CN106345491A - Grafted solid acid catalyst, preparation method thereof and application of grafted solid acid catalyst in saccharification process of lignocellulose - Google Patents
Grafted solid acid catalyst, preparation method thereof and application of grafted solid acid catalyst in saccharification process of lignocellulose Download PDFInfo
- Publication number
- CN106345491A CN106345491A CN201610623755.6A CN201610623755A CN106345491A CN 106345491 A CN106345491 A CN 106345491A CN 201610623755 A CN201610623755 A CN 201610623755A CN 106345491 A CN106345491 A CN 106345491A
- Authority
- CN
- China
- Prior art keywords
- acid catalyst
- carbon
- solid acid
- based solid
- graft type
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
-
- C—CHEMISTRY; METALLURGY
- 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
-
- C—CHEMISTRY; METALLURGY
- 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
- C13K13/002—Xylose
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- General Health & Medical Sciences (AREA)
- Catalysts (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a grafted solid acid catalyst. A preparation method of the grafted solid acid catalyst comprises the following steps: taking lignocelluloses biomass carbon-based material as a raw material, taking a sulfonating agent as an active molecule, and carrying out carbonization reaction for 1-36 hours at the temperature of 120-240 DEG C, wherein the mass ratio of the raw material and the sulfonating agent is 1/10-10; standing black solid obtained by carbonization at high temperature, drying to obtain black solid which is a rough carbon-based solid acid catalyst; and mixing the rough carbon-based solid acid catalyst with an oxidizing agent according to the solid-liquid ratio of 1/10-0-1/10, reacting for 0.5-3 hours at the temperature of 50-60 DEG C, after reaction, filtering and separating to obtain black solid, and washing and drying the black solid to obtain the grafted carbon-based solid acid catalyst. Cellulose-based glucose is used as the raw material of the catalyst, the structural characteristics of the raw material are similar to the structural characteristics of the raw material of lignocelluloses biomass, therefore, catalyzing effect is excellent, and the catalyzing effect of the grafted solid acid catalyst is similar to the catalyzing effect of liquid acid.
Description
Technical field
The invention belongs to solid acid catalyst technical field is and in particular to a kind of graft type solid acid catalyst and its preparation
Method and the application during lignocellulose hydrolysis and saccharification.
Background technology
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.For comprehensive, developing of biomass resource solves the problems, such as that the energy-environment-Urbanization Progress provides one
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 commercial application, can substitute fossil fuels effectively use, to reducing carbon emission and tool of preserving the ecological environment
There is important realistic meaning.
Lignocellulose biomass by hydrolyzation saccharifying prepare fermentable sugars and chemicals be one of its trans-utilization important
Step.Fermentable sugars is prepared in the lignocellulose-like biomass saccharifying that is hydrolyzed, after sugar is fermented, prepares such as second again
The bio-fuels such as alcohol, butanol, it is possible to achieve the part to Fossil fuel or full replacement；Furthermore it is possible to preparation 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 oil.
Liquid acids are the effective catalysts that lignocellulose-like biomass prepares fermentable sugars and chemicals.Concentrated acid hydrolysis are
Refer to using concentration be more than 30% sulphuric acid, hydrochloric acid, the mineral acid such as nitric acid, to wooden fibre under the reaction temperature within 100 DEG C
The plain biolobic material of dimension carries out catalyzing hydrolysis.Dilute acid hydrolysis refer to using concentration be less than 8% sulphuric acid, hydrochloric acid, nitric acid etc. inorganic
Acid and the organic acid such as 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 hydrolysis has higher reaction efficiency, but serious to the corrosivity of equipment, needs the making to consersion unit
Material carries out special handling, and cost is high, and produced hydrolyzed solution has to be neutralized process and just can be discharged, and increased
Processing cost and eco-environmental pressure.
Solid acid catalyst has the advantages that the corrosivity to equipment are little, can recycle, reaction condition is gentle, receives
The concern of vast researcher.Less stable in thermal and hydric environment for traditional solid acid catalyst, and to wood fibre
The Hydrolytic catalyzing of plain biolobic material is low.By in official website of State Intellectual Property Office to the inspection in terms of solid acid catalyst
Rope, has an as follows related publication:
(1) Chinese patent 201310268739.6, disclose one kind with carbon-based biomass as raw material, successively add anhydrous second
This mixture is prepared carbon after mix homogeneously after uniform temperature heated and stirred after washing, being dried by alcohol and concentrated sulphuric acid again
Based solid acid catalyst, this catalyst has the advantages that simplified process equipment and preparation flow, but it is low to equally exist catalysis activity
Shortcoming；
(2) Chinese patent 201010101049.5, disclose a kind of saccharide compound of easy carbonization and contain sulfonic work(
Can compound be raw material, a step hydrothermal carbonization is synthetically prepared to obtain catalyst, and this catalyst has relatively low and green excellent of cost
Point, but catalysis activity needs to be improved further；
In prior art, the preparation to biomass carbon-based solid acid is typically with glucose, Fructose, sucrose, bamboo charcoal, Masson Pine
The material with carbon element such as charcoal and shell be skeleton, by with concentrated sulphuric acid, oleum or organic sulfonic acid ester sulfonation, grafting active group-
so3The methods such as h prepare catalyst, and these methods be all inevitably present acidic active sites density little or preparation work
The inferior positions such as skill complexity, which limits efficiency in catalytic reaction process for these catalyst.
