CN108855135A - A kind of carbon-based solid acid catalyst and its application in lignocellulosic depolymerization - Google Patents
A kind of carbon-based solid acid catalyst and its application in lignocellulosic depolymerization Download PDFInfo
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Abstract
The invention discloses a kind of carbon-based solid acid catalyst and its applications in lignocellulosic depolymerization.A kind of preparation method of carbon-based solid acid catalyst, includes the following steps：(1) after lignosulfonates being mixed with sulfonated reagent, temperature be 120 DEG C~200 DEG C under conditions of reaction 4~for 24 hours, stop heating after the reaction was completed, reaction system is filtered wait be cooled to room temperature, it filters resulting filtrate and retains spare, filter residue is cleaned, carbon-based solid acid catalyst presoma is made after drying；(2) carbon-based solid acid catalyst presoma is made in step (1) to mix in proportion with oxidising agent, 30~120min is reacted at 30 DEG C~70 DEG C, to after reaction, by obtained reaction product after filtering and drying process, obtain carbon-based solid acid catalyst.Catalyst preparation materials own face acidic functionality rich in provided by the present invention is conducive to the generation of lignocellulosic depolymerization reaction.
Description
Technical field：
The present invention relates to solid acid catalyst technical fields, and in particular to a kind of carbon-based solid acid catalyst and its wooden
Application in cellulose depolymerization.
Background technique：
Biomass is that unique one kind can be converted into the renewable cleaning money of gas, liquid and the solid energy on the earth
Source.Biomass resource rich content, is such as realized industrial application, can effectively substitute fossil fuels use, exploitation
Using the reproducible clean energy resource resource such as biomass energy to sustainable energy resource system is established, promote national economic development and ring
Border protection is of great significance.
The platform chemicals that lignocellulose-like biomass raw material prepares alcohol fuel and high added value are always one and grind
Study carefully hot spot, and saccharification is the important step in lignocellulosic conversion.Liquid acids are most normal in lignocellulosic hydrolysis and saccharification
Catalyst includes：Concentrated acid (30%~70%) processing, diluted acid and solid acid processing.Sour toxicity in concentrated acid treatment process
Greatly, big on equipment corrosion and fermentation inhibitor can be generated influence subsequent alcohol fermentation technique.Dilute acid pretreatment generally comprises sulphur
Acid, hydrochloric acid, phosphoric acid and maleic acid, wherein the sulfuric acid most study for being 0.5%~2% with concentration.Although dilute acid pretreatment method
It is at low cost and simple, but its shortcoming is that carbohydrate is largely lost, and the generation of inhibiting compound hinders subsequent enzymatic hydrolysis
And fermentation process.
Some disadvantages based on liquid acid, solid acid catalyst to equipment corrode it is small, be easily isolated, can recycle,
The features such as reaction condition is mild and the discharge no pollution to the environment of waste liquid is widely studied.Traditional solid acid catalyst
Stability in thermal and hydric environment is poor, and low to the Hydrolytic catalyzing of lignocellulose-like biomass, and the present invention is first led to
It crosses and prepares carbon-based solid acid catalyst catalysis lignocellulosic depolymerization and combine the enzymatic hydrolysis of residue to realize the full sugar in raw material
Depolymerization.By, to the retrieval in terms of solid acid catalyst, have in official website of State Intellectual Property Office it is following it is relevant disclose it is special
Benefit：
(1) CN201710026539.8, disclosing the carbon-based renewable carbohydrate of one kind is raw material, and suitable liquid acid is added,
It after reacting in a certain temperature conditions, is dried by high temperature, the carbon-based solid acid catalyst being prepared is dried in washing again, should
Catalyst has the advantages that preparation process is simple, but the activity of catalyst needs to be further improved.
(2) CN201610437789.6, discloses a kind of carbon-based biomass material, is added ionic liquid, organic acid,
After reacting under the conditions of certain temperature, biological carbon-based solid acid is obtained after being freeze-dried heated drying again.The catalyst preparation process
It is avoided in although using liquid acid, its preparation process has used ionic liquid and the activity of catalyst is to be improved.
Summary of the invention：
The object of the present invention is to provide a kind of carbon-based solid acid catalyst and its applications in lignocellulosic depolymerization.This
Invention using paper industry waste lignosulfonates be carbon source, " one kettle way " has synthesized carbon-based solid acid catalyst, water,
Lignocellulosic depolymerization saccharification is carried out in the mixed system of ionic liquid and water and ionic liquid.According to the difference of reaction system
It is different to the processing step of lignocellulosic material, can be achieved after coupling processing hemicellulose in lignocellulosic and cellulose at
Divide complete utilization, is mainly reflected in：(1) when being catalyzed lignocellulosic depolymerization in water phase, the first step be may make in lignocellulosic
Hemicellulose be able to depolymerization, obtain xylose solution.Depolymerization residue after reaction carries out sequential hydrolysis using cellulase, with solution
Cellulose components in poly- lignocellulosic obtain glucose；(2) in ionic liquid and the mixed system of water and ionic liquid
Middle reaction is can to obtain the mixed solution of xylose, glucose, xylan and glucan with a step, can be located again as desired
Reason.
The present invention is achieved by the following technical programs：
It is an object of the invention to propose a kind of preparation method of carbon-based solid acid catalyst, include the following steps：
(1) by lignosulfonates raw material and sulfonated reagent according to 1:1~1:After the ratio mixing of 20g/mL, it is in temperature
Under conditions of 120 DEG C~200 DEG C reaction 4~for 24 hours, after the reaction was completed stop heating, wait be cooled to room temperature to reaction system carry out
Filtering filters resulting filtrate and retains spare, and filter residue is cleaned, carbon-based solid acid catalyst presoma is made after drying；
(2) carbon-based solid acid catalyst presoma and oxidising agent is made according to 1 in step (1):25~1:125g/mL's
Ratio is mixed, and 30~120min is reacted at 30 DEG C~70 DEG C, to after reaction, by obtained reaction product through filtering
After drying process, carbon-based solid acid catalyst is obtained.
