CN103757959B - A kind of method using ionic liquid two-step method to obtain fiber-rich cellulosic material from straw - Google Patents
A kind of method using ionic liquid two-step method to obtain fiber-rich cellulosic material from straw Download PDFInfo
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Abstract
The present invention relates to the use of A and B two class ionic liquid low temperature rapid solution straw in two steps and obtain the new method of fiber-rich cellulosic material.The low temperature that i.e. first step utilizes A class ionic liquid aqueous solution that straw carries out the short time soaks the insoluble residue obtaining part removal lignin, and residual residue is dissolved completely in B class ionic liquid and obtains the fiber-rich cellulosic material that cellulose crystal formation changes, degree of crystallinity substantially reduces, be more conducive to subsequent transformation by second step at short notice.Compare other preprocess methods, the method solution temperature is relatively low, the time is short, easy to operate simply, it is thus achieved that fiber-rich cellulosic material catalyzed conversion can get high yield 5 Hydroxymethylfurfural.The present invention is possible not only to avoid the tradition soda acid pre-treating method corrosion to instrument, and largely on reduce pretreatment energy consumption.The processing mode of this environmental protection low energy consumption both can realize effective pretreatment of straw, significant to the difficult problem solving biomass resource utilization again.
Description
Technical field
The present invention relates to the use of A and B two class ionic liquid low temperature in two steps from straw, obtain cellulose crystal formation rapidly
Change, the method for the fiber-rich cellulosic material that degree of crystallinity substantially reduces.
Background technology
Biomass straw is one of modal ligno-cellulosic materials, and China's straw annual production reaches more than 700,000,000 ton, burns on the spot
Burn and not only waste resource, and cause serious environmental pollution.The limitation of fossil energy and the problem of environmental pollution of initiation thereof
Also in some aspect, promote the flourish of biomass trans-utilization.By the chemicals of biomass derived or intermediate such as
Levulic acid, 5 hydroxymethyl furfural etc. are widely used in Chemical Manufacture, provide sky more, wider array of to biomass economy
Between.It is cellulose, hemicellulose and lignin that straw mainly comprises, due to lignin and hemicellulose mutual winding effect and
The crystalline texture of cellulose makes biomass be difficult to dissolve in common solvents, therefore hinders the later use of straw.Biological
The pretreatment that matter is suitable can break lignin and hemicellulose to the binding effect of cellulose, knot that cellulose is greatly lowered
Crystalline substance degree, thus realize biomass efficient and sufficiently utilize.
In the preprocessing technical field of straw, traditional method is to utilize acid or aqueous slkali to soak biomass for a long time
Bubble, thus remove lignin or hemicellulose, but the waste liquid environmental pollution that these methods produce is serious, is difficult to significantly simultaneously
Degree reduces the degree of crystallinity of cellulose.Additionally, the methods such as steam explosion (such as steam, ammonia steam and ozone), microwave radiation are the widest
In ubiquitous biomass pretreatment, weak point is that reaction pressure is high, and high to equipment requirements, energy consumption is high, and cellulose crystallity
Change is little, is unfavorable for cellulose subsequent transformation.Therefore the eco-friendly preprocess method of mild condition is found extremely urgent.
Ionic liquid, as a kind of novel medium, has the advantage that conventional organic solvents is incomparable, as steam forces down, no
Volatile, fusing point is low, have the strongest solvability, preferable heat stability and chemical stability, wider liquid state range, easily
In cycling and reutilization etc., and it is widely used in the chemical fields such as electrochemistry, catalysis, materials synthesis and separation.In recent years
Coming, ionic liquid achieves bigger progress in terms of separating lignocellulose.
