CN101886143A - Method for preparing reducing sugar by hydrolyzing biomass with super-critical/sub-critical water in two steps - Google Patents
Method for preparing reducing sugar by hydrolyzing biomass with super-critical/sub-critical water in two steps Download PDFInfo
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- CN101886143A CN101886143A CN 201010229952 CN201010229952A CN101886143A CN 101886143 A CN101886143 A CN 101886143A CN 201010229952 CN201010229952 CN 201010229952 CN 201010229952 A CN201010229952 A CN 201010229952A CN 101886143 A CN101886143 A CN 101886143A
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- 239000002028 Biomass Substances 0.000 title claims abstract description 33
- 235000000346 sugar Nutrition 0.000 title claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 21
- 230000003301 hydrolyzing effect Effects 0.000 title claims abstract description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 17
- 230000007062 hydrolysis Effects 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 239000012153 distilled water Substances 0.000 claims description 8
- 239000005457 ice water Substances 0.000 claims description 8
- 238000011175 product filtration Methods 0.000 claims description 8
- 239000007790 solid phase Substances 0.000 claims description 8
- 239000010902 straw Substances 0.000 claims description 7
- 235000007164 Oryza sativa Nutrition 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 235000009566 rice Nutrition 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 241000609240 Ambelania acida Species 0.000 claims description 3
- 239000010905 bagasse Substances 0.000 claims description 3
- 229920000742 Cotton Polymers 0.000 claims description 2
- 240000006394 Sorghum bicolor Species 0.000 claims description 2
- 235000011684 Sorghum saccharatum Nutrition 0.000 claims description 2
- -1 cornstalk Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 229920002488 Hemicellulose Polymers 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000035484 reaction time Effects 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract 1
- 241000209094 Oryza Species 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000012263 liquid product Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 235000014633 carbohydrates Nutrition 0.000 description 3
- 150000001720 carbohydrates Chemical class 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- LPQOADBMXVRBNX-UHFFFAOYSA-N ac1ldcw0 Chemical compound Cl.C1CN(C)CCN1C1=C(F)C=C2C(=O)C(C(O)=O)=CN3CCSC1=C32 LPQOADBMXVRBNX-UHFFFAOYSA-N 0.000 description 2
- 238000005903 acid hydrolysis reaction Methods 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
- 230000004151 fermentation Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 108010059892 Cellulase Proteins 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 239000002154 agricultural waste Substances 0.000 description 1
- 229940106157 cellulase Drugs 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000010791 domestic waste Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229940088598 enzyme Drugs 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Landscapes
- Processing Of Solid Wastes (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
The invention discloses a method for preparing a reducing sugar by hydrolyzing a biomass with super-critical/sub-critical water in two steps, which belongs to the technical field of new energy. The method is characterized in that the high-yield reducing sugar is prepared by hydrolyzing the biomass with the super-critical/sub-critical water through a two-step method, namely a low-temperature section and a high-temperature section. The hydrolysis reaction is performed under the following conditions that: the temperature is 180 to 230 DEG C; the reaction time is 0 to 60 minutes; and the solid-to-liquid ratio is 1:100-1:20. The method of the invention has the advantages that: under two-step method hydrolysis condition of the super-critical/sub-critical water, hemicelluloses in the biomass are reclaimed; the yield of the biologically hydrolyzed reducing sugar is obviously improved; according to different raw materials, the highest total yield of the reducing sugar can reach 40 to 60 percent; and the recovery rate of the raw material and the reducing sugar is over 70 percent.
Description
Technical field
The invention belongs to Green Chemistry and clean energy technology field, relate to the method that a kind of two one-step hydrolysis biomass prepare reducing sugar.
