CN106191135A - Lignocellulose is the biorefinery method of raw material coproduction multi-product - Google Patents
Lignocellulose is the biorefinery method of raw material coproduction multi-product Download PDFInfo
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- CN106191135A CN106191135A CN201610566610.7A CN201610566610A CN106191135A CN 106191135 A CN106191135 A CN 106191135A CN 201610566610 A CN201610566610 A CN 201610566610A CN 106191135 A CN106191135 A CN 106191135A
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
- C12P7/04—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
- C12P7/06—Ethanol, i.e. non-beverage
- C12P7/08—Ethanol, i.e. non-beverage produced as by-product or from waste or cellulosic material substrate
- C12P7/10—Ethanol, i.e. non-beverage produced as by-product or from waste or cellulosic material substrate substrate containing cellulosic material
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
- C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
- C07D307/48—Furfural
- C07D307/50—Preparation from natural products
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/14—Hemicellulose; Derivatives thereof
- C08B37/146—Hemicellulose; Derivatives thereof composed by gluco and/or galactomannans, for example guar gum, locust bean gum (not used)
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H8/00—Macromolecular compounds derived from lignocellulosic materials
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P2201/00—Pretreatment of cellulosic or lignocellulosic material for subsequent enzymatic treatment or hydrolysis
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Abstract
The invention provides a kind of biorefinery method that lignocellulose is raw material coproduction multi-product, it is that 50 80% aqueous formic acids carry out pretreatment to raw material including using mass concentration, realize efficiently separating of cellulose in raw material, hemicellulose and lignin, converting cellulose into ethanol further, lignin conversion is activated carbon and solid acid and hemicellulose is converted into furfural.The biorefinery method that the present invention provides can achieve the diversification of raw material and high-valued conversion, significantly improves process economics, and formic acid can recycle, have significant environmental benefit.
Description
Technical field
The present invention relates to biomass chemical field, be specifically related to the biology that a kind of lignocellulose is raw material coproduction multi-product
Method for refining.
Background technology
Lignocellulose raw material is Organic substance the abundantest in nature.According to estimates, plant passes through photosynthesis every year
The dry produced is up to 1500-2000 hundred million tons, is uniquely can the material object resource of ultra-large regeneration on the earth.In China,
The annual agricultural crop straw produced has more than 700,000,000 ton, is equivalent to 3.5 hundred million tons of standard coals, but every year for industrial process or burning
Cellulose resource only accounts for about 2%, also has the most not utilized.
Biorefinery is with renewable biomass as raw material, in conjunction with multiple physics, chemical and biological method produce fuel,
The refining process of material, chemicals and electric energy.And lignocellulose is one of main processing object of biorefinery.Wooden fibre
Three big key components of dimension element are cellulose, hemicellulose and lignin.Cellulose is the main component constituting lignocellulose,
40-55% is accounted in wood fiber raw material.And account for 25-50% in grass biomass.Cellulose is by pyrans formula Fructus Vitis viniferae
The linear giant molecule that sugar is linked by β-Isosorbide-5-Nitrae-glycosidic bond, its repetitive is cellobiose, obtains single after hydrolysis
Glucose, can be used as carbon source by microorganism and be converted into multi-chemical and fuel, such as ethanol.Hemicellulose is lignocellulose
In main polysaccharide in addition to cellulose.Hemicellulose is not a kind of single compound, but the general name of a group complex plycan,
Mainly include xylan, mannan, xyloglucan etc..Wherein the hemicellulose of grass is mainly araban 4-
O-methyl glucose alduronic acid xylose, obtains the mixed sugar based on xylose after hydrolysis, these sugar also can be further converted to biology
Fuel and other chemicals.Lignin is one of key component of lignocellulose, and its content in cork is 18-35%, firmly
Wood is 18-25%, straw or like vegetable is 10-30%.The amorphous polymer that lignin is made up of phenylpropyl alcohol alkane cellular construction,
There is compared with cellulose and hemicellulose higher carbon content, and be difficult to the utilization that is degraded by microorganisms.
