WO2011094922A1 - 一种完全溶解和快速水解纤维素的方法及其应用 - Google Patents

一种完全溶解和快速水解纤维素的方法及其应用 Download PDF

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WO2011094922A1
WO2011094922A1 PCT/CN2010/001253 CN2010001253W WO2011094922A1 WO 2011094922 A1 WO2011094922 A1 WO 2011094922A1 CN 2010001253 W CN2010001253 W CN 2010001253W WO 2011094922 A1 WO2011094922 A1 WO 2011094922A1
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cellulose
aqueous solution
heating
concentration
heated
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PCT/CN2010/001253
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English (en)
French (fr)
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方真
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中国科学院西双版纳热带植物园
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Priority to US13/259,526 priority Critical patent/US9115215B2/en
Publication of WO2011094922A1 publication Critical patent/WO2011094922A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B1/00—Preparatory treatment of cellulose for making derivatives thereof, e.g. pre-treatment, pre-soaking, activation
    • C08B1/003—Preparation of cellulose solutions, i.e. dopes, with different possible solvents, e.g. ionic liquids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
    • C08B15/02—Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02—Cellulose; Modified cellulose
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel

Definitions

  • the invention belongs to the technical field of biomass dissolution and hydrolysis, and in particular relates to a method for completely dissolving and rapidly hydrolyzing cellulose. At the same time, the invention also relates to the further use of the dissolution and hydrolysis process. Background technique
  • Lignocellulosic biomass in nature such as wood and grass, consists of approximately 50% cellulose, 25% hemicellulose, and 20% lignin.
  • Cellulose can be degraded into sugars by hydrolysis and used to ferment cellulose alcohol.
  • the smear of the smear of the smear of the smear of the smear of the smear of the smear of the smear is 0. 4 ⁇ 0. 8% Hydrolysis in aqueous sulfuric acid (see Institute of Plant Hydrolysis Technology, Nanjing Forestry College, Plant Hydrolysis Technology, Agricultural Press, 1961). No reports of continuous production using a high pressure continuous reactor.
  • the temperature at which cellulose is completely dissolved has a minimum value of 320 ° C and occurs at a water density of 850 kg/m 3 .
  • the above findings are all directed to pure water. The dissolution temperature of cellulose in pure water is higher and the hydrolysis rate is slower.
  • An object of the present invention is to provide a method for completely dissolving and rapidly hydrolyzing cellulose at a lower temperature in order to reduce the production cost in view of the deficiencies of the prior art.
  • a method for completely dissolving and rapidly hydrolyzing cellulose comprising the steps of:
  • steps 1 and 2 the resultant mixture was placed in a reactor, the cellulose concentration of 0.1% to 35%, the concentration of the solution after adjusting the mixing material is 10- 7 ⁇ 1 [H +] acidic or 10- 7 ⁇ 1 [0 ⁇ base Sex, water density is 587 ⁇ 997 kg / ra 3 , set pressure is 6 ⁇ 584 MPa, heating rate is 7.8 ⁇ 14.8 ° C / s, rapid heating to 261 ⁇ 352 ° C, 0.8-2 seconds can completely dissolve Cellulose.
  • the acidic aqueous solution is an aqueous solution of hydrochloric acid (HC1), nitric acid (HNO 3 ) or sulfuric acid (H 2 S0 4 ).
  • the alkaline aqueous solution is an aqueous solution of sodium hydroxide (NaOH), potassium hydroxide (K0H) or calcium hydroxide (Ca(OH) 2 ).
  • the acidic aqueous solution is preferably an aqueous HC 1 solution.
  • the alkaline aqueous solution is preferably an aqueous NaOH solution.
  • the above-mentioned method for completely dissolving and rapidly hydrolyzing cellulose is used in alcohol production. Namely: After the cellulose is completely dissolved, it is heated to 355 °C, then naturally cooled to room temperature, and the cellulose is partially decomposed into sugars (glucose and oligosaccharides), which can be used for fermentation to produce alcohol.
  • the present invention has the following advantages:
  • the subsequent hydrolysis reaction can be carried out under homogeneous conditions, which promotes the hydrolysis reaction and inhibits the thermal decomposition reaction.
  • the total dissolution time is less than 0.8 to 2 seconds, and the hydrolysis reaction time is less than 5 seconds.
  • Solvated cellulose can be conveniently applied to low-temperature, high-pressure flow reactors, further reducing production costs and continuously hydrolyzing sugar and other biofuels and products.
  • the saccharide produced by hydrolysis is more pure and concentrated than the lignocellulosic biomass such as wood flour. It has only oligosaccharides of glucose and glucose, and does not contain five carbon sugars and oligosaccharides.
  • Figure 1 is a schematic view showing the structure of a micro-visible diamond reactor for experimental use of the present invention
  • Figure 5 is an infrared spectrum absorption curve of the experimental product;
  • FIG. 6 is a schematic view showing the connection of the device of the present invention. detailed description
  • the experimental setup is a miniature visual diamond reactor (Diamond Anv il Cel l) which rapidly heats the water in the reaction chamber to a high temperature and observes the dissolution of cellulose in water.
  • a small hole having a diameter of 500 ⁇ m was formed on a piece of iron having a thickness of 250 ⁇ m to form a reaction chamber 4 having a volume of 50 nL.
  • the small holes are pressed by the upper and lower diamonds 3, and the holes are sealed and pressure is generated. If you loosen two diamonds, you can let nitrogen enter the small holes and create bubbles.
  • the cellulose powder and the pure water were placed in the reactor, the cellulose concentration was 30%, the heating rate was set to 12, 1 ° C / s; the water density was 887 kg / m 3 ;
  • cellulose is suspended in water and bubbles before heating
  • the cellulose powder HC1 and the acidic solution was placed in the reactor, the concentration of HC1 solution was mixed material 10-2, a cellulose concentration of 25%, the heating rate was set 11.3'C / s; water density was 958kg / m 3 .
  • cellulose is suspended in an acidic solution and bubbles before heating;
  • the cellulose powder and an alkaline NaOH solution placed in a reactor the concentration of the NaOH solution was mixed materials 10- 2 M, wood flour concentration was 32%, the heating rate is set to 13.4'C / s; density of water 848kg/m 3 .
  • cellulose is suspended in an alkaline solution and bubbles before heating;
  • the cellulose is placed in pure water to form a cellulosic material; the pure water is heated to 349 ° C; the mixed pure water and the cellulosic material are placed in the reactor, and the cellulose concentration after mixing is 20%, and the water density is set to 594kg/m 3 , rapid heating to 349 ° C, heating rate of 10.4 'C / s, to 326 ° C (12 MPa), 1.05 seconds to completely dissolve cellulose.
  • Cellulose is hydrolyzed to polysaccharides and glucose.
  • Example 1 was repeated with the following differences: Pure water was heated to 319 ° C; the cellulose concentration after mixing was 35%, the water density was set to 806 kg/ra 3 , the temperature was rapidly heated to 319 ° C, and the heating rate was 11.1 °. C / s, to 317 ° C (103 MPa), 2 seconds to completely dissolve cellulose. The cellulose is hydrolyzed to a polysaccharide.
  • Example 1 was repeated with the following differences: Pure water was heated to 326 ° C; the cellulose concentration after mixing was 26%, the water density was set to 995 kg/ m 3 , the temperature was rapidly heated to 326 ° C, and the heating rate was 9.6 °. C/s, to 318 ° C (539 MPa), completely dissolve cellulose in 1.7 seconds. The cellulose is hydrolyzed to a polysaccharide.
  • Example 4 (10- 6 HC1) Cellulose was 10_ 6 HC1 acidic aqueous solution to form a cellulose material; 10_ 6 HC1 acidic aqueous solution was heated to 338 ° C; mixed acidic aqueous solution and the cellulose material is placed in a reactor, mixed cellulose at a concentration of 28% , set the water density to 995kg / m 3 , rapid heating to 338 ° C, heating rate of 12 ° C / s, to 337 ° C (581 MPa), 0.9 seconds to completely dissolve cellulose. Heating was continued to 355 ° C and the cellulose was hydrolyzed to polysaccharides and glucose.
  • Example 4 was repeated with the following differences: The acidic aqueous solution was heated to 331 ° C; the cellulose concentration after mixing was 7.5%, the water density was set to 814 kg/m 3 , the heating was fast to 331 , and the heating rate was 12.5 ° C / s, to 327 ° C (127 MPa), completely dissolve cellulose in 1.1 seconds. Heating was continued to 355 °C and the cellulose was hydrolyzed to polysaccharides and glucose.
