident from the drawing, is as follows: the wet cellulose is introduced into the feed hopper 5 (see arrow) and enters reactor 1 after passing through a device 6 with a gas-tight rotary non-return valve.
  • the liquid mass passes into the degassing reactor 3 from where it is sent to the post-hydrolysis tank 4 via a pump 13, while the degassed acid is partially condensed (see condenser 14) in a tank 15 (aqueous hydrochloric acid solution), the gaseous fraction being recycled via line 16.
  • the mass is diluted with water (see line 17) and hydrolyzed to glucose, the solution obtained being cooled in the exchanger 18 and neutralized with CaCO 3 (see line 19) in the tank 20.
  • the titer of the acid solution therefore increased (based on the weight of acid present relative to the total of this acid and the water present) to 42.9%.
  • concentration of dissolved solid products glucose precursors
  • the calculation gives a value of 37%.
  • the solution thus obtained has a density of 1.4 and it is very fluid. It can be easily circulated in pipes and pumped by the usual means.
  • the isothermal absorption operation was carried out at 10 ° C. in 10 min by means of a gas stream of identical flow rate, which made it possible to absorb another 0.74 g of HCl, which corresponds to a total of 3.79 g (titer of the final solution 52.06% by weight of acid relative to the total of water and HCl present).
  • Example 3 The temperature of the mixture was brought to 40 ° C. and was maintained at this value for one hour to complete the hydrolysis. During this operation, the loss of 1.15 g of HCl was noted, which brings the titer of the acid to 43.07%.
  • a degassing was then carried out as described in Example 3 (temperature 80 ° C, pressure 200 Torr (26.6 KPa)). After 15 min of degassing, a weight loss of 2.41 g (water + HCl) was measured by weighing and, after 30 min, an additional loss of 0.99 g (total 3.44 g including 1.27 g of gaseous HCl and 2.17 g of 28.6% acid solution, ie a loss of 55.46% of the water and the acid initially present).
  • the composition of the residue after degassing was as follows: sugars 7.10 g; HCI 0.76 g; H 2 0 1.95 g either as a percentage respectively 72%; 8%; 20%.
  • the residual liquid HCI had a concentration of 28%.
  • solution A was therefore 48.8%.
  • the cellulose in viscous paste as prepared above was added to solution A (at 40 ° C.) where it dissolved in 10 min. Then the whole was left for 1 hour at 40 ° C., time during which 2.8 g of HCl gas was released. The acid titer of the solution therefore decreases to 45.2%.
  • the analytical values concerning the theoretical potential glucose content are obtained by dissolution and quantitative hydrolysis of the first materials in a large excess of H 2 SO 4 at 72% (or hydrochloric acid at 40%), dilution in a rand excess of water, 30 min of post-hydrolysis at reflux then determination of the glucose on the solution by the method called HPLC (high performance liquid chromatography, see JK PALMER, Analytical letters, 8 (3), 215-224 (1975]).
  • HPLC high performance liquid chromatography
  • HCI consumption / kg of glucose 0.5 kg.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • General Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • Organic Chemistry (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Immobilizing And Processing Of Enzymes And Microorganisms (AREA)
  • Materials For Medical Uses (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Paper (AREA)
EP83810172A 1982-04-27 1983-04-25 Procédé pour hydrolyser de la cellulose en glucose Expired EP0093088B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT83810172T ATE16510T1 (de) 1982-04-27 1983-04-25 Verfahren zum hydrolysieren von cellulose zu glukose.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH255882 1982-04-27
CH2558/82 1982-04-27

Publications (3)

Publication Number Publication Date
EP0093088A1 EP0093088A1 (fr) 1983-11-02
EP0093088A2 EP0093088A2 (fr) 1983-11-02
EP0093088B1 true EP0093088B1 (fr) 1985-11-13

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ID=4236501

Family Applications (1)

Application Number Title Priority Date Filing Date
EP83810172A Expired EP0093088B1 (fr) 1982-04-27 1983-04-25 Procédé pour hydrolyser de la cellulose en glucose

Country Status (8)

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EP (1) EP0093088B1 (es)
JP (1) JPS59500648A (es)
AT (1) ATE16510T1 (es)
DE (1) DE3361207D1 (es)
ES (1) ES8406551A1 (es)
FI (1) FI831106L (es)
NO (1) NO834799L (es)
WO (1) WO1983003847A1 (es)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8331108D0 (en) * 1983-11-22 1983-12-29 Shell Int Research Oligosaccharides-containing products from biomass

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB341501A (en) * 1928-10-02 1931-01-19 Commercial Alcohol Company Ltd A process for obtaining sugar from cellulose or cellulose-containing substances
CH228914A (de) * 1940-11-16 1943-09-30 Bergin Ag Verfahren zur Gewinnung von für technische Zwecke bestimmten Zuckerlösungen aus Zellulose.
FR981450A (fr) * 1943-04-10 1951-05-25 Procédé pour l'hydrolyse partielle ou totale des matières cellulosiques

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Publication number Publication date
JPS59500648A (ja) 1984-04-19
ATE16510T1 (de) 1985-11-15
ES521823A0 (es) 1984-07-01
DE3361207D1 (en) 1985-12-19
WO1983003847A1 (fr) 1983-11-10
ES8406551A1 (es) 1984-07-01
FI831106A0 (fi) 1983-03-30
EP0093088A2 (fr) 1983-11-02
FI831106L (fi) 1983-10-28
NO834799L (no) 1983-12-23

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