CN100564667C - A kind of combined pretreatment method of lignocellulose and system thereof - Google Patents
A kind of combined pretreatment method of lignocellulose and system thereof Download PDFInfo
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- CN100564667C CN100564667C CNB2008100202262A CN200810020226A CN100564667C CN 100564667 C CN100564667 C CN 100564667C CN B2008100202262 A CNB2008100202262 A CN B2008100202262A CN 200810020226 A CN200810020226 A CN 200810020226A CN 100564667 C CN100564667 C CN 100564667C
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Abstract
The invention discloses a kind of combined pretreatment method of lignocellulose, in the recirculation reactor of packing into after the lignocellulose pulverizing, and inject diluted acid, opening circulating pump is to carry out circular response under 50 ℃～200 ℃ in temperature, after finishing, reaction, is used for fermentation with the hydrolyzate deacidification that obtains; In the recirculation reactor after the remaining lignocellulose flushing, put into ball mill and add alkali lye and carry out ball milling, ball milling finishes except that being used for follow-up enzymolysis behind the alkali.The present invention can improve hemicellulose conversion ratio in the lignocellulose, lignin removing rate, cellulase hydrolysis conversion ratio effectively and reduce fermentation and suppress product, enzyme dosage in the time of simultaneously can also reducing enzymolysis, shortening reaction time, improve sugared concentration, and can set pretreated water consumption according to the needs of follow-up fermentation concentration.
Description
Technical field
The invention belongs to chemical field, be specifically related to the circulation of a kind of employing diluted acid and combine with alkaline ball milling and carry out the pretreated method and system of lignocellulose.
Background technology
The lignocellulose preliminary treatment is meant and utilizes chemistry and physical method, and its three kinds of composition celluloses and lignin, hemicellulose are separated.Open the inner hydrogen bond of cellulose simultaneously, become unformed cellulose, interrupt the part glycosidic bond, reduce the degree of polymerization, hydrolyzed hemicellulose becomes monose such as wood sugar, arabinose, and improves follow-up enzymolysis efficiency.
Present pretreated method has several different methods such as concentrated acid method, the roasting method of diluted acid temperature, alkali treatment method, sulfur dioxide method, peroxide method, steam explosion, the fine blasting procedure of ammonia, carbon dioxide blasting procedure, wet oxidation, hydrothermal method.But a lot of methods wherein are low because of productive rate, environmental pollution, equipment cost and reasons such as operating cost height, complicated operation are not promoted, and wherein comparatively ripe method only steam explosion and diluted acid temperature is baked two kinds of methods.
Steam explosion (Brownell and Saddler, 1984) is under the situation that does not add any catalyst, utilizes high steam (general 200 ℃～230 ℃) to heat up rapidly, during the H that at high temperature dissociates of the acetate that produces and water
+Most of hydrolysis of hemicellulose in the catalysis lignocellulose, and to change cellulosic crystal formation be that undefined structure is to help follow-up enzymolysis.But, since the acetate that steam explosion produces and the acidity of other number acids a little less than, cause catalytic efficiency lower, reaction rate is slower, half fiber hydrolysis effect is not very desirable (generally only about 65%～70%), and acetate also is that a kind of fermentation suppresses product; Steam explosion lignin removing rate is lower, and the lignin that dissolves when some are not converted into the sugared oligomer of sugar monomer and some high temperature can sedimentation attach to cellulose surface after cooling, influence follow-up enzymolysis; These will not carried out enzymolysis to them with different enzymes by the sugared oligomer of complete hydrolysis simultaneously, therefore will utilize them obviously unrealistic one by one.
It also is the comparatively ripe method of using at present that the diluted acid temperature is baked method (Tsao et al., 1982).Lignocellulose was handled 4～24 hours under near the temperature of 100 ℃ (being generally 90 ℃～95 ℃) with the sulfuric acid (1%～2%) of low concentration, hydrolyzed hemicellulose also changes the cellulose crystal formation, increases its specific area to help follow-up enzymolysis.But the half fiber percent hydrolysis equally also not high (70%～80%) of the roasting method of diluted acid temperature, lignin removing rate is low, and the reaction time of the roasting method of diluted acid temperature is longer, power cost consumes excessive, the long reaction time causes sugar monomer further to generate fermentations such as furfural, formic acid, acetate, hydroxymethylfurfural and suppresses product, influences follow-up enzymolysis.Therefore, pressing for us seeks a kind of new method and replaces existing method to obtain higher sugar yield, lignin removing rate and less inhibition product.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, provide a kind of and can effectively improve hemicellulose conversion ratio in the lignocellulose, lignin removing rate, cellulase hydrolysis conversion ratio and reduce the method that fermentation suppresses product.
Another object of the present invention is to provide a kind of and can cooperate system for carrying out said process.
