CN106345491B - A kind of graft type solid acid catalyst and preparation method thereof and application during lignocellulosic hydrolysis and saccharification - Google Patents
A kind of graft type solid acid catalyst and preparation method thereof and application during lignocellulosic hydrolysis and saccharification Download PDFInfo
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- CN106345491B CN106345491B CN201610623755.6A CN201610623755A CN106345491B CN 106345491 B CN106345491 B CN 106345491B CN 201610623755 A CN201610623755 A CN 201610623755A CN 106345491 B CN106345491 B CN 106345491B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
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- C13—SUGAR INDUSTRY
- C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
- C13K1/00—Glucose; Glucose-containing syrups
- C13K1/02—Glucose; Glucose-containing syrups obtained by saccharification of cellulosic materials
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- C13—SUGAR INDUSTRY
- C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
- C13K13/00—Sugars not otherwise provided for in this class
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Abstract
The present invention relates to a kind of graft type solid acid catalysts, it is obtained with following preparation method: using lignocellulose-like biomass carbon-based material as raw material, sulfonating agent is bioactive molecule, the mass ratio of raw material and sulfonating agent is 1/10~10, carburizing reagent 1~36 hour at a temperature of 120~240 DEG C, resulting black solid will be carbonized through quiescence in high temperature, drying, the black solid after drying is crude carbon-based solid acid catalyst；Crude carbon-based solid acid catalyst and oxidant are mixed by solid-to-liquid ratio for 1/100~1/10,50~60 DEG C at a temperature of react 0.5~3 hour, after the reaction was completed, be separated by filtration to obtain black solid, by black solid washing and drying, as graft type carbon-based solid acid catalyst.The catalyst has similar design feature using cellulose base glucose as raw material, with lignocellulose-like biomass raw material, therefore has excellent catalytic effect, has the catalytic effect similar with liquid acids.
Description
Technical field
The invention belongs to solid acid catalyst technical fields, and in particular to a kind of graft type solid acid catalyst and its preparation
Method and application during lignocellulosic hydrolysis and saccharification.
Background technique
Biomass be on the earth unique renewable carbon source and can be converted into gas, liquid and the solid energy can be again
Raw cleaning resource.The development and utilization of biomass resource solve the problems, such as that the energy-environment-Urbanization Progress provides one for synthesis
Feasible outlet receives the most attention of countries in the world.China is large agricultural country, and the output of annual biomass resource is huge, such as
Realized industrial application, can effectively substitute fossil fuels use, to reducing carbon emission and tool of preserving the ecological environment
There is important realistic meaning.
Lignocellulose biomass by hydrolyzation saccharification prepares fermentable sugars and chemicals is one of its trans-utilization important
Step.Saccharification is hydrolyzed in lignocellulose-like biomass and prepares fermentable sugars, prepares such as second after sugar is fermented again
Part or full substitution to fossil fuel may be implemented in the bio-fuels such as alcohol, butanol；Furthermore it is possible to prepare such as 5- methylol
The petroleum base platform chemicals of the high added values such as furfural, furfural, levulic acid, can effectively reduce the use of petroleum.
Liquid acids are the effective catalysts that lignocellulose-like biomass prepares fermentable sugars and chemicals.Concentrated acid hydrolysis is
Refer to the inorganic acids such as the sulfuric acid, hydrochloric acid, the nitric acid that are 30% or more using concentration, to wooden fibre under the reaction temperature within 100 DEG C
It ties up plain biolobic material and carries out catalyzing hydrolysis.It is that 8% sulfuric acid below, hydrochloric acid, nitric acid etc. are inorganic that dilute acid hydrolysis, which refers to using concentration,
The organic acids such as acid and formic acid, acetic acid, maleic acid, carry out catalyzing hydrolysis to raw material under the reaction temperature within 100-300 DEG C.
Liquid acid catalyst hydrolyzes reaction efficiency with higher, but serious to the corrosivity of equipment, needs the production to consersion unit
Material carries out specially treated, and cost is high, and generated hydrolyzate, which has to be neutralized just, can be carried out discharge, increases
Processing cost and eco-environmental pressure.