Content of the invention
It is an object of the invention 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 is to originate widely cheap carbon-based material and sulfonating agent prepares for raw material
Catalyst, then the groups such as-oh of non-carbonization are further oxidized in a mild condition by-cooh by oxidant, and then
Increase its acidity, improve catalytic efficiency, and applied during lignocellulose hydrolysis and saccharification, so that yield is significantly improved,
Selectivity is high and by-product is few.
In order to realize foregoing invention purpose, 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, and the mass ratio of raw material and sulfonating agent is 1/10～10,120～240 DEG C of temperature
Lower carburizing reagent 1～36 hour, the black solid of carbonization gained through quiescence in high temperature, grinding, washing and is dried, dried black
Color solid is rough carbon-based solid acid catalyst；
Rough carbon-based solid acid catalyst and oxidant are mixed for 1/100～1/10 by solid-to-liquid ratio, 50～60
React 0.5～3 hour at a temperature of DEG C, after the completion of reaction, be isolated by filtration and obtain black solid, this black solid is washed
And drying, dried black solid as graft type carbon-based solid acid catalyst.
The solid-to-liquid ratio proposing in the application refers to the mixed proportion of solid and liquid, and unit: w/v (mass/volume), at this
In application, unit is g/ml.
With covalent bond form knot between the graft type carbon-based solid acid catalyst acidic functionality of the application proposition and carbon skeleton
Close, be physical absorption like that different from general loaded catalyst, thus the stability of catalyst is higher, used catalyst
After separated washing and drying, activity is basically unchanged, and can direct plunge into the next step.
Further object is that provide a kind of preparation method of graft type carbon-based solid acid catalyst, including with
Lower step:
(1) preparation of rough carbon-based solid acid catalyst: the lignocellulose-like biomass that mass ratio is 1/10～10
Carbon-based material and sulfonating agent mix homogeneously, the material of mix homogeneously is positioned in reaction vessel, in 120～240 DEG C of temperature
Lower carburizing reagent 1～36 hour, the black solid of carbonization gained through quiescence in high temperature, grinding, washing and is dried, dried black
Color solid is rough carbon-based solid acid catalyst；
(2) oxidation modification of rough carbon-based solid acid catalyst: by step (1) be obtained rough carbon-based solid acid catalyst and
Oxidant is mixed for 1/100～1/10 by solid-to-liquid ratio, reacts 0.5～3 hour, reaction completes at a temperature of 50～60 DEG C
Afterwards, it is isolated by filtration and obtains black solid, this black solid is washed and is dried, dried black solid 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, are not damaged with environment to human body, overcome that conventional solid acid catalyst preparation cost is high simultaneously, complex process and
The shortcomings of high to equipment requirements, it is that the commercialization of catalyst is laid a good foundation.
Preferably, lignocellulose-like biomass carbon-based material described in step (1) is selected from lignocellulose-like biomass
Derivant, natural wooden fiber element one of biolobic material or biomass carbon sill；Described lignocellulose-like biomass
Derivant is selected from one of glucose, xylose, Fructose, sucrose, starch or Microcrystalline Cellulose, described natural wooden fiber element class
Biomass are selected from one of corn cob, energy grass or bagasse, and described biomass carbon sill is bamboo charcoal or activated carbon.
Preferably, the mass ratio of lignocellulose-like biomass carbon-based material and sulfonating agent described in step (1) be 1/2～
5.
Preferably, sulfonating agent described in step (1) is p-methyl benzenesulfonic acid or p-aminobenzene sulfonic acid.
Preferably, by lignocellulose-like biomass carbon-based material and sulfonating agent mixed material mix homogeneously in step (1)
Step be: mixed material is put into ball milling 0.5～2.0 hour in ball mill, makes two kinds of material mix homogeneously.
Preferably, in step (1), the material of mix homogeneously is positioned in reaction vessel, carbonization at a temperature of 180 DEG C
Reaction 24 hours.