The amino acid ion liquid (patent CN102533907 A) of report and degradable ionic liquid (patent
CN103031762 A) although the pretreatment to Oryza sativa L. and corn straw can be realized to a certain extent, but implement temperature and divide
Not between 50 DEG C～130 DEG C, 100 DEG C～180 DEG C, the process time reaches even a couple of days a few hours, and reaction temperature is high, the time
Length makes ion liquid section used decompose, thus reduces the service life of ionic liquid.It is used alone functionalized ion liquid
Process straw and be difficult to accomplish to complete at short notice the enrichment being completely dissolved, realizing cellulose of straw.Therefore, the present invention from from
The synthesis of sub-liquid is set out with performance perspective, and having selected under stable in properties, room temperature is liquid, it is easy to synthesis, cheap, and
Eco-friendly A and B two class ionic liquid, as solvent, is removed lignin from straw and is obtained fiber-rich cellulosic material.The method
Solution temperature is relatively low, the time is short, easy to operate simple.After first step A class ionic liquid solution low temperature soaks
Straw residue can be dissolved completely in realizing several minutes in second step in B class ionic liquid, then regeneration obtain cellulose
Crystal formation changes, the fiber-rich cellulosic material that degree of crystallinity substantially reduces.Compared with other preprocess methods, this invention mild condition, anti-
Between Ying Shi short, and the fiber-rich cellulosic material obtained can catalyzed conversion obtain high yield 5 hydroxymethyl furfural, further illustrate
This ionic liquid two-step method is a kind of straw pretreatment method the most efficiently.
Summary of the invention
The present invention be primarily directed to straw this cheap, be easy to get and the crops of rich cellulose are in the conversion profit of biomass
By aspect, there are huge potentiality, the green efficient advantage of coupled ion liquid, with ionic liquid as solvent, develop straw biological
The preprocess method of the energy-conserving and environment-protective of matter.The present invention is possible not only to the corrosion avoiding classical acid oxygenation pretreatment method to instrument, with
Time be substantially reduced with method phase specific energy consumptions such as microwaves, the processing mode of this environmental protection can be effectively improved the profit of biomass resource
Use efficiency.The present invention develops the method utilizing A and B two class ionic liquid to obtain fiber-rich cellulosic material in two steps from straw,
Realize from straw, under low temperature, quickly remove lignin Sync enrichment crystal formation to change, the cellulose that degree of crystallinity substantially reduces.Utilize
This fiber-rich cellulosic material catalyzed conversion prepares the 5 hydroxymethyl furfural of high yield, illustrates the efficient of this two-step method pretreated straw
Property, also prepare biodiesel for biomass and cellulose derivative provides effective ways.
Comprising the following steps that of intermediate ion liquid two-step method pretreated straw of the present invention
(1) first step use mass fraction 1wt%～99wt% A class ionic liquid aqueous solution soak straw, A class from
The volume ratio of sub-liquid aqueous solution and straw between 5:1～50:1, low temperature soak time between 10min～300min,
Temperature, between 5 DEG C～50 DEG C, makes ionic liquid be fully contacted with stalk powder by stirring, and this process mainly makes part
Lignin and hemicellulose are dissolved in A class ionic liquid aqueous solution, it is thus achieved that part removes lignin and the straw of hemicellulose
Residue.
(2) second step adds in B class ionic liquid by obtaining residue in the first step, straw residue and B class ionic liquid body constitution
Amount ratio is between 1:40～1:2, and temperature is between 30 DEG C～180 DEG C, and the time controls between 5min～360min, by stirring
Mix so that straw is substantially dissolved in B class ionic liquid, after dissolving completely, be cooled to room temperature, add 10mL DMSO diluting reaction
Solution, add extractant regeneration obtain spawn, acetone in extractant: water ratio control 1:20～20:1 it
Between, extractant and B class ionic liquid volume ratio are between 5:1～20:1, through filtering, being dried to obtain fiber-rich cellulosic material.
(3) content of different component in the regrown material that Fan Shi methods analyst obtains is utilized, first with 2M HCl to sample
Product carry out first step acid hydrolysis, and 2M HCl solution volume (mL) is 50:1 with quality (g) ratio of sample, sample with obtain not
The difference of molten thing is the amount of hemicellulose in sample.Second step utilizes 72%H2SO4Continue the remaining sample of the hydrolysis first step, solution
Volume (mL) is 5:1 with quality (g) ratio of sample, and the difference of the sample before and after process is the content of cellulose, the most remaining
Black residue is lignin, is obtained the content of three kinds of components by conversion.