Background technology
Biomass resource is renewable, and is widely distributed, agricultural wastes such as agricultural crop straw, husk, and forestry waste such as timber, sawdust, trade wastes such as bagasse, and domestic waste etc. all is utilizable biomass resource.Taked direct incendiary mode for the utilization of biomass, although method is simple, utilization ratio is low, problem of environmental pollution is arranged more in the past.By thermochemistry and biological chemistry means biomass are transformed into the chemical of tractable biomass fuel of high heating value and high added value, have effectively improved efficiency of energy utilization.For example, by the bio-ethanol of biomass by hydrolyzation saccharification secondary fermentation preparation, butanols etc. both can be used as useful chemical, still the liquid fuel of cleaning.The many forms with polymkeric substance of carbohydrate in the biomass exist, and for biomass-bio-ethanol process, must earlier the polymkeric substance hydrolysis be changed into monose, and these monose further are converted into ethanol by fermentation again.
The method of biomass by hydrolyzation mainly contains acid-catalyzed hydrolysis method and enzyme hydrolysis method at present.The acid hydrolysis process maturation, but have the equipment corrosion problem, and waste reaction solution has pollution, post-processing step complexity to environment.Advantage such as enzymic hydrolysis has that selectivity is good, reaction conditions is gentle, environmental friendliness, equipment are simple, but reaction time is long, and cellulase prepares purification difficult, cost height, can't realize large-scale industrial production.Super/subcritical water law hydrolyzing biomass is a kind of new technology of biomass resource utilization, have distinct advantages such as fast, the solvent-free pollution of speed of reaction, transformation efficiency height, but it is ripe that is that all right technically at present, the equipment requirements height, and sugar yield is with a certain distance from realizing that industrialization also has.
Hemicellulose in the biomass needs different temperature and time conditions with cellulose hydrolysis, the two-step approach hydrolysis process is handled biomass under different condition, hemicellulose sugar and cellulose sugar multipotency are effectively recycled, thereby improved the utilising efficiency of biomass material.
Summary of the invention
The purpose of this invention is to provide a kind of surpassing/subcritical water two one-step hydrolysis biomass and prepare the method for reducing sugar, solve super/subcritical water single stage method hydrolyzing biomass technology causes the loss of hemicellulose carbohydrate in the biomass under single condition, and the unfavorable shortcoming of sugar yield.
Technical scheme of the present invention is:
Biomass by hydrolyzation is carried out in two steps, and the low temperature hydrolysis solid residue of the first step makes full use of starting material as the pyrohydrolysis raw material in second step, thus preparation high yield reducing sugar.
Preparation method of the present invention may further comprise the steps:
(1) be that 1: 100~1: 20 ratio joins in the reactor with biomass and distilled water with mass ratio, control reaction temperature is 180~230 ℃, stirring reaction 0~60min.
(2) after reaction finished, the ice-water bath cooling with product filtration, centrifugal in (1), obtained containing the product of reducing sugar in the liquid phase.The drip washing of solid phase residue distilled water is colourless to filtrate, is used for step pyroreaction raw material down.
(3) solid phase residue that the step reaction obtains on and distilled water add in another reactor with 1: 100 solid-to-liquid ratio, and control reaction temperature is 300~380 ℃, reaction 20~120s.
(4) after reaction finished, the ice-water bath cooling with product filtration, centrifugal in (3), obtained containing the product of reducing sugar in the liquid phase.
Above-described biomass are rice straw, cornstalk, straw, sorghum stalk, bagasse, cotton seed hulls, and particle diameter is 40~100 orders.
Effect of the present invention and benefit are: the two-step approach hydrolyzing biomass, can effectively extract the hemicellulose carbohydrate in the biomass; Destroy the raw fibre structure in low-temperature zone, help the carrying out of one-step hydrolysis down; Total reducing sugars output significantly improves, and has improved raw material availability.
Embodiment
Be described in detail the specific embodiment of the present invention below in conjunction with technical scheme.