  • Example 4 was repeated with the following differences: The acidic aqueous solution was heated to 336 ° C; the cellulose concentration after mixing was 18%, the water density was set to 682 kg/m 3 , the heating was rapidly heated to 336 ° C, and the heating rate was irC/ s, to 333 ° C (28 MPa), completely dissolve cellulose in 1.1 seconds. Continue heating to 355 °C. Cellulose is hydrolyzed to polysaccharides and glucose.
  • the cellulose is placed in an acidic lO-HCl aqueous solution to form a cellulosic material; the acidic lO-HC1 aqueous solution is heated to 339 ° C; the mixed acidic aqueous solution and the cellulose material are placed in the reactor, and the cellulose concentration after mixing is 33%.
  • Set the water density to 992kg/m 3 , rapidly heat to 339 ° C, heating rate of 11.6 ° C / s, to 335 ° C (565 MPa), 0.85 seconds to completely dissolve cellulose. Heating was continued to 355 ° C and the cellulose was hydrolyzed to polysaccharides and glucose.
  • Example 7 was repeated with the following differences: The acidic aqueous solution was heated to 313 ° C; the cellulose concentration after mixing was 23.4%, the water density was set to 754 kg/ra 3 , the temperature was rapidly heated to 313 ° C, and the heating rate was 11.7 °. C/s, to 308 ° C (42 MPa), 1.95 seconds to completely dissolve cellulose. Heating was continued to 355 ° C and the cellulose was hydrolyzed to a polysaccharide.
  • Example 9 (1 ( ⁇ 5 HC1)
  • Example 7 was repeated with the following differences: The acidic aqueous solution was heated to 337 ° C; the cellulose concentration after mixing was 13.4%, the water density was set to 726 kg/m 3 , the temperature was rapidly heated to 337 ° C, and the heating rate was 10.2 °. C/s, to 326 ° C (43 MPa), 1.11 seconds to completely dissolve cellulose. Heating was continued to 355 ° C and the cellulose was hydrolyzed to polysaccharides and glucose.
  • the cellulose is placed in an acidic 1 ( ⁇ 4 ⁇ 0 3 aqueous solution to form a cellulose material; the acidic 1 ( ⁇ 4 HN 0 3 aqueous solution is heated to 337 ° C; the mixed acidic aqueous solution and the cellulose material are placed in the reactor, after mixing
  • the cellulose concentration is 34%
  • the water density is set to 995kg/ m 3
  • the heating is fast to 337 ° C
  • the heating rate is 12.6 ° C / s, to 332 ° C (570 MPa)
  • 1.44 seconds to completely dissolve the cellulose Heating was continued to 355 ° C and the cellulose was hydrolyzed to polysaccharides and glucose.
  • Example 10 was repeated with the following differences: The acidic aqueous solution was heated to 324 ° C; the cellulose concentration after mixing was 27%, the water density was set to 890 kg An 3 , the temperature was rapidly heated to 324 ° C, and the heating rate was 12.6 ° C / s, to 324 ° C (251 MPa), 1.65 seconds to completely dissolve cellulose. Heating was continued to 355 ° C and the cellulose was hydrolyzed to polysaccharides and glucose.
  • Example 10 was repeated with the following differences: The acidic aqueous solution was heated to 346 ° C; the cellulose concentration after mixing was 27.3%, the water density was set to 774 kg/m 3 , and the temperature was rapidly heated to 346. C, heating rate is 12.7 ° C / s, to 346 ° C (106 MPa), 1.55 seconds can completely dissolve cellulose. Heating was continued to 355 ° C and the cellulose was hydrolyzed to polysaccharides and glucose.
  • the cellulose is placed in an acidic 10 - 3 H 2 SO 4 aqueous solution to form a cellulosic material; the acidic 1 (aqueous solution of ⁇ 3 H 2 SO 4 is heated to 337 ° C; the mixed acidic aqueous solution and the cellulose material are placed in the reactor After mixing, the cellulose concentration is 19.6%, the water density is set to 990 kg/m 3 , and the heating is fast to 337 ° C, and the heating rate is ll. 7 ° C / s, to 3 34 ° C (556 MPa) , 1.54 seconds Completely dissolve the cellulose. Heating to 355 ° C, the cellulose is hydrolyzed to polysaccharides and glucose.
  • Example 13 was repeated with the following differences: The acidic aqueous solution was heated to 322 ° C; the cellulose concentration after mixing was 12%, the water density was set to 818 kg/ra 3 , the heating was rapidly carried out to 322 ° C, and the heating rate was 10.9 °. C/s, up to 3irC (109 MPa), completely dissolves cellulose in 1.22 seconds. Heating was continued to 355 ° C and the cellulose was hydrolyzed to polysaccharides and glucose.
  • Example 13 was repeated with the following differences: The acidic aqueous solution was heated to 335 ° C; the cellulose concentration after mixing was 35%, the water density was set to 636 kg/m 3 , the rapid heating was 335 ° C, and the heating rate was 9.7 °. C/s, to 335 ° C (16 MPa), 1.67 seconds to completely dissolve cellulose. Heating was continued to 355 V and the cellulose was hydrolyzed to polysaccharides and glucose.
  • the cellulose is placed in an acidic 1 (T 2 HC1 aqueous solution to form a cellulose material; the acidic 10 2 HCl aqueous solution is heated to 334 ° C; the mixed acidic aqueous solution and the cellulose material are placed in the reactor, and the cellulose concentration after mixing 0.5%, set the water density to 993kg/m 3 , rapid heating to 334 ° C, heating rate of 13.4 ° C / s, to 329 ° C (556 MPa), 1.25 seconds to completely dissolve cellulose.
  • cellulose is hydrolyzed to polysaccharides and glucose.
  • Example 16 was repeated with the following differences: The acidic aqueous solution was heated to 314 ° C; the cellulose concentration after mixing was 10.5%, the water density was set to 810 kg/m 3 , the rapid heating was 314 ° C, and the heating rate was 12.5 °. C/s, to 310 ° C (98 MPa), completely dissolve cellulose in 1.2 seconds. Heating was continued to 355 ° C and the cellulose was hydrolyzed to polysaccharides and glucose.
  • Example 16 was repeated with the following differences: The acidic aqueous solution was heated to 333 ° C; the cellulose concentration after mixing was 23%, the water density was set to 670 k g / m 3 , and the heating was rapidly heated to 333 ° C, and the heating rate was 11.8. °C/s, to 321 ° C (13 MPa), completely dissolve cellulose in 1.6 seconds. Continue heating to 355 °C, cellulose is hydrolyzed to polysaccharides and glucose.
  • the cellulose is placed in an acidic 0. aqueous solution to form a cellulosic material;
  • the HC1 aqueous solution is heated to 309 ° C; the mixed acidic aqueous solution and the cellulose material are placed in the reactor, the cellulose concentration after mixing is 1.5%, the water density is set to 995 kg/m 3 , and the heating is rapidly heated to 309 ° C, and the heating rate is 9.7 ° C / s, to 300 ° C (499 MPa), 1.15 seconds to completely dissolve cellulose. Heating was continued to 355 ° C and the cellulose was hydrolyzed to polysaccharides and glucose.
  • Example 19 was repeated with the following differences: The acidic aqueous solution was heated to 284; the cellulose concentration after mixing was 31%, the water density was set to 782 kg/m 3 , the temperature was rapidly heated to 284 ° C, and the heating rate was 9.9 ° C / s, to 277 ° C (25 MPa), completely dissolve cellulose in 0.9 seconds. Continue heating to 355 °C. Cellulose is hydrolyzed to polysaccharides and glucose.
  • Example 19 was repeated with the following differences: The acidic aqueous solution was heated to 348 ° C; the cellulose concentration after mixing was 7%, the water density was set to 611 kg/m 3 , the rapid heating was carried out to 348 ° C, and the heating rate was 10.7 °. C/s, to 286 ° C (7 MPa), completely dissolve cellulose in 1.3 seconds. Heating was continued to 355 ° C and the cellulose was hydrolyzed to polysaccharides and glucose.
  • the cellulose is placed in an acidic 1 HCl aqueous solution to form a cellulosic material; the acidic 1 HCl aqueous solution is heated to 283 ° C; the mixed acidic aqueous solution and the cellulose material are placed in the reactor, and the cellulose concentration after mixing is 5.5%.