(4) by the fiber-rich cellulosic material of acquisition in step 2 at ionic liquid [Bmim] Cl and catalyst CrCl3Effect under
Prepare 5 hydroxymethyl furfural, verify this two-step method pretreating effect to straw.Conversion temperature control 25 DEG C～150 DEG C it
Between, ionic liquid [Bmim] Cl and sample quality ratio are between 5:1～20:1, and catalyst and ionic liquid mass ratio are between 1:
Between 100～1:5, the time controls at 10min～300min, and liquid phase HPLC mensuration temperature, between 25 DEG C～80 DEG C, flows
Between phase flow rate 0.1mL/min～1.0mL/min, sample size controls between 0.1 μ L～10 μ L, UV-detector wavelength
284nm, retention time is 10min.In the fiber-rich cellulosic material obtained, cellulose converts the conversion ratio of 5 hydroxymethyl furfural up to
87.21%, see accompanying drawing 5: the catalyzed conversion of different materials prepares the contrast of 5 hydroxymethyl furfural conversion ratio.
Utilize two-step method comprehensive A and the B two class ionic liquid not same-action to straw, soak through low temperature, rapid solution
Efficiently remove lignin and obtain fiber-rich cellulosic material.This method avoid and use ionic liquid to process straw the most for a long time
The ionic liquid that stalk causes decomposes and the degraded of straw, and the method reaction condition is gentle simultaneously, and the time is short, removes lignin efficiency
High, it is thus achieved that the cellulose crystal formation of fiber-rich cellulosic material changes, and degree of crystallinity substantially reduces, and production cost is low, equipment is simple, easily
In realizing industrialization.
Accompanying drawing explanation
Fig. 1 is the fiber-rich cellulosic material of independent second step acquisition, microcrystalline Cellulose, stalk, the first step in the present invention
The FT-IR infrared contrast spectrogram of the regeneration fiber-rich cellulosic material that the residue obtained and two-step method obtain.A: individually second step obtains
Fiber-rich cellulosic material, b: microcrystalline Cellulose, c: stalk, the residue that d: the first step obtains, the regeneration that e: two-step method obtains
Fiber-rich cellulosic material.The spectrogram of the regeneration fiber-rich cellulosic material that two-step method obtains finds cellulose infrared signature peak 1644cm-1,
1370cm-1, and 898cm-1Peak value increases, the characteristic peak 1733cm of lignin-1,1513cm-1,1603cm-1Peak value reduces, table
This two-step method bright has the effect well removing lignin enrichment cellulosic.
Fig. 2 is the residue that in the present invention, microcrystalline Cellulose, stalk, the first step obtain, the richness of independent second step acquisition
Cellulosic material and the XRD figure of two-step method regeneration fiber-rich cellulosic material.A: microcrystalline Cellulose b: stalk, c: the first step obtains
Residue, d: the fiber-rich cellulosic material that individually second step obtains, e: two-step method regeneration fiber-rich cellulosic material.Fibre is characterized according to XRD
Dimension element degree of crystallinity result show through two-step method process after fiber-rich cellulosic material compare stalk, residue degree of crystallinity bright
Aobvious reduction, degree of crystallinity change order is as follows: MCC (78.19) > stalk (36.83) > first step residue (30.47) > two-step method
Regeneration fiber-rich cellulosic material (14.99) > fiber-rich cellulosic material (8.78) that individually second step obtains.Cellulose Ⅰ type feature simultaneously
Peak 2 θ angle, at 14.7 °, 16.4 °, 22.5 ° and 34.4 °, and cellulose Ⅱ type characteristic peak is 20.0 ° and 21.7 °, is tied from figure
Fruit can be seen that the cellulose crystal formation of two-step method regeneration fiber-rich cellulosic material becomes II type from I type, and through pretreated
The degree of crystallinity of regeneration fiber-rich cellulosic material substantially reduces the carrying out of beneficially later use process.