Embodiment 1
In the solid-liquid mass ratio is that 1: 100 ratio takes by weighing the 1.5g rice straw and the 150ml deionized water joins in the reactor, and control reaction temperature is 190 ℃, stirring reaction 40min.After reaction finished, reactor was put into ice-water bath and is cooled off, and with product filtration, centrifugal, liquid product was carried out the absorbancy analysis, and reducing sugar yield is 21%.It is colourless that the solid phase residue is washed till filtrate with distilled water, dries to weight.Take by weighing 0.05g solid phase residue at 1: 100 and 5ml water joins in another tubular reactor by the solid-liquid mass ratio, putting into controlled temperature and be 380 ℃ tin bath pond heats, behind the reaction 20s, the cooling of taking-up ice-water bath, with product filtration, centrifugal, liquid product is carried out the absorbancy analysis, and reducing sugar yield is 24%.Rice bar reductive hydrolysis sugar overall yield is 45%.
Embodiment 2
In the solid-liquid mass ratio is that 1: 40 ratio takes by weighing the 1.5g rice straw and the 150ml deionized water joins in the reactor, and control reaction temperature is 190 ℃, stirring reaction 20min.After reaction finished, reactor was put into ice-water bath and is cooled off, and with product filtration, centrifugal, liquid product was carried out the absorbancy analysis, and reducing sugar yield is 21%.It is colourless that the solid phase residue is washed till filtrate with distilled water, dries to weight.Take by weighing 0.05g solid phase residue at 1: 100 and 5ml water joins in another tubular reactor by the solid-liquid mass ratio, putting into controlled temperature and be 380 ℃ tin bath pond heats, behind the reaction 20s, the cooling of taking-up ice-water bath, with product filtration, centrifugal, liquid product is carried out the absorbancy analysis, and reducing sugar yield is 24%.Rice bar reductive hydrolysis sugar overall yield is 45%.
Claims (3)
1. super/subcritical water two one-step hydrolysis biomass prepare the method for reducing sugar, and its feature comprises the steps:
(1) be that 1: 100~1: 20 ratio joins in the reactor with biomass and distilled water with mass ratio, control reaction temperature is 180~230 ℃, stirring reaction 0~60min;
(2) after reaction finished, the ice-water bath cooling with product filtration, centrifugal in (1), obtained containing the product of reducing sugar in the liquid phase.The drip washing of solid phase residue distilled water is colourless to filtrate, is used for step pyroreaction raw material down;
(3) solid phase residue that the step reaction obtains on and distilled water add in another reactor with 1: 100 solid-to-liquid ratio, and control reaction temperature is 300~380 ℃, reaction 20~120s;
(4) after reaction finished, the ice-water bath cooling with product filtration, centrifugal in (3), obtained containing the product of reducing sugar in the liquid phase.
2. a kind of surpassing according to claim 1/subcritical water two one-step hydrolysis biomass prepare the method for reducing sugar, it is characterized in that used biomass are rice straw, cornstalk, straw, sorghum stalk, bagasse or cotton seed hulls, and particle diameter is 40~100 orders.
3. according to claim 1 a kind of super/subcritical water two one-step hydrolysis biomass prepare the method for reducing sugar, it is characterized in that adopting pyritous two-step process hydrolyzing biomass behind the first low temperature.
