CN101886143B - 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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- CN101886143B CN101886143B CN 201010229952 CN201010229952A CN101886143B CN 101886143 B CN101886143 B CN 101886143B CN 201010229952 CN201010229952 CN 201010229952 CN 201010229952 A CN201010229952 A CN 201010229952A CN 101886143 B CN101886143 B CN 101886143B
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- 239000002028 Biomass Substances 0.000 title claims abstract description 31
- 235000000346 sugar Nutrition 0.000 title claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 16
- 230000003301 hydrolyzing effect Effects 0.000 title description 4
- 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 31
- 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
- 239000007791 liquid phase 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
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 2
- 230000035484 reaction time Effects 0.000 abstract description 2
- 150000008163 sugars Chemical class 0.000 abstract description 2
- 229920002488 Hemicellulose Polymers 0.000 abstract 1
- 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
- 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
- 235000014633 carbohydrates Nutrition 0.000 description 2
- 150000001720 carbohydrates Chemical class 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
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product 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
- 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
- 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
- 230000009466 transformation Effects 0.000 description 1
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- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
一种超/亚临界水两步水解生物质制备还原糖的方法，属于新能源技术领域。其特征是采用超/亚临界水低温段+高温段两步法水解生物质，从而实现制备高产量还原糖的目的。水解反应在温度180～230℃，反应时间0～60min，固液比1∶100～1∶20的条件下进行。本发明的效果和益处是在超/亚临界水两步法水解条件下，生物质中的半纤维素糖类得到回收利用，生物质水解还原糖产率有明显的提高，依据原料不同，最大总还原糖产率可达到40％～60％，原料还原糖回收率达70％以上。The invention discloses a method for preparing reducing sugar by super/subcritical water two-step hydrolysis of biomass, which belongs to the technical field of new energy. It is characterized in that it adopts a two-step method of super/subcritical water low-temperature section + high-temperature section to hydrolyze biomass, so as to achieve the purpose of preparing high-yield reducing sugar. The hydrolysis reaction is carried out at a temperature of 180-230° C., a reaction time of 0-60 minutes, and a solid-liquid ratio of 1:100-1:20. The effects and benefits of the present invention are that under the conditions of super/subcritical water two-step hydrolysis, the hemicellulose sugars in the biomass are recycled, and the yield of reducing sugar in the hydrolysis of the biomass is significantly improved. According to different raw materials, the maximum The total reducing sugar yield can reach 40%-60%, and the raw material reducing sugar recovery rate can reach more than 70%.
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, distributes extensively, and agricultural wastes such as agricultural crop straw, husk, 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 glucide 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 through fermentation again.
The method of biomass by hydrolyzation mainly contains acid-catalyzed hydrolysis method and enzyme hydrolysis method at present.Acid hydrolysis process is ripe, but has the equipment corrosion problem, and waste reaction solution has pollution, post-processing step complicacy to environment.Advantages 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 is high, can't realize large-scale industrial production.Ultra/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, and equipment requirements is high, and sugar yield is with a certain distance from realizing that industriallization also has.
Semicellulose in the biomass and cellulose hydrolysis need different temperature and time conditions; The two-step approach hydrolysis process is handled biomass under different condition; Semicellulose 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 ultra/subcritical water single stage method hydrolyzing biomass technology causes the loss of semicellulose 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.
Preparing method of the present invention may further comprise the steps:
(1) be that 1: 100～1: 20 ratio joins in the reaction kettle with biomass and zero(ppm) 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 zero(ppm) water is colourless to filtrating, and is used for step pyroreaction raw material down.