Carbon-based solid acid catalyst proposed by the present invention is using papermaking byproduct lignosulfonates as carbon source raw material, with sulfonation
Carbon-based solid acid catalyst is made by a step hydrothermal carbonization after reagent mixing.With the preparation method phase of Conventional solid acid catalyst
Than this method has the advantage that preparation process is easy to operate, the reaction temperature low time is short, reaction process energy consumption is small.With liquid acids
Compare, the catalyst in the case where hydrolysis efficiency and similar result, have it is small to the corrosivity of reaction unit, without to waste liquid
The advantages that progress subsequent processing, catalyst good hydrothermal stability can recycle, can effectively solve cellulose fuel ethanol skill
Pollutant process problem in art commercialized running.
It is preferred that lignosulfonates described in step (1) are selected from sodium lignin sulfonate, calcium lignosulfonate, lignin
One of sulfonic acid magnesium and potassium lignosulfonate.
It is preferred that sulfonated reagent described in step (1) be selected from one of the concentrated sulfuric acid, oleum or sulfur trioxide with
On.
It is preferred that the mass concentration of oxidant described in step (2) is 1%~30%, the oxidant is selected from dioxygen
One of water, sodium hypochlorite and liquor potassic permanganate.
A second object of the present invention is to provide the carbon-based solid acid catalysts that above-mentioned preparation method is prepared.This is urged
It is combined in the form of covalent bond between agent acidic functionality and carbon skeleton, different from the physical absorption of loaded catalyst, thus is urged
The high stability of agent still keeps higher activity after being used for multiple times.
Third object of the present invention is to provide application of the carbon-based solid acid catalyst in lignocellulosic depolymerization.
Preferably, carbon-based solid acid catalyst can be carried out in lignocellulosic depolymerization in different reaction systems, instead
Answering system includes water phase and/or ionic liquid phase.
Application of the carbon-based solid acid catalyst in lignocellulosic depolymerization, reaction system are water phase or ionic liquid phase
When, specifically comprise the following steps：
It (1) is 1 according to mass ratio by carbon-based solid acid catalyst and lignocellulosic:4~4:1 mixing after be added water or from
Sub- liquid obtains mixed liquor, lignocellulosic and the ratio of mixed liquor be 1:20~1:100g/mL, at 115 DEG C~160 DEG C
Reaction 3~16h after obtain reaction solution, after filtered reaction solution washing and drying, isolated carbon-based solid acid catalyst and
Lignocellulosic residue；
(2) sodium citrate and citric acid that pH is 4.0~6.0 are added in the lignocellulosic residue obtained to step (1)
The quality of lignocellulosic residue in the mixed solution of buffer, lignocellulosic residue and sodium citrate and citrate buffer solution
Score is 20%, adds cellulase by the amount that the cellulase of 10~40FPU/g is added in every gram of lignocellulosic residue,
48h is reacted at 37 DEG C~55 DEG C, obtains saccharide solution.
Preferably, carbon-based solid acid catalyst is catalyzed the specific step of lignocellulosic depolymerization in ionic liquid and water phase
Suddenly include：
It according to mass ratio is 1 by carbon-based solid acid catalyst and lignocellulosic:4~4:Ionic liquid is added after 1 mixing
Be mixed to get mixed liquor with the mixed solvent of water, lignocellulosic and the ratio of mixed solvent be 1:20~1:100g/
ML, the mass fraction of in the mixed solvent ionic liquid are 1%~100%, and mixed liquor reacts 2~10h at 110 DEG C~150 DEG C
Saccharide solution is obtained, is washed and recycled ionic liquid after reaction to reactant using sodium hydroxide solution, ionic liquid can
It reuses.
Preferably, the lignocellulosic is selected from one of corncob, energy grass, bagasse, rice husk and Eucalyptus.Wood
Matter cellulose can be agricultural wastes and the forestry wastes such as corncob, energy grass, bagasse, rice husk, Eucalyptus.
It is preferred that the ionic liquid is 1- allyl -3- methylimidazole villaumite (AMIMCL) or 1- butyl -3- methyl miaow
Azoles villaumite (BMIMCL).
Beneficial effects of the present invention are as follows：
1) the catalyst preparation materials own face acidic functionality rich in, it is anti-to be conducive to lignocellulosic depolymerization
It should occur.Meanwhile in the selectivity of catalyzing hydrolysis process height, hydrolysate is relatively simple and does not cause monosaccharide to degrade substantially.
2) it is combined in the form of covalent bond between the acidity of catalyst functional group and carbon skeleton, different from the object of loaded catalyst
Reason absorption, thus the high stability of catalyst, still keep higher activity after being used for multiple times.
3) source of the catalyst preparation is paper industry waste, is different from generally fine using glucose, fructose, crystallite
Dimension element etc. is carbon source, cheap, from a wealth of sources, while overcoming conventional solid acid catalyst preparation cost height, complex process
And the disadvantages of the high requirements on the equipment.
4) it is catalyzed in lignocellulosic hydrolytic process in water phase, catalyst main selective catalysis wherein hemicellulose
Degradation, a large amount of cellulose are retained in residue, subsequent cellulase degradation residue, be can be further improved lignocellulosic and are turned
Change ability improves the utilization rate of lignocellulosic to greatest extent.The Catalytic lignin degradation process in ion liquid system, can be with
Realize hemicellulose and cellulose catalytic degradation simultaneously, product is based on glycan.