Fig. 3 is fiber-rich cellulosic material, two-step method regeneration fiber-rich cellulosic material, the straw that in the present invention, independent second step obtains
The SEM figure of the residue that raw material, the first step obtain.A. the fiber-rich cellulosic material that individually second step obtains, the regeneration of b. two-step method is rich fine
Dimension cellulosic material, the residue that the c. stalk d. first step obtains.Result shows the fiber-rich obtained after this two-step method processes
Material structure there occurs that change, coarse straw fragment obtain the thin film of smooth densification, and cellulose crystals after treatment
Type changes, and obtains material of regenerated cellulose and can prepare 5 hydroxymethyl furfural by Efficient Conversion.
Fig. 4 is fiber-rich cellulosic material, the crystallite that in the present invention, two-step method regeneration fiber-rich cellulosic material, independent second step obtain
The TGA spectrogram of the residue that cellulose, stalk and the first step obtain.A: two-step method regeneration fiber-rich cellulosic material, b: independent the
The fiber-rich cellulosic material that two steps obtain, c: microcrystalline Cellulose, d: stalk, the residue that e: the first step obtains.According to different materials
The decomposition temperature of material, the decomposition temperature of microcrystalline Cellulose is at 337.44 DEG C, and the residue decomposition temperature obtained from the first step exists
351.04 DEG C, the fiber-rich cellulosic material decomposition temperature that independent second step obtains is at 218.68 DEG C, and the fiber-rich that two-step method obtains is plain
The decomposition temperature of material is 277.45 DEG C.Result proves that the fiber-rich cellulosic material decomposition temperature that two-step method obtains is relatively low, and structure becomes
Change big, process 3 hours acquisition fiber-rich cellulosic material decomposition temperatures through independent second step lower, but individually second step processes straw
Dissolving relatively low, regeneration obtain fiber-rich element amount less.Through the regeneration fiber-rich cellulosic material cellulose that ionic liquid processes
Degree of crystallinity substantially reduces, and crystal formation changes, and these are all easier to catalyzed conversion and prepare 5 hydroxymethyl furfural.
Fig. 5 be the residue that in the present invention, stalk, the first step obtain, independent second step obtain fiber-rich cellulosic material and
The fiber-rich cellulosic material catalyzed conversion respectively that two-step method obtains prepares the productivity comparison diagram of 5-hydroxyl furfural.Wherein 1: straw is former
Material, 2: the residue that the first step obtains, 3: the fiber-rich cellulosic material that individually second step obtains, 4: the fiber-rich material that two-step method obtains
Material.Although result from figure is it can be seen that the regrown material after processing individually with functionalized ion liquid can obtain higher
Cellulose conversion ratio, but process with this ionic liquid merely that the dissolubility of straw is the lowest is only 38.53%, most of residue
In cellulose cannot be completely transferred in regrown material, difficulty realizes the enrichment of cellulose.Utilize merely first step A class ionic liquid
The residue conversion ratio obtained of body aqueous solution is 69.91%, slightly higher than stalk.Two-step method processes straw can be the most molten
Solve, be possible not only to improve significantly the dissolution rate of straw, and reaction condition is relatively mild, the time in second step processes
Being greatly shortened in can realizing several minutes and be completely dissolved, the fiber-rich cellulosic material not only cellulose amount simultaneously obtained is high but also crystallizes
Degree and pattern all there occurs significant change, are more beneficial for follow-up utilization, and cellulose catalytic conversion ratio reaches 87.21%.
Detailed description of the invention
Present invention following example illustrate, but the present invention is not limited to following embodiment, without departing from the most described ancestor
In the range of purport, change is included in the technical scope of the present invention.
Embodiment 1
Weigh the stalk powder about 1.0964g after neutral detergent carrying out washing treatment, join equipped with 20mL 50wt%
In bursine (ChOH) aqueous solution, centrifugation residue and supernatant after stirring at normal temperature 3h, then steam residue 60mL
Distilled water is washed in three times, and filtration drying obtains residue 0.5218g, and straw dissolution rate in this solution reaches 47.59%.Analyze
Residue component hemicellulose level is 31.22%, and content of cellulose is 56.71%, i.e. holocellulose content is 87.93%, wood
Lignin content is 12.07%.