Preferably, in step (1), the black solid of just carbonization gained through quiescence in high temperature, grinding, washing and is dried, its tool
Body step is: the black solid of carbonization gained is positioned in Muffle furnace, stands 24 hours, by black at a temperature of 180 DEG C
Solid is fully ground, and after fully being washed with more than 80 DEG C of deionized water, is put in 105 DEG C of baking oven and stands 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) described in, black solid is washed and be dried, it concretely comprises the following steps: by the black solid after filtration separation with more than 80 DEG C
Deionized water carries out cyclic washing, takes out black solid and is placed in standing 12 hours in 105 DEG C of baking oven.
Further object is that additionally provide a kind of graft type solid acid catalyst hydrolyzing in lignocellulose
Application in saccharifying.By mass ratio be 1/2～10:1 graft type solid acid catalyst and lignocellulose add reaction
In container, add water, at 60～170 DEG C, react 1-20h.
The application prepares catalyst with lignocellulose-like biomass carbon-based material and sulfonating agent for raw material, then passes through
The groups such as-the oh of non-carbonization are further oxidized to-cooh by oxidising agent in a mild condition, and then increase its acidity,
Improve catalytic efficiency, applied during lignocellulose hydrolysis and saccharification, so that yield is significantly improved, selectivity is high and by-product
Thing is few.
The invention has the beneficial effects as follows:
(1) this acidity of catalyst significantly improves, and acidity can increase twice or more, and catalytic efficiency greatly improves, meanwhile,
In the reaction of catalysis lignocellulose biomass by hydrolyzation, generated monosaccharide is not substantially caused to degrade further；
(2) combined with covalent bond form between this acidity of catalyst functional group and carbon skeleton, different from general supported catalyst
Agent is physical absorption like that, thus the stability of catalyst is higher, active group after the separated washing and drying of used catalyst
This is constant, can direct plunge into the next step；
(3) this modified catalyst preparation cost is low, and raw material used is all basic chemical industry articles for use cheap and easy to get, to human body
Do not damage with environment.Overcome that conventional solid acid catalyst preparation cost is high simultaneously, complex process and to equipment requirements height etc.
Shortcoming, is that the commercialization of catalyst is laid a good foundation；
(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.
Brief description
Fig. 1 is obtained the xrd figure of graft type solid acid catalyst for the embodiment of the present invention 1；
Fig. 2 is obtained the ft-ir figure of graft type solid acid catalyst for the embodiment of the present invention 1.
Specific embodiment
With reference to instantiation, it is further elucidated with the present invention.It should be understood that these embodiments are merely to illustrate this
Bright, rather than limit protection scope of the present invention.Technical staff makes according to the present invention in actual applications improvement and tune
Whole, still fall within protection scope of the present invention.
The equipment using except special instruction, the present invention and reagent are the art routine commercial products.Sodium hypochlorite and
Nitric acid is that analysis is pure.
A kind of preparation method of graft type carbon-based solid acid catalyst that the application proposes, comprises the following steps:
(1) preparation of rough carbon-based solid acid catalyst: the lignocellulose-like biomass that mass ratio is 1/10～10
Carbon-based material and sulfonating agent mix homogeneously, the material of mix homogeneously is positioned in reaction vessel, in 120～240 DEG C of reaction
At a temperature of carbonization 1～36 hour, the black solid of carbonization gained through quiescence in high temperature, grinding, washing and is dried, dried black
Color solid is rough carbon-based solid acid catalyst；
(2) oxidation modification of rough carbon-based solid acid catalyst: by step (1) be obtained rough carbon-based solid acid catalyst and
Oxidant is mixed for 1/100～1/10 by solid-to-liquid ratio, reacts 0.5～3 hour, reaction completes at a temperature of 50～60 DEG C
Afterwards, it is isolated by filtration and obtains black solid, this black solid is washed and is dried, dried black solid is graft type
Carbon-based solid acid catalyst.The h mentioning in the application2o2Aqueous solution its be mass fraction be 30%, density is approximately 1g
cm-3.
Embodiment 1
By the glucose for 3:1 for the mass ratio and p-methyl benzenesulfonic acid after in ball mill, ball milling 2h is with abundant mixing, in
Hydrothermal carbonization 24h at 120 DEG C in 100ml teflon-lined autoclave, prepared black solid, it is placed in 180
24h is dried in DEG C Muffle furnace to remove the micromolecular compound of surface adsorption, grinds, repeatedly washed with the deionized water higher than 80 DEG C
Wash until water lotion is in neutrality, collect solid and 4h is dried in 105 DEG C of baking ovens, prepare rough carbon-based solid acid catalyst.