Solid acid catalyst have many advantages, such as it is small to the corrosivity of equipment, can recycle, reaction condition it is mild, receive
The concern of numerous researchers.Stability of traditional solid acid catalyst in thermal and hydric environment is poor, and to wood fibre
The Hydrolytic catalyzing of plain biolobic material is low.By in official website, State Intellectual Property Office to the inspection in terms of solid acid catalyst
Rope has following relevant publication:
(1) Chinese patent 201310268739.6 disclose one kind using carbon-based biomass as raw material, anhydrous second are successively added
The pure and mild concentrated sulfuric acid, the mixture is washed again after certain temperature heating stirring after mixing, dry after carbon is prepared
Based solid acid catalyst, which has the advantages that simplified process equipment and preparation flow, but it is low to equally exist catalytic activity
The shortcomings that；
(2) Chinese patent 201010101049.5 disclose saccharide compound and contain sulfonic function that one kind is easily carbonized
Can compound be raw material, a step hydrothermal carbonization is synthetically prepared to obtain catalyst, the catalyst have that cost is relatively low and green it is excellent
Point, but catalytic activity needs to be further increased；
It in the prior art, is usually with glucose, fructose, sucrose, bamboo charcoal, pine to the preparation of biomass carbon based solid acid
The carbon materials such as charcoal and shell be skeleton, by with the concentrated sulfuric acid, oleum or organic sulfonic acid ester sulfonation, graft active group-
SO3The methods of H is prepared catalyst, and these methods are all inevitably present that acidic active sites density is small or preparation work
The disadvantages such as skill complexity, which limits efficiency of these catalyst in catalytic reaction process.
Summary of the invention
The purpose of the present invention is to provide a kind of graft type solid acid catalyst and preparation method thereof and in wood fibre
Application during plain hydrolysis and saccharification, the application are prepared using source extensive cheap carbon-based material and sulfonating agent as raw material
Catalyst, then the groups such as-OH of non-carbonization are further oxidized in a mild condition by-COOH by oxidant, in turn
Increase its acidity, improve catalytic efficiency, and applied during lignocellulosic hydrolysis and saccharification, significantly improve yield,
Selectivity is high and by-product is few.
In order to achieve the above-mentioned object of the invention, technical scheme is as follows:
A kind of graft type carbon-based solid acid catalyst, is obtained with following preparation method: with lignocellulose-like biomass carbon
Sill is raw material, and sulfonating agent is bioactive molecule, the temperature that the mass ratio of raw material and sulfonating agent is 1/10~10,120~240 DEG C
Lower carburizing reagent 1~36 hour, the resulting black solid that will be carbonized are black after drying through quiescence in high temperature, grinding, washing and drying
Color solid is crude carbon-based solid acid catalyst；
Crude carbon-based solid acid catalyst and oxidant are mixed by solid-to-liquid ratio for 1/100~1/10,50~60
It is reacted 0.5~3 hour at a temperature of DEG C, after the reaction was completed, is isolated by filtration to obtain black solid, which is washed
And drying, the black solid after drying is graft type carbon-based solid acid catalyst.
The solid-to-liquid ratio proposed in the application refers to the mixed proportion of solid and liquid, unit: W/V (mass/volume), at this
Unit is g/ml in application.
The application propose graft type carbon-based solid acid catalyst acidic functionality and carbon skeleton between in the form of covalent bond knot
It closes, is like that physical absorption different from general loaded catalyst, thus the high stability of catalyst, used catalyst
Activity is basically unchanged after separating washing and drying, can direct plunge into the next step.
It is another object of the present invention to provide a kind of preparation methods of graft type carbon-based solid acid catalyst, including with
Lower step:
(1) preparation of crude carbon-based solid acid catalyst: the lignocellulose-like biomass for being 1/10~10 by mass ratio
Carbon-based material and sulfonating agent are uniformly mixed, and uniformly mixed material are placed in reaction vessel, in 120~240 DEG C of temperature
Lower carburizing reagent 1~36 hour, the resulting black solid that will be carbonized are black after drying through quiescence in high temperature, grinding, washing and drying
Color solid is crude carbon-based solid acid catalyst；
(2) oxidation modification of crude carbon-based solid acid catalyst: by step (1) be made crude carbon-based solid acid catalyst and
Oxidant is 1/100~1/10 to be mixed by solid-to-liquid ratio, 50~60 DEG C at a temperature of react 0.5~3 hour, reaction is completed
Afterwards, it is isolated by filtration to obtain black solid, which is washed and dried, the black solid after drying is graft type
Carbon-based solid acid catalyst.
The graft type solid acid catalyst preparation cost that the application proposes is low, and raw material used is all cheap and easy to get basic
Chemical products do not damage human body with environment, at the same overcome high conventional solid acid catalyst preparation cost, complex process and
The disadvantages of the high requirements on the equipment, lays a good foundation for the commercialization of catalyst.