Detailed description of the invention：
Fig. 1 is the XRD diagram for the carbon-based solid acid catalyst that embodiment 5 obtains；
Fig. 2 is the FT-IR figure for the carbon-based solid acid catalyst that embodiment 5 obtains.
Specific embodiment：
Below with reference to embodiment, technical solution of the present invention is further illustrated, following embodiments be it is illustrative, be not
It is limited, it cannot be limited the scope of protection of the present invention with following embodiments.
Embodiment 1：
By sodium lignin sulfonate and the concentrated sulfuric acid according to 1:It is put into voltage-resistant reactor after the ratio mixing of 20g/mL at 130 DEG C
Under the conditions of react 10h, after the reaction was completed, rinsed with 80 DEG C or more of deionized water until filtrate pH is put into 105 after being 7 after filtering
Dry 12h, obtains carbon-based solid acid catalyst presoma in DEG C baking oven.By carbon-based solid acid catalyst presoma obtained above
The hydrogen peroxide for being 10% with mass fraction is 1 by solid-to-liquid ratio:The ratio mixing of 75g/mL is placed in pressure bottle, in 30 DEG C of conditions
Lower reaction 30min is filtered simultaneously with the flushing of 80 DEG C or more of deionized water to after reaction, after solid is placed in 105 DEG C of baking ovens
Middle dry 12h, obtains carbon-based solid acid catalyst.
Carbon-based solid acid catalyst reacts in water phase：By carbon-based solid acid catalyst obtained above and corncob according to
Mass ratio is 1：It is put into voltage-resistant reactor after 1 mixing, 30mL deionized water is added thereto, so that the quality of corncob and water
Volume ratio is 1:20g/mL reacts 12h under the conditions of 130 DEG C, after fully reacting, filtering reacting liquid, and be washed with deionized,
After be put into 105 DEG C of baking ovens dry 12h.With 200 meshes to carbon-based solid acid catalyst and lignocellulosic residue after to be dried
Carry out screening process.The sodium citrate and lemon acid buffering that pH is 4.0~6.0 are added into obtained lignocellulosic residue
The content of liquid, lignocellulosic residue and lignocellulosic residue in the mixed solution of sodium citrate and citrate buffer solution is
20%, cellulase is added by the amount that the cellulase of 10FPU/g is added in every gram of lignocellulosic residue, is reacted at 50 DEG C
48h.After the reaction was completed, what statistics two-step hydrolysis reacted obtains sugar amount, and total reducing sugar yield is 70.6%, includes xylose and grape in total reducing sugar
Sugar, the mass fraction of xylose are about 82%.
Carbon-based solid acid catalyst reaction in 1- allyl -3- methylimidazole villaumite (AMIMCL)：It will be obtained above
Carbon-based solid acid catalyst and corncob are 1 according to mass ratio:It is put into voltage-resistant reactor after 1 mixing, while into reactor
It is 1 according to corncob and the mass volume ratio of 1- allyl -3- methylimidazole villaumite (AMIMCL):20 addition 1- allyl-
3- methylimidazole villaumite (AMIMCL), moisture content is 3% in 1- allyl -3- methylimidazole villaumite (AMIMCL).Closing is anti-
Device is answered, 2h is reacted in the case where 130 DEG C, carries out being separated by solid-liquid separation and using the sodium hydroxide solution of homogenous quantities to 1- alkene after reaction
Propyl -3- methylimidazole villaumite (AMIMCL) is cleaned, and saccharide solution is obtained, total reducing sugars in saccharide solution (xylan and
Glucan) yield be 75.1%.
The mixed solvent that carbon-based solid acid catalyst is formed in water phase and 1- allyl -3- methylimidazole villaumite (AMIMCL)
Middle reaction：It according to mass ratio is 1 by carbon-based solid acid catalyst obtained above and corncob:Pressure-resistant reaction is put into after 1 mixing
It in device, while being 1 according to the mass volume ratio of corncob and mixed solvent into reactor:20 addition mixed solvent, 1- alkene
The mass fraction of water is 3% in propyl -3- methylimidazole villaumite (AMIMCL), in the mixed solvent 1- allyl -3- methylimidazole
The mass fraction of villaumite (AMIMCL) is 60%.Closed reactor reacts 2h in the case where 130 DEG C, carries out solid-liquid after reaction
It separates and the sodium hydroxide solution of homogenous quantities is used to clean 1- allyl -3- methylimidazole villaumite (AMIMCL), obtain
Saccharide solution, the yield of total reducing sugars (xylan and glucan) is 85% in saccharide solution.
Embodiment 2：
By calcium lignosulfonate and the concentrated sulfuric acid according to solid-to-liquid ratio 1:It is put into voltage-resistant reactor after 1g/mL mixing at 120 DEG C
Under the conditions of react 4h, rinsed with 80 DEG C or more of deionized water after the reaction was completed, after filtering until filtrate pH is 7 or so, after put
Enter dry 12h in 105 DEG C of baking ovens, obtains carbon-based solid acid catalyst presoma.By carbon-based solid acid catalyst obtained above
The hydrogen peroxide that presoma and mass fraction are 1% is 1 by solid-to-liquid ratio:25g/mL mixing is placed in pressure bottle, in 30 DEG C of conditions
Lower reaction 120min is filtered simultaneously with the flushing of 80 DEG C or more of deionized water to after reaction, after solid is placed in 105 DEG C of bakings
Dry 12h, obtains carbon-based solid acid catalyst in case.