In lignocellulose raw material bioconversion produces fermentable sugars and ethanol process, due to cellulose by hemicellulose and
The spatial network parcel of lignin composition, reduces its accessibility to cellulase, therefore to obtain higher enzymolysis sugared
Rate, raw material generally requires through pretreatment to improve its enzymolysis performance.The effect of pretreatment mainly changes the knot of natural fiber
Structure, reduce the degree of crystallinity of cellulose, slough lignin and/or hemicellulose, increase the contact area of enzyme and cellulose.People at present
Have been developed for multiple improving the physics of cellulase hydrolysis efficiency, process for chemically pretreating, such as radiation treatment, pulverizing, high pressure
Hot water, organic solvent, diluted acid, low temperature concentrated acid, the hydrolysis of acid catalyzed steam, steam explosion, quick-fried broken, the basic hydrolysis of liquefied ammonia and use non-
Ionic surface active agent etc..But the pretreating process developed at present is often the most merely emphasized to improve cellulase hydrolysis efficiency,
Less effective utilization in view of lignin and hemicellulose.Additionally, the most of pretreating process developed at present, the dilutest
Low-kappa number, steam explosion etc., improve the enzymolysis of cellulose by approach such as hydrolyzed hemicellulose and change lignin structures
Efficiency, and major part lignin remains in cellulose solids.On the one hand this reduce the content of cellulose, limits synchronization
Diastatic fermentation produces the concentration of glucose in ethanol process, on the other hand result in the ineffective adsorption of cellulase, causes fiber
The loss of element enzyme.Additionally, the existence of lignin can increase the stirring energy consumption in the inhomogeneities of system and sweat, limit and send out
Ferment mass transfer is carried out, and the lignin residue after fermenting reclaims heat by burning and only makes the utilization of lignin be in minimum added value
Level.Therefore, the added value of product that lignocellulose to be improved converts is necessary for realizing the diversification of raw material and high-valued turn
Change, and realize it is critical only that of this target and the three of lignocellulosic material big components are efficiently separated, not only make cellulose abundant
Expose, improve its enzymolysis performance, lignin is removed, it is to avoid the series of negative problem that high lignin content brings simultaneously.And
Traditional dilute acid pretreatment, alkali process and Steam explosion treatment are difficult to i.e. reach component high efficiency separation by simple step.
Therefore, exploitation simply and effectively lignocellulose Component seperation technology is for improving lignocellulose transformation efficiency and process warp
Ji property is most important.
Summary of the invention
It is an object of the invention to provide a kind of biorefinery method that lignocellulose is raw material coproduction multi-product, for reality
Existing goal of the invention, scheme is as follows:
The biorefinery method of lignocellulose, it comprises the following steps:
(1) carry out pretreatment after being mixed with aqueous formic acid by lignocellulosic material, obtain liquid-solid mixture；
(2) liquid-solid mixture obtained by separating step (1), obtains pretreatment black liquor and cellulose solids；
(3) cellulose solids obtained by using in aqueous formic acid washing step (2), after obtaining washing black liquid and washing
Cellulose solids, and this solid is evaporated under reduced pressure further, obtains dried cellulose solids, reclaim solid simultaneously
In formic acid；
(4) pretreatment black liquor obtained in step (2) is mixed, to institute with washing black liquid obtained in step (3)
The mixed liquor obtained carries out formic acid recovery, the formic acid solution being recycled and concentrated black liquor；
(5) in the concentrated black liquor obtained by step (4), aqueous precipitation goes out lignin, obtains lignin product after filtration
With hemicellulose sugar liquid.
Pretreatment condition in described step (1) is as follows: liquid-solid ratio is 3:1 (L/kg) to 20:1 (L/kg), and formic acid is water-soluble
The formic acid mass concentration of liquid is 50% to 80%, and temperature is 50 DEG C to 110 DEG C, and the time is 0.10 hour to 5.0 hours.