(3) go up the solid phase residue that the step reaction obtains and add in another reaction kettle with the solid-to-liquid ratio of zero(ppm) water with 1: 100, control reaction temperature is 300～380 ℃, reacts 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 semicellulose 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 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 reaction kettle, and control reaction temperature is 190 ℃, stirring reaction 40min.After reaction finished, reaction kettle 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 filtrating with zero(ppm) 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, take out the ice-water bath cooling, 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 reaction kettle, and control reaction temperature is 190 ℃, stirring reaction 20min.After reaction finished, reaction kettle 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 filtrating with zero(ppm) 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, take out the ice-water bath cooling, 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 (1)
1. ultra/subcritical water two one-step hydrolysis biomass prepare the method for reducing sugar, and its characteristic comprises the steps:
(1) be that 1: 100～1: 20 ratio joins in the reaction kettle with biomass and zero(ppm) 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, and the drip washing of solid phase residue zero(ppm) water is colourless to filtrating, and is used for step pyroreaction raw material down;
(3) go up the solid phase residue that the step reaction obtains and add in another reaction kettle with 1: 100 solid-to-liquid ratio of mass ratio with zero(ppm) water, control reaction temperature is 300～380 ℃, reacts 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;
(5) described biomass are rice straw, cornstalk, straw, sorghum stalk, bagasse or cotton seed hulls, and particle diameter is 40～100 orders.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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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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| 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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| CN101886143B true CN101886143B (en) | 2012-12-26 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US8409357B2 (en) | 2011-05-04 | 2013-04-02 | Renmatix, Inc. | Self-cleaning apparatus and method for thick slurry pressure control |
| US8546561B2 (en) | 2008-07-16 | 2013-10-01 | Renmatix, Inc. | Nano-catalytic-solvo-thermal technology platform bio-refineries |
| US8546560B2 (en) | 2008-07-16 | 2013-10-01 | Renmatix, Inc. | Solvo-thermal hydrolysis of cellulose |
| US8759498B2 (en) | 2011-12-30 | 2014-06-24 | Renmatix, Inc. | Compositions comprising lignin |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP3719145A1 (en) | 2010-01-19 | 2020-10-07 | 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 | Manufacturing method and equipment of reducing sugar |
| JP5967730B2 (en) | 2011-05-04 | 2016-08-10 | レンマティックス, インコーポレイテッドRenmatix, Inc. | Production of lignin from lignocellulosic biomass |
| 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 |
| JP6077854B2 (en) * | 2012-12-27 | 2017-02-08 | 川崎重工業株式会社 | Method for recovering sugar from saccharification slurry and cleaning device for cleaning residue |
| EP4357434A3 (en) | 2014-09-26 | 2024-11-20 | Renmatix, Inc. | Adhesive compositions comprising type-ii cellulose |
| CN104357588B (en) * | 2014-11-05 | 2017-12-22 | 广西大学 | One kind surpasses/subcritical water CO2The method that hydrolysis sugarcane marrow prepares reduced sugar |
| CN116042734A (en) * | 2022-09-23 | 2023-05-02 | 浙江大学杭州国际科创中心 | Method for producing glucaric acid by directly integrating biological processing lignocellulose |
| CN115895846A (en) * | 2022-10-21 | 2023-04-04 | 浙江大学杭州国际科创中心 | A closed loop system for the preparation of glucaric acid by green organisms |
| 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 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP4330839B2 (en) * | 2002-01-18 | 2009-09-16 | 旭化成ケミカルズ株式会社 | Method for producing glucose and / or water-soluble cellooligosaccharide |
| ES2566672T3 (en) * | 2006-10-26 | 2016-04-14 | Kawasaki Jukogyo Kabushiki Kaisha | Method and system for hydrolytic saccharification of a cellulosic biomass |
| CN101613377B (en) * | 2009-07-21 | 2012-06-27 | 清华大学 | Biomass supercritical and subcritical combined continuous type pretreatment and hydrolysis equipment and method |
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2010
- 2010-07-13 CN CN 201010229952 patent/CN101886143B/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8546561B2 (en) | 2008-07-16 | 2013-10-01 | Renmatix, Inc. | Nano-catalytic-solvo-thermal technology platform bio-refineries |
| US8546560B2 (en) | 2008-07-16 | 2013-10-01 | Renmatix, Inc. | Solvo-thermal hydrolysis of cellulose |
| US8409357B2 (en) | 2011-05-04 | 2013-04-02 | Renmatix, Inc. | Self-cleaning apparatus and method for thick slurry pressure control |
| US8759498B2 (en) | 2011-12-30 | 2014-06-24 | Renmatix, Inc. | Compositions comprising lignin |
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| CN101886143A (en) | 2010-11-17 |
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