Carbon-based solid acid catalyst reacts in water phase：By carbon-based solid acid catalyst obtained above and corncob according to
Mass ratio is 1：It is put into voltage-resistant reactor after 1 mixing, deionized water is added thereto, so that the quality volume of corncob and water
Than being 1:100g/mL.16h is reacted under the conditions of 115 DEG C, after fully reacting, filtering reacting liquid, and be washed with deionized, after
Dry 12h is put into 105 DEG C of baking ovens.After to be dried with 200 meshes to carbon-based solid acid catalyst and lignocellulosic residue into
Row screening process.The sodium citrate and citrate buffer solution that pH is 4.0~6.0 are added into obtained lignocellulosic residue,
The content of lignocellulosic residue is 20% in the mixed solution of lignocellulosic residue and sodium citrate and citrate buffer solution,
Cellulase is added by the amount that the cellulase of 40FPU is added in every gram of lignocellulosic residue, reacts 48h at 50 DEG C.Instead
After the completion of answering, it includes xylose and glucose, wood in total reducing sugar that statistics two-step hydrolysis reaction, which obtains sugar amount, and total reducing sugar yield is 71.3%
The mass fraction of sugar is about 82%.
Carbon-based solid acid catalyst reaction in 1- butyl -3- methylimidazole villaumite (BMIMCL)：By carbon obtained above
Based solid acid catalyst and corncob are 1 according to mass ratio:It is put into voltage-resistant reactor after 1 mixing, while being pressed into reactor
It is 1 according to corncob and the mass volume ratio of 1- butyl -3- methylimidazole villaumite (BMIMCL):100 ratio adds 1- butyl -3-
Methylimidazole villaumite (BMIMCL).Closed reactor reacts 10h in the case where 150 DEG C, is separated by solid-liquid separation and is made after reaction
1- butyl -3- methylimidazole villaumite (BMIMCL) is cleaned with the sodium hydroxide solution of homogenous quantities, obtains saccharide solution, sugar
The yield of total reducing sugars (xylan and glucan) is 45.6% in class solution.
The in the mixed solvent that carbon-based solid acid catalyst is formed in water phase and 1- butyl -3- methylimidazole villaumite (BMIMCL)
Reaction：It according to mass ratio is 1 by carbon-based solid acid catalyst obtained above and corncob:Voltage-resistant reactor is put into after 1 mixing
In, while being 1 according to the mass volume ratio of corncob and mixed solvent into reactor:100 ratio adds mixed solvent, 1-
The mass fraction of water is 3% in butyl -3- methylimidazole villaumite (BMIMCL), in the mixed solvent 1- butyl -3- methylimidazole chlorine
The mass fraction of salt (BMIMCL) is 60%.Closed reactor reacts 10h in the case where 150 DEG C, and solid-liquid point is carried out after reaction
1- butyl -3- methylimidazole villaumite (BMIMCL) is cleaned from and using the sodium hydroxide solutions of homogenous quantities, obtains carbohydrate
Solution, the yield of total reducing sugars (xylan and glucan) is 80% in saccharide solution.
Embodiment 3：
By magnesium lignosulfonate and the concentrated sulfuric acid according to 1:It is put into voltage-resistant reactor after the ratio mixing of 20g/mL at 200 DEG C
Under the conditions of react for 24 hours, rinsed with 80 DEG C or more of deionized water after the reaction was completed, after filtering until filtrate pH is 7 or so, after put
Enter dry 12h in 105 DEG C of baking ovens, obtains carbon-based solid acid catalyst presoma.By carbon-based solid acid catalyst obtained above
The sodium hypochlorite that presoma and mass fraction are 30% is 1 by solid-to-liquid ratio:25g/mL mixing is placed in voltage-resistant reactor, 30
React 30min under the conditions of DEG C, to after reaction, filter simultaneously with the flushing of 80 DEG C or more of deionized water, after solid is placed in 105
Dry 12h, obtains final highly selective carbon-based solid acid catalyst in DEG C baking oven.
Carbon-based solid acid catalyst reacts in water phase：High carbon-based solid acid catalyst obtained above and energy grass are pressed
It is 1 according to mass ratio：It is put into voltage-resistant reactor after 1 mixing, 30mL deionized water is added thereto, so that the matter of corncob and water
Measuring volume ratio is 1:100g/mL.3h is reacted under the conditions of 160 DEG C, after fully reacting, filtering reacting liquid, and be washed with deionized water
Wash, after be put into 105 DEG C of baking ovens dry 12h.Screening process is carried out to catalyst and lignocellulosic residue after to be dried.Xiang get
To lignocellulosic residue in be added pH be 4.0~6.0 sodium citrate and citrate buffer solution, lignocellulosic residue with
The content of lignocellulosic residue is 20% in the mixed solution of sodium citrate and citrate buffer solution, by every gram of lignocellulosic
The amount that the cellulase of 40FPU is added in residue adds cellulase, reacts 48h at 55 DEG C.After the reaction was completed, two steps are counted
Hydrolysis obtains sugar amount, and it includes xylose and glucose in total reducing sugar, the mass fraction of xylose is about that total reducing sugar yield, which is 72.5%,
82%.
Carbon-based solid acid catalyst reaction in 1- allyl -3- methylimidazole villaumite (AMIMCL)：It will be obtained above
Carbon-based solid acid catalyst and corncob are 1 according to mass ratio:It is put into voltage-resistant reactor after 1 mixing, while into reactor
It is 1 according to corncob and the mass volume ratio of 1- allyl -3- methylimidazole villaumite (AMIMCL):100 ratio adds 1- alkene
Propyl -3- methylimidazole villaumite (AMIMCL), the mass fraction of water is in 1- allyl -3- methylimidazole villaumite (AMIMCL)
3%.Closed reactor reacts 3h in the case where 150 DEG C, carries out being separated by solid-liquid separation and using the sodium hydroxide of homogenous quantities after reaction
Solution cleans 1- allyl -3- methylimidazole villaumite (AMIMCL), obtains saccharide solution, total reducing sugars in saccharide solution
The yield of (xylan and glucan) is 63.9%.