Purpose of the present invention can reach by following measure:
A kind of combined pretreatment method of lignocellulose, in the recirculation reactor of packing into after the lignocellulose pulverizing, and inject diluted acid, opening circulating pump is to carry out circular response under 50 ℃～200 ℃ in temperature, after finishing, reaction, is used for fermentation with the hydrolyzate deacidification that obtains; In the recirculation reactor after the remaining lignocellulose flushing, put into ball mill and add alkali lye and carry out ball milling, ball milling finishes except that being used for follow-up enzymolysis behind the alkali.
During 50 ℃～100 ℃ circular responses is synthesis under normal pressure; Adopt nitrogen pressure during 100 ℃～200 ℃ circular responses, be pressurized to 2MPa～4MPa.Alkali lye is that concentration is 1%～20% the NaOH aqueous solution, Ca (OH)
2The aqueous solution, Ca (OH)
2Turbid liquid or ammoniacal liquor.
A kind of associating pretreatment system of lignocellulose, comprise reactor, acid storage tank and fluid reservoir, wherein the top of reactor communicates with acid storage tank by pipeline, the bottom of reactor communicates with fluid reservoir by pipeline, it is characterized in that between the import and export of reactor, being serially connected with circulating pump, the inlet of circulating pump communicates with reactor bottom, and outlet of circulating pump communicates with the spray head that is located at reactor head; The inlet of reactor solids material communicates with the outlet of pulverizer, and the outlet of reactor solids material communicates with the ball mill that is connected with storage alkali jar.
Purpose of the present invention specifically can reach by following measure:
A kind of preprocess method of lignocellulose, with lignocellulose (corn stalk, wheat straw, the rice husk straw, bagasse, withy, maize leaves, corncob etc.) be ground into 5～50 purpose particles by pulverizer (as Universalpulverizer), pack into then in the recirculation reactor, and injection diluted acid, opening circulating pump is 50 ℃～200 ℃ (50 ℃～100 ℃ synthesis under normal pressure in temperature, 100 ℃～200 ℃ nitrogen pressure to 2～4MPa reactions) carry out circular response under, soon reactant liquor is ceaselessly extracted out and is added in the reactor again and reacts, after reaction finishes the hydrolyzate (overwhelming majority is the hydrolysis of hemicellulose gained) that obtains is deacidified, filter, be used for fermentation.Wherein said diluted acid is that mass fraction is 0.1%～5% sulfuric acid or hydrochloric acid; The solid-liquid mass ratio of lignocellulose and diluted acid is 1: 5～15.The flow velocity of circulating pump can be 5mL～20L/min.Circular response adopts nitrogen pressure in time more than 100 ℃, is pressurized to 2～4MPa.Reaction time is generally 0.3～5h, and (generally being 0.5～4h), serves as to judge terminal point with the concentration of the hydrolyzate that finally obtains.The interior remaining lignocellulose of recirculation reactor (overwhelming majority is cellulose), was put into ball mill subsequently and is added alkali lye (NaOH/Ca (OH) to remove residual acid with the hot water injection after reaction finished
2/ ammoniacal liquor) carry out ball milling, further to remove delignification, wherein alkali lye (NaOH/Ca (OH)
2/ ammoniacal liquor) mass concentration is 1～20%, the solid-to-liquid ratio of residue lignocellulose and alkali lye is 1: 1～1: 15, the ball milling time is 0.1～5h, reaction temperature is a normal temperature, the ball mill revolution speed is 20～500 commentaries on classics/min, rotational velocity is 50～800 commentaries on classics/min, and ball milling finishes except that being used for follow-up enzymolysis behind the alkali.
A kind of lignocellulose pretreatment system comprises the pulverizing of A lignocellulose, B diluted acid circular treatment, three parts of C ball milling.The lignocellulose pulverising step is pulverized with Universalpulverizer, and diluted acid circular treatment step comprises reactor, acid storage tank and fluid reservoir, and wherein the top of reactor communicates with acid storage tank by pipeline, and the bottom of reactor communicates with fluid reservoir by pipeline; Be serially connected with circulating pump between the import and export of reactor, the inlet of circulating pump communicates with reactor bottom, and outlet of circulating pump communicates with the spray head that is located at reactor head.Also comprise nitrogen cylinder, wherein nitrogen cylinder communicates with described reactor head via pipeline.Top at reactor is provided with the hot water inlet, is provided with waste liquid outlet in the bottom of described reactor.Wherein circulating pump is anti-acid circulating pump.The third step ball milling promptly adds the alkali ball milling with ball mill to the residue lignocellulose, can use 1～6 ball grinder, preferably uses 4 ball grinders, and 4 slack tanks; The material of ball grinder has Stainless Steel, agate, pottery, engineering plastics, polytetrafluoroethylene (PTFE) or polyamine fat.The material of abrading-ball is identical with ball grinder in the ball grinder, and the diameter of abrading-ball is 20mm and 10mm, and the ratio of big ball and bead is 1: 5 or 1: 6.
Lignocellulose pretreatment system provided by the invention, first is a pulverizer; Second portion mainly is made up of reactor, circulating pump, acid storage tank, fluid reservoir, nitrogen cylinder and plurality of pipelines and valve.Reactor is preferably cylindrical, and the above and below is respectively equipped with charging aperture and discharging opening; Top and bottom are hemispherical structure, the top is connected to spray head and links to each other with exterior line, contain acid reaction liquid during preliminary treatment and pass back into reactor again through spray head, spray head contains acid reaction liquid and is distributed in uniformly and is beneficial on the lignocellulosic material the reaction except allowing, and can also suppress the volatilization (temperature below 100 ℃ time) of water when synthesis under normal pressure.The reactor below also is provided with a perforated filter plate, and solid material just can be stayed sustained response in the reactor by stopping of filter plate like this.Circulating pump adopts anti-acid circulating pump.More than 100 ℃ during thermotonus, can also by nitrogen in the nitrogen cylinder to the whole reaction system pressurization so that reaction normally carry out.Third part is made up of ball mill and one storage alkali jar, and four ball grinders can be adorned in ball mill inside, and it is 20mm and 10mm abrading-ball that diameter wherein is housed, and material is put into ball grinder and added the back taking-up of ground caustic mill and be used for follow-up fermentation.
This method provided by the invention is pulverized lignocellulose by first lignocellulose pulverising step and is smaller particle size, increases its specific area, has increased itself and the contact-making surface of catalyst reaction thing, the raising reaction yield.
Second step diluted acid circulation becomes dynamic reactive mode to static in the past reactive mode.Static reactive mode is a still reaction, after lignocellulose hydrolysis a period of time, sugared concentration around it can exceed much than other places, so just be unfavorable for that molecular balance carries out to the direction that generates product, lignocellulose just can not get further hydrolysis, and the diluted acid round-robin method can be taken away near the sugar that generates the lignocellulose by continuous circulation, be diffused in the whole reaction system and go, make to remain lower sugared concentration near the lignocellulose, help its further hydrolysis; Simultaneously, adopt dynamic round-robin method to break up and be blocked in the slower long-chain wood sugar oligomer of lignocellulose surface dissolution, make acid solution can contact with lignocellulose better so that it is carried out catalytic reaction, and can quicken the dissolving of lignin; Therefore this method has improved the lignocellulose particularly percent hydrolysis and the lignin removing rate (Fig. 2) of hemicellulose under the prerequisite that does not influence sugared concentration.All right by the diluted acid round-robin method: 1, react with fixing, the less water yield, reduce water consumption also cuts down the consumption of energy, and itself and fermentation concentration are complementary; 2, according to the difference of follow-up fermentation concentration, also can set the water yield as required during preliminary treatment; 3, the spray head in the device can suppress the volatilization of acid solution, reacting under non-pressurized condition under 100 ℃, cuts down the consumption of energy; 4, during circular response after sugar generates in reactor, in the rapid flow ipe of meeting, this moment, the temperature in the reacting pipe was not as high in the reactor, so sugar can not be continued reaction and be accessory substances such as furfural, therefore needn't consider the problem that accessory substance increases in course of reaction.
The 3rd step alkalescence ball milling can further remove delignification and increase the specific area of lignocellulose, is beneficial to follow-up enzymolysis.Lignocellulose is after the second step diluted acid circular treatment, still some lignin is wherein residual, the existence of these lignin can hinder cellulosic enzymolysis, after adding alkali, can destroy the structure of lignin, arrive the purpose of dissolved lignin, alkali lye opens lignocellulose cell membrane top hydrogen bond by limited swelling in addition, increase the porosity on the cell wall, improve the permeability of timber.Pass through infinite swelling, cellulose is dissolved, this phenomenon especially easily occurs on the cellulose of low polymerization degree in the amorphous region, so alkali lye is to the dissolving of the low polymerization degree carbohydrate tool in cellulose extracting effect, the pit and the capillary channel of partial blockage are opened, be of value to the infiltration of solution, it can impel cellulosic crystalline form to change, make its expansion, cellulosic crystalline form from parallel (parallel) structure via transition state to antiparallel (anti-parallel) structure (Fig. 1), the cellulosic degree of disorder increases, entropy increases, reaching a more stable structure on thermodynamics, is corresponding with foregoing expansion promptly.Under this structure, the degree of polymerization of microfiber reduces.These make that all in enzymolysis process, enzyme can fully contact with reactant, save the consumption of cellulase and reach desirable hydrolysis result.Abrading-ball in the ball milling adopts the method for big ball collocation bead, can be used for counterweight and smash sample and disperse bead by big ball, is used for mixing and ground sample by bead, can make ball milling reach the highest efficient like this, make abrasive grains littler, specific area is bigger, is more conducive to follow-up enzymolysis.