Preferably, lignocellulose-like biomass carbon-based material described in step (1) is selected from lignocellulose-like biomass
One of derivative, natural wooden fiber's element biolobic material or biomass carbon sill；The lignocellulose-like biomass
Derivative is selected from one of glucose, xylose, fructose, sucrose, starch or microcrystalline cellulose, natural wooden fiber's element class
Biomass is selected from one of corncob, energy grass or bagasse, and the biomass carbon sill is bamboo charcoal or active carbon.
Preferably, the mass ratio of lignocellulose-like biomass carbon-based material described in step (1) and sulfonating agent be 1/2~
5。
Preferably, sulfonating agent described in step (1) is p-methyl benzenesulfonic acid or p-aminobenzene sulfonic acid.
Preferably, lignocellulose-like biomass carbon-based material and sulfonating agent mixed material are uniformly mixed in step (1)
The step of are as follows: mixed material is put into ball milling 0.5~2.0 hour in ball mill, is uniformly mixed two kinds of materials.
Preferably, uniformly mixed material is placed in reaction vessel in step (1), 180 DEG C at a temperature of be carbonized
Reaction 24 hours.
Preferably, resulting black solid will will be carbonized in step (1) through quiescence in high temperature, grinding, washing and drying, tool
Body step are as follows: the resulting black solid that will be carbonized is placed in Muffle furnace, 180 DEG C at a temperature of stand 24 hours, by black
Solid is fully ground, and is carried out after sufficiently washing with 80 DEG C or more of deionized water, is put in 105 DEG C of baking oven and is stood 12
Hour is dried.
Preferably, oxidant described in step (2) is selected from one or more of hydrogen peroxide, sodium hypochlorite or nitric acid.Step
(2) by black solid washing and drying described in, the specific steps are that: by the black solid after being separated by filtration with 80 DEG C or more
Deionized water is washed repeatedly, and taking-up black solid, which is placed in 105 DEG C of baking oven, stands 12 hours.
It is another object of the present invention to additionally provide a kind of graft type solid acid catalyst to hydrolyze in lignocellulosic
Application in saccharifying.Reaction is added in graft type solid acid catalyst and lignocellulosic that mass ratio is 1/2~10:1
In container, water is added, reacts 1-20h at 60~170 DEG C.
Catalyst is prepared using lignocellulose-like biomass carbon-based material and sulfonating agent as raw material in the application, then passes through
The groups such as-the OH of non-carbonization are further oxidized to-COOH in a mild condition by oxidising agent, and then increase its acidity,
Catalytic efficiency is improved, is applied during lignocellulosic hydrolysis and saccharification, significantly improves yield, selectivity height and by-product
Object is few.
The beneficial effects of the present invention are:
(1) acidity of catalyst significantly improves, and acidity can increase by twice or more, and catalytic efficiency greatly improves, meanwhile,
It is catalyzed in the reaction of lignocellulose biomass by hydrolyzation, does not cause monosaccharide generated further to degrade substantially；
(2) it is combined in the form of covalent bond between the acidity of catalyst functional group and carbon skeleton, is different from general supported catalyst
Agent is physical absorption like that, thus the high stability of catalyst, used catalyst active group after separating washing and drying
This is constant, can direct plunge into the next step；
(3) the modified catalyst preparation cost is low, and raw material used is all basic chemical industry articles cheap and easy to get, to human body
It is not damaged with environment.High conventional solid acid catalyst preparation cost, complex process and the high requirements on the equipment etc. are overcome simultaneously
Disadvantage is laid a good foundation for the commercialization of catalyst；
(4) excellent catalytic effect and applied widely, for general acid catalyzed reaction, such as hydrolysis, hydration, esterification and alkyl
Change etc. has good catalytic effect.
Detailed description of the invention
Fig. 1 is the XRD diagram that graft type solid acid catalyst is made in the embodiment of the present invention 1；
Fig. 2 is the FT-IR figure that graft type solid acid catalyst is made in the embodiment of the present invention 1.
Specific embodiment
Below with reference to specific example, the present invention is furture elucidated.It should be understood that these embodiments are merely to illustrate this hair
It is bright, rather than limit the scope of protection of the present invention.The improvement and tune that technical staff makes according to the present invention in practical applications
It is whole, still fall within protection scope of the present invention.
Except special instruction, the equipment and reagent that the present invention uses are the art regular market purchase product.Sodium hypochlorite and
Nitric acid is that analysis is pure.