The mixed solvent that carbon-based solid acid catalyst is formed in water phase and 1- allyl -3- methylimidazole villaumite (AMIMCL)
Middle reaction：It according to mass ratio is 1 by carbon-based solid acid catalyst obtained above and corncob:Pressure-resistant reaction is put into after 1 mixing
It in device, while being 1 according to the mass volume ratio of corncob and mixed solvent into reactor:100 ratio adds mixed solvent,
The mass fraction of in the mixed solvent 1- allyl -3- methylimidazole villaumite (AMIMCL) is 60%, 1- allyl -3- methylimidazole
The mass fraction of water is 3% in villaumite (AMIMCL).Closed reactor reacts 3h in the case where 150 DEG C, is consolidated after reaction
Liquid separates and the sodium hydroxide solution of homogenous quantities is used to clean 1- allyl -3- methylimidazole villaumite (AMIMCL), obtains
To saccharide solution, the yield of total reducing sugars (xylan and glucan) is 82.5% in saccharide solution.
Embodiment 4：
By potassium lignosulfonate and the concentrated sulfuric acid according to 1:It is put into voltage-resistant reactor after the ratio mixing of 20g/mL at 130 DEG C
Under the conditions of react 10h, rinsed with 80 DEG C or more of deionized water after the reaction was completed, after filtering until filtrate pH is 7 or so, after put
Enter dry 12h in 105 DEG C of baking ovens, obtains carbon-based solid acid catalyst presoma.By carbon-based solid acid catalyst obtained above
The potassium permanganate that presoma and mass fraction are 5% is 1 by solid-to-liquid ratio:75g/mL mixing is placed in pressure bottle, in 70 DEG C of items
Anti- 120min under part is filtered simultaneously with the flushing of 80 DEG C or more of deionized water to after reaction, after solid is placed in 105 DEG C of bakings
Dry 12h, obtains final highly selective carbon-based solid acid catalyst in case.
Carbon-based solid acid catalyst reacts in water phase：By highly selective solid acid catalyst and bagasse according to mass ratio
It is 1：It is put into 75mL pressure bottle after 1 mixing, the deionized water of 30mL is added thereto, reacts 12h under the conditions of 130 DEG C, instead
Should completely after, filtering reacting liquid, and being washed with deionized, after be put into 105 DEG C of baking ovens dry 12h.To catalysis after to be dried
Agent and lignocellulosic residue carry out screening process.The lemon that pH is 4.0~6.0 is added into obtained lignocellulosic residue
Wood fibre in the mixed solution of sour sodium and citrate buffer solution, lignocellulosic residue and sodium citrate and citrate buffer solution
The content of plain residue is 20%, adds cellulase by the amount that the cellulase of 40FPU is added in every gram of lignocellulosic residue,
48h is reacted at 50 DEG C.After the reaction was completed, what statistics two-step hydrolysis reacted obtains sugar amount, and total reducing sugar yield is 73.6%, wraps in total reducing sugar
Xylose and glucose is included, the mass fraction of xylose is about 82%.
Carbon-based solid acid catalyst reaction in 1- allyl -3- methylimidazole villaumite (AMIMCL)：It will be obtained above
Carbon-based solid acid catalyst and corncob are 1 according to mass ratio:It is put into voltage-resistant reactor after 1 mixing, while into reactor
It is 1 according to corncob and the mass volume ratio of 1- allyl -3- methylimidazole villaumite (AMIMCL):100 ratio adds 1- alkene
Propyl -3- methylimidazole villaumite (AMIMCL), the mass fraction of water is in 1- allyl -3- methylimidazole villaumite (AMIMCL)
3%.Closed reactor reacts 2h in the case where 130 DEG C, carries out being separated by solid-liquid separation and using the sodium hydroxide of homogenous quantities after reaction
Solution cleans 1- allyl -3- methylimidazole villaumite (AMIMCL), obtains saccharide solution, total reducing sugars in saccharide solution
The yield of (xylan and glucan) is 75.1%.
The mixed solvent that carbon-based solid acid catalyst is formed in water phase and 1- allyl -3- methylimidazole villaumite (AMIMCL)
Middle reaction：It according to mass ratio is 1 by carbon-based solid acid catalyst obtained above and corncob:Pressure-resistant reaction is put into after 1 mixing
It in device, while being 1 according to the mass volume ratio of corncob and mixed solvent into reactor:100 ratio adds mixed solvent,
The mass fraction of in the mixed solvent 1- allyl -3- methylimidazole villaumite (AMIMCL) is 60%, 1- allyl -3- methylimidazole
The mass fraction of water is 3% in villaumite (AMIMCL).Closed reactor reacts 2h in the case where 130 DEG C, is consolidated after reaction
Liquid separates and the sodium hydroxide solution of homogenous quantities is used to clean 1- allyl -3- methylimidazole villaumite (AMIMCL), obtains
To saccharide solution, the yield of total reducing sugars (xylan and glucan) is 84.1% in saccharide solution.
Embodiment 5：
In N2Under the protection of gas, a certain amount of sodium lignin sulfonate is placed in tube furnace, 6h is carbonized at 250 DEG C, instead
After the completion of answering, filtering after being washed with deionized until filtrate be it is colourless, after be put into 105 DEG C of baking ovens dry 12h, obtain black
Solid.According to solid-to-liquid ratio 1:20g/mL is put into voltage-resistant reactor under the conditions of 130 DEG C after mixing black solid and the concentrated sulfuric acid
React 10h, rinsed with 80 DEG C or more of deionized water after the reaction was completed, after filtering until filtrate pH is 7 or so, after be put into 105
Dry 12h, obtains carbon-based solid acid catalyst in DEG C baking oven.It is by carbon-based solid acid catalyst obtained above and mass fraction
10% hydrogen peroxide is 1 by solid-to-liquid ratio:75g/mL mixing is placed in voltage-resistant reactor, reacts 90min under the conditions of 50 DEG C, to
After reaction, filter and with 80 DEG C or more of deionized water rinse, after by solid be placed in 105 DEG C of baking ovens dry 12h, obtain
Carbon-based solid acid catalyst.