The above-mentioned prepared rough carbon-based solid acid catalyst of 2g and 100ml mass is added to divide in the heavy wall pressure bottle of 150ml
The h for 30% for the number2o2(density is approximately 1g cm-3) aqueous solution, heat 1h in 50 DEG C of oil bath pans, after oxidation reaction terminates,
Filtration separation, collects filtering residue, dries overnight, obtain graft type carbon-based solid acid catalyst after modified in 105 DEG C of baking ovens.
Record rear catalyst acid amount before modified with chemical acid alkali titrimetry and rise to 3.59mmol/g from 1.73mmol/g.
Fig. 1 is the xrd figure that the present embodiment is obtained graft type solid acid catalyst, as shown in Figure 1, the carbon skeleton of this catalyst
For amorphous structure；Fig. 2 is the ft-ir figure that the present embodiment is obtained graft type solid acid catalyst, as shown in Figure 2,3700～
3200cm-1Peak belongs to o-h stretching vibration, in 1162cm-1Peak belong to-so3H stretching vibration, 1007cm-1Stretch for s=o
Contracting vibration, 1705cm-1Belong to c=o bending vibration, 2597cm-1Belong to s-h stretching vibration.Understand the carbon bone of this catalyst
- cooh ,-oh ,-sh and-so are connected with frame3Tetra- kinds of acidic-groups of h.
Embodiment 2
By the starch for 1:10 for the mass ratio and p-methyl benzenesulfonic acid after in ball mill, ball milling 2h is with abundant mixing, in
Hydrothermal carbonization 1h at 240 DEG C in 100ml teflon-lined autoclave, prepared black solid, it is placed in 180 DEG C
24h is dried in Muffle furnace to remove the micromolecular compound of surface adsorption, grinds, with the deionized water cyclic washing higher than 80 DEG C
Until water lotion is in neutrality, collects solid and 4h is dried in 105 DEG C of baking ovens, prepare rough carbon-based solid acid catalyst.
The above-mentioned prepared rough carbon-based solid acid catalyst of 1g and 100ml 30% is added in the heavy wall pressure bottle of 150ml
h2o2Aqueous solution, heats 0.5h in 50 DEG C of oil bath pans, after oxidation reaction terminates, filtration separation, and collect filtering residue, in 105 DEG C of baking ovens
Middle drying overnight, obtains graft type carbon-based solid acid catalyst after modified.
Rough for 1g carbon-based solid acid catalyst, 0.5g corn cob and 50ml deionized water are added to 75ml heavy wall pressure bottle
In, react 14h at 140 DEG C；1g graft type carbon-based solid acid catalyst, 0.5g corn cob and 50ml deionized water are added to
In 75ml heavy wall pressure bottle, at 140 DEG C, react 14h, result shows, rough 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 the sucrose for 5:1 for the mass ratio and p-methyl benzenesulfonic acid after in ball mill, ball milling 2h is with abundant mixing, in 100ml
Hydrothermal carbonization 24h at 180 DEG C in teflon-lined autoclave, prepared black solid, it is placed in 180 DEG C of Muffles
24h is dried in stove removing the micromolecular compound of surface adsorption, grinds, with the deionized water cyclic washing higher than 80 DEG C until
Water lotion is in neutrality, collects solid and 4h is dried in 105 DEG C of baking ovens, prepares rough carbon-based solid acid catalyst.
The above-mentioned prepared rough carbon-based solid acid catalyst of 2g and 100ml 30% is added in the heavy wall pressure bottle of 150ml
h2o2Aqueous solution, heats 1h in 50 DEG C of oil bath pans, after oxidation reaction terminates, filtration separation, and collect filtering residue, in 105 DEG C of baking ovens
Dry overnight, obtain graft type carbon-based solid acid catalyst after modified.
Rough for 1g carbon-based solid acid catalyst, 0.5g corn cob and 50ml deionized water are added to 75ml heavy wall pressure bottle
In, react 14h at 140 DEG C；1g graft type carbon-based solid acid catalyst, 0.5g corn cob and 50ml deionized water are added to
In 75ml heavy wall pressure bottle, at 140 DEG C, react 14h；Result shows, rough carbon-based solid acid catalyst xylose yield is
39.1%, graft type carbon-based solid acid catalyst xylose yield is 67.4%, therefore, the oxidized modification of carbon-based solid acid catalyst
Afterwards, xylose yield is significantly improved.