A kind of preparation method for graft type carbon-based solid acid catalyst that the application proposes, comprising the following steps:
(1) preparation of crude carbon-based solid acid catalyst: the lignocellulose-like biomass for being 1/10~10 by mass ratio
Carbon-based material and sulfonating agent are uniformly mixed, and uniformly mixed material are placed in reaction vessel, in 120~240 DEG C of reaction
At a temperature of be carbonized 1~36 hour, the resulting black solid that will be carbonized through quiescence in high temperature, grinding, washing and drying, it is dry after it is black
Color solid is crude carbon-based solid acid catalyst；
(2) oxidation modification of crude carbon-based solid acid catalyst: by step (1) be made crude carbon-based solid acid catalyst and
Oxidant is 1/100~1/10 to be mixed by solid-to-liquid ratio, 50~60 DEG C at a temperature of react 0.5~3 hour, reaction is completed
Afterwards, it is isolated by filtration to obtain black solid, which is washed and dried, the black solid after drying is graft type
Carbon-based solid acid catalyst.The H mentioned in the application2O2Aqueous solution its be mass fraction be 30%, density is approximately 1g
cm-3。
Embodiment 1
By glucose and p-methyl benzenesulfonic acid that mass ratio is 3:1 after ball milling 2h is in the ball mill to mix well, in
Hydrothermal carbonization for 24 hours, is made black solid, it is placed in 180 at 120 DEG C in the autoclave of 100mL polytetrafluoroethyllining lining
It is dried in DEG C Muffle furnace for 24 hours to remove the small molecule compound of adsorption, grinding is washed repeatedly with the deionized water higher than 80 DEG C
It washs until water lotion is in neutrality, crude carbon-based solid acid catalyst is prepared in collection solid dry 4h in 105 DEG C of baking ovens.
Addition 2g is above-mentioned in the heavy wall pressure bottle of 150mL is made crude carbon-based solid acid catalyst and 100mL mass point
The H that number is 30%2O2(density is approximately 1gcm-3) aqueous solution, heat 1h in 50 DEG C of oil bath pans, after oxidation reaction,
It is separated by filtration, collects filter residue, dried overnight in 105 DEG C of baking ovens, obtain graft type carbon-based solid acid catalyst after modified.
Rear catalyst acid amount before modified, which is measured, with chemical acid alkali titration from 1.73mmol/g rises to 3.59mmol/g.
Fig. 1 is the XRD diagram that graft type solid acid catalyst is made in the present embodiment, as shown in Figure 1, the carbon skeleton of the catalyst
For amorphous structure；Fig. 2 is the FT-IR figure that graft type solid acid catalyst is made in the present embodiment, as shown in Figure 2,3700~
3200cm-1Peak belongs to O-H stretching vibration, in 1162cm-1Peak belong to-SO3H stretching vibration, 1007cm-1It is stretched for S=O
Contracting vibration, 1705cm-1Belong to C=O bending vibration, 2597cm-1Belong to S-H stretching vibration.Know the carbon bone of the catalyst
- COOH ,-OH ,-SH and-SO are connected on frame3Tetra- kinds of acidic-groups of H.
Embodiment 2
By starch and p-methyl benzenesulfonic acid that mass ratio is 1:10 after ball milling 2h is in the ball mill to mix well, in
Hydrothermal carbonization 1h at 240 DEG C in the autoclave of 100mL polytetrafluoroethyllining lining is made black solid, it is placed in 180 DEG C
It is dried in Muffle furnace for 24 hours to remove the small molecule compound of adsorption, grinding is washed repeatedly with the deionized water higher than 80 DEG C
Until water lotion is in neutrality, solid dry 4h in 105 DEG C of baking ovens is collected, crude carbon-based solid acid catalyst is prepared.
It is added that 1g is above-mentioned that crude carbon-based solid acid catalyst and 100mL 30% is made in the heavy wall pressure bottle of 150mL
H2O2Aqueous solution, heats 0.5h in 50 DEG C of oil bath pans, after oxidation reaction, is separated by filtration, and filter residue is collected, in 105 DEG C of baking ovens
Middle drying overnight, obtains graft type carbon-based solid acid catalyst after modified.