Weigh above-mentioned residue about 0.5000g, join 10.0028g 1-ethyl-3-methylimidazole dimethyl phosphate
In ([Emim] [DMP]) ionic liquid, it is heated to 130 DEG C and magnetic agitation reaction 5-10min and is completely dissolved, remain without residue,
Dissolution rate reaches 100%.It is cooled to room temperature after stopped reaction, adds 10mL DMSO diluting reaction solution, add in the solution
The acetone of 100mL and water isopyknic extraction solution, hence it is evident that have colloid substance to separate out, sucking filtration, wash the most namely regenerated
The CRM 0.3740g of film like, regeneration rate is 74.84%.The component respectively hemicellulose analyzing regeneration CRM is 43.66%,
Cellulose is 52.14%, i.e. holocellulose content is 95.80%, and lignin is 4.20%.
Embodiment 2
Weigh the stalk powder about 1.0964g after neutral detergent carrying out washing treatment, join equipped with 20mL 50wt%
In bursine (ChOH) aqueous solution, centrifugation residue and supernatant after stirring at normal temperature 3h, then steam residue 60mL
Distilled water is washed in three times, and filtration drying obtains residue 0.5218g, and straw dissolution rate in this solution reaches 47.59%.Analyze
Residue component hemicellulose level is 31.22%, and content of cellulose is 56.71%, i.e. holocellulose content is 87.93%, wood
Lignin content is 12.07%.
Weigh above-mentioned residue about 0.5022g, join 10.0244g 1-ethyl-3-methylimidazole acetic acid ([Emim]
[OAc]) in ionic liquid, it is heated to 130 DEG C and magnetic agitation reaction 30min and is completely dissolved, without residue residue, dissolution rate reaches
100%.It is cooled to room temperature after stopped reaction, adds 10mL DMSO diluting reaction solution.The acetone of 100mL is added in filtrate
Extraction solution isopyknic with water, hence it is evident that have colloid substance to separate out, filters, washs the film like material CRM being dried to obtain regeneration
0.4143g, regeneration rate is 82.49%.Analyzing the component hemicellulose 38.15% of regeneration CRM, cellulose is 47.20%, the most comprehensive
Content of cellulose is 85.34%, and lignin is 14.66%.
Embodiment 3
Weigh the stalk powder about 1.0964g after neutral detergent carrying out washing treatment, join equipped with 20mL 50wt%
In bursine (ChOH) aqueous solution, centrifugation residue and supernatant after stirring at normal temperature 3h, then steam residue 60mL
Distilled water is washed in three times, and filtration drying obtains residue 0.5218g, and straw dissolution rate in this solution reaches 47.59%.Analyze
Residue component hemicellulose level is 31.22%, and content of cellulose is 56.71%, i.e. holocellulose content is 87.93%, wood
Lignin content is 12.07%.
Weigh above-mentioned residue about 0.5000g, join 9.8572g 1-ethyl-3-methylimidazole villaumite ([Emim] Cl) from
In sub-liquid, being heated to 130 DEG C and magnetic agitation reaction 50min and be completely dissolved, remain without residue, dissolution rate reaches 100%.Stop
Only it is cooled to room temperature after reaction, adds 10mL DMSO diluting reaction solution.Add the bodies such as the acetone of 100mL and water in the solution
Long-pending extraction solution, hence it is evident that have colloid substance to separate out, sucking filtration, washs the most namely regenerated film like material CRM
0.4153g, regeneration rate is 83.08%.Analyzing the component hemicellulose 37.18% of regeneration CRM, cellulose is 41.27%, the most comprehensive
Content of cellulose is 78.45%, and lignin is 21.55%.