Embodiment 4
By the glucose for 1:2 for the mass ratio and p-methyl benzenesulfonic acid after in ball mill, ball milling 2h is with abundant mixing, in
Hydrothermal carbonization 24h at 180 DEG C in 100ml teflon-lined autoclave, prepared black solid, it is placed in 180
24h is dried in DEG C Muffle furnace to remove the micromolecular compound of surface adsorption, grinds, repeatedly washed with the deionized water higher than 80 DEG C
Wash until water lotion is in neutrality, collect solid and 4h is dried in 105 DEG C of baking ovens, prepare rough carbon-based solid acid catalyst.
The above-mentioned prepared rough carbon-based solid acid catalyst of 2g and 100ml 30% is added in the heavy wall pressure bottle of 150ml
h2o2Aqueous solution, heats 1h in 50 DEG C of oil bath pans, after oxidation reaction terminates, filtration separation, and collect filtering residue, in 105 DEG C of baking ovens
Dry overnight, obtain graft type carbon-based solid acid catalyst after modified.
Rough for 0.5g carbon-based solid acid catalyst and 0.5g graft type carbon-based solid acid catalyst are added separately to 38ml
In heavy wall pressure bottle, all add 0.25g soluble starch and 25ml deionized water respectively, at 140 DEG C, react 12h.Result table
Bright, rough carbon-based solid acid catalyst glucose yield is 28.8%, modified graft type carbon-based solid acid catalyst glucose
Yield is 90.4%, and carbon-based solid acid catalyst is oxidized modified, and glucose yield is significantly increased.
Embodiment 5
By the Microcrystalline Cellulose for 1:2 for the mass ratio and p-methyl benzenesulfonic acid after in ball mill, ball milling 2h is with abundant mixing,
Hydrothermal carbonization 24h in 100ml teflon-lined autoclave, prepared black solid, it is placed in 180 DEG C of Muffles
24h is dried in stove removing the micromolecular compound of surface adsorption, grinds, with the deionized water cyclic washing higher than 80 DEG C until
Water lotion is in neutrality, collects solid and 4h is dried in 105 DEG C of baking ovens, prepares rough carbon-based solid acid catalyst.
The above-mentioned prepared rough carbon-based solid acid catalyst of 2g and 100ml 30% is added in the heavy wall pressure bottle of 150ml
h2o2Aqueous solution, heats 1h in 50 DEG C of oil bath pans, after oxidation reaction terminates, filtration separation, and collect filtering residue, in 105 DEG C of baking ovens
Dry overnight, obtain graft type carbon-based solid acid catalyst after modified.
Rough for 0.5g carbon-based solid acid catalyst and 0.5g graft type carbon-based solid acid catalyst are added separately to 38ml
In heavy wall pressure bottle, all add 0.25g corn cob and 25ml deionized water respectively, at 140 DEG C, react 12h.Result shows, 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
Based solid acid catalyst is oxidized modified, and xylose yield is significantly improved.
Embodiment 6
By the bagasse for 2:1 for the mass ratio and p-methyl benzenesulfonic acid after in ball mill, ball milling 2h is with abundant mixing, in
Hydrothermal carbonization 24h in 100ml teflon-lined autoclave, prepared black solid, it is placed in 180 DEG C of Muffle furnaces
The middle 24h that is dried, to remove the micromolecular compound of surface adsorption, grinds, with the deionized water cyclic washing higher than 80 DEG C up to water
Washing liquid is in neutrality, collects solid and 4h is dried in 105 DEG C of baking ovens, prepares rough carbon-based solid acid catalyst.
The above-mentioned prepared rough carbon-based solid acid catalyst of 2g and 100ml 30% is added in the heavy wall pressure bottle of 150ml
h2o2Aqueous solution, heats 1h in 50 DEG C of oil bath pans, after oxidation reaction terminates, filtration separation, and collect filtering residue, in 105 DEG C of baking ovens
Dry overnight, obtain graft type carbon-based solid acid catalyst after modified.
Catalyst modified for 0.5g, 0.25g corn cob and 25ml deionized water are added in 38ml heavy wall pressure bottle,
React 14h at 140 DEG C, after the completion of hydrolysis, this catalyst is repeatedly washed and separates, put into next time after 105 DEG C of oven for drying again
Reaction, so repeatedly, after recycling 5 times, xylose yield drops to 69.0% from 77.5%.