  • the fixed water density is 991kg/ m 3 , rapid heating to 283 ° C, heating rate of 9.5 ° C / s, to 272 ° C (424 MPa), 1.2 seconds to completely dissolve cellulose. Heating was continued to 355 ° C and the cellulose was hydrolyzed to polysaccharides and glucose within 5 s.
  • Example 22 was repeated with the following differences: The acidic aqueous solution was heated to 276 ° C; the cellulose concentration after mixing was 31.5%, the water density was set to 942 kg/m 3 , and the rapid heating was carried out to 276 ° C, the heating rate. From 11.7 ° C / s to 261 ° C (256 MPa), 1.34 seconds can completely dissolve cellulose. Heating was continued to 355 ° C and the cellulose was hydrolyzed to polysaccharides and glucose.
  • Example 22 was repeated with the following differences: The acidic aqueous solution was heated to 277 ° C; the cellulose concentration after mixing was 31.5%, the water density was set to 751 kg/m 3 , the temperature was rapidly heated to 277 ° C, and the heating rate was 10.1 °. C/s, to 273 ° C (6 MPa), completely dissolve cellulose in 1.3 seconds. Heating was continued to 355 ° C and the cellulose was hydrolyzed to polysaccharides and glucose.
  • Cellulose was 10- 6 NaOH aqueous alkaline form a cellulose material; 10- 6 NaOH aqueous alkaline solution was heated to 329 ° C; mixed alkaline aqueous solution and the cellulose material is placed in a reactor, mixed fibers
  • concentration of the pigment is 32.5%
  • the water density is set to 665 kg/m 3
  • the temperature is rapidly heated to 329 ° C
  • the heating rate is 9.5 ° C / s, to 329 ° C (18 MPa)
  • Heating was continued to 355 ° C and the cellulose was hydrolyzed to polysaccharides and glucose.
  • Example 25 was repeated with the following differences: The alkaline aqueous solution was heated to 326 ° C; the cellulose concentration after mixing was 28.5%, the water density was set to 802 kg/m 3 , the temperature was rapidly heated to 326 ° C, and the heating rate was 9.7. . C/s, to 318 ° C (100 MPa), completely dissolve cellulose in 2 seconds. Continue heating to 355 °C. Cellulose is hydrolyzed to polysaccharides and glucose.
  • Example 25 was repeated with the following differences: The alkaline aqueous solution was heated to 330 ° C; the cellulose concentration after mixing was 21.5%, the water density was set to 997 kg/m 3 , the rapid heating was carried out to 330 ° C, and the heating rate was 9.2. °C/s, to 327 ° C (566 MPa), 1.85 seconds to completely dissolve cellulose. Heating was continued to 355 ° C and the cellulose was hydrolyzed to polysaccharides and glucose.
  • Cellulose was 10- 5 KOH alkaline aqueous solution to form a cellulose material; 10- 5 K0H alkaline aqueous solution was heated to 343 ° C; mixed alkaline aqueous solution and the cellulose material in a reactor, mixed After the combination, the cellulose concentration is 7%, the water density is set to 621kg/m 3 , the heating is fast to 343 ° C, the heating rate is irC/s, to 319 ° C (11 MPa), and the cellulose can be completely dissolved in 1.1 seconds. . Heating was continued to 355 ° C and the cellulose was hydrolyzed to polysaccharides and glucose.
  • Example 28 was repeated with the following differences: The alkaline aqueous solution was heated to 320 ° C; the cellulose concentration after mixing was 23%, the water density was set to 808 kg/m 3 , and the heating was fast to 32 (TC, heating rate was 11.8). 'C/s, to 318 ° C (107 MPa), complete dissolution of cellulose in 1.8 seconds. Continue heating to 355 ° C, cellulose hydrolysis to polysaccharides and glucose.
  • Example 28 was repeated with the following differences: The alkaline aqueous solution was heated to 339 ° C; the cellulose concentration after mixing was 10%, the water density was set to 971 kg/m 3 , and the heating was rapidly carried out to 339 ° C, and the heating rate was 12.4. °C/s, to 327 ° C (475 MPa), complete dissolution of cellulose in 1 second. Continue heating to 355 °C. Cellulose is hydrolyzed to polysaccharides and glucose.
  • the cellulose is placed in an alkaline l (T 4 Ca(0H) 2 aqueous solution to form a cellulosic material; the alkaline l(T 4 ) Ca(OH) 2 aqueous solution is heated to 352 ° C; mixed alkaline aqueous solution and fiber
  • the material is placed in the reactor, the cellulose concentration after mixing is 32%, the water density is set to 587kg/m 3 , the heating is fast to 352 °C, and the heating rate is 8.8'C/s to 343 °C (40 MPa). ), the cellulose is completely dissolved in 1.6 seconds. Heating is continued to 355 ° C, and the cellulose is hydrolyzed into polysaccharides and glucose.
  • Example 31 was repeated with the following differences: The alkaline aqueous solution was heated to 321 ° C; the cellulose concentration after mixing was 13%, the water density was set to 886 kg/m 3 , the heating was rapidly carried out to 32 rC, and the heating rate was 7.8 ° C. /s, to 315 ° C (227 MPa), completely dissolve cellulose in 1.4 seconds. Heating was continued to 355 °C and the cellulose was hydrolyzed to polysaccharides and glucose.
  • Example 31 was repeated with the following differences: The alkaline aqueous solution was heated to 332 ° C; The concentration of vitamins is 26%, the water density is 997kg/m 3 , the heating is fast to 332 ° C, the heating rate is 8.4 ° C / s, to 325 ° C (562 MPa)), 1.66 seconds can completely dissolve the fiber Prime. Heating was continued to 355 ° C and the cellulose was hydrolyzed to polysaccharides and glucose.
  • the cellulose is placed in an alkaline aqueous solution of 10 - 3 NaOH to form a cellulosic material; the aqueous alkaline NaOH solution is heated to 35 ITC; the mixed alkaline aqueous solution and the cellulosic material are placed in the reactor, and the cellulose concentration after mixing is 12%.
  • Set the water density to 708kg/m 3 , rapidly heat to 350 ° C, and heat the rate from 13. rC / s to 337 ° C (45 MPa), completely dissolve cellulose in 1.7 seconds. Heating was continued to 355 ° C and the cellulose was hydrolyzed to polysaccharides and glucose.
  • Example 34 was repeated with the following differences: The alkaline aqueous solution was heated to 321 ° C; the cellulose concentration after mixing was 29%, the water density was set to 848 kg/m 3 , the temperature was rapidly heated to 321 ° C, and the heating rate was 13.4. °C/s, to 311 ° C (152 MPa), 1.88 seconds to completely dissolve cellulose. Heating was continued to 355 ° C and the cellulose was hydrolyzed to polysaccharides and glucose.
  • Example 34 was repeated with the following differences: The alkaline aqueous solution was heated to 337 ° C; the cellulose concentration after mixing was 0.1%, the water density was set to 996 kg/m 3 , and the heating was rapidly heated to 337 ° C, and the heating rate was 13.7. °C / s, to 331 ° C (571 MPa), 1.3 seconds to completely dissolve cellulose. Heating was continued to 355 °C and the cellulose was hydrolyzed to polysaccharides and glucose.
  • Cellulose was 10- 2 NaOH aqueous alkaline form a cellulose material; 10_ 2 NaOH aqueous alkaline solution was heated to 352 ° C; mixed alkaline aqueous solution and the cellulose material is placed in a reactor, mixed cellulose The concentration is 1%, the water density is set to 636kg/m 3 , the heating is fast to 352 ° C, the heating rate is 10.8 ° C / s, to 352 ° C (29 MPa), and the cellulose can be completely dissolved in 1.21 seconds. Heating was continued to 355 ° C and the cellulose was hydrolyzed to polysaccharides and glucose.
  • Example 38 (10" 2 NaOH) Example 37 was repeated with the following differences: The alkaline aqueous solution was heated to 331 ° C; the cellulose concentration after mixing was 8%, the water density was set to 9 54 kg/m 3 , and the heating was rapidly carried out to 33 r C, and the heating rate was 9.1 °. C/s, to 320 ° C (407 MPa), completely dissolve cellulose in 1.4 seconds. Heating was continued to 355 ° C and the cellulose was hydrolyzed to polysaccharides and glucose.