Embodiment 4
Weigh the stalk powder about 1.0964g after neutral detergent carrying out washing treatment, join equipped with 20mL 50wt%
In bursine (ChOH) aqueous solution, centrifugation residue and supernatant after stirring at normal temperature 3h, then steam residue 60mL
Distilled water is washed in three times, and filtration drying obtains residue 0.5218g, and straw dissolution rate in this solution reaches 47.59%.Analyze
Residue component hemicellulose level is 31.22%, and content of cellulose is 56.71%, i.e. holocellulose content is 87.93%, wood
Lignin content is 12.07%.
Weigh above-mentioned residue about 0.5002g, join 10.1202g 1-ethyl-3-methylimidazole bromide ([Emim] Br)
In ionic liquid, being heated to 130 DEG C and magnetic agitation reaction 99min and be completely dissolved, remain without residue, dissolution rate reaches 100%.
It is cooled to room temperature after stopped reaction, adds 10mL DMSO diluting reaction solution.Add acetone and the water of 100mL in the solution
Isopyknic extraction solution, hence it is evident that have colloid substance to separate out, sucking filtration, the most namely regenerated film like material CRM of washing
0.3732g, regeneration rate is 74.61%.The component analyzing regeneration CRM is respectively hemicellulose 27.44%, and cellulose is
50.06%, i.e. holocellulose content is 77.50%, and lignin is 22.50%.
Embodiment 5
Weigh the stalk powder about 1.0020g after neutral detergent washs, join equipped with 20mL 40wt% hydrogen-oxygen
Change in choline (ChOH) aqueous solution, centrifugation residue and supernatant after stirring at normal temperature 3h, then residue is used 60mL distilled water
Washing in three times, filtration drying obtains residue 0.5370g, and straw dissolution rate in this solution reaches 46.41%；Analyze residue
Component respectively hemicellulose level is 29.76%, and content of cellulose is 54.51%, i.e. holocellulose content is 84.27%,
Content of lignin is 15.73%.
Weigh above-mentioned residue about 0.5028g, join 10.062g 1-pi-allyl-3-Methylimidazole. villaumite ([Amim] Cl)
In ionic liquid, being heated to 130 DEG C and magnetic agitation reaction 23min and be completely dissolved, remain without residue, dissolution rate reaches 100%.
It is cooled to room temperature after stopped reaction, adds 10mL DMSO diluting reaction solution.Add acetone and the water of 100mL in the solution
Isopyknic extraction solution, hence it is evident that have colloid substance to separate out, sucking filtration, the most namely regenerated film like CRM film like of washing
Material 0.4528g, regeneration rate is 90.05%.Analyzing the component hemicellulose 30.66% of regeneration CRM, cellulose is 61.65%,
I.e. holocellulose content is 92.31%, and lignin is 7.69%.
Claims (3)
1. one kind uses the method that two step ionic liquid obtain fiber-rich cellulosic material from straw, it is characterised in that this two step
Ionic liquid pretreatment method has low temperature, quick advantage, and described method comprises the steps:
1) first step ionic liquid pretreatment is to utilize the A class ionic liquid aqueous solution leaching that mass fraction is 1wt%～99wt%
Bubble straw, the volume ratio of A class ionic liquid aqueous solution and straw, between 5:1～50:1, is soaked at a temperature of 5 DEG C～50 DEG C
Straw 10min～300min, it is thus achieved that part removes lignin and the straw residue of hemicellulose, and described A class ionic liquid is hydrogen
Choline, cation is cholinium ion, and anion is hydroxide ion；
2) second step ionic liquid pretreatment is the straw residue utilizing the B class ion liquid dissolving first step to obtain, straw residue
Being 1:40～1:2 with B class ionic liquid mass ratio, temperature is between 30 DEG C～180 DEG C, and dissolution time is 5min～360min,
By stirring, straw is substantially dissolved in B class ionic liquid, after dissolving completely, is cooled to room temperature, add 10mL DMSO dilute
Release reaction solution, add extractant regeneration and obtain gelatinous fertile absorber, acetone in extractant: water ratio controls 1:
Between 20～20:1, extractant and B class ionic liquid volume ratio are between 5:1～20:1, through filtering, being dried to obtain purity relatively
High fiber-rich cellulosic material；
Described B class ionic liquid general structure is M+N-, wherein M+There is structure as shown below formula: R in formula1And R2For containing 1-
The alkyl of 10 carbon atoms, thiazolinyl or aryl, R3、R4And R5For H or containing the alkyl of 1-10 carbon atom, thiazolinyl or aryl；
Described N-For halide ion (F-,Cl-,Br-,I-), acetate ion (OAc-), dimethyl phosphate ion (DMP-), di(2-ethylhexyl)phosphate
Ethyl ester ion (DEP-), methyl sulfate ion (CH3OSO2 -) and triflate ion (CF3SO3 -), the knot of these aniones
Structure is as follows:
F-, Cl-, Br-,
Halide ion acetate ion dimethyl phosphate ion diethyl phosphate ion methyl sulfate ion trifluoromethanesulfonic acid
Ester ion.