Embodiment 7
By the bamboo charcoal for 2:3 for the mass ratio and p-aminobenzene sulfonic acid after in ball mill, ball milling 2h is with abundant mixing, in 100ml
Hydrothermal carbonization 24h in teflon-lined autoclave, prepared black solid, it is placed in 180 DEG C of Muffle furnaces dry
Dry 24h, to remove the micromolecular compound of surface adsorption, grinds, with the deionized water cyclic washing higher than 80 DEG C up to water lotion
In neutrality, collect solid and 4h is dried in 105 DEG C of baking ovens, prepare rough carbon-based solid acid catalyst.Heavy wall in 150ml
The above-mentioned prepared rough carbon-based solid acid catalyst of 2g and 100ml 30%h is added in pressure bottle2o2Aqueous solution, in 50 DEG C of oil bath pans
Middle heating 1h, after oxidation reaction terminates, filtration separation, collect filtering residue, dry in 105 DEG C of baking ovens overnight, obtain after modified
Graft type carbon-based solid acid catalyst.
Rough for 1g carbon-based solid acid catalyst, 0.5g corn cob and 50ml deionized water are added to 75ml heavy wall pressure bottle
In, react 14h at 140 DEG C；1g graft type carbon-based solid acid catalyst, 0.5g corn cob and 50ml deionized water are added to
In 75ml heavy wall pressure bottle, at 140 DEG C, react 14h, result shows, rough 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 oxidized modified, wood
Sugared yield is significantly improved.
Embodiment 8
By the activated carbon for 10:1 for the mass ratio and p-aminobenzene sulfonic acid after in ball mill, ball milling 2h is with abundant mixing, in
Hydrothermal carbonization 24h at 120 DEG C in 100ml teflon-lined autoclave, prepared black solid, it is placed in 180
24h is dried in DEG C Muffle furnace to remove the micromolecular compound of surface adsorption, grinds, repeatedly washed with the deionized water higher than 80 DEG C
Wash until water lotion is in neutrality, collect solid and 4h is dried in 105 DEG C of baking ovens, prepare rough carbon-based solid acid catalyst.
Add the above-mentioned prepared rough carbon-based solid acid catalyst of 10g and 100ml sodium hypochlorite in the heavy wall pressure bottle of 150ml, 50
Heat 3h in DEG C oil bath pan, after oxidation reaction terminates, filtration separation, collect filtering residue, dry in 105 DEG C of baking ovens overnight, obtain
Graft type carbon-based solid acid catalyst after modified.
Rough for 0.25g carbon-based solid acid catalyst, 0.5g corn cob and 50ml deionized water are added to 75ml heavy wall resistance to
In pressure bottle, at 60 DEG C, react 1h；0.25g graft type carbon-based solid acid catalyst, 0.5g corn cob and 50ml deionized water are added
Enter in 75ml heavy wall pressure bottle, at 60 DEG C, react 1h；Result shows, rough 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 oxidized modified, wood
Sugared yield is significantly improved.
Embodiment 9
By the xylose for 5:1 for the mass ratio and p-aminobenzene sulfonic acid after in ball mill, ball milling 0.5h is with abundant mixing, in
Hydrothermal carbonization 36h at 120 DEG C in 100ml teflon-lined autoclave, prepared black solid, it is placed in 180
24h is dried in DEG C Muffle furnace to remove the micromolecular compound of surface adsorption, grinds, repeatedly washed with the deionized water higher than 80 DEG C
Wash until water lotion is in neutrality, collect solid and 4h is dried in 105 DEG C of baking ovens, prepare rough carbon-based solid acid catalyst.
Add the above-mentioned prepared rough carbon-based solid acid catalyst of 2g and 100ml nitric acid in the heavy wall pressure bottle of 150ml, in 60 DEG C of oil baths
Heat 3h in pot, after oxidation reaction terminates, filtration separation, collect filtering residue, dry in 105 DEG C of baking ovens overnight, obtain modified
Graft type carbon-based solid acid catalyst afterwards.
Rough for 5g carbon-based solid acid catalyst, 0.5g corn cob and 50ml deionized water are added to 75ml heavy wall pressure bottle
In, react 20h at 170 DEG C；5g graft type carbon-based solid acid catalyst, 0.5g corn cob and 50ml deionized water are added to
In 75ml heavy wall pressure bottle, at 170 DEG C, react 20h；Result shows, rough 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 oxidized modified, wood
Sugared yield is significantly improved.
Above-listed detailed description is illustrating for possible embodiments of the present invention, and this embodiment simultaneously is not used to limit this
Bright the scope of the claims, all equivalence enforcements done without departing from the present invention or change, are intended to be limited solely by the scope of patent protection of this case
In.