  • Example 37 was repeated with the following differences: The alkaline aqueous solution was heated to 335 ° C; the cellulose concentration after mixing was 32%, the water density was set to 993 kg/m 3 , the temperature was rapidly heated to 335 ° C, and the heating rate was 9.8. °C/s, to 330 ° C (558 MPa), completely dissolve cellulose in 1.9 seconds. Heating was continued to 355 °C and the cellulose was hydrolyzed to polysaccharides and glucose. ,
  • the cellulose is placed in an alkaline 0.1 NaOH aqueous solution to form a cellulosic material; the alkaline 0.1 NaOH aqueous solution is heated to 346 ° C; the mixed alkaline aqueous solution and the cellulose material are placed in the reactor, and the cellulose concentration after mixing is 32%, set the water density to 655kg/m 3 , rapid heating to 346 ° C, heating rate of 11.8 ° C / s, to 339 ° C (24 MPa), 1.41 seconds to completely dissolve cellulose. Heating was continued to 355 ° C and the cellulose was hydrolyzed to polysaccharides and glucose.
  • Example 40 was repeated with the following differences: The alkaline aqueous solution was heated to 352 ° C; the cellulose concentration after mixing was 23.9%, the water density was set to 980 k g /m 3 , and the heating was rapidly heated to 352 ° C. The heating rate was 13.8 ° C / s, to 344 ° C (541 MPa), 1.23 seconds to completely dissolve cellulose. Heating was continued to 355 ° C and the cellulose was hydrolyzed to polysaccharides and glucose within 5 s.
  • Example 40 was repeated with the following differences: The alkaline aqueous solution was heated to 350 ° C; the cellulose concentration after mixing was 31.5%, the water density was set to 997 kg/m 3 , the temperature was rapidly heated to 350 ° C, and the heating rate was 12.7. °C/s, to 335 ° C (584 MPa), 1.55 seconds to completely dissolve cellulose. Continue to heat to 355. C, within 5 s, the cellulose is hydrolyzed into polysaccharides and glucose.
  • Example 43 (l NaOH) The cellulose is placed in an alkaline l NaOH aqueous solution to form a cellulosic material; the alkaline l NaOH aqueous solution is heated to 335 ° C; the mixed alkaline aqueous solution and the cellulose material are placed in the reactor, and the cellulose concentration after mixing is 29%, set the water density to 726kg/m 3 , rapid heating to 335 ° C, heating rate of 9.8 ° C / s, to 325 ° C (42 MPa), 1.76 seconds to completely dissolve cellulose. Heating was continued to 355 ° C and the cellulose was hydrolyzed to polysaccharides and glucose.
  • Example 43 was repeated with the following differences: The alkaline aqueous solution was heated to 279 ° C; the cellulose concentration after mixing was 26.5%, the water density was set to 818 k g / m 3 , and the heating was rapidly heated to 279 ° C. The heating rate was 10.7 ° C / s, to 274 ° C (56 MPa), 1.33 seconds to completely dissolve cellulose. Heating was continued to 355 ° C and the cellulose was hydrolyzed to polysaccharides and glucose.
  • Example 43 was repeated with the following differences: The alkaline aqueous solution was heated to 330 ° C; the cellulose concentration after mixing was 29.5%, the water density was set to 996 kg/m 3 , and the heating was rapidly carried out to 330 ° C, and the heating rate was 10.2. °C / s, to 321 ° C (549 MPa), 1.53 seconds to completely dissolve cellulose. Heating was continued to 355 ° C and the cellulose was hydrolyzed to polysaccharides and glucose within 5 s.
  • an acid (or alkali) aqueous solution container 1 is connected to a injection port of a tubular reactor 6 through a high pressure pump 2, a high pressure pump and a tubular reactor
  • a preheater 3 is disposed between the injection ports, and the cellulose material container 4 is connected to the acid (or alkali) water delivery pipe at the injection port of the tubular reactor 6 through a high pressure mud pump 5, and the tubular reactor 6 is externally
  • An electric heating furnace 7 is provided, and the product container 10 is connected to the discharge port of the tubular reactor 6 through a pressure regulating valve 9 and a cooler 8.