Method the most according to claim 1, it is characterised in that Straw bale is containing corn and soybean, Oryza sativa L. and the stem of Cotton Gossypii
Stalk, root, branch material.
Method the most according to claim 1, it is characterised in that obtain the content of lignin in regeneration fiber-rich cellulosic material and exist
Between 0.7%～30.0%, content of cellulose is 40%～80%.
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| CN105646402A (en) * | 2015-12-17 | 2016-06-08 | 山东大学 | Preparation method of 5-hydroxymethyl furfural from fructose at room temperature |
| JP6906140B2 (en) * | 2016-10-18 | 2021-07-21 | パナソニックＩｐマネジメント株式会社 | Ionic liquids and methods of using them to dissolve cellulose |
| CN106755189B (en) * | 2016-10-31 | 2021-01-05 | 广东工业大学 | Green method for improving enzymolysis efficiency of cellulose in rice straw by utilizing two deep eutectic solvents for step-by-step pretreatment |
| CN106702800B (en) * | 2016-12-30 | 2019-02-26 | 中国科学院过程工程研究所 | A method of straw lignin and hemicellulose are removed with proton type ionic liquid |
| CN110038488A (en) * | 2019-04-29 | 2019-07-23 | 南开大学 | A method of hydrogen is produced using organic solid castoff |
| CN113046176A (en) * | 2019-12-27 | 2021-06-29 | 丰益(上海)生物技术研发中心有限公司 | Method for removing plasticizer from fluid material |
| CN111154817B (en) * | 2020-02-19 | 2022-04-08 | 中国科学院过程工程研究所 | Method for efficiently separating lignocellulose and carrying out enzymolysis by using ionic liquid-high-boiling-point alcohol composite system |
| CN115677716A (en) * | 2022-09-09 | 2023-02-03 | 华北电力大学 | High-value utilization method of cotton processing waste |
| CN116003639B (en) * | 2023-01-31 | 2024-02-09 | 新疆农业大学 | Cellulose aldehyde and preparation method and application thereof |
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| DE10109502A1 (en) * | 2001-02-28 | 2002-09-12 | Rhodia Acetow Gmbh | Removal of hemicellulose from biomaterial, especially wood pulp, involves extraction by treatment with an aqueous solution of metal complex, e.g. nickel tris-2-aminoethyl-amine di-hydroxide |
| CN103031762B (en) * | 2011-09-30 | 2014-11-05 | 中国科学院过程工程研究所 | Method for preparing material rich in cellulose in degradable ionic liquid solvent |
| CN102321055A (en) * | 2011-09-30 | 2012-01-18 | 中国科学院过程工程研究所 | Method for preparing 5-hydroxymethylfurfural from woody biomasses |
| CN102617523B (en) * | 2012-03-09 | 2014-08-27 | 中南大学 | Method for preparing 5-hydroxymethylfurfural by hydrothermally decomposing wood fibers |
| CN103450122B (en) * | 2013-08-22 | 2015-09-30 | 中国科学院过程工程研究所 | The ionic liquid-catalyzed Microcrystalline Cellulose of a kind of microwave-assisted is converted into the method for 5 hydroxymethyl furfural |
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