CN102586493B - Method for promoting biomass hydrolysis and preparing reducing sugar through supercritical carbon dioxide and ultrasonic coupled pretreatment - Google Patents
Method for promoting biomass hydrolysis and preparing reducing sugar through supercritical carbon dioxide and ultrasonic coupled pretreatment Download PDFInfo
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Abstract
The invention discloses a method for promoting biomass hydrolysis and preparing reducing sugar through supercritical carbon dioxide and ultrasonic coupled pretreatment, and belongs to the technical field of new energy. Biomass is pretreated by supercritical CO2 and ultrasound to fulfill the aims of promoting hydrolysis and improving the yield of reducing sugar. The supercritical CO2 pretreatment is carried out in a liquid-solid ratio of 1:1-3:1 at the temperature of between 80 and 160DEG C and pressure of between 5 and 20MPa for 15 to 60 minutes; the ultrasonic pretreatment is carried out at the frequency of 20-80kHz, the power of 50-500w and the temperature of between 0 and 50DEG C for 10 to 60 minutes; and the hydrolysis is carried out at the temperature of between 120 and 160DEG C and the liquid-solid ratio of 20:1-100:1 for 30 to 60 minutes. The method has the advantages that after supercritical CO2 and ultrasonic pretreatment, the yield of biomass hydrolyzed reducing sugar is obviously improved, and the yield ranges from 40 to 70 percent according to different raw materials.
Description
Technical field
The invention belongs to Green Chemistry and clean energy technology field, relate to a kind of supercritical co and ultrasonic coupling pre-treatment and promote biomass by hydrolyzation to produce the method for reducing sugar.
Background technology
Biomass resource distribute wide, renewable and kind abundant, as agricultural wastes such as agricultural crop straw, husks, trade waste such as sawdust, bagasse and domestic refuse etc. all are available biomass resources.Taked to bury for the utilization of biomass or the direct mode of burning, though simple and convenient, utilization ratio is low, contaminate environment more in the past.Biomass by hydrolyzation is prepared reducing sugar, is a biomass resource utilization technology efficiently through producing fuel ethyl alcohol by ferment again.But exist with polymer form because the carbohydrate in the biomass is many, direct hydrolysis condition harshness and efficient are low.If biomass are done suitable pre-treatment, the reaction that is hydrolyzed again then is expected to improve hydrolysising condition, raise the efficiency.
At present, the pretreated method of biomass is mainly contained acid-base pretreatment, steam explosion pre-treatment and ammonia fiber explosion pre-treatment.The acid-base pretreatment technical maturity, but there is etching problem in equipment, must carry out neutralizing treatment after the pre-treatment, the step complexity, waste liquid has pollution to environment.Steam explosion and ammonia fiber explosion pre-treatment have advantages such as processing speed is fast, but condition is harsh, needs high pressure vessel.The steam explosion energy consumption is big, temperature is higher, can make the degraded of small molecules carbohydrate, reduces total sugar yield; Ammonia is poisonous in the explosion of ammonia fiber, and environment is had pollution, and reclaiming to use increases facility investment.In recent years, the novel pretreatment process of environmental friendliness, mild condition becomes development trend, gains great popularity.
Supercritical co is a kind of green solvent, can produce swelling action to polymkeric substance, and then changes its degree of crystallinity, second-order transition temperature etc.Use the supercritical carbon dioxide treatment biomass, then might change wherein cellulosic structure, reduce degree of crystallinity, thereby improve hydrolysising condition.
Ultrasonic wave is widely used in many fields such as mechanical workout, chemical productions as a kind of form of energy.Utilize effects such as Hydrodynamic cavitation that ultrasonic energy produces, mechanical oscillation, can the wash machine part or strengthen chemical reaction.Ultrasonic energy is acted on biomass, also may cause the biomass weave construction to change by above-mentioned effect, and then be conducive to hydrolysis.
As seen, if supercritical co and ultrasonic wave effect be coupled together biomass are done pre-treatment, then can bring into play the advantage of the two, further promote biomass by hydrolyzation prepared in reaction reducing sugar.
Summary of the invention
The purpose of this invention is to provide a kind of supercritical co and ultrasonic coupling pre-treatment promotes biomass by hydrolyzation to produce the method for reducing sugar, solve traditional soda acid pre-processing device burn into last handling process complexity, steam explosion pre-treatment energy consumption is big, reducing sugar yield is not high, and ammonia fiber explosion pretreatment gas reclaims loaded down with trivial details, problem of environment pollution caused.