Method of the present invention can improve hemicellulose conversion ratio in the lignocellulose, lignin removing rate, cellulase hydrolysis conversion ratio effectively and reduce fermentation and suppress product, enzyme dosage in the time of simultaneously can also reducing enzymolysis, shortening reaction time, improve sugared concentration, and can set pretreated water consumption according to the needs of follow-up fermentation concentration.
Description of drawings
The change schematic diagram of cellulose crystal formation after Fig. 1 alkali treatment.
The comparison diagram of the roasting method preliminary treatment maize straw wood sugar conversion ratio of this pretreatment system of Fig. 2 and diluted acid temperature.
Fig. 3 embodiment 1 (A) and Comparative Examples 1 (B) enzymolysis conversion ratio comparison diagram under different cellulase activities.
Fig. 4 is a diluted acid circulating device flow chart.
Among the figure: 1-8. valve, 9. circulating pump, 10. reactor, 11. discharging openings, 12. charging apertures, 13. filter plate, 14. spray heads, 15. acid storage tanks, 16. fluid reservoirs, 17. nitrogen cylinders, 18. nitrogen valve, 19. Universalpulverizers, 20. storage alkali jars, 21. ball mills, 22-25. stainless steel jar mill.
The specific embodiment
Embodiment 1
Air-dry corn stalk (moisture 12.82%, alcohol benzene extractive 17.44%, cellulose 40.08%, hemicellulose 20.03%, lignin 19.95%, ash content 5.52%) is ground into 40 purpose particles through Universalpulverizer 19, then from the charging aperture 12 diluted acid circulating device 10 of packing into, open valve 1, valve 2, from acid storage tank 15, inject 0.8% rare H
2SO
4In reactor, maize straw and rare H
2SO
4Solid-to-liquid ratio be 1: 10; Open valve 3, valve 4, shut off valve 1, valve 2, start circulating pump 9, flow is made as 10L/min, liquid level is positioned at the upper end of filter plate 13 during reaction, and at 95 ℃ of following circular response 4h, the liquid part circulates by filter plate 13 during reaction, the solid material part stops by filter plate 13 to be stayed in the reactor, and liquid is partly through getting back in the reactor in the mode of spray by spray head 14 behind the pump 9 again; Reaction finishes back shut off valve 4 and pump 9, opens valve 2, valve 5 and breather valve 7, and reactant liquor flows into fluid reservoir 16, through Ca (OH)
2Neutralization is used for follow-up fermentation; Shut off valve 5 and breather valve 7 are opened valve 8 and valve 6, and logical 95 ℃ of hot water (PL) flushing solid, residual diluted acid of flush away and lignin, waste liquid (CS) are discharged through valve 6 and be used for subsequent processes; Open discharging opening 11 at last, remaining cellulose is taken out, four stainless steel jar mill 22,23,24,25 of input ball mill 21, from storage alkali jar 20, import 5% (WT) NaOH simultaneously in wherein, solid-to-liquid ratio is 1: 6 in the ball grinder, take out behind the opening power ball milling 30min, after removing alkali, be used for follow-up enzymatic hydrolysis and fermentation.Half fiber conversion ratio reaches 98%, and xylose concentration is 15.7g/L; Lignin removing rate reaches 94.3%; Cellulose (50 ℃ of enzymolysis 48h under the cellulase effect of 10FPU/g glucan, pH4.8), yield 95.2%, enzymolysis 48h is (50 ℃ under the cellulase effect of 15FPU/g glucan, pH4.8), yield 96.7%, and enzymolysis 48h under the cellulase of 20FPU/g glucan (50 ℃, pH4.8), yield 96.9%, enzymolysis 48h under the cellulase of 60FPU/g glucan (0 ℃, pH4.8), yield 99.1%.
Embodiment 2
Air-dry corn stalk (moisture 12.82%, alcohol benzene extractive 17.44%, cellulose 40.08%, hemicellulose 20.03%, lignin 19.95%, ash content 5.52%) is ground into 50 purpose particles through Universalpulverizer 19, then from the charging aperture 12 diluted acid circulating device 10 of packing into, open valve 1, valve 2, from acid storage tank 15, inject 0.8% rare H
2SO
4In reactor, maize straw and rare H
2SO
4Solid-to-liquid ratio be 1: 10; Open valve 3, valve 4, shut off valve 1, valve 2, start circulating pump 9, flow is made as 10L/min, liquid level is positioned at the upper end of filter plate 13 during reaction, and at 90 ℃ of following circular response 4h, the liquid part circulates by filter plate 13 during reaction, the solid material part stops by filter plate 13 to be stayed in the reactor, and liquid is partly through getting back in the reactor in the mode of spray by spray head 14 behind the pump 9 again; Reaction finishes back shut off valve 4 and pump 9, opens valve 2, valve 5 and breather valve 7, and reactant liquor flows into fluid reservoir 16, through Ca (OH)
2Neutralization is used for follow-up fermentation; Shut off valve 5 and breather valve 7 are opened valve 8 and valve 6, and logical 95 ℃ of hot water (PL) flushing solid, residual diluted acid of flush away and lignin, waste liquid (CS) are discharged through valve 6 and be used for subsequent processes; Open discharging opening 11 at last, remaining cellulose is taken out, four stainless steel jar mill 22,23,24,25 of input ball mill 21, from storage alkali jar 20, import 3% (WT) NaOH simultaneously in wherein, solid-to-liquid ratio is 1: 7 in the ball grinder, take out behind the opening power ball milling 30min, after removing alkali, be used for follow-up enzymatic hydrolysis and fermentation.Half fiber conversion ratio reaches 79.9%, and xylose concentration is 12.8g/L; Lignin removing rate reaches 90.7%; Cellulose under the cellulase effect of 10FPU/g glucan enzymolysis 48h (50 ℃, pH4.8), yield 91.4%.
Embodiment 3
Air-dry corn stalk (moisture 12.82%, alcohol benzene extractive 17.44%, cellulose 40.08%, hemicellulose 20.03%, lignin 19.95%, ash content 5.52%) is ground into 50 purpose particles through Universalpulverizer 19, then from the charging aperture 12 diluted acid circulating device 10 of packing into, open valve 1, valve 2, from acid storage tank 15, inject 0.98% rare H
2SO
4In reactor, maize straw and rare H
2SO
4Solid-to-liquid ratio be 1: 6; Open valve 3, valve 4, shut off valve 1 is opened nitrogen valve 18, feeds N from nitrogen cylinder 17
2Be pressurized to 2.5MP, start circulating pump 9, flow is made as 10L/min, liquid level is positioned at the upper end of filter plate 13 during reaction, and at 105 ℃ of following circular response 2h, the liquid part circulates by filter plate 13 during reaction, the solid material part stops by filter plate 13 to be stayed in the reactor, and liquid is partly through getting back in the reactor in the mode of spray by spray head 14 behind the pump 9 again; Reaction finishes back shut off valve 4 and pump 9, closes nitrogen valve 18, opens valve 5 and breather valve 7, and reactant liquor flows into fluid reservoir 16, through Ca (OH)
2Neutralization is used for follow-up fermentation; Shut off valve 5 and breather valve 7 are opened valve 8 and valve 6, and logical 95 ℃ of hot water (PL) flushing solid, residual diluted acid of flush away and lignin, waste liquid (CS) are discharged through valve 6 and be used for subsequent treatment; Open discharging opening 11 at last, remaining cellulose is taken out, four stainless steel jar mill 22,23,24,25 of input ball mill 21, from storage alkali jar 20, import 3% (WT) NaOH simultaneously in wherein, solid-to-liquid ratio is 1: 7 in the ball grinder, take out behind the opening power ball milling 30min, after removing alkali, be used for follow-up enzymatic hydrolysis and fermentation.Half fiber conversion ratio reaches 95.4%, and xylose concentration is 25.4g/L; Lignin removing rate reaches 96.7%; Cellulose under the cellulase effect of 10FPU/g glucan enzymolysis 48h (50 ℃, pH4.8), yield 97.4%.
Embodiment 4
Air-dry corn stalk (moisture 12.82%, alcohol benzene extractive 17.44%, cellulose 40.08%, hemicellulose 20.03%, lignin 19.95%, ash content 5.52%) is ground into 50 purpose particles through Universalpulverizer 19, then from the charging aperture 12 diluted acid circulating device 10 of packing into, open valve 1, valve 2, from acid storage tank 15, inject 0.98% rare H
2SO
4In reactor, maize straw and rare H
2SO
4Solid-to-liquid ratio be 1: 8; Open valve 3, valve 4, shut off valve 1 is opened nitrogen valve 18, feeds N from nitrogen cylinder 17
2Be pressurized to 2.5MP, start circulating pump 9, flow is made as 10L/min, liquid level is positioned at the upper end of filter plate 13 during reaction, and at 120 ℃ of following circular response 30min, the liquid part circulates by filter plate 13 during reaction, the solid material part stops by filter plate 13 to be stayed in the reactor, and liquid is partly through getting back in the reactor in the mode of spray by spray head 14 behind the pump 9 again; Reaction finishes back shut off valve 4 and pump 9, closes nitrogen valve 18, opens valve 5 and breather valve 7, and reactant liquor flows into fluid reservoir 16, through Ca (OH)
2Neutralization is used for follow-up fermentation; Shut off valve 5 and breather valve 7 are opened valve 8 and valve 6, and logical 95 ℃ of hot water (PL) flushing solid, residual diluted acid of flush away and lignin, waste liquid (CS) are discharged through valve 6 and be used for subsequent treatment; Open discharging opening 11 at last, remaining cellulose is taken out, four stainless steel jar mill 22,23,24,25 of input ball mill 21, from storage alkali jar 20, import 3% (WT) NaOH simultaneously in wherein, solid-to-liquid ratio is 1: 7 in the ball grinder, take out behind the opening power ball milling 30min, after removing alkali, be used for follow-up enzymatic hydrolysis and fermentation.Half fiber conversion ratio reaches 96.8%, and xylose concentration is 19.1g/L; Lignin removing rate reaches 93.7%; Cellulose under the cellulase effect of 10FPU/g glucan enzymolysis 48h (50 ℃, pH4.8), yield 98.9%.
Embodiment 5
Air-dry corn stalk (moisture 12.82%, alcohol benzene extractive 17.44%, cellulose 40.08%, hemicellulose 20.03%, lignin 19.95%, ash content 5.52%) is ground into 40 purpose particles through Universalpulverizer 19, then from the charging aperture 12 diluted acid circulating device 10 of packing into, open valve 1, valve 2, inject 1.2% watery hydrochloric acid in reactor from acid storage tank 15, the solid-to-liquid ratio of maize straw and watery hydrochloric acid is 1: 10; Open valve 3, valve 4, shut off valve 1, valve 2, start circulating pump 9, flow is made as 10L/min, liquid level is positioned at the upper end of filter plate 13 during reaction, and at 95 ℃ of following circular response 4h, the liquid part circulates by filter plate 13 during reaction, the solid material part stops by filter plate 13 to be stayed in the reactor, and liquid is partly through getting back in the reactor in the mode of spray by spray head 14 behind the pump 9 again; Reaction finishes back shut off valve 4 and pump 9, opens valve 2, valve 5 and breather valve 7, and reactant liquor flows into fluid reservoir 16, through Ca (OH)
2Neutralization is used for follow-up fermentation; Shut off valve 5 and breather valve 7 are opened valve 8 and valve 6, and logical 95 ℃ of hot water (PL) flushing solid, residual diluted acid of flush away and lignin, waste liquid (CS) are discharged through valve 6 and be used for subsequent processes; Open discharging opening 11 at last, remaining cellulose is taken out, four stainless steel jar mill 22,23,24,25 of input ball mill 21, from storage alkali jar 20, import 5% (WT) NaOH simultaneously in wherein, solid-to-liquid ratio is 1: 6 in the ball grinder, take out behind the opening power ball milling 30min, after removing alkali, be used for follow-up enzymatic hydrolysis and fermentation.Half fiber conversion ratio reaches 93.7%, and xylose concentration is 16.7g/L; Lignin removing rate reaches 92.3%; Cellulose under the cellulase of 10FPU/g glucan enzymolysis 48h (50 ℃, pH4.8), yield 97.1%.
Comparative Examples 1
In the reactor of packing into after the air-dry pulverizing of corn stalk (moisture 12.82%, alcohol benzene extractive 17.44%, cellulose 40.08%, hemicellulose 20.03%, lignin 19.95%, ash content 5.52%), inject 0.8% rare H
2SO
4In reactor, maize straw and rare H
2SO
4Solid-to-liquid ratio be 1: 10; React 8h down at 95 ℃; Reaction finishes afterreaction liquid through Ca (OH)
2Neutralization is used for follow-up fermentation, and solid portion leads to 95 ℃ of hot water injections, and residual diluted acid of flush away and lignin, waste liquid are discharged and be used for subsequent treatment; Last remaining cellulose takes out, and is used for follow-up enzymatic hydrolysis and fermentation.Half fiber conversion ratio reaches 75.1%, and xylose concentration is 12.03g/L; Lignin removing rate reaches 15.5%; Cellulose (50 ℃ of enzymolysis 48h under the cellulase effect of 10FPU/g glucan, pH4.8), yield 39.4%, cellulose (50 ℃ of enzymolysis under the cellulase effect of 15FPU/g glucan, pH4.8), yield 47.3%, cellulose under the cellulase effect of 20FPU/g glucan enzymolysis 48h (50 ℃, pH4.8), yield 53.7%, cellulose under the cellulase of 60FPU/g glucan enzymolysis 48h (50 ℃, pH4.8), yield 70.4%.