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CN 201010229952 CN101886143B (en) | 2010-07-13 | 2010-07-13 | Method for preparing reducing sugar by hydrolyzing biomass with super-critical/sub-critical water in two steps |
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Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102586493A (en) * | 2012-01-07 | 2012-07-18 | 大连理工大学 | Method for promoting biomass hydrolysis and preparing reducing sugar through supercritical carbon dioxide and ultrasonic coupled pretreatment |
CN102676706A (en) * | 2011-03-09 | 2012-09-19 | 逢甲大学 | Preparation method and preparation equipment for reducing saccharide |
CN103898248A (en) * | 2012-12-27 | 2014-07-02 | 川崎重工业株式会社 | Method for collecting sugar from saccharification slurry and washing device for washing residue |
US8840995B2 (en) | 2011-05-04 | 2014-09-23 | Renmatix, Inc. | Lignin production from lignocellulosic biomass |
CN104357588A (en) * | 2014-11-05 | 2015-02-18 | 广西大学 | Method for preparing reducing sugar by using supercritical/subcritical water-CO2 hydrolyzed bagasse pith |
US9963555B2 (en) | 2011-12-30 | 2018-05-08 | Renmatix, Inc. | Compositions comprising lignin |
US10053745B2 (en) | 2010-01-19 | 2018-08-21 | Renmatix, Inc. | Production of fermentable sugars and lignin from biomass using supercritical fluids |
US10793646B2 (en) | 2014-09-26 | 2020-10-06 | Renmatix, Inc. | Adhesive compositions comprising type-II cellulose |
WO2024060407A1 (en) * | 2022-09-23 | 2024-03-28 | 浙江大学杭州国际科创中心 | Method for processing lignocelluloses to produce d-glucaric acid |
Families Citing this family (3)
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US8546560B2 (en) | 2008-07-16 | 2013-10-01 | Renmatix, Inc. | Solvo-thermal hydrolysis of cellulose |
CA2730766C (en) | 2008-07-16 | 2016-11-01 | Sriya Innovations, Inc. | Method of extraction of furfural and glucose from biomass using one or more supercritical fluids |
US8801859B2 (en) | 2011-05-04 | 2014-08-12 | Renmatix, Inc. | Self-cleaning apparatus and method for thick slurry pressure control |
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CN101346476A (en) * | 2006-10-26 | 2009-01-14 | 川崎成套设备股份有限公司 | Method of saccharifying/decomposing cellulose-based biomass and saccharification/decomposition device |
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JP2003212888A (en) * | 2002-01-18 | 2003-07-30 | Asahi Kasei Corp | Method for producing glucose and/or water-soluble cellooligosaccharide |
CN101346476A (en) * | 2006-10-26 | 2009-01-14 | 川崎成套设备股份有限公司 | Method of saccharifying/decomposing cellulose-based biomass and saccharification/decomposition device |
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Cited By (12)
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US10053745B2 (en) | 2010-01-19 | 2018-08-21 | Renmatix, Inc. | Production of fermentable sugars and lignin from biomass using supercritical fluids |
US10858712B2 (en) | 2010-01-19 | 2020-12-08 | Renmatix, Inc. | Production of fermentable sugars and lignin from biomass using supercritical fluids |
CN102676706A (en) * | 2011-03-09 | 2012-09-19 | 逢甲大学 | Preparation method and preparation equipment for reducing saccharide |
US8840995B2 (en) | 2011-05-04 | 2014-09-23 | Renmatix, Inc. | Lignin production from lignocellulosic biomass |
US9963555B2 (en) | 2011-12-30 | 2018-05-08 | Renmatix, Inc. | Compositions comprising lignin |
CN102586493A (en) * | 2012-01-07 | 2012-07-18 | 大连理工大学 | Method for promoting biomass hydrolysis and preparing reducing sugar through supercritical carbon dioxide and ultrasonic coupled pretreatment |
CN102586493B (en) * | 2012-01-07 | 2013-08-07 | 大连理工大学 | Method for promoting biomass hydrolysis and preparing reducing sugar through supercritical carbon dioxide and ultrasonic coupled pretreatment |
CN103898248A (en) * | 2012-12-27 | 2014-07-02 | 川崎重工业株式会社 | Method for collecting sugar from saccharification slurry and washing device for washing residue |
CN103898248B (en) * | 2012-12-27 | 2016-06-08 | 川崎重工业株式会社 | Reclaim the method for sugar from saccharifying slurry and clean the rinser of residue |
US10793646B2 (en) | 2014-09-26 | 2020-10-06 | Renmatix, Inc. | Adhesive compositions comprising type-II cellulose |
CN104357588A (en) * | 2014-11-05 | 2015-02-18 | 广西大学 | Method for preparing reducing sugar by using supercritical/subcritical water-CO2 hydrolyzed bagasse pith |
WO2024060407A1 (en) * | 2022-09-23 | 2024-03-28 | 浙江大学杭州国际科创中心 | Method for processing lignocelluloses to produce d-glucaric acid |
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