Claims (10)
1. a kind of graft type carbon-based solid acid catalyst is it is characterised in that obtained with following preparation method: with lignocellulose
Biomass carbon sill is raw material, and sulfonating agent is bioactive molecule, and raw material is 1/10～10,120～240 with the mass ratio of sulfonating agent
Carburizing reagent 1～36 hour at a temperature of DEG C, the black solid of carbonization gained through quiescence in high temperature, grinding, washing and is dried, does
Black solid after dry is rough carbon-based solid acid catalyst；
Rough carbon-based solid acid catalyst and oxidant are mixed for 1/100～1/10 by solid-to-liquid ratio, at 50～60 DEG C
At a temperature of react 0.5～3 hour, after the completion of reaction, be isolated by filtration and obtain black solid, by this black solid washing and dry
Dry, dried black solid is graft type carbon-based solid acid catalyst.
2. a kind of preparation method of graft type carbon-based solid acid catalyst described in claim 1 is it is characterised in that include following walking
Rapid:
(1) preparation of rough carbon-based solid acid catalyst: the lignocellulose-like biomass that mass ratio is 1/10～10 is carbon-based
Material and sulfonating agent mix homogeneously, the material of mix homogeneously is positioned in reaction vessel, carbon at a temperature of 120～240 DEG C
Change reaction 1～36 hour, the black solid of carbonization gained through quiescence in high temperature, grinding, washing and is dried, dried black is solid
Body is rough carbon-based solid acid catalyst；
(2) oxidation modification of rough carbon-based solid acid catalyst: step (1) is obtained rough carbon-based solid acid catalyst and oxidation
Agent is mixed for 1/100～1/10 by solid-to-liquid ratio, reacts 0.5～3 hour at a temperature of 50～60 DEG C, after the completion of reaction,
It is isolated by filtration and obtains black solid, by the washing of this black solid and dry, dried black solid as graft type carbon
Based solid acid catalyst.
3. according to claim 2 graft type carbon-based solid acid catalyst preparation method it is characterised in that: in step (1)
Described lignocellulose-like biomass carbon-based material is selected from lignocellulose-like biomass derivant, natural wooden fiber's element class life
One of material or biomass carbon sill；Described lignocellulose-like biomass derivant is selected from glucose, xylose, really
One of sugar, sucrose, starch or Microcrystalline Cellulose, described natural wooden fiber element biolobic material is selected from corn cob, energy grass
One of or bagasse, described biomass carbon sill is bamboo charcoal or activated carbon.
4. according to claim 2 graft type carbon-based solid acid catalyst preparation method it is characterised in that: in step (1)
The mass ratio of described lignocellulose-like biomass carbon-based material and sulfonating agent is 1/2～5.
5. according to claim 2 or 4 graft type carbon-based solid acid catalyst preparation method it is characterised in that: step (1)
Described in sulfonating agent be p-methyl benzenesulfonic acid or p-aminobenzene sulfonic acid.
6. according to claim 2 graft type carbon-based solid acid catalyst preparation method it is characterised in that: in step (1)
Step by lignocellulose-like biomass carbon-based material and sulfonating agent mixed material mix homogeneously is: mixed material is put into ball
Ball milling 0.5～2.0 hour in grinding machine, makes two kinds of material mix homogeneously.
7. according to claim 2 graft type carbon-based solid acid catalyst preparation method it is characterised in that: in step (1)
The material of mix homogeneously is positioned in reaction vessel, carburizing reagent 24 hours at a temperature of 180 DEG C.
8. according to claim 2 graft type carbon-based solid acid catalyst preparation method it is characterised in that: in step (1)
The black solid of carbonization gained through quiescence in high temperature, grinding, washing and is dried, it concretely comprises the following steps: by the black of carbonization gained
Solid is positioned in Muffle furnace, stands 24 hours, black solid is fully ground at a temperature of 180 DEG C, and with 80 DEG C
After above deionized water is fully washed, it is put in standing in 105 DEG C of baking oven and is dried.
9. according to claim 2 graft type carbon-based solid acid catalyst preparation method it is characterised in that: in step (2)
Described oxidant is selected from one or more of hydrogen peroxide, sodium hypochlorite or nitric acid.
