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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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, 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.
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US8409357B2 (en) | 2011-05-04 | 2013-04-02 | Renmatix, Inc. | Self-cleaning apparatus and method for thick slurry pressure control |
US8546560B2 (en) | 2008-07-16 | 2013-10-01 | Renmatix, Inc. | Solvo-thermal hydrolysis of cellulose |
US8546561B2 (en) | 2008-07-16 | 2013-10-01 | Renmatix, Inc. | Nano-catalytic-solvo-thermal technology platform bio-refineries |
US8759498B2 (en) | 2011-12-30 | 2014-06-24 | Renmatix, Inc. | Compositions comprising lignin |
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RU2597588C2 (en) | 2010-01-19 | 2016-09-10 | Ренмэтикс, Инк. | 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 |
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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 |
EP2520672B1 (en) * | 2006-10-26 | 2015-07-15 | 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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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8546560B2 (en) | 2008-07-16 | 2013-10-01 | Renmatix, Inc. | Solvo-thermal hydrolysis of cellulose |
US8546561B2 (en) | 2008-07-16 | 2013-10-01 | Renmatix, Inc. | Nano-catalytic-solvo-thermal technology platform bio-refineries |
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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