Wash conditions in described step (3) is as follows: the formic acid mass concentration of aqueous formic acid is 50% to 80%, consumption
For lignocellulosic material 3 times to 20 times.
The condition that obtain be dried cellulose solids is evaporated under reduced pressure in described step (3) as follows: pressure be 0.1kpa extremely
100kpa, temperature is 20 DEG C to 100 DEG C.
Formic acid in described step (4) is reclaimed and is carried out by distillation or rectification；Preferably, described distillation or rectification exist
Carry out under normal pressure or decompression；It is highly preferred that the volume of obtained concentrated black liquor is the 1/10-1/30 of mixeding liquid volume.
Deposition condition in described step (5) is as follows: use volume is concentrated black liquor volume 1 times of water to 30 times, temperature
Degree is 20 DEG C to 100 DEG C.
Described method also includes that the cellulose solids by obtained is converted into the step of ethanol；Preferably, described conversion bar
Part is as follows: temperature is 30 DEG C to 40 DEG C, and pH is 4.5 to 5.5, cellulase consumption be 5FPU/g solid to 30FPU/g solid, just
Beginning solids content is 1% to 30%, and saccharomyces cerevisiae seed liquor volume inoculum concentration is 2% to 20%.
Described method also includes that by obtained lignin conversion be the step of activated carbon；Preferably, described conversion be
Carry out under the conditions of following: use molten to the phosphoric acid that mass concentration is 40%-85% of 20 times again based on over dry lignin quality 1
Liquid carries out impregnating active 0.5 hour to 48 hours at 20 DEG C to 100 DEG C, further at 200 DEG C to 500 DEG C and air or nitrogen
Carbonization is carried out 0.1 hour to 5 hours under atmosphere.
Described method also includes that by obtained lignin conversion be the step of solid acid；Preferably, first lignin is turned
Turning to activated carbon, further sulfonation obtains solid acid；It is highly preferred that described sulfonating conditions is as follows: concentrated sulphuric acid consumption is activity
1 times of carbonaceous amount is to 20 times, and temperature is 100 DEG C to 200 DEG C, and the time is 5 minutes to 2 hours.
Described method also includes that the hemicellulose sugar liquid by obtained is converted into the step of furfural；Preferably, described conversion
Hemicellulose sugar liquid is directly heated to 140 DEG C to 220 DEG C realizations；It is highly preferred that described heating process is as follows: at 10 points
Clock is to hemicellulose sugar liquid being warming up in 1 hour 140 DEG C to 220 DEG C and keeping 10 minutes to 2 hours, and every 5 minutes
Let off steam to 20 minutes intervals.
Use method provided by the present invention lignocellulosic material can be carried out Component seperation and be further processed into
Corresponding high-valued product.Cellulosic hydrolysates in lignocellulosic material is glucose, is the most former of production ethanol
Material, and hydrolysis of hemicellulose product to be xylose be main mixed sugar, conventional brew yeast is difficult to effectively be translated into ethanol.And
Xylose can be dehydrated under acid catalysis and be converted into furfural.Furfural is the most important Organic chemical products of furans, can pass through
Aoxidize, reduce, the method such as condensation is further converted to multiple product.Lignin phosphorus content is higher, is prepare material with carbon element good
Raw material.Therefore, the method that the present invention provides is to combine the features of lignocellulose key component, is translated into corresponding
Product, to realize the higher value application of raw material.The method that the present invention provides uses aqueous formic acid as pretreatment of raw material
Reagent.On the one hand, formic acid has acidity, can be catalyzed the fracture of link button, shape in hydrolysis of hemicellulose and lignin molecule
Become lignin fragment；On the other hand, formic acid is the good solvent of lignin fragment, has higher dissolubility to lignin, can
To use relatively low liquid-solid ratio can effectively remove the lignin in raw material.Secondly, formic acid is easily recycled, by distillation or rectification
The most recyclable and recycle, and the residual formic acid in hemicellulose sugar liquid can turn as the dehydration of catalyst xylose
Turn to furfural.The method provided by the present invention can significantly improve the added value of lignocellulosic material, with traditional fibre element
Ethanol is compared, and can obtain higher profit margin.