The crude carbon-based solid acid catalyst of 1g, 0.5g corncob and 50mL deionized water are added to 75mL heavy wall pressure bottle
In, 14h is reacted at 140 DEG C；1g graft type carbon-based solid acid catalyst, 0.5g corncob and 50mL deionized water are added to
In 75mL heavy wall pressure bottle, 14h is reacted at 140 DEG C, the results showed that, crude carbon-based solid acid catalyst xylose yield is
39.1%, graft type carbon-based solid acid catalyst xylose yield is 67.4%, therefore, carbon-based solid acid catalyst oxidation modification
Afterwards, xylose yield is significantly improved.
Embodiment 3
By sucrose and p-methyl benzenesulfonic acid that mass ratio is 5:1 after ball milling 2h is in the ball mill to mix well, in 100mL
Hydrothermal carbonization for 24 hours, is made black solid, it is placed in 180 DEG C of Muffles at 180 DEG C in the autoclave of polytetrafluoroethyllining lining
The grinding for 24 hours to remove the small molecule compound of adsorption is dried in furnace, with higher than 80 DEG C of deionized water wash repeatedly up to
Water lotion is in neutrality, and collects solid dry 4h in 105 DEG C of baking ovens, crude carbon-based solid acid catalyst is prepared.
It is added that 2g is above-mentioned that crude carbon-based solid acid catalyst and 100mL 30% is made in the heavy wall pressure bottle of 150mL
H2O2Aqueous solution, heats 1h in 50 DEG C of oil bath pans, after oxidation reaction, is separated by filtration, and filter residue is collected, in 105 DEG C of baking ovens
Drying overnight, obtains graft type carbon-based solid acid catalyst after modified.
The crude carbon-based solid acid catalyst of 1g, 0.5g corncob and 50mL deionized water are added to 75mL heavy wall pressure bottle
In, 14h is reacted at 140 DEG C；1g graft type carbon-based solid acid catalyst, 0.5g corncob and 50mL deionized water are added to
In 75mL heavy wall pressure bottle, 14h is reacted at 140 DEG C；The result shows that crude carbon-based solid acid catalyst xylose yield is
39.1%, graft type carbon-based solid acid catalyst xylose yield is 67.4%, and therefore, carbon-based solid acid catalyst is through oxidation modification
Afterwards, xylose yield is significantly improved.
Embodiment 4
By glucose and p-methyl benzenesulfonic acid that mass ratio is 1:2 after ball milling 2h is in the ball mill to mix well, in
Hydrothermal carbonization for 24 hours, is made black solid, it is placed in 180 at 180 DEG C in the autoclave of 100mL polytetrafluoroethyllining lining
It is dried in DEG C Muffle furnace for 24 hours to remove the small molecule compound of adsorption, grinding is washed repeatedly with the deionized water higher than 80 DEG C
It washs until water lotion is in neutrality, crude carbon-based solid acid catalyst is prepared in collection solid dry 4h in 105 DEG C of baking ovens.
It is added that 2g is above-mentioned that crude carbon-based solid acid catalyst and 100mL 30% is made in the heavy wall pressure bottle of 150mL
H2O2Aqueous solution, heats 1h in 50 DEG C of oil bath pans, after oxidation reaction, is separated by filtration, and filter residue is collected, in 105 DEG C of baking ovens
Drying overnight, obtains graft type carbon-based solid acid catalyst after modified.
The crude carbon-based solid acid catalyst of 0.5g and 0.5g graft type carbon-based solid acid catalyst are added separately to 38mL
In heavy wall pressure bottle, 0.25g soluble starch and 25mL deionized water are all added respectively, reacts 12h at 140 DEG C.As a result table
Bright, crude carbon-based solid acid catalyst glucose yield is 28.8%, modified graft type carbon-based solid acid catalyst glucose
Yield is 90.4%, and after oxidation modification, glucose yield is significantly increased carbon-based solid acid catalyst.
Embodiment 5
By microcrystalline cellulose and p-methyl benzenesulfonic acid that mass ratio is 1:2 after ball milling 2h is in the ball mill to mix well,
Hydrothermal carbonization for 24 hours, is made black solid, it is placed in 180 DEG C of Muffles in the autoclave of 100mL polytetrafluoroethyllining lining
The grinding for 24 hours to remove the small molecule compound of adsorption is dried in furnace, with higher than 80 DEG C of deionized water wash repeatedly up to
Water lotion is in neutrality, and collects solid dry 4h in 105 DEG C of baking ovens, crude carbon-based solid acid catalyst is prepared.
It is added that 2g is above-mentioned that crude carbon-based solid acid catalyst and 100mL 30% is made in the heavy wall pressure bottle of 150mL
H2O2Aqueous solution, heats 1h in 50 DEG C of oil bath pans, after oxidation reaction, is separated by filtration, and filter residue is collected, in 105 DEG C of baking ovens
Drying overnight, obtains graft type carbon-based solid acid catalyst after modified.
The crude carbon-based solid acid catalyst of 0.5g and 0.5g graft type carbon-based solid acid catalyst are added separately to 38mL
In heavy wall pressure bottle, 0.25g corncob and 25mL deionized water are all added respectively, reacts 12h at 140 DEG C.The result shows that slightly
Carbon-based solid acid catalyst xylose yield processed is 54.7%, and graft type carbon-based solid acid catalyst xylose yield is 79.7%, carbon
After oxidation modification, xylose yield is significantly improved based solid acid catalyst.
Embodiment 6
By bagasse and p-methyl benzenesulfonic acid that mass ratio is 2:1 after ball milling 2h is in the ball mill to mix well, in
Hydrothermal carbonization for 24 hours, is made black solid, it is placed in 180 DEG C of Muffle furnaces in the autoclave of 100mL polytetrafluoroethyllining lining
For 24 hours to remove the small molecule compound of adsorption, grinding is washed with the deionized water higher than 80 DEG C repeatedly until water for middle drying
Washing lotion is in neutrality, and collects solid dry 4h in 105 DEG C of baking ovens, crude carbon-based solid acid catalyst is prepared.
It is added that 2g is above-mentioned that crude carbon-based solid acid catalyst and 100mL 30% is made in the heavy wall pressure bottle of 150mL
H2O2Aqueous solution, heats 1h in 50 DEG C of oil bath pans, after oxidation reaction, is separated by filtration, and filter residue is collected, in 105 DEG C of baking ovens
Drying overnight, obtains graft type carbon-based solid acid catalyst after modified.
The modified catalyst of 0.5g, 0.25g corncob and 25mL deionized water are added in 38mL heavy wall pressure bottle,
14h is reacted at 140 DEG C, after the completion of hydrolysis, puts into next time again by the multiple washing separation of the catalyst, after 105 DEG C of baking ovens are dried
Reaction, repeatedly, after being recycled 5 times, xylose yield drops to 69.0% from 77.5%.
Embodiment 7
By bamboo charcoal and p-aminobenzene sulfonic acid that mass ratio is 2:3 after ball milling 2h is in the ball mill to mix well, in 100mL
For 24 hours, black solid is made in hydrothermal carbonization in the autoclave of polytetrafluoroethyllining lining, it is placed in 180 DEG C of Muffle furnaces and is done
It is dry to be ground for 24 hours to remove the small molecule compound of adsorption, it is washed repeatedly with the deionized water higher than 80 DEG C until water lotion
It is in neutrality, collects solid dry 4h in 105 DEG C of baking ovens, crude carbon-based solid acid catalyst is prepared.In the heavy wall of 150mL
It is added that 2g is above-mentioned that crude carbon-based solid acid catalyst and 100mL 30%H is made in pressure bottle2O2Aqueous solution, in 50 DEG C of oil bath pans
Middle heating 1h after oxidation reaction, is separated by filtration, and collects filter residue, is dried overnight, is obtained after modified in 105 DEG C of baking ovens
Graft type carbon-based solid acid catalyst.
The crude carbon-based solid acid catalyst of 1g, 0.5g corncob and 50mL deionized water are added to 75mL heavy wall pressure bottle
In, 14h is reacted at 140 DEG C；1g graft type carbon-based solid acid catalyst, 0.5g corncob and 50mL deionized water are added to
In 75mL heavy wall pressure bottle, 14h is reacted at 140 DEG C, the results showed that, crude carbon-based solid acid catalyst xylose yield is
50.4%, graft type carbon-based solid acid catalyst xylose yield is 80.6%, and carbon-based solid acid catalyst is after oxidation modification, wood
Sugared yield is significantly improved.
Embodiment 8
By active carbon and p-aminobenzene sulfonic acid that mass ratio is 10:1 after ball milling 2h is in the ball mill to mix well, in
Hydrothermal carbonization for 24 hours, is made black solid, it is placed in 180 at 120 DEG C in the autoclave of 100mL polytetrafluoroethyllining lining
It is dried in DEG C Muffle furnace for 24 hours to remove the small molecule compound of adsorption, grinding is washed repeatedly with the deionized water higher than 80 DEG C
It washs until water lotion is in neutrality, crude carbon-based solid acid catalyst is prepared in collection solid dry 4h in 105 DEG C of baking ovens.