From fig. 1, it can be seen that the carbon skeleton of the catalyst is amorphous structure.As can be seen from Figure 2, in 3419cm-1Peak belongs to O-H
Stretching vibration, in 1169cm-1Peak belong to-SO3H stretching vibration, 1034cm-1For S=O stretching vibration, 1705cm-1Ownership
In C=O bending vibration, 1616cm-1For the skeletal vibration of phenyl ring.Known to the catalyst carbon skeleton on be connected with-COOH ,-OH,
With-SO3Tri- kinds of acidic-groups of H.
Carbon-based solid acid catalyst reacts in water phase：It according to mass ratio is 1 by carbon-based solid acid catalyst and corncob：
It is put into 75mL pressure bottle after 1 mixing, the deionized water of 30mL is added thereto, reacts 12h under the conditions of 130 DEG C, has reacted
Quan Hou, filtering reacting liquid, and being washed with deionized, after be put into 105 DEG C of baking ovens dry 12h.With 200 meshes pair after to be dried
Carbon-based solid acid catalyst and lignocellulosic residue carry out screening process.PH is added into obtained lignocellulosic residue is
4.0~6.0 sodium citrate and citrate buffer solution, the mixing of lignocellulosic residue and sodium citrate and citrate buffer solution
The content of lignocellulosic residue is 20% in solution, and the amount of the cellulase of 40FPU is added by every gram of lignocellulosic residue
Cellulase is added, reacts 48h under conditions of 50 DEG C.After the reaction was completed, what statistics two-step hydrolysis reacted obtains sugar amount, total reducing sugar
Yield is 82.1%.After reaction the carbon-based solid acid catalyst after separation is reacted at this point in the reaction again, is used
Total reducing sugar yield after 10 times is 75.4%, includes xylose and glucose in total reducing sugar, the mass fraction of xylose is about 82%.
Carbon-based solid acid catalyst reaction in 1- allyl -3- methylimidazole villaumite (AMIMCL)：It will be obtained above
Carbon-based solid acid catalyst and corncob are 1 according to mass ratio:It is put into voltage-resistant reactor after 1 mixing, while into reactor
It is 1 according to corncob and the mass volume ratio of 1- allyl -3- methylimidazole villaumite (AMIMCL):60 ratio adds 1- allyl
Base -3- methylimidazole villaumite (AMIMCL), the mass fraction of water is 3% in 1- allyl -3- methylimidazole villaumite (AMIMCL).
Closed reactor reacts 2h in the case where 130 DEG C, carries out being separated by solid-liquid separation and using the sodium hydroxide solution of homogenous quantities after reaction
1- allyl -3- methylimidazole villaumite (AMIMCL) is cleaned, saccharide solution is obtained, total reducing sugars (wood in saccharide solution
Glycan and glucan) yield be 75.1%.By the carbon-based solid acid catalyst after separation again in this reaction condition after reaction
Under reacted, using total reducing sugars (the xylan and glucan) yield after 10 times be 67.3%.
The mixed solvent that carbon-based solid acid catalyst is formed in water phase and 1- allyl -3- methylimidazole villaumite (AMIMCL)
Middle reaction：It according to mass ratio is 1 by carbon-based solid acid catalyst obtained above and corncob:Pressure-resistant reaction is put into after 1 mixing
It in device, while being 1 according to the mass volume ratio of corncob and mixed solvent into reactor:60 ratio adds mixed solvent,
The mass fraction of in the mixed solvent 1- allyl -3- methylimidazole villaumite (AMIMCL) is 60%, 1- allyl -3- methylimidazole
The mass fraction of water is 3% in villaumite (AMIMCL).Closed reactor reacts 2h in the case where 130 DEG C, is consolidated after reaction
Liquid separates and the sodium hydroxide solution of homogenous quantities is used to clean 1- allyl -3- methylimidazole villaumite (AMIMCL), obtains
To saccharide solution, the yield of total reducing sugars (xylan and glucan) is 78.1% in saccharide solution.It will be after separation after reaction
Carbon-based solid acid catalyst is reacted at this point in the reaction again, uses total reducing sugars (xylan and the Portugal after 10 times
Glycan) yield be 67.3%.
Embodiment 6：
In N2Under the protection of gas, a certain amount of sodium lignin sulfonate is placed in tube furnace, 6h is carbonized at 250 DEG C, instead
After the completion of answering, filtering after being washed with deionized until filtrate be it is colourless, after be put into 105 DEG C of baking ovens dry 12h, obtain black
Solid.According to solid-to-liquid ratio 1:20g/mL is put into voltage-resistant reactor under the conditions of 130 DEG C after mixing black solid and the concentrated sulfuric acid
React 10h, rinsed with 80 DEG C or more of deionized water after the reaction was completed, after filtering until filtrate pH is 7 or so, after be put into 105
Dry 12h, obtains carbon-based solid acid catalyst presoma in DEG C baking oven.By carbon-based solid acid catalyst presoma obtained above
The hydrogen peroxide for being 10% with mass fraction is 1 by solid-to-liquid ratio:75g/mL mixing is placed in pressure bottle, is reacted under the conditions of 50 DEG C
90min is filtered and is simultaneously rinsed with 80 DEG C or more of deionized water to after reaction, after solid be placed in 105 DEG C of baking ovens dry
12h obtains carbon-based solid acid catalyst.