Accompanying drawing explanation
1, pretreatment；2, liquid-solid separator；3, scrubber；4, flash tank；5, diastatic fermentation reactor；6, formic acid reclaims
Tower；7, lignin deposit device；8, liquid-solid separator；9, activation carbonization reactor；10, xylose dehydration reactor；11, sulfonating reaction
Device.
Fig. 1 be lignocellulose provided by the present invention be the biology of raw material co-producing ethanol, activated carbon, solid acid and furfural
Refining techniqueflow.
Fig. 2 is that method provided by the present invention carries out the enzymolysis time curve of cellulose solids after pretreatment to straw.Its
Formic acid concn used by is 88%, and pretreatment temperature is a:70 DEG C；B:80 DEG C；C:90 DEG C；D:100 DEG C；E:107 DEG C.
Detailed description of the invention
In order to illustrate in greater detail the present invention, provide following example.But the scope of the present invention is not limited thereto.
Embodiment 1
The formic acid pretreatment of straw
Lignocellulose raw material used is straw, and original producton location is Shandong Province.It is standby that straw is cut into 1-2cm length.According to the U.S.
The lignocellulose compound mensuration method of regenerative resource laboratory carries out principal component analysis to straw used, and result is: water
Point 5.1%, glucosan 33.40%, xylan, 22.26%, arabinan 3.10%, lignin 20.08%, acetyl group
2.01%, ash 6.48%, other soluble solids 7.57%.
Use formic acid solution liquid-solid ratio (L/kg) pretreatment different time under different temperatures at 10:1 of variable concentrations,
After pretreatment, mixture uses vacuum to filter, and solid matter uses the formic acid with preprocessing process same concentrations based on initial solid
Washed once final vacuum under the 5:1 liquid-solid ratio of soma weight to filter, solid matter 90 DEG C, be evaporated under reduced pressure back under 5kpa absolute pressure
Receive major part formic acid.Gained solid uses tap water to be dried after fully washing, and carries out Main chemical component mensuration, such as following table institute
Show.
Interpretation of result: formic acid concn and temperature are two most important factor affecting pretreating effect, along with formic acid solution
The raising of concentration, after pretreatment, in solid matter, beta-dextran content raises, and xylan and content of lignin reduce；At identical formic acid
Under concentration, along with pretreatment temperature improves, after pretreatment, in solid matter, xylan content and content of lignin decline.So,
Raising formic acid concn and pretreatment temperature are conducive to the removing of hemicellulose and lignin, cellulose solids after raising pretreatment
Content of cellulose.
Embodiment 2: the enzymolysis performance of cellulose solids after pretreatment
Raw materials used and preprocessing process is with embodiment 1.Straw is carried out pre-by formic acid at different temperatures that use 88%
Process.After pretreatment, cellulose solids is in 2.5% initial solids content, the cellulase consumption of 20FPU/g solid, 50 DEG C,
It is hydrolyzed under conditions of pH4.8,150rpm.Its enzymolysis time curve such as accompanying drawing 2 shows.
Interpretation of result: in certain time, raising temperature and pretreatment time can improve the enzymolysis conversion ratio of glucosan, locate in advance
After the reason time exceedes certain time, enzymolysis conversion ratio begins to decline.Increase mainly due to along with pretreatment time, cellulose first
Acylated degree increases, and is unfavorable for the cellulase identification to cellulose.Therefore, preprocessing process needs to control the formyl of cellulose
Change reaction, in order to avoid cellulase hydrolysis is adversely affected.