Technical scheme of the present invention is:
Water and the biomass of certain liquid-solid ratio are placed in the reactor, use supercritical co and ultrasonicly carry out pre-treatment, re-use diluted acid and make catalyzer and pretreated biomass are hydrolyzed the preparation reducing sugar.
Preparation method of the present invention may further comprise the steps:
(1) pretreatment process can use first supercritical carbon dioxide treatment supersound process again among the present invention, and perhaps first supersound process supercritical carbon dioxide treatment is perhaps ultrasonicly handled simultaneously with supercritical co, and is specific as follows:
Supercritical carbon dioxide treatment technology: deionized water and biomass are joined in the high-pressure reactor with 1: 1～3: 1 ratio of mass ratio (liquid-solid ratio) or pure biomass (not adding deionized water), in reactor, inject high-pressure carbon dioxide, under 50～160 ℃ of temperature, pressure 8～20MPa, keep 15～60min; Supercritical carbon dioxide treatment is opened the rapid pressure release of valve after finishing, and has let out in 10～60s; Take out drying materials after the pressure release to constant weight.
Ultrasonic processing technique: deionized water and biomass are joined in the reactor in 5: 1～10: 1 ratio of liquid-solid ratio, mix the back fully and use supersound process, processing finishes the back and takes out drying materials to constant weight; Frequency 20～80kHz, power 50～500W, 0～50 ℃ of temperature, time 10～60min.
(2) pretreated biomass are carried out the diluted acid catalytic hydrolysis to produce reducing sugar, biomass and the dilute acid soln of handling the back oven dry in (1) are joined in the reactor with certain liquid-solid ratio, keep for some time at a certain temperature, cool off rapidly then, filtration, centrifugal, get supernatant liquid and carry out the reducing sugar yield analysis.Concrete processing parameter is as follows:
120～160 ℃ of temperature, time 30～60min, liquid-solid ratio 20: 1～100: 1, acid catalyst is the aqueous sulfuric acid of mass concentration 1～4%.
Above-described biomass are corn cob, rice straw, cornstalk, straw, sorghum stalk, jerusalem artichoke, Chinese silvergrass, bagasse or cotton seed hulls, and particle diameter is 10～80 orders.
Effect of the present invention and benefit are: supercritical co and ultrasonic biomass are carried out pre-treatment, can effectively destroy the structure of biomass, and be the follow-up hydrolysis reaction condition that facilitates.Utilize this green solvent of supercritical co, to the biomass fiber explosion, help biomass are twined loose that fine and close space structure becomes; The cavatition that the recycling ultrasonic energy produces is destroyed biomass surface and internal structure; The total reducing sugars productive rate significantly improves, and has increased utilization ratio of raw materials, and unifacial leaf biomass by hydrolyzation productive rates such as unpretreated rice straw, cornstalk, sorghum stalk only are 20～30%, and biomass by hydrolyzation productive rates such as jerusalem artichoke, Chinese silvergrass only are 25～35%; But through after the pre-treatment, productive rate all can reach more than 40%, even near 70%; The severe condition (about 300 ℃) of common pyrohydrolysis have been improved.
Description of drawings
Accompanying drawing 1 is the biomass by hydrolyzation reducing sugar yield comparison diagram after not adopting the biomass of pretreatment process and adopting pretreatment process.
Embodiment
Be described in detail the specific embodiment of the present invention below in conjunction with technical scheme.
Embodiment 1
Take by weighing the 1.5g rice straw and the 4.5g deionized water joins in the high-pressure reactor in 3: 1 ratio of liquid-solid ratio, in reactor, inject high-pressure carbon dioxide, 120 ℃ of control temperature, pressure 10MPa opens valve after handling 45min, lets out to normal pressure in 30s.Open after reactor takes out all substances and 15g water mixes, at 60kHz, 200W, 0 ℃ of following supersound process 30min.To take by weighing 0.2g rice straw and 20g mass concentration at 100: 1 by liquid-solid ratio be that 1% aqueous sulfuric acid joins in the reactor with getting after the solid matter oven dry, behind reaction 30min under 140 ℃, product is filtered, centrifugal, liquid product is carried out ultra-violet analysis, and reducing sugar yield is 54.2%.
Embodiment 2
Take by weighing after 1.5g corn cob and 15g deionized water mix in 10: 1 ratio of liquid-solid ratio, at 20kHz, 500W, 50 ℃ of following supersound process 30min.Solid matter oven dry back is taken by weighing the 1.5g corn cob in 3: 1 ratio of liquid-solid ratio and the 4.5g deionized water joins in the high-pressure reactor, in reactor, inject high-pressure carbon dioxide, 100 ℃ of control temperature, pressure 15MPa, open valve after handling 30min, in 30s, let out to normal pressure.With after the solid matter oven dry, taking by weighing 0.4g corn cob and 20g mass concentration at 50: 1 by liquid-solid ratio is that 4% aqueous sulfuric acid joins in the reactor, 140 ℃ react 40min down after, product is filtered, centrifugal, liquid product is carried out ultra-violet analysis, reducing sugar yield is 57.6%.
Comparative Examples 3
Take by weighing the 1.5g cornstalk and the 3g deionized water joins in the high-pressure reactor in 2: 1 ratio of liquid-solid ratio, in reactor, inject high-pressure carbon dioxide, 80 ℃ of control temperature, pressure 10MPa opens valve after handling 60min, lets out to normal pressure in 30s.Open reactor, after the solid matter oven dry, taking by weighing 0.4g cornstalk and 20g mass concentration at 50: 1 by liquid-solid ratio is that 1% aqueous sulfuric acid joins in the reactor, behind reaction 40min under 160 ℃, product is filtered, centrifugal, liquid product is carried out ultra-violet analysis, reducing sugar yield is 35.3%.
Comparative Examples 4
Take by weighing after 1.5g rice straw and 15g deionized water mix in 10: 1 ratio of liquid-solid ratio, at 40kHz, 300W, 0 ℃ of following supersound process 10min.With after the solid matter oven dry, taking by weighing 0.5g rice straw and 20g mass concentration at 40: 1 by liquid-solid ratio is that 1% aqueous sulfuric acid joins in the reactor, 160 ℃ react 40min down after, product is filtered, centrifugal, liquid product is carried out ultra-violet analysis, reducing sugar yield is 34.2%.
Embodiment 5
Take by weighing the 1.5g jerusalem artichoke and the 1.5g deionized water joins in the high-pressure reactor in 1: 1 ratio of liquid-solid ratio, in reactor, inject high-pressure carbon dioxide, 100 ℃ of control temperature, pressure 20MPa opens valve after handling 30min, lets out to normal pressure in 20s.After opening reactor and taking out all substances and 10g water and mix, at 30kHz, 100W, 0 ℃ of following supersound process 30min.With after the solid matter oven dry, taking by weighing 1g jerusalem artichoke and 20g mass concentration at 20: 1 by liquid-solid ratio is that 2% aqueous sulfuric acid joins in the reactor, 120 ℃ react 60min down after, product is filtered, centrifugal, liquid product is carried out ultra-violet analysis, reducing sugar yield is 64.2%.
Embodiment 6
Take by weighing after 1.5g Chinese silvergrass and 15g deionized water mix in 10: 1 ratio of liquid-solid ratio, at 80kHz, 500W, 30 ℃ of following supersound process 60min.Solid matter oven dry back is taken by weighing the 1.5g Chinese silvergrass in 2: 1 ratio of liquid-solid ratio and the 3g deionized water joins in the high-pressure reactor, in reactor, inject high-pressure carbon dioxide, 160 ℃ of control temperature, pressure 15MPa, open valve after handling 30min, in 50s, let out to normal pressure.With after the solid matter oven dry, taking by weighing 0.4g corn cob and 20g mass concentration at 50: 1 by liquid-solid ratio is that 2% aqueous sulfuric acid joins in the reactor, 140 ℃ react 40min down after, product is filtered, centrifugal, liquid product is carried out ultra-violet analysis, reducing sugar yield is 53.4%.
Embodiment 7
Take by weighing 1.5g bagasse and the 3g deionized water joins in the high-pressure reactor in 2: 1 ratio of liquid-solid ratio, in reactor, inject high-pressure carbon dioxide, pressure 20MPa, at 60kHz, 300W opens valve behind 50 ℃ of following supersound process 50min, lets out to normal pressure in 20s.With after the solid matter oven dry, taking by weighing 1g bagasse and 20g mass concentration at 20: 1 by liquid-solid ratio is that 2% aqueous sulfuric acid joins in the reactor, 140 ℃ react 40min down after, product is filtered, centrifugal, liquid product is carried out ultra-violet analysis, reducing sugar yield is 41.7%.
As shown in drawings, whether biomass adopt pretreatment process for the reductive hydrolysis sugar yield tangible influence to be arranged.
Claims (2)
1. a supercritical co and ultrasonic coupling pre-treatment promote biomass by hydrolyzation to produce the method for reducing sugar, it is characterized in that:
The first step, supercritical co and ultrasonic coupling preprocessing biomass: first supercritical carbon dioxide treatment is supersound process again, and perhaps first supersound process supercritical carbon dioxide treatment more specifically comprises the steps:
Supercritical carbon dioxide treatment technology: deionized water and biomass ratio or the pure biomass with mass ratio 1:1 ~ 3:1 are joined in the high-pressure reactor, in reactor, inject high-pressure carbon dioxide, under 50 ~ 160 ℃ of temperature, pressure 8 ~ 20MPa, keep 15 ~ 60min; Supercritical carbon dioxide treatment finishes back pressure release rapidly, lets out in 10 ~ 60s to normal pressure; Take out drying materials after the pressure release to constant weight;
Ultrasonic processing technique: deionized water and the biomass ratio in liquid-solid ratio 5:1 ~ 10:1 is joined in the reactor, mix the back and use supersound process, processing finishes the back and takes out drying materials to constant weight; Frequency 20 ~ 80kHz, power 50 ~ 500W, 0 ~ 50 ℃ of temperature, time 10 ~ 60min;
Second step, pre-treatment artifact matter is carried out the diluted acid catalytic hydrolysis to produce reducing sugar, concrete processing parameter is as follows:
120 ~ 160 ℃ of temperature, time 30 ~ 60min, liquid-solid ratio 20:1 ~ 100:1, acid catalyst are the aqueous sulfuric acid of mass concentration 1 ~ 4%.
2. a kind of supercritical co according to claim 1 and ultrasonic coupling pre-treatment promote biomass by hydrolyzation to produce the method for reducing sugar, it is characterized in that the biomass of using are corn cob, rice straw, cornstalk, straw, sorghum stalk, jerusalem artichoke, Chinese silvergrass, bagasse or cotton seed hulls, particle diameter is 10 ~ 80 orders.
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| CN103509368B (en) * | 2013-10-09 | 2015-03-18 | 邵阳学院 | Method for hydrolyzing and preparing gardenia cyanine by using supercritical CO2 to catalyze geniposide |
| CN110485187A (en) * | 2019-07-02 | 2019-11-22 | 华南理工大学 | A method of releasing steam blasting plant fiber biochemical resistance |
| CN110791596B (en) * | 2019-11-11 | 2020-10-30 | 西南科技大学 | Method for realizing regeneration and utilization of waste biomass by adopting alkaline electrolyzed water |
| CN110791595B (en) * | 2019-11-11 | 2020-10-09 | 西南科技大学 | Method for realizing regeneration and utilization of waste biomass by adopting acidic electrolyzed water |
| CN112013632A (en) * | 2020-09-10 | 2020-12-01 | 河南科技大学 | Drying method |
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| CN101255479A (en) * | 2008-04-22 | 2008-09-03 | 南京工业大学 | Pre-treatment method for highly-effective saccharification of lignocellulose |
| CN101886143A (en) * | 2010-07-13 | 2010-11-17 | 大连理工大学 | Method for preparing reducing sugar by hydrolyzing biomass with super-critical/sub-critical water in two steps |
| CN101886144A (en) * | 2010-07-13 | 2010-11-17 | 大连理工大学 | Method for preparing reducing sugar by catalyzing biomass hydrolysis with carbon dioxide |
| CN102261004A (en) * | 2010-05-26 | 2011-11-30 | 中国科学院成都生物研究所 | Biological-chemical combined pretreatment method of lignocellulosic materials |
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| CN101255479A (en) * | 2008-04-22 | 2008-09-03 | 南京工业大学 | Pre-treatment method for highly-effective saccharification of lignocellulose |
| CN102261004A (en) * | 2010-05-26 | 2011-11-30 | 中国科学院成都生物研究所 | Biological-chemical combined pretreatment method of lignocellulosic materials |
| CN101886143A (en) * | 2010-07-13 | 2010-11-17 | 大连理工大学 | Method for preparing reducing sugar by hydrolyzing biomass with super-critical/sub-critical water in two steps |
| CN101886144A (en) * | 2010-07-13 | 2010-11-17 | 大连理工大学 | Method for preparing reducing sugar by catalyzing biomass hydrolysis with carbon dioxide |
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