It is added that 10g is above-mentioned that crude carbon-based solid acid catalyst and 100mL sodium hypochlorite is made in the heavy wall pressure bottle of 150mL, 50
It heats 3h in DEG C oil bath pan, after oxidation reaction, is separated by filtration, collects filter residue, dry overnight, obtain in 105 DEG C of baking ovens
Graft type carbon-based solid acid catalyst after modified.
It is resistance to that the crude carbon-based solid acid catalyst of 0.25g, 0.5g corncob and 50mL deionized water are added to 75mL heavy wall
In pressure bottle, 1h is reacted at 60 DEG C；0.25g graft type carbon-based solid acid catalyst, 0.5g corncob and 50mL deionized water are added
Enter into 75mL heavy wall pressure bottle, reacts 1h at 60 DEG C；The result shows that crude carbon-based solid acid catalyst xylose yield is
57.2%, graft type carbon-based solid acid catalyst xylose yield is 88.7%, and carbon-based solid acid catalyst is after oxidation modification, wood
Sugared yield is significantly improved.
Embodiment 9
By xylose and p-aminobenzene sulfonic acid that mass ratio is 5:1 after ball milling 0.5h is in the ball mill to mix well, in
Hydrothermal carbonization 36h at 120 DEG C in the autoclave of 100mL polytetrafluoroethyllining lining is made black solid, it is placed in 180
It is dried in DEG C Muffle furnace for 24 hours to remove the small molecule compound of adsorption, grinding is washed repeatedly with the deionized water higher than 80 DEG C
It washs until water lotion is in neutrality, crude carbon-based solid acid catalyst is prepared in collection solid dry 4h in 105 DEG C of baking ovens.
It is added that 2g is above-mentioned that crude carbon-based solid acid catalyst and 100mL nitric acid is made in the heavy wall pressure bottle of 150mL, in 60 DEG C of oil baths
3h is heated in pot, after oxidation reaction, is separated by filtration, filter residue is collected, and is dried overnight, is obtained modified in 105 DEG C of baking ovens
Graft type carbon-based solid acid catalyst afterwards.
The crude carbon-based solid acid catalyst of 5g, 0.5g corncob and 50mL deionized water are added to 75mL heavy wall pressure bottle
In, 20h is reacted at 170 DEG C；5g graft type carbon-based solid acid catalyst, 0.5g corncob and 50mL deionized water are added to
In 75mL heavy wall pressure bottle, 20h is reacted at 170 DEG C；The result shows that crude carbon-based solid acid catalyst xylose yield is
48.3%, graft type carbon-based solid acid catalyst xylose yield is 79.9%, and carbon-based solid acid catalyst is after oxidation modification, wood
Sugared yield is significantly improved.
Above-listed detailed description is illustrating for possible embodiments of the present invention, and the embodiment is not to limit this hair
Bright the scope of the patents, all equivalence enforcements or change without departing from carried out by the present invention, is intended to be limited solely by the scope of patent protection of this case
In.
Claims (9)
1. a kind of preparation method of graft type carbon-based solid acid catalyst, which comprises the following steps:
(1) preparation of crude carbon-based solid acid catalyst: the lignocellulose-like biomass for being 1/10~10 by mass ratio is carbon-based
Material and sulfonating agent are uniformly mixed, and uniformly mixed material are placed in reaction vessel, in 120~240 DEG C of at a temperature of carbon
Change reaction 1~36 hour, for the resulting black solid that will be carbonized through quiescence in high temperature, grinding, washing and drying, the black after drying is solid
Body is crude carbon-based solid acid catalyst；
(2) crude carbon-based solid acid catalyst and oxidation the oxidation modification of crude carbon-based solid acid catalyst: is made in step (1)
Agent is 1/100~1/10 to be mixed by solid-to-liquid ratio, 50~60 DEG C at a temperature of react 0.5~3 hour, after the reaction was completed,
It is isolated by filtration to obtain black solid, which is washed and dried, the black solid after drying is graft type carbon
Based solid acid catalyst；Sulfonating agent described in step (1) is p-methyl benzenesulfonic acid or p-aminobenzene sulfonic acid.