Comparative Examples 2
The air-dry pulverizing of corn stalk (moisture 12.82%, alcohol benzene extractive 17.44%, cellulose 40.08%, hemicellulose 20.03%, lignin 19.95%, ash content 5.52%) is packed in the reactor, inject 0.8% rare H
2SO
4In reactor, maize straw and rare H
2SO
4Solid-to-liquid ratio be 1: 10; React 8h down at 90 ℃; After reaction finished, reactant liquor was through Ca (OH)
2Neutralization is used for follow-up fermentation, and solid portion leads to 95 ℃ of hot water injections, and residual diluted acid of flush away and lignin, waste liquid are discharged and be used for subsequent processes; Last remaining cellulose takes out, and is used for follow-up enzymatic hydrolysis and fermentation.Half fiber conversion ratio reaches 61.3%, and xylose concentration is 9.8g/L; Lignin removing rate reaches 11.3%; Cellulose under the cellulase of 60FPU/g glucan enzymolysis 48h (50 ℃, pH4.8), yield 57.5%.
Comparative Examples 3
In the reactor of packing into after the air-dry pulverizing of corn stalk (moisture 12.82%, alcohol benzene extractive 17.44%, cellulose 40.08%, hemicellulose 20.03%, lignin 19.95%, ash content 5.52%), inject 0.8% rare H
2SO
4In reactor, maize straw and rare H
2SO
4Solid-to-liquid ratio be 1: 10; At 105 ℃ of 2.5MP reaction 8h that pressurize down; Reaction finishes afterreaction liquid through Ca (OH)
2Neutralization is used for follow-up fermentation, and solid portion leads to 95 ℃ of hot water injections, and residual diluted acid of flush away and lignin, waste liquid are discharged and be used for subsequent treatment; Last remaining cellulose takes out, and is used for follow-up enzymatic hydrolysis and fermentation.Half fiber conversion ratio reaches 81.3%, and xylose concentration is 13.0g/L; Lignin removing rate reaches 33.7%; Cellulose under the cellulase effect of cellulose at the 60FPU/g glucan enzymolysis 48h (50 ℃, pH4.8), yield 76.8%.
Comparative Examples 4
In the reactor of packing into after the air-dry pulverizing of corn stalk (moisture 12.82%, alcohol benzene extractive 17.44%, cellulose 40.08%, hemicellulose 20.03%, lignin 19.95%, ash content 5.52%), inject 0.8% rare H
2SO
4In reactor, maize straw and rare H
2SO
4Solid-to-liquid ratio be 1: 10; At 120 ℃ of 2.5MP reaction 8h that pressurize down; Reaction finishes afterreaction liquid through Ca (OH)
2Neutralization is used for follow-up fermentation, and solid portion leads to 95 ℃ of hot water injections, and residual diluted acid of flush away and lignin, waste liquid are discharged and be used for subsequent treatment; Last remaining cellulose takes out, and is used for follow-up enzymatic hydrolysis and fermentation.Half fiber conversion ratio reaches 85.9%, and xylose concentration is 13.7g/L; Lignin removing rate reaches 39.6%; Cellulose under the cellulase effect of 60FPU/g glucan enzymolysis 48h (50 ℃, pH4.8), yield 80.2%.
Claims (9)
1, a kind of combined pretreatment method of lignocellulose, it is characterized in that in the recirculation reactor of packing into after the lignocellulose pulverizing, and inject diluted acid, opening circulating pump is to carry out circular response under 50～200 ℃ in temperature, after finishing, reaction, is used for fermentation with the hydrolyzate deacidification that obtains; In the recirculation reactor after the remaining lignocellulose flushing, put into ball mill and add alkali lye and carry out ball milling, ball milling finishes except that being used for follow-up enzymolysis behind the alkali; Wherein said diluted acid is that mass fraction is 0.1%～5% sulfuric acid or hydrochloric acid.
2, preprocess method according to claim 1 is characterized in that before the circular response be 5～50 purpose particles with the lignocellulose pulverizing earlier.
3, preprocess method according to claim 1, the solid-liquid mass ratio that it is characterized in that lignocellulose and diluted acid is 1: 5～15.
4, preprocess method according to claim 1 is a synthesis under normal pressure when it is characterized in that 50 ℃～100 ℃ circular responses; Adopt nitrogen pressure during smaller or equal to 200 ℃ of circular responses greater than 100 ℃, be pressurized to 2～4MPa.
5, preprocess method according to claim 1 is characterized in that described alkali lye is that concentration is 1～20% the NaOH aqueous solution, Ca (OH)
2The aqueous solution, Ca (OH)
2Turbid liquid or ammoniacal liquor.
6, preprocess method according to claim 1, the solid-to-liquid ratio that it is characterized in that remaining lignocellulose and alkali lye is 1: 1～1: 15, the ball milling time is 0.1～5h.