The mixed solvent that carbon-based solid acid catalyst is formed in water phase and 1- allyl -3- methylimidazole villaumite (AMIMCL)
Middle reaction：It according to mass ratio is 1 by carbon-based solid acid catalyst and bagasse：It is put into 75mL pressure bottle after 1 mixing, while to
In reactor according to the mass volume ratio of bagasse and mixed solvent be 1:60 ratio adds mixed solvent, in the mixed solvent 1-
The mass fraction of allyl -3- methylimidazole villaumite (AMIMCL) is 1%, 1- allyl -3- methylimidazole villaumite (AMIMCL)
The mass fraction of middle water is 3%, and closed reactor reacts 10h in the case where 110 DEG C, is separated by solid-liquid separation and made after reaction
1- allyl -3- methylimidazole villaumite (AMIMCL) is cleaned with the sodium hydroxide solution of homogenous quantities, obtains saccharide solution,
Total reducing sugars (xylan and glucan) in saccharide solution.Yield is 78.5%.
Embodiment 7：
In N2Under the protection of gas, a certain amount of sodium lignin sulfonate is placed in tube furnace, 6h is carbonized at 250 DEG C, instead
After the completion of answering, filtering after being washed with deionized until filtrate be it is colourless, after be put into 105 DEG C of baking ovens dry 12h, obtain black
Solid.According to solid-to-liquid ratio 1:20g/mL is put into voltage-resistant reactor under the conditions of 130 DEG C after mixing black solid and the concentrated sulfuric acid
React 10h, rinsed with 80 DEG C or more of deionized water after the reaction was completed, after filtering until filtrate pH is 7 or so, after be put into 105
Dry 12h, obtains carbon-based solid acid catalyst presoma in DEG C baking oven.By carbon-based solid acid catalyst presoma obtained above
The hydrogen peroxide for being 10% with mass fraction is 1 by solid-to-liquid ratio:75g/mL mixing is placed in voltage-resistant reactor, under the conditions of 50 DEG C
React 90min, to after reaction, filter simultaneously with the flushing of 80 DEG C or more of deionized water, after solid is placed in 105 DEG C of baking ovens
Dry 12h, obtains carbon-based solid acid catalyst.
The mixed solvent that carbon-based solid acid catalyst is formed in water phase and 1- allyl -3- methylimidazole villaumite (AMIMCL)
Middle reaction：It according to mass ratio is 1 by carbon-based solid acid catalyst and rice husk：It is put into 75mL pressure bottle after 1 mixing, while to anti-
Answer in device according to the mass volume ratio of rice husk and mixed solvent be 1:60 ratio adds mixed solvent, in the mixed solvent 1- allyl
The mass fraction of base -3- methylimidazole villaumite (AMIMCL) is water in 30%, 1- allyl -3- methylimidazole villaumite (AMIMCL)
Mass fraction be 3%, closed reactor reacts 6h in the case where 130 DEG C, carries out being separated by solid-liquid separation and using homogeneity after reaction
The sodium hydroxide solution of amount cleans 1- allyl -3- methylimidazole villaumite (AMIMCL), obtains saccharide solution, and carbohydrate is molten
Total reducing sugars (xylan and glucan) yield is 79.4% in liquid.
Embodiment 8：
In N2Under the protection of gas, a certain amount of sodium lignin sulfonate is placed in tube furnace, 6h is carbonized at 250 DEG C, instead
After the completion of answering, filtering after being washed with a large amount of deionized water until filtrate be it is colourless, after be put into 105 DEG C of baking ovens dry 12h, obtain
To black solid.According to solid-to-liquid ratio 1:20g/mL is put into voltage-resistant reactor after mixing black solid and the concentrated sulfuric acid at 130 DEG C
Under the conditions of react 10h, rinsed with 80 DEG C or more of deionized water after the reaction was completed, after filtering until filtrate pH is 7 or so, after put
Enter dry 12h in 105 DEG C of baking ovens, obtains carbon-based solid acid catalyst presoma.By carbon-based solid acid catalyst obtained above
The oxidant that presoma and mass fraction are 10% is 1 by solid-to-liquid ratio:75g/mL mixing is placed in pressure bottle, in 50 DEG C of conditions
Lower reaction 90min is filtered simultaneously with the flushing of 80 DEG C or more of deionized water to after reaction, after solid is placed in 105 DEG C of baking ovens
Middle dry 12h, obtains carbon-based solid acid catalyst.
The mixed solvent that carbon-based solid acid catalyst is formed in water phase and 1- allyl -3- methylimidazole villaumite (AMIMCL)
Middle reaction：It according to mass ratio is 1 by carbon-based solid acid catalyst and energy grass：It is put into 75mL pressure bottle after 1 mixing, while to
In reactor according to the mass volume ratio of energy grass and mixed solvent be 1:60 ratio adds mixed solvent, in the mixed solvent
The mass fraction of 1- allyl -3- methylimidazole villaumite (AMIMCL) is 60%, 1- allyl -3- methylimidazole villaumite
(AMIMCL) mass fraction of water is 3% in, and closed reactor reacts 2h in the case where 130 DEG C, and solid-liquid point is carried out after reaction
1- allyl -3- methylimidazole villaumite (AMIMCL) is cleaned from and using the sodium hydroxide solutions of homogenous quantities, obtains sugar
Class solution, total reducing sugars (xylan and glucan) yield is 79.5% in saccharide solution.