Embodiment 3: after pretreatment, cellulose solids is converted into ethanol
Raw materials used and preprocessing process is with embodiment 1.Use 80% formic acid after pretreatment 1.5h at 100 DEG C, use
The initial solids content of 15%, the cellulase consumption of 25FPU/g solid, 50 DEG C, pH 5.0, prehydrolysis under conditions of 150rpm
After 24h, by pH regulator to 5.5, temperature is down to 38 DEG C, carries out simultaneous saccharification and fermentation, in 48h after fermentation liquid after inoculation saccharomyces cerevisiae
Concentration of alcohol is 35.2g/L, and alcohol getting rate is 72.3%.
Interpretation of result: pretreated cellulose solids can be efficiently converted into ethanol.
Embodiment 4: lignin separation and compound mensuration
It is concentrated into stock solution volume by being evaporated under reduced pressure at 50 DEG C after the pretreatment black liquor implemented in row 1 and washing black liquid mixing
1/10 after add the water of 5 times of concentrated black liquor volumes, have a Precipitation, vacuum filter after lignin solid, use go from
The washing of sub-water obtains lignin product to filtering after neutrality, be dried.Lignin product yield based on raw material is that 12.5g is wooden
Element/100g straw.Through analyzing, the C of this lignin, H, O, N element content are respectively 59.25%, 5.74%, 34.43% and
0.58%, the content of sour insoluble lignin is 91.1%, and sour molten content of lignin is 8.05%, and carbohydrate content is
1.85%.
Interpretation of result: the method that the present invention provides can obtain higher lignin yield and product purity.
Embodiment 5: Preparation of Activated Carbon with Lignin, solid acid.
By the lignin product of gained in embodiment 4 and 85% strong phosphoric acid in the ratio that liquid-solid mass ratio is 4:1 in room temperature
Lower activation 1h, is then dried 24h at 105 DEG C, then is placed in carbonization 1h in the Muffle furnace of 400 DEG C, use hot water and cold water after cooling
Wash to neutrality at 105 DEG C, be dried 24h, obtain activated carbon product.The methylene blue adsorption value of this product is 190mg/g.
Activated carbon obtained by part is used the concentrated sulphuric acid of 98% liquid-solid ratio be 10:1 (ml/g), sulfonation at 200 DEG C
After 2h, wash with hot water and cold water after using sand core funnel to filter and obtain solid acid product at 105 DEG C of dry 24h to neutrality.
Reacting with methanol esterification with this solid acid for catalyst oleic acid, catalyst amount is based on oleic acid weight 2%, 100 DEG C
It is 50% and 98% with methyl oleate yield after 150 DEG C respectively reaction 5h.
Interpretation of result: the method that the present invention provides can obtain and can obtain the activated carbon with higher methylene blue adsorption value,
The solid acid catalyst with preferably catalysis activity can be obtained simultaneously.
Embodiment 6: the Non-intermittent xylose under operating condition that lets off steam is converted into furfural under Catalyzed by Formic Acid
Black liquor after having filtered lignin in embodiment 4 heats in autoclave, utilizes remaining Catalyzed by Formic Acid black liquor
Furfural is prepared in middle xylose dehydration, and period Non-intermittent lets off steam, but reaction measures the furfural content in reactant liquor after terminating.Should
In system, xylose concentration, temperature, response time and formic acid concn are as shown in the table on the impact of furaldehyde yield.
Interpretation of result: the xylose that residual formic acid can effectively be catalyzed in black liquor is furfural, prepares in closed system
During furfural, optimal reaction condition be xylose concentration be 100g/L, formic acid concn is 60g/L, and reaction temperature is 170 DEG C, reaction
120min, product yield now is 45.7%.
Embodiment 7: under the operating condition that intermittently lets off steam, xylose is converted into furfural under Catalyzed by Formic Acid
The furfural steam generated, with embodiment 6, is simply passed through reactor in course of reaction by operating process off and on
The gas phase extraction mouth at top is released, thus reduces the furfural time of staying in pyroreaction system, it is to avoid furfural occurs secondary anti-
Should or degrade.Xylose concentration, temperature and formic acid concn are as shown in the table on the impact of furaldehyde yield:
Interpretation of result: under the conditions of interval lets off steam, xylose can be efficiently converted into furfural under Catalyzed by Formic Acid, and
Let off steam than the Non-intermittent of embodiment 6 under the conditions of interval lets off steam and obtain higher furaldehyde yield under operating condition,
150g/L xylose, when reacting at 40g/L formic acid concn and 190 DEG C, product yield is 50.1%.
The above, the only present invention preferably detailed description of the invention, but protection scope of the present invention is not limited thereto,
Any those of ordinary skill in the art in the technical scope that the invention discloses, the change that can readily occur in or replacement, all answer
Contain within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with scope of the claims.
Claims (10)
1. lignocellulose is the biorefinery method of raw material coproduction multi-product, and it comprises the following steps:
(1) carry out pretreatment after being mixed with aqueous formic acid by lignocellulosic material, obtain liquid-solid mixture；
(2) liquid-solid mixture obtained by separating step (1), obtains pretreatment black liquor and cellulose solids；
(3) cellulose solids obtained by using in aqueous formic acid washing step (2), obtains the fibre after washing black liquid and washing
Dimension element solid, and this solid is evaporated under reduced pressure further, obtain dried cellulose solids, reclaim in solid simultaneously
Formic acid；
(4) pretreatment black liquor obtained in step (2) is mixed, to obtained with washing black liquid obtained in step (3)
Mixed liquor carry out formic acid recovery, the formic acid solution being recycled and concentrated black liquor；
(5) in the concentrated black liquor obtained by step (4), aqueous precipitation goes out lignin, obtains lignin product and half after filtration
Cellulose sugar liquid.
2. the method for claim 1, the pretreatment condition in wherein said step (1) is as follows: liquid-solid ratio is 3:1(L/
Kg) to 20:1(L/kg), the formic acid mass concentration of aqueous formic acid is 50% to 80%, and temperature is 50 DEG C to 110 DEG C, and the time is
0.10 hour to 5.0 hours.
3. the method as according to any one of claim 1 or 2, the wash conditions in wherein said step (3) is as follows: formic acid water
The formic acid mass concentration of solution is 50% to 80%, and consumption is 3 times to 20 times of lignocellulosic material.
4. method as claimed any one in claims 1 to 3, is evaporated under reduced pressure in wherein said step (3) and obtains being dried fiber
The condition of element solid is as follows: pressure is 0.1 kpa to 100 kpa, and temperature is 20 DEG C to 100 DEG C.
5. the method as according to any one of Claims 1-4, it is by distillation that the formic acid in wherein said step (4) reclaims
Or rectification is carried out；Preferably, described distillation or rectification are carried out under normal pressure or decompression；It is highly preferred that obtained concentration
The volume of black liquor is the 1/10-1/30 of mixeding liquid volume.
6. the method as according to any one of claim 1 to 5, the deposition condition in wherein said step (5) is as follows: use water
Volume is concentrated black liquor volume 1 times to 30 times, temperature is 20 DEG C to 100 DEG C.
7. the method as according to any one of claim 1 to 6, described method also includes converting obtained cellulose solids
Step for ethanol；Preferably, described conversion condition is as follows: temperature is 30 DEG C to 40 DEG C, and pH is 4.5 to 5.5, cellulase
Consumption be 5 FPU/g solids to 30 FPU/g solids, initial solids content is 1% to 30%, and saccharomyces cerevisiae seed liquid
Long-pending inoculum concentration is 2% to 20%.
8. the method as according to any one of claim 1 to 7, it also includes that by obtained lignin conversion be activated carbon
Step；Preferably, described conversion is carried out under the following conditions: use based on over dry lignin quality 1 again to the matter of 20 times
Amount concentration is that the phosphoric acid solution of 40%-85% carries out impregnating active 0.5 hour to 48 hours at 20 DEG C to 100 DEG C, further 200
DEG C to 500 DEG C and air or nitrogen atmosphere, carry out carbonization 0.1 hour to 5 hours.