  • the working principle of the continuous production equipment preheats the solution in the acid (or alkali) aqueous solution container 1 to 261 ⁇ 352 (6 ⁇ 5841 ⁇ &), and presses the high pressure pump 2 into the tubular reactor 6
  • the cellulose and the acid (or alkali) aqueous solution are mixed in the cellulose material container 4, they are pumped by the high pressure mud pump 5 to the tubular reactor injection port and mixed with the preheated acid (or alkali) solution, and Immediate access to the tubular reactor In 6 quickly heated to 355 ⁇ , the cellulose is completely dissolved in the reactor and subjected to homogeneous hydrolysis.
  • the fully hydrolyzed cellulose is output from the reactor discharge port to the product container 10, and the cooling rate is controlled by the cooler 8, which is controlled by the pressure regulating valve 9.
  • reaction time such as reaction time, pressure and temperature
  • reaction time such as reaction time, pressure and temperature
  • the solvated cellulose is further heated to less than 355 ° C and maintained within 0 ⁇ 2 s, and the structure of the cellulose under homogeneous conditions is broken.
  • the polysaccharide can be fermented to produce alcohol or other biological products by biotransformation (e.g., fermentation to produce antibiotics, lysine, lactic acid, sodium glutamate, etc.).
  • the solvated cellulose was heated to 355 ° C and held within 5 s, and the cellulose was homogeneously hydrolyzed to glucose and its polysaccharide.
  • Sugar can be used to produce alcohol. Sugars can also be biotransformed to produce biological products.
  • the tubular reactor is filled with a catalyst in the latter stage.
  • a catalyst in the latter stage.
  • the cellulose is then passed to the latter stage for homogeneous catalytic reaction. Since the solvated cellulose is more susceptible to contact with the activation point of the catalyst, it is more reactive.
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Description

一种完全溶解和快速水解纤维素的方法及其应用 技术领域
本发明属于生物质溶解和水解技术领域， 具体涉及一种完全溶解和快速 水解纤维素的方法。 同时， 本发明还涉及该溶解和水解方法的进一步应用。 背景技术
自然界中的木质纤维素生物质如木材和草类， 大约是由 50%的纤维素， 25%的半纤维素和 20%的木质素组成。 纤维素经水解能够降解为糖类，进而用 于发酵生产纤维素酒精。 由于木质纤维素生物质不溶于水， 现有的工业化生 物质水解方法主要是以半连续式渗透反应器、在 180 ~ 19(TC和 12 - 14 大气 压下的 0. 4 ~ 0. 8%稀硫酸水溶液中水解（参见 南京林学院植物水解工艺学教 研组， 植物水解工艺学， 农业出版社， 1961 )。 未见使用高压连续反应器进 行连续生产的报道。
最新研究表明， 高压热水是一种弱极性溶剂， 既呈酸性也呈碱性， 因而 它能溶解生物质， 并使水解反应在均相中进行。 Sasaki等人发现， 纤维素在 320°C和水密度大于 1000 kg/m3的条件下，能够完全溶于水（参见 Sasaki, M.； Fang, Z.； Fukushima, Y.； Adschi r i , T. & Ara i, K. "在亚临界和超临 界水中溶解和水解纤维素" 工业工程化学研究， 39 , 2883-2890, 2000 )。 之后 Ogihara等人进一步发现： 在水密度 550至 l OOOkg/m3范围内， 完全溶 解纤维素的温度有一极小值 320°C，发生于水密度 850kg/m3。 (参见 Ogihara, Y.； Smi th Jr. , R. L.； Inoraata, H. & Kunio A. "在亚临界和超临界水 中， 水密度 550至 1000 kg/m3范围内， 直接观察纤维素的溶解" 纤维素， 12 , 595 606 , 2005 )。 上述发现均针对纯水， 纤维素在纯水中的溶解温度 较高， 水解速率较慢。 在此基础上， 本发明人经研究发现， 在纯水中加入微 量的碱性盐后可使木质纤维素生物质如木粉在 329 °C ~ 36rC中完全溶解并 进行均相水解， 并据此申报了中国专利 （专利号： 20071014Π65.3)。
受当时条件的限制， 该专利申请中尚未涉及酸性溶液对纤维素溶解的影 响。 同时， 如何在较低的反应温度下、 利用高压连续反应器实现纤维素的完 全溶解和快速水解， 也是需要进一步解决的技术问题。 发明内容
本发明的目的在于针对现有技术的不足，提供一种在较低温度下完全溶 解和快速水解纤维素的方法， 以降低生产成本。
本发明的目的还在于提供上述溶解和快速水解方法在工业生产中的进 一步应用。
本发明的目的通过以下技术方案予以实现。
除非另有说明， 本发明所釆用的百分数均为体积百分数。
本发明人在深入研究后发现， 在溶解和快速水解纤维素之前， 先将其置 于酸性或碱性溶液中， 然后再将得到的混合物与高温稀酸或稀碱溶液混合， 并以一定的加热速率加热至一定的温度， 则可以实现纤维素的完全溶解和快 速水解。 在此基础上， 发明人提出如下技术方案：
一种完全溶解和快速水解纤维素的方法， 包括以下步骤：
1、 将纤维素置于浓度为 10— 7~ 1 [Η+]酸性或 10-7~1 [OH—]碱性水溶液 中， 固液体积比为（0.003 1.05): 1;
2、将 10—7~ 1 [H+]酸性或 1(Γ7~ 1 [0H— ]碱性水溶液加热至 261 ~ 352°C;
3、 混合步骤 1和 2所得物置于反应器中， 纤维素浓度为 0.1%~ 35%， 调 节混合后的物料溶液浓度为 10—7~ 1 [H+]酸性或 10-7~ 1 [0ΗΊ碱性， 水密 度为 587 ~ 997 kg/ra3, 设定压力为 6 ~ 584 MPa, 加热速率为 7.8 ~ 14.8°C/s, 快速加热至 261 ~ 352°C, 0.8-2秒即能完全溶解纤维素。
所述的酸性水溶液为盐酸 (HC1 ), 硝酸 ( HN03 )或硫酸 ( H2S04 ) 的水溶 液。 所述的碱性水溶液为氢氧化钠 （NaOH ), 氢氧化钾 （K0H ) 或氢氧化钙 ( Ca (OH) 2 ) 的水溶液。
所述的酸性水溶液优选 HC 1水溶液。
所述的碱性水溶液优选 NaOH水溶液。
上述完全溶解和快速水解纤维素的方法在酒精生产中的应用。 即： 待纤 维素完全溶解后， 继续加热至 355 °C , 然后自然冷却至室温， 纤维素全部分 解为糖类物质（葡萄糖和低聚糖）， 该糖类物质可用于发酵生产酒精。
相对于现有技术， 本发明具有如下优点：
1、 首次实现了纤维素在较低的温度下完全溶解和快速水解， 不仅大大 降低生产成本， 也提高了生产的安全性， 延长了设备的使用寿命。
2、 后续的水解反应能够在均相的条件下进行， 促进了水解反应， 抑制 了热分解反应。 整个溶解的时间小于 0. 8 ~ 2秒， 水解反应的时间小于 5秒。
3、 溶剂化的纤维素可以很方便地应用于低温的高压流动式的反应器， 进一步降低了生产成本， 连续水解生产糖类及别的生物燃料和产品。
4、 加入低成本的稀酸和稀碱均可大大降低完全溶解温度和加快水解。
5、 水解生成的糖类物质比用木质纤维素生物质如木粉生产的更纯、 浓 度更高， 只有葡萄糖和葡萄糖的低聚糖， 不含五碳糖及其低聚糖等。 附图说明
图 1本发明实验用微型可视钻石反应器结构示意图；
图 2纤维素溶解于纯水过程的普通光学显微镜照片（加热速率 =12. l°C/s, 水密度 -887 kg/m3)；
图 3添加酸性溶液时纤维素完全溶解于浓度为 10—2 HC1溶液过程的普 通光学显微镜照片片（加热速率 -11. 3 C/s，水密度 =958 kg/m3)；
图 4添加碱性溶液时纤维素完全溶解于浓度为 1 (T2 NaOH溶液过程的 普通光学显微镜照片（加热速率 =1 3. 4°C/s,水密度 =848 kg/m3)； 图 5实验产物的红外光谱吸收曲线图；
图 6本发明设备的连接示意图。 具体实施方式
下面结合附图和实施例对本发明作进一步地详细说明，但它们并不是对 本发明的限定。
实验例
为了更好地理解本发明的实质， 下面将用纤维素粉末的完全溶解实验来 说明本发明的技术效果及其在工业生产中的应用前景。
如图 1所示，实验装置为一微型可视钻石反应器（Diamond Anv i l Cel l )， 该反应器可将反应室中的水快速加热到高温， 并可观察纤维素在水中溶解的 过程。在一块厚度为 250 μ ηι的铁片上开设一直径为 500 μ m的小孔形成反应 室 4， 其容积为 50nL。 当水和纤维素装入反应室 4后， 由上下两块钻石 3挤 压小孔， 密封该孔并产生压力。 如松开二个钻石， 可让氮气进入小孔并产生 气泡。 通过调节气泡的大小， 就可得到水的不同密度（=水的质量 /反应器的 容积， kg/tn3 )。 反应室中的水被电加热器 2迅速地加热， 同时在 110倍大的 普通光学显微镜 1下观察并录像。 反应后， 残留在钻石表面的生成物用红外 显微镜分析其化学结构。 由于反应室容积是不变的， 在已知水密度和反应器 温度（由热电偶测出）条件下， 压力可以用状态方程算出。
称量纤维素粉末 5mL，配置 10-7 ~ 1M [Hi或 [0H_]各种水溶液各 5mL备用。 实验 1 (比较例 1 )
将纤维素粉末和纯水置于反应器中， 纤维素浓度为 30%, 设定加热速率 为 12, l °C /s; 水密度为 887kg/m3;
如图 2所示：
a: 加热前， 纤维素悬浮于水和气泡中；
b: 加热 24. 36s， 温度达到 32 (TC， 纤维素变透明并开始溶解 （气泡于 18(TC消失）；
c: 加热 24.9s, 温度达到 326Γ时， 更多的纤维素溶解；
d: 加热 25.16s, 温度达到 329°C时， 大多数的纤维素溶解；
e: 加热 25.45s, 随着温度进一步升至 333°C (260 MPa) , 纤维素完全溶 解， 溶解时间 1.09s。
反应后， 打开反应器， 可见糖状的物质留在钻石表面。 红外分析显示该 物质已水解并具有葡萄糖的特征（图 5， 曲线 5 vs. 曲线 1和 2)。
实验结论： 快速加热能使纤维素完全溶解于纯水。
实验 2
将纤维素粉末和酸性 HC1溶液置于反应器中， 混合后物料溶液的 HC1浓 度为 10—2 ， 纤维素浓度为 25%, 设定加热速率为 11.3'C/s; 水密度为 958kg/m3。
如图 3所示：
a: 加热前， 纤维素悬浮于酸性溶液和气泡中；
b:加热 23.92s，温度达到 312°C,纤维素仍无变化（气泡于 101'C消失）； c: 加热 24.98s， 温度达到 321°C， 纤维素变透明并开始溶解
d: 加热 25.52s， 温度达到 324°C时， 更多的纤维素溶解；
e: 加热 26. ls， 随着温度进一步升至 327°C (433 MPa) , 纤维素完全溶 解， 溶解时间 1. 12s。 继续加热至 355°C。
反应后， 打开反应器， 可见糖状的物质留在钻石表面。 红外分析显示该 物质已水解并具有葡萄糖的特征（图 5, 曲线 3 vs. 曲线 1和 2)。
实验结论： 快速加热至 355°C, 能使纤维素在较低的温度下， 完全溶解 和水解于 HC1浓度为 10_2 酸性溶液。
实验 3
将纤维素粉末和碱性 NaOH溶液置于反应器中， 混合后物料溶液的 NaOH 浓度为 10—2 M, 木粉浓度为 32%, 设定加热速率为 13.4'C/s; 水密度为 848kg/m3。
如图 4所示：
a: 加热前， 纤维素悬浮于碱性溶液和气泡中；
b: 加热 20.06s， 温度达到 293°C, 溶液变黄（气泡于 214°C消失）； c: 加热 20.46s, 温度达到 299°C， 纤维素变透明并开始溶解
d: 加热 20.66s, 温度达到 302°C时， 更多的纤维素溶解；
e: 加热 21.34s， 随着温度进一步升至 3irC(152 MPa) , 纤维素完全溶 解， 溶解时间 0.88s。 继续加热至 355°C。
反应后， 打开反应器， 可见糖状的物质留在钻石表面。 红外分析显示该 物质已水解并具有葡萄糖的特征（图 5, 曲线 4 vs. 曲线 1和 2)。
实验结论： 快速加热至 355°C， 能使纤维素在较低的温度下， 完全溶解 和水解于 NaOH浓度为 10—2 碱性水溶液。
实施例 1 (纯水）
将纤维素置于纯水中， 形成纤维素物料； 将纯水加热至 349°C; 混合纯 水和纤维素物料置于反应器中， 混合后纤维素浓度为 20%， 设定水密度为 594kg/m3, 快速加热至 349°C， 加热速率为 10.4'C/s, 至 326°C (12 MPa) , 1.05秒即可完全溶解纤维素。 纤维素水解为多聚糖和葡萄糖。
实施例 2 (纯水）
重复实施例 1， 有以下不同点： 将纯水加热至 319'C; 混合后纤维素浓 度为 35%, 设定水密度为 806kg/ra3， 快速加热至 319°C, 加热速率为 11.1°C /s, 至 317°C (103 MPa) , 2秒即可完全溶解纤维素。 纤维素水解为多聚糖。
实施例 3 (纯水）
重复实施例 1， 有以下不同点： 将纯水加热至 326°C; 混合后纤维素浓 度为 26%，设定水密度为 995kg/m 3，快速加热至 326°C,加热速率为 9.6°C/s, 至 318°C (539 MPa) , 1.7秒即可完全溶解纤维素。 纤维素水解为多聚糖。
实施例 4(10- 6 HC1) 将纤维素置于酸性 10_6 HC1水溶液中， 形成纤维素物料； 将酸性 10_6 HC1水溶液加热至 338°C; 混合酸性水溶液和纤维素物料置于反应器中， 混 合后纤维素浓度为 28%, 设定水密度为 995kg/m3， 快速加热至 338°C， 加热 速率为 12°C/s, 至 337°C (581MPa), 0.9秒即可完全溶解纤维素。 继续加热 至 355°C, 纤维素水解为多聚糖和葡萄糖。
实施例 5(10"6 HC1)
重复实施例 4， 有以下不同点： 将酸性水溶液加热至 331°C; 混合后纤 维素浓度为 7.5%, 设定水密度为 814kg/m3， 快速加热至 331 , 加热速率为 12.5°C/s, 至 327°C (127 MPa)， 1.1秒即可完全溶解纤维素。继续加热至 355 °C, 纤维素水解为多聚糖和葡萄糖。
实施例 6(10 HC1)
重复实施例 4， 有以下不同点： 将酸性水溶液加热至 336°C; 混合后纤 维素浓度为 18%, 设定水密度为 682kg/m3, 快速加热至 336°C, 加热速率为 irC/s, 至 333°C (28 MPa) , 1.1 秒即可完全溶解纤维素。 继续加热至 355 °C 纤维素水解为多聚糖和葡萄糖。
实施例 7(10- 5 HC1)
将纤维素置于酸性 lO— HCl水溶液中， 形成纤维素物料； 将酸性 lO— HC1 水溶液加热至 339°C; 混合酸性水溶液和纤维素物料置于反应器中， 混 合后纤维素浓度为 33%， 设定水密度为 992kg/m3, 快速加热至 339°C, 加热 速率为 11.6°C/s， 至 335°C (565 MPa) , 0.85秒即可完全溶解纤维素。 继续 加热至 355°C， 纤维素水解为多聚糖和葡萄糖。
实施例 8(1(Γ5 HC1)
重复实施例 7, 有以下不同点： 将酸性水溶液加热至 313'C; 混合后纤 维素浓度为 23.4%, 设定水密度为 754kg/ra3, 快速加热至 313°C, 加热速率 为 11.7°C/s, 至 308°C (42MPa) , 1.95秒即可完全溶解纤维素。 继续加热至 355'C, 纤维素水解为多聚糖。 实施例 9(1(Γ5 HC1)
重复实施例 7， 有以下不同点： 将酸性水溶液加热至 337°C; 混合后纤 维素浓度为 13.4%, 设定水密度为 726kg/m3, 快速加热至 337°C, 加热速率 为 10.2°C/s, 至 326°C (43MPa)， 1.11秒即可完全溶解纤维素。 继续加热至 355°C, 纤维素水解为多聚糖和葡萄糖。
实施例 10(1(Τ ΗΝ03)
将纤维素置于酸性 1(Γ4 ΗΝ03水溶液中， 形成纤维素物料； 将酸性 1(Γ4 HN03水溶液加热至 337°C; 混合酸性水溶液和纤维素物料置于反应器中， 混 合后纤维素浓度为 34%, 设定水密度为 995kg/m 3, 快速加热至 337°C, 加热 速率为 12.6°C/s, 至 332°C (570 MPa), 1.44秒即可完全溶解纤维素。 继续 加热至 355°C， 纤维素水解为多聚糖和葡萄糖。
实施例 11(10 画 3)
重复实施例 10， 有以下不同点： 将酸性水溶液加热至 324°C; 混合后纤 维素浓度为 27%， 设定水密度为 890kgAn3， 快速加热至 324°C, 加热速率为 12.6°C/s, 至 324°C (251 MPa) , 1.65秒即可完全溶解纤维素。 继续加热至 355°C, 纤维素水解为多聚糖和葡萄糖。
实施例 12(10"4 画3)
重复实施例 10, 有以下不同点： 将酸性水溶液加热至 346°C; 混合后纤 维素浓度为 27.3%, 设定水密度为 774kg/m3, 快速加热至 346。C, 加热速率 为 12.7°C/s, 至 346°C (106 MPa), 1.55秒即可完全溶解纤维素。 继续加热 至 355°C, 纤维素水解为多聚糖和葡萄糖。
实施例 13(10_3 H2S04)
将纤维素置于酸性 10—3 H2SO4水溶液中， 形成纤维素物料； 将酸性 1(Γ3 H2S04水溶液加热至 337°C; 混合酸性水溶液和纤维素物料置于反应器中， 混 合后纤维素浓度为 19.6%, 设定水密度为 990kg/m3， 快速加热至 337°C, 加 热速率为 ll.7°C/s, 至 334°C (556 MPa) , 1.54秒即可完全溶解纤维素。 继 续加热至 355°C, 纤维素水解为多聚糖和葡萄糖。
实施例 14(10 H2S04)
重复实施例 13， 有以下不同点： 将酸性水溶液加热至 322°C; 混合后纤 维素浓度为 12%， 设定水密度为 818kg/ra3， 快速加热至 322°C， 加热速率为 10.9°C/s, 至 3irC(109 MPa) , 1.22秒即可完全溶解纤维素。 继续加热至 355°C, 纤维素水解为多聚糖和葡萄糖。
实施例 15(10—3 H2S04)
重复实施例 13, 有以下不同点： 将酸性水溶液加热至 335°C; 混合后纤 维素浓度为 35%, 设定水密度为 636kg/m3, 快速加热至 335°C, 加热速率为 9.7°C/s, 至 335°C (16MPa), 1.67秒即可完全溶解纤维素。 继续加热至 355 V, 纤维素水解为多聚糖和葡萄糖。
实施例 16(10—2 HC1)
将纤维素置于酸性 1(T2 HC1水溶液中， 形成纤维素物料； 将酸性 10-2 HC1水溶液加热至 334°C; 混合酸性水溶液和纤维素物料置于反应器中， 混 合后纤维素浓度为 0.5%， 设定水密度为 993kg/m3, 快速加热至 334°C， 加热 速率为 13.4°C/s， 至 329°C (556 MPa) , 1.25秒即可完全溶解纤维素。 继续 加热至 355°C, 纤维素水解为多聚糖和葡萄糖。
实施例 17(10"2 HC1)
重复实施例 16, 有以下不同点： 将酸性水溶液加热至 314°C; 混合后纤 维素浓度为 10.5%, 设定水密度为 810kg/m3, 快速加热至 314°C, 加热速率 为 12.5°C/s, 至 310°C (98 MPa) , 1.2秒即可完全溶解纤维素。 继续加热至 355°C, 纤维素水解为多聚糖和葡萄糖。
实施例 18(10—2 HC1)
重复实施例 16， 有以下不同点： 将酸性水溶液加热至 333°C; 混合后纤 维素浓度为 23%， 设定水密度为 670kg/m3, 快速加热至 333'C, 加热速率为 11.8°C/s， 至 321°C (13MPa), 1.6秒即可完全溶解纤维素。 继续加热至 355 °C, 纤维素水解为多聚糖和葡萄糖。
实施例 19(0.1 HC1)
将纤维素置于酸性 0. 水溶液中， 形成纤维素物料； 将酸性 0.1
HC1水溶液加热至 309°C; 混合酸性水溶液和纤维素物料置于反应器中， 混 合后纤维素浓度为 1.5%， 设定水密度为 995kg/m3， 快速加热至 309°C, 加热 速率为 9.7°C/s, 至 300°C (499 MPa)， 1.15秒即可完全溶解纤维素。 继续加 热至 355°C, 纤维素水解为多聚糖和葡萄糖。
实施例 20(0. IMHCI)
重复实施例 19， 有以下不同点： 将酸性水溶液加热至 284 ； 混合后纤 维素浓度为 31%, 设定水密度为 782kg/m3, 快速加热至 284°C, 加热速率为 9.9°C/s, 至 277°C (25 MPa) , 0.9秒即可完全溶解纤维素。 继续加热至 355 °C 纤维素水解为多聚糖和葡萄糖。
实施例 21 (0.1M HC1)
重复实施例 19, 有以下不同点： 将酸性水溶液加热至 348°C; 混合后纤 维素浓度为 7%,设定水密度为 611kg/m3，快速加热至 348°C,加热速率为 10.7 °C/s, 至 286°C (7 MPa), 1.3秒即可完全溶解纤维素。 继续加热至 355°C， 纤维素水解为多聚糖和葡萄糖。
实施例 22(1 HC1)
将纤维素置于酸性 1 HC1水溶液中， 形成纤维素物料； 将酸性 1 HC1 水溶液加热至 283°C; 混合酸性水溶液和纤维素物料置于反应器中， 混合后 纤维素浓度为 5.5%, 设定水密度为 991kg/m 3, 快速加热至 283°C， 加热速率 为 9.5°C/s， 至 272°C (424 MPa) , 1.2秒即可完全溶解纤维素。 继续加热至 355°C, 5s之内纤维素水解为多聚糖和葡萄糖。
实施例 23(1 HC1)
重复实施例 22， 有以下不同点： 将酸性水溶液加热至 276'C; 混合后纤 维素浓度为 31.5%， 设定水密度为 942kg/m3, 快速加热至 276°C, 加热速率 为 11.7°C/s, 至 261°C (256 MPa) , 1.34秒即可完全溶解纤维素。 继续加热 至 355°C, 纤维素水解为多聚糖和葡萄糖。
实施例 24(1 HC1)
重复实施例 22, 有以下不同点： 将酸性水溶液加热至 277°C; 混合后纤 维素浓度为 31.5%， 设定水密度为 751kg/m3, 快速加热至 277°C, 加热速率 为 10.1°C/s， 至 273°C (6 MPa), 1.3秒即可完全溶解纤维素。 继续加热至 355°C, 纤维素水解为多聚糖和葡萄糖。
实施例 25(10"6 NaOH)
将纤维素置于碱性 10—6 NaOH水溶液中，形成纤维素物料；将碱性 10— 6 NaOH水溶液加热至 329°C; 混合碱性水溶液和纤维素物料置于反应器中， 混 合后纤维素浓度为 32.5%， 设定水密度为 665kg/m3， 快速加热至 329°C, 加 热速率为 9.5°C/s, 至 329°C (18 MPa) , 1.14秒即可完全溶解纤维素。 继续 加热至 355°C, 纤维素水解为多聚糖和葡萄糖。
实施例 26(l(T6yl NaOH)
重复实施例 25, 有以下不同点： 将碱性水溶液加热至 326°C; 混合后纤 维素浓度为 28.5%， 设定水密度为 802kg/m3， 快速加热至 326°C, 加热速率 为 9.7。C/s， 至 318°C (100MPa)， 2秒即可完全溶解纤维素。 继续加热至 355 °C 纤维素水解为多聚糖和葡萄糖。
实施例 27(10"6 NaOH)
重复实施例 25, 有以下不同点： 将碱性水溶液加热至 330°C; 混合后纤 维素浓度为 21.5%, 设定水密度为 997kg/m3， 快速加热至 330°C, 加热速率 为 9.2°C/s, 至 327°C (566 MPa)， 1.85秒即可完全溶解纤维素。 继续加热至 355°C, 纤维素水解为多聚糖和葡萄糖。
实施例 28(10—5 K0H)
将纤维素置于碱性 10—5 KOH水溶液中， 形成纤维素物料； 将碱性 10—5 K0H水溶液加热至 343°C; 混合碱性水溶液和纤维素物料置于反应器中， 混 合后纤维素浓度为 7%, 设定水密度为 621kg/m3， 快速加热至 343°C， 加热速 率为 irC/s, 至 319°C (11 MPa) , 1.1秒即可完全溶解纤维素。 继续加热至 355°C, 纤维素水解为多聚糖和葡萄糖。
实施例 29(1(Γ5 0Η)
重复实施例 28, 有以下不同点： 将碱性水溶液加热至 320°C; 混合后纤 维素浓度为 23%, 设定水密度为 808kg/m3, 快速加热至 32(TC, 加热速率为 11.8'C/s, 至 318°C (107MPa)， 1.8秒即可完全溶解纤维素。继续加热至 355 °C, 纤维素水解为多聚糖和葡萄糖。
实施例 30(10"5 K0H)
重复实施例 28, 有以下不同点： 将碱性水溶液加热至 339°C; 混合后纤 维素浓度为 10%， 设定水密度为 971kg/m3, 快速加热至 339°C， 加热速率为 12.4°C/s, 至 327°C (475 MPa) , 1秒即可完全溶解纤维素。 继续加热至 355 °C 纤维素水解为多聚糖和葡萄糖。
实施例 31(10— 4 Ca(0H)2)
将纤维素置于碱性 l(T4 Ca(0H)2水溶液中， 形成纤维素物料； 将碱性 l(T4) Ca(OH)2水溶液加热至 352°C; 混合碱性水溶液和纤维素物料置于反应 器中， 混合后纤维素浓度为 32%， 设定水密度为 587kg/m3, 快速加热至 352 °C， 加热速率为 8.8'C/s， 至 343°C (40 MPa)， 1.6秒即可完全溶解纤维素。 继续加热至 355°C, 纤维素水解为多聚糖和葡萄糖。
实施例 32(10_4 Ca(OH)2)
重复实施例 31, 有以下不同点： 将碱性水溶液加热至 321°C; 混合后纤 维素浓度为 13%， 设定水密度为 886kg/m3, 快速加热至 32rC, 加热速率为 7.8°C/s, 至 315°C (227 MPa)， 1.4秒即可完全溶解纤维素。 继续加热至 355 °C, 纤维素水解为多聚糖和葡萄糖。
