CN101235606B - Lignocellulose pretreatment method and system - Google Patents
Lignocellulose pretreatment method and system Download PDFInfo
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- CN101235606B CN101235606B CN2008100202281A CN200810020228A CN101235606B CN 101235606 B CN101235606 B CN 101235606B CN 2008100202281 A CN2008100202281 A CN 2008100202281A CN 200810020228 A CN200810020228 A CN 200810020228A CN 101235606 B CN101235606 B CN 101235606B
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Abstract
The invention discloses a pretreatment method of lignocellulose, which comprises the steps of loading the lignocellulose into a circulating reactor, injecting dilute acid, opening a circulating pump to carry out circulating reaction at the temperature of 50-200 ℃, and removing acid and filtering obtained hydrolysate for fermentation after the reaction is finished. The invention also discloses a system applied to the method. The method can effectively improve the conversion rate of hemicellulose and the cellulose enzymolysis conversion rate in the lignocellulose, reduce fermentation inhibition products, shorten the pretreatment time and reduce the energy consumption.
Description
Technical field
The invention belongs to the chemical industry equipment field, be specifically related to a kind of diluted acid that utilizes and carry out the pretreated method and apparatus 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; 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, 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, press for us and seek a kind of new method to obtain higher sugar yield and less inhibition product replaces existing method.
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 equipment that can cooperate said method.
Purpose of the present invention 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.) pack 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 are to 2MPa～4MPa reaction) under carry out circular response, 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 is 5～10L/min.Circular response adopts nitrogen pressure in time more than 100 ℃, is pressurized to 2MPa～4MPa.
Reaction finishes remaining lignocellulose in the recirculation reactor of back (overwhelming majority is cellulose) water flushing back takes out and is used for follow-up enzymolysis, promptly earlier with the hot water injection to remove residual acid and residual lignin, taking-up subsequently is used for follow-up enzymolysis.Reaction time of the present invention is generally 0.3h～5h, and (generally being 0.5h～4h), is endpoint with the concentration of the hydrolyzate that finally obtains.
A kind of lignocellulose pretreatment system 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.
This pretreatment system also comprises nitrogen cylinder, and 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.
This method provided by the invention becomes dynamic reactive mode to static in the past reactive mode by the diluted acid circulation.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. 1) of hemicellulose under the prerequisite that does not influence sugared concentration.
The present invention is 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.
Lignocellulose pretreatment system provided by the invention 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 filter plate with holes, 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.
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, can also cut down the consumption of energy simultaneously, shorten the reaction time, improve sugared concentration, and can set pretreated water consumption according to the needs of follow-up fermentation concentration.
Description of drawings
Fig. 1 is the comparison diagram of diluted acid round-robin method (reaction 4h) and the roasting method of diluted acid temperature (reaction 8h) preliminary treatment maize straw wood sugar conversion ratio.
Fig. 2 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 plates, 14. spray heads, 15. acid storage tanks, 16. fluid reservoirs, 17. nitrogen cylinders, 18. nitrogen valves.
The specific embodiment
Embodiment 1
With 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%) back 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 treatment; Open discharging opening 11 at last, remaining cellulose is taken out, be used for follow-up enzymatic hydrolysis and fermentation.Half fiber conversion ratio reaches 98.0%, and xylose concentration is 15.7g/L; Lignin removing rate reaches 75%; Cellulose under the cellulase effect of 15FPU/g glucan enzymolysis 48h (50 ℃, pH4.8), yield 73.7%.
With 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%) back 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 treatment; Open discharging opening 11 at last, remaining cellulose is taken out, 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 69.2%; Cellulose under the cellulase effect of 15FPU/g glucan enzymolysis 48h (50 ℃, pH4.8), yield 65.4%.
Embodiment 3
With 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%) back 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 85 ℃ 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 treatment; Open discharging opening 11 at last, remaining cellulose is taken out, be used for follow-up enzymatic hydrolysis and fermentation.Half fiber conversion ratio reaches 63.2%, and xylose concentration is 10.1g/L; Lignin removing rate reaches 62.3%; Cellulose under the cellulase effect of 15FPU/g glucan enzymolysis 48h (50 ℃, pH4.8), yield 52.1%.
Embodiment 4
With 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%) back 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 80 ℃ 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 treatment; Open discharging opening 11 at last, remaining cellulose is taken out, be used for follow-up enzymatic hydrolysis and fermentation.Half fiber conversion ratio reaches 56.7%, and xylose concentration is 9.1g/L; Lignin removing rate reaches 53.6%; Cellulose under the cellulase effect of 15FPU/g glucan enzymolysis 48h (50 ℃, pH4.8), yield 41.8%.
With 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%) back 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 75 ℃ 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 treatment; Open discharging opening 11 at last, remaining cellulose is taken out, be used for follow-up enzymatic hydrolysis and fermentation.Half fiber conversion ratio reaches 39.3%, and xylose concentration is 6.2g/L; Lignin removing rate reaches 45.3%; Cellulose under the cellulase effect of 15FPU/g glucan enzymolysis 48h (50 ℃, pH4.8), yield 23.3%.
Embodiment 6
With 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%) back 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: 9; 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 treatment; Open discharging opening 11 at last, remaining cellulose is taken out, 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 75.3%; Cellulose under the cellulase effect of cellulose at the 15FPU/g glucan enzymolysis 48h (50 ℃, pH4.8), yield 71.3%.
With 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%) back 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: 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 150 ℃ 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, 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 68.9%; Cellulose under the cellulase effect of 15FPU/g glucan enzymolysis 48h (50 ℃, pH4.8), yield 78.4%.
With 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%) back from the charging aperture 12 diluted acid circulating device 10 of packing into, open valve 1, valve 2, inject 1.5% watery hydrochloric acid in reactor from acid storage tank 15, the solid-to-liquid ratio of maize straw and watery hydrochloric acid is 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 150 ℃ 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, be used for follow-up enzymatic hydrolysis and fermentation.Half fiber conversion ratio reaches 92.6%, and xylose concentration is 18.6g/L; Lignin removing rate reaches 71.5%; Cellulose under the cellulase effect of 15FPU/g glucan enzymolysis 48h (50 ℃, pH4.8), yield 77.9%.
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; 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 12.1g/L; Lignin removing rate reaches 15.5%; Cellulose under the cellulase effect of 15FPU/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 ℃, reaction finishes afterreaction liquid through Ca (OH)
2Neutralization is used for follow-up fermentation; 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 61.3%, and xylose concentration is 9.8g/L; Lignin removing rate reaches 11.3%; Cellulose under the cellulase effect of 15FPU/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; React 8h down at 85 ℃, reaction finishes afterreaction liquid through Ca (OH)
2Neutralization is used for follow-up fermentation; 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 54.5%, and xylose concentration is 8.7g/L; Lignin removing rate reaches 8.7%; Cellulose under the cellulase effect of 15FPU/g glucan enzymolysis 48h (50 ℃, pH4.8), yield 49.8%.
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; React 8h down at 80 ℃, reaction finishes afterreaction liquid through Ca (OH)
2Neutralization is used for follow-up fermentation; 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 32.2%, and xylose concentration is 5.2g/L; Lignin removing rate reaches 7.1%; Cellulose under the cellulase effect of 15FPU/g glucan enzymolysis 48h (50 ℃, pH4.8), yield 37.9%.
Comparative Examples 5
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 75 ℃, reaction finishes reactant liquor through Ca (OH)
2Neutralization is used for follow-up fermentation; 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 17.3%, and xylose concentration is 2.8g/L; Lignin removing rate reaches 5.5%; Cellulose under the cellulase effect of 15FPU/g glucan enzymolysis 48h (50 ℃, pH4.8), yield 13.5%.
Claims (3)
1. the preprocess method of a lignocellulose, it is characterized in that lignocellulose is packed in the recirculation reactor, and injection diluted acid, opening circulating pump is to carry out the normal pressure circular response under 50～100 ℃ in temperature, during circular response, after sugar generates in reactor, rapidly in the flow ipe, temperature in the reacting pipe is lower than reactor, the liquid that reaction generates is partly through getting back in the reactor in the mode of spray by spray head behind the circulating pump again, after finishing, reaction, is used for fermentation with the hydrolyzate deacidification, the filtration that obtain; Wherein said diluted acid is that mass fraction is 0.1%～5% sulfuric acid or hydrochloric acid.
2. 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.
3. preprocess method according to claim 1 is characterized in that remaining lignocellulose water flushing back taking-up is used for follow-up enzymolysis in the recirculation reactor of reaction end back.
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| CN103045692B (en) * | 2011-10-11 | 2014-10-01 | 济南圣泉集团股份有限公司 | Comprehensive utilization method of lignocellulose biomass |
| WO2013124460A2 (en) * | 2012-02-24 | 2013-08-29 | Chemtex Italia S.P.A. | Continuous process for conversion of lignin to useful compounds |
| CN102605020B (en) * | 2012-03-29 | 2013-07-31 | 天津大学 | Method for improving lignocellulose enzymolysis and saccharification efficiency |
| 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 |
| CN104611391B (en) * | 2013-11-05 | 2018-08-14 | 中国石油化工股份有限公司 | A kind of method that lignocellulosic material prepares hydrolysis sugar |
| CN105112459A (en) * | 2015-09-23 | 2015-12-02 | 大连工业大学 | Lignocellulose biomass circulating, strengthening and pre-hydrolyzing process |
| CN106311081A (en) * | 2016-10-21 | 2017-01-11 | 大连理工大学 | Disacidifying device and method in intermittent hydrolysis kettle |
| CN110549456B (en) * | 2019-08-01 | 2021-09-28 | 四川金象赛瑞化工股份有限公司 | Method for preparing furfural and co-producing glue-free fiberboard from reed |
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