7, a kind of associating pre-processing device of lignocellulose, comprise reactor, acid storage tank and fluid reservoir, wherein the top of reactor communicates with acid storage tank by pipeline, the bottom of reactor communicates with fluid reservoir by pipeline, it is characterized in that between the import and export of reactor, being serially connected with circulating pump, the inlet of circulating pump communicates with reactor bottom, and outlet of circulating pump communicates with the spray head that is located at reactor head; The inlet of reactor solids material communicates with the outlet of pulverizer, and the outlet of reactor solids material communicates with the ball mill that is connected with storage alkali jar.
8, the associating pre-processing device of lignocellulose according to claim 7 is characterized in that also comprising nitrogen cylinder, and wherein nitrogen cylinder communicates with described reactor head via pipeline.
9, the associating pre-processing device of lignocellulose according to claim 7 is characterized in that being provided with the hot water inlet at the top of described reactor, is provided with waste liquid outlet in the bottom of described reactor.
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Families Citing this family (29)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103045691B (en) * | 2011-10-11 | 2014-04-30 | 济南圣泉集团股份有限公司 | Comprehensive utilization method of lignocellulose biomass |
| CN103045684B (en) * | 2011-10-11 | 2014-03-12 | 济南圣泉集团股份有限公司 | Comprehensive utilization method of lignocellulose biomass |
| CN103045694B (en) * | 2011-10-11 | 2014-03-12 | 济南圣泉集团股份有限公司 | Comprehensive utilization method of lignocellulose biomass |
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| CN103131021A (en) * | 2013-02-21 | 2013-06-05 | 中国科学院过程工程研究所 | Method for improving lignin activity by wet ball milling |
| CN104611392B (en) * | 2013-11-05 | 2018-04-10 | 中国石油化工股份有限公司 | A kind of method for removing diluted acid and steaming mortifier in quick-fried lignocellulosic material |
| CN103669065B (en) * | 2013-12-15 | 2016-02-03 | 兰州大学 | A kind of method utilizing wheat stalk to prepare string |
| CN104498562A (en) * | 2014-12-17 | 2015-04-08 | 江苏大学 | Method for pretreating agricultural waste biomass by adopting sodium hydroxide/urea/water system |
| CN104911164A (en) * | 2015-05-11 | 2015-09-16 | 镇江博睿兴邦生物科技有限公司 | Method for improving cellulase use efficiency, and apparatus thereof |
| CN105969821A (en) * | 2016-06-02 | 2016-09-28 | 广西大学 | Lignocellulose biomass saccharifying method with mechanical activation cooperated with sodium hydroxide solid phase reinforcement |
| CN105886575A (en) * | 2016-06-02 | 2016-08-24 | 广西大学 | Method for saccharifying wood fiber raw material through mechanical activation in cooperation with alkali solid phase reinforcement |
| CN106047962A (en) * | 2016-06-02 | 2016-10-26 | 广西大学 | Saccharifying method for achieving solid-phase strengthening of lignocellulosic materials by means of mechanical activation and calcium hydroxide |
| CN107201685B (en) * | 2017-05-17 | 2019-01-22 | 武汉理工大学 | The pilot production line and its technique of Cellulose nanocrystal are extracted from biomass resource |
| CN110669806A (en) * | 2019-09-29 | 2020-01-10 | 北京林业大学 | Synergistic pretreatment method for improving tobacco stalk hemicellulose yield and cellulose enzymolysis rate |
| CN112170460A (en) * | 2020-09-30 | 2021-01-05 | 王礼红 | Organic garbage high-temperature dry-type anaerobic fermentation equipment |
| CN113355934A (en) * | 2021-05-13 | 2021-09-07 | 广东宝杰环保科技有限公司 | Lignocellulose extraction device and method |
-
2008
- 2008-02-28 CN CNB2008100202262A patent/CN100564667C/en not_active Expired - Fee Related
Non-Patent Citations (6)
| Title |
|---|
| 利用木质纤维原料制取燃料乙醇预处理方法的研究进展. 幸婷等.现代化工，第27卷第增刊(2)期. 2007 |
| 利用木质纤维原料制取燃料乙醇预处理方法的研究进展. 幸婷等.现代化工，第27卷第增刊(2)期. 2007 * |
| 木质纤维素生物质生产乙醇的预处理技术. 辛芬等.能源工程，第3期. 2006 |
| 木质纤维素生物质生产乙醇的预处理技术. 辛芬等.能源工程，第3期. 2006 * |
| 木质纤维素预处理技术研究进展. 朱跃钊等.生物加工过程，第2卷第4期. 2004 |
| 木质纤维素预处理技术研究进展. 朱跃钊等.生物加工过程，第2卷第4期. 2004 * |
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