Embodiment 9：
In N2Under the protection of gas, a certain amount of sodium lignin sulfonate is placed in tube furnace, 6h is carbonized at 250 DEG C, instead
After the completion of answering, filtering after being washed with deionized until filtrate be it is colourless, after be put into 105 DEG C of baking ovens dry 12h, obtain black
Solid.According to solid-to-liquid ratio 1:20g/mL is put into voltage-resistant reactor under the conditions of 130 DEG C after mixing black solid and the concentrated sulfuric acid
React 10h, rinsed with 80 DEG C or more of deionized water after the reaction was completed, after filtering until filtrate pH is 7 or so, after be put into 105
Dry 12h, obtains carbon-based solid acid catalyst presoma in DEG C baking oven.By carbon-based solid acid catalyst presoma obtained above
The hydrogen peroxide for being 10% with mass fraction is 1 by solid-to-liquid ratio:75g/mL mixing is placed in pressure bottle, is reacted under the conditions of 50 DEG C
90min is filtered and is simultaneously rinsed with 80 DEG C or more of deionized water to after reaction, after solid be placed in 105 DEG C of baking ovens dry
12h obtains carbon-based solid acid catalyst.
The mixed solvent that carbon-based solid acid catalyst is formed in water phase and 1- allyl -3- methylimidazole villaumite (AMIMCL)
Middle reaction：It according to mass ratio is 1 by carbon-based solid acid catalyst and Eucalyptus：It is put into 75mL pressure bottle after 1 mixing, while to anti-
Answer in device according to the mass volume ratio of Eucalyptus and mixed solvent be 1:60 ratio adds mixed solvent, in the mixed solvent 1- allyl
The mass fraction of base -3- methylimidazole villaumite (AMIMCL) is water in 70%, 1- allyl -3- methylimidazole villaumite (AMIMCL)
Mass fraction be 3%, closed reactor reacts 2h in the case where 130 DEG C, carries out being separated by solid-liquid separation and using homogeneity after reaction
The sodium hydroxide solution of amount cleans 1- allyl -3- methylimidazole villaumite (AMIMCL), obtains saccharide solution, and carbohydrate is molten
Total reducing sugars (xylan and glucan) yield is 75.2% in liquid.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention etc.
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of carbon-based solid acid catalyst, is characterized in that, includes the following steps：
(1) by lignosulfonates and sulfonated reagent according to 1:1~1:20g/mL ratio mixing after, temperature be 120 DEG C~
Under conditions of 200 DEG C reaction 4~for 24 hours, after the reaction was completed stop heating, reaction system is filtered wait be cooled to room temperature, mistake
It filters resulting filtrate and retains spare, filter residue is cleaned, carbon-based solid acid catalyst presoma is made after drying；
(2) carbon-based solid acid catalyst presoma and oxidising agent is made according to 1 in step (1):25~1:The ratio of 125g/mL
It is mixed, 30~120min is reacted at 30 DEG C~70 DEG C, to after reaction, obtained reaction product be filtered and done
After dry processing, carbon-based solid acid catalyst is obtained.
2. the preparation method of carbon-based solid acid catalyst according to claim 1, which is characterized in that described in step (1)
Sulfonated reagent be selected from one or more of the concentrated sulfuric acid, oleum or sulfur trioxide.
3. the preparation method of carbon-based solid acid catalyst according to claim 1, which is characterized in that described in step (2)
Oxidant be selected from one of hydrogen peroxide, sodium hypochlorite and liquor potassic permanganate, the mass concentration of the oxidant is 1%
~30%.
4. the carbon-based solid acid catalyst that the preparation method of carbon-based solid acid catalyst described in claim 1 is prepared.
5. application of the carbon-based solid acid catalyst as claimed in claim 4 in lignocellulosic depolymerization.
6. application of the carbon-based solid acid catalyst according to claim 5 in lignocellulosic depolymerization, which is characterized in that
The reaction system of the lignocellulosic depolymerization is water phase and/or ionic liquid phase.
7. application of the carbon-based solid acid catalyst according to claim 6 in lignocellulosic depolymerization, which is characterized in that
Include the following steps：
It (1) is 1 according to mass ratio by carbon-based solid acid catalyst and lignocellulosic:4~4:Water or ionic liquid is added after 1 mixing
Body obtains mixed liquor, lignocellulosic and the ratio of mixed liquor be 1:20~1:100g/mL reacts at 115 DEG C~160 DEG C
Reaction solution is obtained after 3~16h, after filtered reaction solution washing and drying, isolated carbon-based solid acid catalyst and wooden
Cellulose residue；
(2) sodium citrate and lemon acid buffering that pH is 4.0~6.0 are added in the lignocellulosic residue obtained to step (1)
Liquid adds cellulase, lignocellulosic by the amount that the cellulase of 10~40FPU/g is added in every gram of lignocellulosic residue
The mass fraction of lignocellulosic residue is 20% in the mixed solution of residue and sodium citrate and citrate buffer solution, at 37 DEG C
It is reacted at~55 DEG C, obtains saccharide solution.
8. application of the carbon-based solid acid catalyst according to claim 6 in lignocellulosic depolymerization, which is characterized in that
Include the following steps：It according to mass ratio is 1 by carbon-based solid acid catalyst and lignocellulosic:4~4:Ion is added after 1 mixing
The in the mixed solvent of liquid and water be mixed to get mixed liquor, lignocellulosic and the ratio of mixed solvent be 1:20~1:
100g/mL, the mass fraction of in the mixed solvent ionic liquid are 1%~100%, and mixed liquor reacts 2 at 110 DEG C~150 DEG C
~10h obtains saccharide solution.
9. application of the carbon-based solid acid catalyst according to claim 7 or 8 in lignocellulosic depolymerization, feature exist
In the lignocellulosic is selected from one of corncob, energy grass, bagasse, rice husk and Eucalyptus.
10. application of the carbon-based solid acid catalyst according to claim 7 or 8 in lignocellulosic depolymerization, feature
It is, the ionic liquid is 1- allyl -3- methylimidazole villaumite or 1- butyl -3- methylimidazole villaumite.
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