9. the method as according to any one of claim 1 to 8, it also includes that by obtained lignin conversion be solid acid
Step；Preferably, being first activated carbon by lignin conversion, further sulfonation obtains solid acid；It is highly preferred that described sulfonation bar
Part is as follows: concentrated sulphuric acid consumption is 1 times to 20 times of quality of activated carbon, and temperature is 100 DEG C to 200 DEG C, the time be 5 minutes little to 2
Time.
10. method as claimed in any one of claims 1-9 wherein, it also includes being converted into obtained hemicellulose sugar liquid
The step of furfural；Preferably, hemicellulose sugar liquid is directly heated to 140 DEG C to 220 DEG C realizations by described conversion；More preferably
Ground, described heating process is as follows: in 10 minutes to 1 hours, hemicellulose sugar liquid is warming up to 140 DEG C and to 220 DEG C and keeps
10 minutes to 2 hours, and let off steam every 5 minutes to 20 minutes intervals.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN110092379A (en) * | 2019-04-12 | 2019-08-06 | 蚌埠学院 | It is a kind of using biomass as the method and application of raw material one-step synthesis sulfonation active carbon |
| CN110230228A (en) * | 2019-06-24 | 2019-09-13 | 清华大学 | The method of stalk coproduction cellulosic material, furfural and lignin |
| CN110684204A (en) * | 2019-09-23 | 2020-01-14 | 广东工业大学 | Method for separating wood fiber by organic acid and homologously preparing furfural |
| CN110983844A (en) * | 2019-12-31 | 2020-04-10 | 宏业生物科技股份有限公司 | Method for extracting cellulose and lignin by using biomass material and method for recovering formic acid and furfural by using residual liquid after extraction |
| CN111395025A (en) * | 2020-04-07 | 2020-07-10 | 齐鲁工业大学 | Comprehensive utilization method of lignocellulose biomass |
| CN115109271A (en) * | 2022-08-10 | 2022-09-27 | 广州楹鼎生物科技有限公司 | Method for biologically refining plant fiber raw material and device used by method |
| CN116374990A (en) * | 2023-03-08 | 2023-07-04 | 华南理工大学 | Method for preparing powder/block biomass grade pore carbon by pretreatment of lignocellulose biomass with formic acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109897363A (en) * | 2019-03-14 | 2019-06-18 | 江苏爱索新材料科技有限公司 | For the biomass-based polyurethane material of tubing, polyurethane flexible pipe and preparation method thereof |
| CN110092379A (en) * | 2019-04-12 | 2019-08-06 | 蚌埠学院 | It is a kind of using biomass as the method and application of raw material one-step synthesis sulfonation active carbon |
| CN110230228A (en) * | 2019-06-24 | 2019-09-13 | 清华大学 | The method of stalk coproduction cellulosic material, furfural and lignin |
| CN110684204A (en) * | 2019-09-23 | 2020-01-14 | 广东工业大学 | Method for separating wood fiber by organic acid and homologously preparing furfural |
| CN110983844A (en) * | 2019-12-31 | 2020-04-10 | 宏业生物科技股份有限公司 | Method for extracting cellulose and lignin by using biomass material and method for recovering formic acid and furfural by using residual liquid after extraction |
| CN111395025A (en) * | 2020-04-07 | 2020-07-10 | 齐鲁工业大学 | Comprehensive utilization method of lignocellulose biomass |
| CN115109271A (en) * | 2022-08-10 | 2022-09-27 | 广州楹鼎生物科技有限公司 | Method for biologically refining plant fiber raw material and device used by method |
| CN116374990A (en) * | 2023-03-08 | 2023-07-04 | 华南理工大学 | Method for preparing powder/block biomass grade pore carbon by pretreatment of lignocellulose biomass with formic acid |
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