实施例 33(10—4 Ca(OH)2)
重复实施例 31, 有以下不同点： 将碱性水溶液加热至 332°C; 混合后纤 维素浓度为 26%, 设定水密度为 997kg/m3, 快速加热至 332°C, 加热速率为 8.4°C/s, 至 325°C (562 MPa))， 1.66秒即可完全溶解纤维素。 继续加热至 355°C, 纤维素水解为多聚糖和葡萄糖。
实施例 34(10"3 NaOH)
将纤维素置于碱性 10—3 NaOH水溶液中， 形成纤维素物料； 将碱性 NaOH水溶液加热至 35ITC; 混合碱性水溶液和纤维素物料置于反应器中， 混 合后纤维素浓度为 12%， 设定水密度为 708kg/m3, 快速加热至 350°C, 加热 速率为 13. rC/s， 至 337°C (45 MPa)， 1.7秒即可完全溶解纤维素。 继续加 热至 355°C， 纤维素水解为多聚糖和葡萄糖。
实施例 35(10— 3 NaOH)
重复实施例 34, 有以下不同点： 将碱性水溶液加热至 321°C; 混合后纤 维素浓度为 29%, 设定水密度为 848kg/m3， 快速加热至 321°C, 加热速率为 13.4°C/s, 至 311°C (152 MPa), 1.88秒即可完全溶解纤维素。 继续加热至 355°C, 纤维素水解为多聚糖和葡萄糖。
实施例 36(10— 3 NaOH)
重复实施例 34， 有以下不同点： 将碱性水溶液加热至 337°C; 混合后纤 维素浓度为 0.1%, 设定水密度为 996kg/m3, 快速加热至 337°C, 加热速率为 13.7°C/s,至 331°C (571 MPa) , 1.3秒即可完全溶解纤维素。继续加热至 355 °C, 纤维素水解为多聚糖和葡萄糖。
实施例 37(10"2 NaOH)
将纤维素置于碱性 10—2 NaOH水溶液中，形成纤维素物料；将碱性 10_2 NaOH水溶液加热至 352°C; 混合碱性水溶液和纤维素物料置于反应器中， 混 合后纤维素浓度为 1%, 设定水密度为 636kg/m3， 快速加热至 352°C， 加热速 率为 10.8°C/s, 至 352°C (29MPa) , 1.21秒即可完全溶解纤维素。 继续加热 至 355°C, 纤维素水解为多聚糖和葡萄糖。
实施例 38(10"2 NaOH) 重复实施例 37, 有以下不同点： 将碱性水溶液加热至 331°C; 混合后纤 维素浓度为 8%，设定水密度为 954kg/m3,快速加热至 33rC，加热速率为 9.1 °C/s， 至 320°C (407 MPa), 1.4秒即可完全溶解纤维素。 继续加热至 355°C, 纤维素水解为多聚糖和葡萄糖。
实施例 39(10"2 NaOH)
重复实施例 37, 有以下不同点： 将碱性水溶液加热至 335°C; 混合后纤 维素浓度为 32%， 设定水密度为 993kg/m3, 快速加热至 335°C, 加热速率为 9.8°C/s, 至 330°C (558 MPa) , 1.9秒即可完全溶解纤维素。 继续加热至 355 °C， 纤维素水解为多聚糖和葡萄糖。 、
实施例 40(0.1M NaOH)
将纤维素置于碱性 0.1^ NaOH水溶液中， 形成纤维素物料； 将碱性 0.1 NaOH水溶液加热至 346°C; 混合碱性水溶液和纤维素物料置于反应器中， 混 合后纤维素浓度为 32%, 设定水密度为 655kg/m3， 快速加热至 346°C， 加热 速率为 11.8°C/s, 至 339°C (24MPa) , 1.41秒即可完全溶解纤维素。 继续加 热至 355°C, 纤维素水解为多聚糖和葡萄糖。
实施例 41(0.1M NaOH)
重复实施例 40， 有以下不同点： 将碱性水溶液加热至 352°C; 混合后纤 维素浓度为 23.9%, 设定水密度为 980kg/m3, 快速加热至 352°C, 加热速率 为 13.8°C/s， 至 344°C (541 MPa) , 1.23秒即可完全溶解纤维素。 继续加热 至 355°C, 5s之内纤维素水解为多聚糖和葡萄糖。
实施例 42(0.1 NaOH)
重复实施例 40, 有以下不同点： 将碱性水溶液加热至 350°C; 混合后纤 维素浓度为 31.5%, 设定水密度为 997kg/m3, 快速加热至 350°C， 加热速率 为 12.7°C/s， 至 335°C (584 MPa), 1.55秒即可完全溶解纤维素。 继续加热 至 355。C, 5s之内纤维素水解为多聚糖和葡萄糖。
实施例 43(l NaOH) 将纤维素置于碱性 l^NaOH水溶液中，形成纤维素物料； 将碱性 l NaOH 水溶液加热至 335°C; 混合碱性水溶液和纤维素物料置于反应器中， 混合后 纤维素浓度为 29%, 设定水密度为 726kg/m3, 快速加热至 335°C， 加热速率 为 9.8°C/s, 至 325°C(42 MPa), 1.76秒即可完全溶解纤维素。 继续加热至 355°C, 纤维素水解为多聚糖和葡萄糖。
实施例 44(l NaOH)
重复实施例 43, 有以下不同点： 将碱性水溶液加热至 279°C; 混合后纤 维素浓度为 26.5%, 设定水密度为 818kg/m3， 快速加热至 279°C, 加热速率 为 10.7°C/s, 至 274°C(56MPa)， 1.33秒即可完全溶解纤维素。 继续加热至 355°C, 纤维素水解为多聚糖和葡萄糖。
实施例 45(1 NaOH)
重复实施例 43, 有以下不同点： 将碱性水溶液加热至 330°C; 混合后纤 维素浓度为 29.5%, 设定水密度为 996kg/m3， 快速加热至 330°C, 加热速率 为 10.2°C/s， 至 321°C(549 MPa), 1.53秒即可完全溶解纤维素。 继续加热 至 355°C， 5s之内纤维素水解为多聚糖和葡萄糖。
实施例 46
一种完全溶解和快速水解纤维素的设备， 如图 6所示， 酸 (或碱）性水溶 液容器 1通过高压泵 2与管式反应器 6的注料口相连， 高压泵与管式反应器 注料口之间设置有预热器 3, 纤维素物料容器 4通过高压泥浆泵 5与管式反 应器 6注料口处的酸 (或碱）性水输送管道相连，管式反应器 6外部设置电加 热炉 7， 生成物容器 10通过调压阀 9、 冷却器 8与管式反应器 6的出料口连 接。
该连续生产设备的工作原理： 预热器 3将酸 (或碱)性水溶液容器 1中的 溶液预热至261~ 352 （6~ 5841^&), 用高压泵 2压入管式反应器 6; 纤维 素和酸 (或碱）性水溶液在纤维素物料容器 4中混合后，用高压泥浆泵 5泵送 至管式反应器注料口前与预热的酸（或碱）溶液混合， 并立即进入管式反应器 6 中快速加热至 355 Ό , 纤维素在反应器中完全溶解并进行均相水解。 完全 水解的纤维素由反应器出料口输出至生成物容器 10，通过冷却器 8来控制冷 却速率， 反应压力由调压阀 9控制。
用该连续生产装置可很容易控制溶剂化的纤维素的反应， 如反应时间， 压力和温度等。 主要应用有：
( 1 )对纤维素进行预处理
将该溶剂化的纤维素进一步加热至小于 355 °C并保持在 0 ~ 2s之内， 纤 维素在均相条件下的结构被打破。 经过此预处理， 其中的多糖可用生物转化 的方法来发酵生产酒精或其他的生物制品 （如发酵生产抗生素、 赖氨酸、 乳 酸和谷氨酸钠等）。
( 2 ) 完全水解纤维素为糖类
将该溶剂化的纤维素加热至 355 °C并保持在 5s之内，纤维素将均相水解 为葡萄糖及其多聚糖。 糖类可用来生产酒精。 糖类也可再经生物转化， 生产 生物制品。
( 3 )连续生产气体、 液体燃料或化学品
该管式反应器后段装满催化剂， 当纤维素完全溶解后， 接着进入后段进 行均相催化反应。由于溶剂化的纤维素更易接触催化剂的活化点，更易反应。 溶剂化的纤维素在液相热水中催化或非催化， 均相地生产气体 (如用 Ni催化 剂生产 H2)和液体 (如用 Pt催化剂生产烃类)燃料以及合成化学品（如生产 5 - 羟甲基糠醛和糠醛， 用 Pt/- A1203催化剂生产醇类）和食品。

Claims

权 利 要 求 书
1、 一种完全溶解和快速水解纤维素的方法， 包括以下步骤：
(1 )将纤维素置于浓度为 10_7~1 [H+]酸性或 1(Γ7~ 1 [0H— ]碱性水溶 液中， 固液体积比为（0.003 1.05): 1;
(2)将 10—7~ 1MH+]酸性或 1(Τ~ 1 [0ΗΊ碱性水溶液加热至 261 ~ 352
°C;
( 3) 混合步骤 1和 2所得物置于反应器中， 纤维素浓度为 0.1%~ 35%, 调节混合后的物料溶液浓度为 10-7~ 1 [H+]酸性或 10—7~ 1 [0ΗΊ碱性, 水 密度为 587 - 997 kg/m3, 设定压力为 6 ~ 584 MPa, 加热速率为 7.8 ~ 14.8°C /s, 快速加热至 261 ~ 352'C, 0.8~2秒即能完全溶解纤维素。
2、 根据权利要求 1所述的完全溶解和快速水解纤维素的方法， 其特征 在于： 所述的酸性水溶液为盐酸， 硝酸或硫酸的水溶液。
3、 根据权利要求 1所述的完全溶解和快速水解纤维素的方法， 其特征 在于： 所述的碱性水溶液为氢氧化钠， 氢氧化钾或氢氧化钙的水溶液。
4、 根据权利要求 1所述的完全溶解和快速水解纤维素的方法， 其特征 在于： 所述的酸性水溶液为盐酸水溶液。
5、 根据权利要求 1所述的完全溶解和快速水解纤维素的方法， 其特征 在于： 所述的碱性水溶液为氢氧化钠水溶液。
6、 权利要求 1所述完全溶解和快速水解纤维素的方法在酒精生产中的 应用。 '
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