2. the preparation method of graft type carbon-based solid acid catalyst according to claim 1, it is characterised in that: in step (1)
It is raw that the lignocellulose-like biomass carbon-based material is selected from lignocellulose-like biomass derivative, natural wooden fiber's element class
One of substance or biomass carbon sill；The lignocellulose-like biomass derivative is selected from glucose, xylose, fruit
One of sugar, sucrose, starch or microcrystalline cellulose, natural wooden fiber's element biolobic material are selected from corncob, energy grass
Or one of bagasse, the biomass carbon sill are bamboo charcoal or active carbon.
3. the preparation method of graft type carbon-based solid acid catalyst according to claim 1, it is characterised in that: in step (1)
The mass ratio of the lignocellulose-like biomass carbon-based material and sulfonating agent is 1/2~5.
4. the preparation method of graft type carbon-based solid acid catalyst according to claim 1, it is characterised in that: in step (1)
By the uniformly mixed step of lignocellulose-like biomass carbon-based material and sulfonating agent mixed material are as follows: mixed material is put into ball
Ball milling 0.5~2.0 hour in grinding machine is uniformly mixed two kinds of materials.
5. the preparation method of graft type carbon-based solid acid catalyst according to claim 1, it is characterised in that: in step (1)
Uniformly mixed material is placed in reaction vessel, 180 DEG C at a temperature of carburizing reagent 24 hours.
6. the preparation method of graft type carbon-based solid acid catalyst according to claim 1, it is characterised in that: in step (1)
Resulting black solid will be carbonized through quiescence in high temperature, grinding, washing and drying, the specific steps are that: will be carbonized resulting black
Solid is placed in Muffle furnace, 180 DEG C at a temperature of stand 24 hours, black solid is fully ground, and with 80 DEG C
Above deionized water carries out after sufficiently washing, and is put in standing in 105 DEG C of baking oven and is dried.
7. the preparation method of graft type carbon-based solid acid catalyst according to claim 1, it is characterised in that: in step (2)
The oxidant is selected from one or more of hydrogen peroxide, sodium hypochlorite or nitric acid.
8. a kind of graft type that the preparation method of graft type carbon-based solid acid catalyst described in claim 1 is prepared is carbon-based
Solid acid catalyst, which is characterized in that obtained with following preparation method: being original with lignocellulose-like biomass carbon-based material
Material, sulfonating agent are bioactive molecule, and the mass ratio of raw material and sulfonating agent is carburizing reagent at a temperature of 1/10~10,120~240 DEG C
1~36 hour, for the resulting black solid that will be carbonized through quiescence in high temperature, grinding, washing and drying, the black solid after drying was thick
Carbon-based solid acid catalyst processed；
Crude carbon-based solid acid catalyst and oxidant are mixed by solid-to-liquid ratio for 1/100~1/10, at 50~60 DEG C
At a temperature of react 0.5~3 hour, after the reaction was completed, be isolated by filtration to obtain black solid, which washed and done
Dry, the black solid after drying is graft type carbon-based solid acid catalyst.
9. a kind of application of the graft type solid acid catalyst described in claim 8 during lignocellulosic hydrolysis and saccharification.
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| CN107876088B (en) * | 2017-11-07 | 2020-06-19 | 济南大学 | Method for preparing stable solid acid catalyst by electrophilic substitution reaction |
| CN108273526A (en) * | 2018-02-05 | 2018-07-13 | 中国科学院青岛生物能源与过程研究所 | A kind of sulfonation carbon solid acid catalyst and its preparation method and application |
| CN108855135A (en) * | 2018-04-26 | 2018-11-23 | 中国科学院广州能源研究所 | A kind of carbon-based solid acid catalyst and its application in lignocellulosic depolymerization |
| CN108950090A (en) * | 2018-07-20 | 2018-12-07 | 江苏理工学院 | A kind of method for hydrolysis of saccharide compound |
| CN111346673A (en) * | 2020-03-19 | 2020-06-30 | 济南大学 | Preparation method and application of high-acid-density solid acid catalyst |
| CN111844307B (en) * | 2020-06-11 | 2021-04-16 | 东北林业大学 | Carbonized wood, preparation method thereof and solar steam generation device |
| CN115518656A (en) * | 2022-10-25 | 2022-12-27 | 陕西科技大学 | Lignin-PVC carbon-based solid acid and preparation method and application thereof |
| CN115975058A (en) * | 2022-11-14 | 2023-04-18 | 福建星海通信科技有限公司 | Cellulose material hydrolysis method |
| CN116272942A (en) * | 2023-03-24 | 2023-06-23 | 西安交通大学 | Method for functionalizing biomass tar derived carbon-based material |
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