10. application during lignocellulose hydrolysis and saccharification for the graft type solid acid catalyst described in a kind of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610623755.6A CN106345491B (en) | 2016-07-29 | 2016-07-29 | A kind of graft type solid acid catalyst and preparation method thereof and application during lignocellulosic hydrolysis and saccharification |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610623755.6A CN106345491B (en) | 2016-07-29 | 2016-07-29 | A kind of graft type solid acid catalyst and preparation method thereof and application during lignocellulosic hydrolysis and saccharification |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106345491A true CN106345491A (en) | 2017-01-25 |
| CN106345491B CN106345491B (en) | 2019-03-05 |
Family
ID=57843422
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610623755.6A Active CN106345491B (en) | 2016-07-29 | 2016-07-29 | A kind of graft type solid acid catalyst and preparation method thereof and application during lignocellulosic hydrolysis and saccharification |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106345491B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107876088A (en) * | 2017-11-07 | 2018-04-06 | 济南大学 | A kind of method that electrophilic substitution reaction prepares stability solid acid catalyst |
| 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101298566A (en) * | 2008-06-27 | 2008-11-05 | 大连理工大学 | Method for preparing biocarbon solid acid catalyst and biodiesel |
| US20090137384A1 (en) * | 2006-03-03 | 2009-05-28 | Katay Janos | Hydrophobic oil adsorbent material and process for production and use |
| CN102559941A (en) * | 2011-12-21 | 2012-07-11 | 中国科学院青岛生物能源与过程研究所 | Method for hydrolyzing and saccharifying corncobs |
| CN104177447A (en) * | 2014-08-04 | 2014-12-03 | 中国科学院广州能源研究所 | Method for preparing phenolic chemicals by catalyzing degradation of lignin with carbon-based solid acid |
-
2016
- 2016-07-29 CN CN201610623755.6A patent/CN106345491B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090137384A1 (en) * | 2006-03-03 | 2009-05-28 | Katay Janos | Hydrophobic oil adsorbent material and process for production and use |
| CN101298566A (en) * | 2008-06-27 | 2008-11-05 | 大连理工大学 | Method for preparing biocarbon solid acid catalyst and biodiesel |
| CN102559941A (en) * | 2011-12-21 | 2012-07-11 | 中国科学院青岛生物能源与过程研究所 | Method for hydrolyzing and saccharifying corncobs |
| CN104177447A (en) * | 2014-08-04 | 2014-12-03 | 中国科学院广州能源研究所 | Method for preparing phenolic chemicals by catalyzing degradation of lignin with carbon-based solid acid |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107876088A (en) * | 2017-11-07 | 2018-04-06 | 济南大学 | A kind of method that electrophilic substitution reaction prepares stability solid acid catalyst |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106345491B (en) | 2019-03-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106345491B (en) | A kind of graft type solid acid catalyst and preparation method thereof and application during lignocellulosic hydrolysis and saccharification | |
| Varga et al. | Optimization of steam pretreatment of corn stover to enhance enzymatic digestibility | |
| Qing et al. | Improving enzymatic saccharification of bamboo shoot shell by alkalic salt pretreatment with H2O2 | |
| CN108855135A (en) | A kind of carbon-based solid acid catalyst and its application in lignocellulosic depolymerization | |
| CN102559941B (en) | Method for hydrolyzing and saccharifying corncobs | |
| CN102247871B (en) | Preparation method of solid acid catalyst used for biomass hydrolysis | |
| CN100497647C (en) | Method for adsorbing and decomposing stalk cellulose using cellulase | |
| Ayeni et al. | Optimization of pretreatment conditions using full factorial design and enzymatic convertibility of shea tree sawdust | |
| CN102515156B (en) | Simple method for synchronous preparation of water glass and activated carbon with rice husk pyrolyzed ash | |
| CN110272509A (en) | A kind of fiber biomass high-efficiency pretreatment separation hemicellulose and its method of comprehensive utilization | |
| CN104630307A (en) | Bio-refinery integrated process for separating and classifying whole-plant corn component | |
| CN106191135A (en) | Lignocellulose is the biorefinery method of raw material coproduction multi-product | |
| CN108273526A (en) | A kind of sulfonation carbon solid acid catalyst and its preparation method and application | |
| CN108097312A (en) | A kind of preparation method and applications of lignocellulosic based solid acid catalyst | |
| CN102516209A (en) | Method for coproducing furfural, ethanol and lignin from corncob | |
| CN106672963A (en) | Active carbon and preparation method thereof | |
| CN109759112A (en) | The preparation method of temperature-responsive solid catalyst for biomass upgrading | |
| CN103055898B (en) | Biomass carbon-based catalyst prepared by utilizing wastes in furfural production in recycling manner and application thereof | |
| CN104888655B (en) | Wood fibre glycosyl surfactant active and preparation method thereof | |
| CN110791532A (en) | Method for preparing ethanol from cellulose and comprehensively utilizing biomass | |
| CN103509194B (en) | Porous biomass acidic solid material, and preparation and application thereof | |
| CN102321489B (en) | Method for catalyzing and liquefying agricultural wastes by using ion liquid | |
| CN105131128A (en) | Method for efficiently preparing cellulose acetate through catalyzing waste biomass by organic solvents | |
| CN105838743A (en) | Method for fermenting cellulosic ethanol by thick mash semi-simultaneous saccharification by batch material supplementation | |
| CN106904591B (en) | A kind of preparation method and application of step hole tobacco rod carbon |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |