CN108940313A - A kind of biomass carbon based solid acid catalyst and its preparation method and application - Google Patents
A kind of biomass carbon based solid acid catalyst and its preparation method and application Download PDFInfo
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- CN108940313A CN108940313A CN201810783996.6A CN201810783996A CN108940313A CN 108940313 A CN108940313 A CN 108940313A CN 201810783996 A CN201810783996 A CN 201810783996A CN 108940313 A CN108940313 A CN 108940313A
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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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
- C07D307/48—Furfural
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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- Y02P20/584—Recycling of catalysts
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Abstract
The present invention provides a kind of preparation method and application of biomass carbon based solid acid catalyst, comprising: A) biomass of nitrogenous compound is impregnated in acid solution, solid product is obtained by filtration；B) solid product is carbonized to obtain porous carbon support；C) porous carbon support is reacted with p-aminobenzene sulfonic acid and nitrous acid isoamyl rouge, sulfonation obtains catalyst.The biomass dipping charing of nitrogenous compound is obtained porous high-area carbon by the present invention；Its multifarious surface chemical composition after carbonization, the surface compared to height carbonization have better sulfonic acid group loading, improve its bronsted acid load capacity, promote the transformation efficiency of all kinds of sugar.The regulatable carbon-based supports porous structure that the present invention is formed, is supported on sulfonic acid group firmly inside duct, and duct is mesoporous and macropore after load, contacts conducive to substrate with acidic site, and keep better circulation and stress.Biomass carbon based solid acid catalyst catalytic activity of the invention is high, and stability is good, and catalytic conversion is high-efficient.
Description
Technical field
The present invention relates to biomass chemical utilization technical fields, more particularly, to a kind of biomass carbon based solid acid catalyst
And its preparation method and application.
Background technique
As traditional fossil energy is increasingly serious using bring environmental pollution and energy shortage problem, with recyclable organism
Matter waste chemicals and liquid fuel are greatly paid close attention to by people.5 hydroxymethyl furfural (HMF) is a kind of important life
Substance based platform compound can be converted into levulic acid, 2,5- dimethyl furan, 2,5- furans diformazan by all kinds of chemical reactions
Acid, 2,5- furyl dimethyl carbinol, 1,6-HD and maleic anhydride etc. can be used for medicine, fuel, plastic products and fine chemistry industry
All kinds of chemicals.
5 hydroxymethyl furfural mainly passes through carbohydrate acid-catalyzed dehydration and converts to obtain, and carbohydrate can be six carbon
Monosaccharide is also possible to glycan even direct biomass material, wherein the widest as the research of reactant using fructose and glucose
It is general.Prepared by the acid catalyst that HMF is used for hexose catalyzed conversion and is broadly divided into homogeneous catalyst and solid catalyst.Wherein
Common homogeneous catalyst includes inorganic acid (hydrochloric acid, sulfuric acid and nitric acid), organic acid (formic acid, acetic acid and citric acid) and metal
Chloride (aluminium chloride, chromium chloride and copper chloride), but using homogeneous catalyst because equipment burn into is difficult to recycle and environmental pollution etc.
Problem has unsustainable property.
Solid catalyst is because of higher reactivity, recuperability and environmental-friendly by the higher concern of researcher, mesh
The preceding solid catalyst used includes resin, carbon-based solid acid, zeolite, metal oxide etc., obtains preferable effect.But permitted
More solid catalysts have that the unstable, structural instability of activity, cyclicity be low, low efficiency.And to improve yield, often
Use ionic liquid, dimethyl sulfoxide etc. expensive or toxic substance is as solvent, industrial applicability is not strong.In addition for glucose
Be converted into HMF, need stronger bronsted acid (Acid) and lewis acid (Lewis acid) could be real
Now preferable catalytic effect, and conventional solid acid is often only comprising single type acidic site.
The cyclicity effect of existing biomass carbon based solid acid catalyst is general, during catalysis prepares HMF often
Only initial effect is preferable, and generally contains only bronsted acid, too low to glucose conversion HMF yield.Therefore, seek one
Efficient, the stable solid acid of kind and environmental-friendly catalysis process have key effect to the preparation of industrialization for pushing HMF.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that providing a kind of biomass carbon based solid acid catalyst, originally
The biomass carbon based solid acid catalyst catalytic activity of invention is high, and stability is good, and catalytic conversion is high-efficient.
The present invention provides a kind of preparation methods of biomass carbon based solid acid catalyst, comprising:
A the biomass of nitrogenous compound is impregnated in acid solution), solid product is obtained by filtration；
B) solid product is carbonized to obtain porous carbon support；
C) porous carbon support is reacted with p-aminobenzene sulfonic acid and nitrous acid isoamyl rouge, sulfonation obtains catalyst.
Preferably, step A) biomass of the nitrogenous compound is offal, eggplant straw or beanstalk stalk；The acid solution
For the phosphoric acid or pyrophosphate solution of 10%~50% mass concentration.
Preferably, step A) dip time is 1~for 24 hours；The biomass of the nitrogenous compound and the matter of acid solution
Measure ratio are as follows: 1:(0.4~2)；The mass ratio of the p-aminobenzene sulfonic acid and nitrous acid isoamyl rouge is 1:3~3:1.
Preferably, step B) it is described reaction carry out under inert gas protection；The carbonization temperature is 300~700 DEG C；Institute
Stating carbonization time is 1~10h.
Preferably, step C) reaction temperature is 60~100 DEG C；The reaction time be 4~for 24 hours.
The present invention provides a kind of biomass carbon based solid acid catalyst, the system as described in above-mentioned technical proposal any one
Preparation Method is prepared.
The present invention provides a kind of preparation methods of 5 hydroxymethyl furfural, comprising:
Catalyst is prepared in preparation method described in glucose or fructose, solvent and above-mentioned technical proposal any one
Reaction is mixed, obtains 5 hydroxymethyl furfural.
Preferably, the reaction temperature is 80~250 DEG C, and the catalytic dehydration time is 1~600min.
The present invention provides a kind of preparation methods of furfural, comprising:
Catalyst is prepared in preparation method described in xylose, solvent and Claims 1 to 5 any one to be mixed
Reaction, obtains furfural.
The present invention provides preparation methods described in above-mentioned technical proposal any one, and catalyst is prepared in preparation 5-
Application in hydroxymethylfurfural or furfural.
Compared with prior art, the present invention provides a kind of preparation methods of biomass carbon based solid acid catalyst, comprising:
A the biomass of nitrogenous compound is impregnated in acid solution), solid product is obtained by filtration；B) solid product is carbonized to obtain more
Hole carbon carrier；C) porous carbon support is reacted with p-aminobenzene sulfonic acid and nitrous acid isoamyl rouge, sulfonation obtains catalyst.The present invention
The biomass dipping charing of nitrogenous compound is obtained into porous high-area carbon；Its multifarious surface chemical composition, is compared after carbonization
The surface of height carbonization has better sulfonic acid group loading, improve its bronsted acid (Acid it) loads
Amount promotes the transformation efficiency of all kinds of sugar；Then it is prepared into using the hydrolysis of nitrous acid isoamyl rouge and p-aminobenzene sulfonic acid sulfonating reaction
To catalyst.The regulatable carbon-based supports porous structure that the present invention is formed, makes sulfonic acid group firmly be supported on duct and table
Inside face, duct is all mesoporous and macroporous structure after load, is contacted conducive to substrate with acidic site, while keeping preferably being recycled back to
The property received.Biomass carbon based solid acid catalyst catalytic activity of the invention is high, and stability is good, and catalytic conversion is high-efficient.
Specific embodiment
The present invention provides a kind of biomass carbon based solid acid catalyst and its preparation method and application, those skilled in the art
Member can use for reference present disclosure, be suitably modified realization of process parameters.In particular, it should be pointed out that all similar substitutions and modifications
Apparent to those skilled in the art, they shall fall within the protection scope of the present invention.It method of the invention and answers
With being described by preferred embodiment, related personnel can obviously not depart from the content of present invention, in spirit and scope
To methods herein and application is modified or appropriate changes and combinations, carrys out implementation and application the technology of the present invention.
The present invention provides a kind of preparation methods of biomass carbon based solid acid catalyst, comprising:
A the biomass of nitrogenous compound is impregnated in acid solution), solid product is obtained by filtration；
B) solid product is carbonized to obtain porous carbon support；
C) porous carbon support is reacted with p-aminobenzene sulfonic acid and nitrous acid isoamyl rouge, sulfonation obtains catalyst.
The present invention first impregnates the biomass of nitrogenous compound in acid solution.
The biomass of nitrogenous compound of the present invention includes but is not limited to offal or beanstalk stalk；The embodiment of the present invention is to adopt
Use offal.
The present invention preferably first preferably by the biomass of nitrogenous compound through 100~105 DEG C of dryings, grind.The present invention couple
It is well known to those skilled in the art in the concrete mode ground without limiting；The present invention is ground for described
Mesh number preferably can be 40-60 mesh without limiting.
The biomass of nitrogenous compound after grinding is impregnated in acid solution.
According to the present invention, the acid solution is preferably the phosphoric acid or pyrophosphate solution of 10%~50% mass concentration；More
The phosphoric acid or pyrophosphate solution of preferably 15%~48% mass concentration.The dip time is preferably 1~for 24 hours；More preferably
For 5~20h；Most preferably 6~15h.
Wherein, the biomass of the nitrogenous compound and the mass ratio of acid solution are preferably 1:(0.4~2)；More preferably
1:(0.8~1.8)；Most preferably 1:(1~1.6).
The present invention for the dipping concrete mode without limit, it is well known to those skilled in the art.
It is filtered after dipping, obtains filtrate and solid product.
Solid product is carbonized to obtain porous carbon support.
Charing of the present invention preferably carries out under inert gas protection；The inert gas can be nitrogen, helium etc..
1~10h is carbonized under the conditions of preferably 300~700 DEG C of charing of the present invention；More preferably 300~600 DEG C of conditions
1~8h of lower charing；1~6h is carbonized under the conditions of most preferably 300~500 DEG C.
Black solid is obtained after charing, adopt be washed with water to pH value for neutrality, the present invention for the washing number and
Mode is well known to those skilled in the art without limiting.
Moisture, which is dried and removed, after washing of the present invention obtains porous carbon support.
Porous carbon support is reacted with p-aminobenzene sulfonic acid and nitrous acid isoamyl rouge, sulfonation obtains catalyst.
Porous carbon dipping is stirred first in water specially, then sequentially adds p-aminobenzene sulfonic acid and nitrous acid isoamyl
Rouge.
The present invention for the stirring concrete mode without limit, it is well known to those skilled in the art.
The mass ratio of p-aminobenzene sulfonic acid of the present invention and nitrous acid isoamyl rouge is preferably 1:3~3:1；More preferably 1:
0.5~1.The mass ratio of porous carbon support of the present invention and p-aminobenzene sulfonic acid and nitrous acid isoamyl rouge is preferably 1:1~6:
0.5~3；Most preferably 1:4:2.
After stirring, in 60~100 DEG C of heating reflux reactions 4~for 24 hours；It is furthermore preferred that in 80~90 DEG C of heating reflux reactions
10~20h；Most preferably, in 80~85 DEG C of 12~18h of heating reflux reaction.After be separated by solid-liquid separation and wash, vacuum 60~
Obtain catalyst within dry 2~24 hours under the conditions of 120 DEG C.It is furthermore preferred that 12~20 hours dry under the conditions of 80~100 DEG C of vacuum
Obtain catalyst.
The present invention provides a kind of biomass carbon based solid acid catalyst, the system as described in above-mentioned technical proposal any one
Preparation Method is prepared.
The present invention provides a kind of preparation methods of biomass carbon based solid acid catalyst, comprising: A) by nitrogenous compound
Biomass impregnated in acid solution, solid product is obtained by filtration；B) solid product is carbonized to obtain porous carbon support；It C) will be more
Hole carbon carrier is reacted with p-aminobenzene sulfonic acid with nitrous acid isoamyl rouge, and sulfonation obtains catalyst.The present invention is by nitrogenous compound
Biomass dipping charing obtains porous high-area carbon；Its multifarious surface chemical composition after carbonization, compared to the surface of height carbonization
It is loading with better sulfonic acid group, improve its bronsted acid (Acid) load capacity promotes all kinds of sugar
Transformation efficiency；Catalyst is then prepared using the hydrolysis of nitrous acid isoamyl rouge and p-aminobenzene sulfonic acid sulfonating reaction.This hair
The regulatable carbon-based supports porous structure of bright formation, makes sulfonic acid group firmly be supported on duct and interior surface, after load
Duct is all mesoporous and macroporous structure, is contacted conducive to substrate with acidic site, while keeping better circulation and stress.Of the invention
Biomass carbon based solid acid catalyst catalytic activity is high, and stability is good, and catalytic conversion is high-efficient.
The present invention provides a kind of preparation methods of 5 hydroxymethyl furfural, comprising:
Catalyst is prepared in preparation method described in glucose or fructose, solvent and above-mentioned technical proposal any one
Reaction is mixed, obtains 5 hydroxymethyl furfural.
The present invention is preferably in pressure-resistant reaction vessel, by glucose or fructose, solvent and above-mentioned technical proposal any one
The preparation method is prepared catalyst and reaction is mixed.
Solvent of the present invention include but is not limited to the pure organic solvents such as γ-penta lactones (GVL), γ-fourth lactones (GBL) or
Its mixed solvent formed with water.The present invention to its source without limit, it is commercially available.
The present invention using can convert to obtain from biomass, nontoxic green solvent, be conducive to environmental protection and circular economy.
The mass ratio of sugar (glucose or fructose) of the invention and solvent is preferably preferably 0.01-0.05) sugared (grape of the present invention
Sugar or fructose) with catalyst quality ratio preferably 20~1, more preferably 2~5, organic solvent and water under mixed solvent of the present invention
Mass ratio preferably 1~200:1；More preferably 5~100:1；Most preferably 10~50:1.
Mixed solvent of the present invention can also be pure organic solvent, and water is not added.
The reaction temperature is preferably 80~250 DEG C, more preferably 100~200 DEG C, most preferably 120~180 DEG C, institute
Stating the catalytic dehydration time is preferably 1~600min；More preferably 10~300min；Most preferably 20~60min.
The reaction is preferably stirred to react, and the revolving speed of the stirring is preferably 300~600r/min；More preferably 400
~500r/min.
Filtering reacting liquid after reaction obtains 5 hydroxymethyl furfural.
The present invention provides a kind of preparation methods of furfural, comprising:
Catalyst is prepared in preparation method described in xylose, solvent and Claims 1 to 5 any one to be mixed
Reaction, obtains furfural.
The present invention is preferably in pressure-resistant reaction vessel, by system described in xylose, solvent and above-mentioned technical proposal any one
Preparation Method is prepared catalyst and reaction is mixed.
Solvent of the present invention include but is not limited to the pure organic solvents such as γ-penta lactones, γ-fourth lactones (GBL) or its with
The mixed solvent that water is formed.The present invention to its source without limit, it is commercially available.
The mass ratio of sugar (glucose or fructose) of the invention and solvent preferably can be 0.01-0.05), present invention sugar (Portugal
Grape sugar or fructose) with catalyst quality than preferably 20~1, most preferably 2~5), under mixed solvent of the present invention organic solvent with
The mass ratio of water preferably 1~200:1；More preferably 5~100:1；Most preferably 10~50:1.Mixed solvent of the present invention can be with
For pure organic solvent, water is not added.
(the sugar conversion) reaction temperature is preferably 80~250 DEG C, more preferably 100~200 DEG C, most preferably 120
~180 DEG C, the catalytic dehydration time is preferably 1~600min；More preferably 10~300min；Most preferably 20~60min.
The reaction is preferably stirred to react, and the revolving speed of the stirring is preferably 300~600r/min；More preferably 400
~500r/min.
Filtering reacting liquid after reaction obtains furfural.
The present invention provides preparation methods described in above-mentioned technical proposal any one, and catalyst is prepared in preparation 5-
Application in hydroxymethylfurfural or furfural.
Catalyst prepared by the present invention is prepared using protist matter, is turned waste into wealth, good economy performance, using containing
The protist matter of nitrogen compound is raw material, and the carbon-based supports surface of preparation has hydroxyl abundant, carboxyl and all kinds of nitrogenous
Functional group, preparing HMF by acid-catalyzed dehydration to sugar has good catalyzing cooperation facilitation.
Its multifarious surface chemical composition after solid product carbonization of the present invention has more preferable compared to the surface of height carbonization
Sulfonic acid group it is loading, improve its bronsted acid (Acid) load capacity promotes the conversion effect of all kinds of sugar
Rate；Some mineral metals that raw material protist matter of the present invention is rich in can form the position lewis acid (Lewis acid) after carbonization,
Without applied load, there is good action to glucose catalyzed conversion；The porous knot of regulatable carbon-based supports that the present invention is formed
Structure makes sulfonic acid group firmly be supported on duct and interior surface, and duct is all mesoporous and macroporous structure after load, is conducive to substrate
It is contacted with acidic site, while keeping better circulation and stress.Present invention catalysis is swift in response, in 10~30min of reaction time
It is interior, 93.7% can reach to the yield of its fructose converting HMF, the yield for converting its HMF to glucose can reach 43.8%.
The present invention is using the nontoxic green solvent or itself and water mixed solvent that can be converted by biomass, process green, yield
It is high.In summary feature, the present invention turn waste into wealth abandoned biomass, the carbon-based solid acid catalyst prepared, can be efficient
It is catalyzed carbohydrate and obtains HMF, target product yield is high, and catalyst circulation is good, and reaction system is environmentally protective, has extraordinary work
Industry application value.
In order to further illustrate the present invention, with reference to embodiments to a kind of biomass carbon based solid acid provided by the invention
Catalyst and its preparation method and application is described in detail.
The preparation of embodiment 1-4. catalyst A-D
It takes the offal powder of 10g milled as the protist matter raw material for being rich in nitrogenous compound, is immersed in 45%
Pyrophosphate solution in 12h, pyrophosphoric acid and tobacco stalk quality ratio are 1.3:1, later filter filtrate；By obtained solid in inertia
Under gas shield, black solid number is obtained after charing 1h under the conditions of 350,400,450,500 DEG C and is followed successively by 1~4, is used respectively
Deionized water is washed to pH value to neutrality, is then dried and removed moisture and is obtained porous carbon support number 1~4.Sulfonation process is first
A certain amount of porous carbon dipping is stirred in water, then sequentially add p-aminobenzene sulfonic acid and nitrous acid isoamyl rouge (quality: 2:
1) flow back 12 hours at 80 DEG C, after be separated by solid-liquid separation and washes clean, obtain phase within dry 12 hours under the conditions of 80 DEG C of vacuum
The catalyst answered numbers successively A-D.
Embodiment 5-8
By 0.1g fructose, 4.7ml γ-penta lactones, 0.3ml water, 0.05g catalyst is added in the pressure pipe of 15ml,
Revolving speed be 500r/min under, react 30min at 130 DEG C of temperature, after filtering reacting liquid, use HPLC detection sugar and HMF produce
Object.Concrete outcome such as table 1.
The different conversion ratios for being catalyzed lower fructose of table 1., the yield and selectivity of HMF
| Catalyst | Conversion ratio (%) | Yield (%) | Selectivity (%) |
| A | 99.95 | 93.69 | 93.73 |
| B | 99.42 | 91.26 | 91.79 |
| C | 99.27 | 90.28 | 90.95 |
| D | 99.06 | 89.70 | 90.55 |
Embodiment 9-12
By 0.1g glucose, 4.7ml γ-penta lactones, 0.3ml water, 0.05g catalyst is added in the pressure pipe of 15ml,
Revolving speed be 500r/min under, react 30min at 180 DEG C of temperature, after filtering reacting liquid, use HPLC detection sugar and HMF
Product.Concrete outcome such as table 2.
The different conversion ratios for being catalyzed lower glucose of table 2., the yield and selectivity of HMF
Embodiment 13~16
By 0.1g xylose, 5.0ml γ-penta lactones, 0.05g catalyst is added in the pressure pipe of 15ml, is in revolving speed
Under 500r/min, react 30min at 170 DEG C of temperature, after filtering reacting liquid, use HPLC detection sugar and HMF product.Specifically
As a result such as table 3.
The yield and selectivity of the different conversion ratio furfurals for being catalyzed lower xylose of table 3
| Catalyst | Conversion ratio (%) | Yield (%) | Selectivity (%) |
| A | 98.95 | 83.52 | 84.41 |
| B | 98.28 | 82.32 | 83.77 |
| C | 97.67 | 79.64 | 81.54 |
| D | 97.18 | 77.27 | 79.52 |
Embodiment 17-20
In the pressure pipe of 15ml, 0.1g fructose is added or glucose, 0.05g catalyst A, solvent use 5ml pure respectively
GVL, 4.55ml GVL and 0.45ml water mixed solvent react 30min at a temperature of 130 DEG C of fructose in the case where revolving speed is 500r/min,
React 30min at a temperature of 180 DEG C of glucose, after filtering reacting liquid, use HPLC detection sugar and HMF product.Concrete outcome
Such as table 4.
Sugared conversion ratio, the yield and selectivity of HMF under 4. differential responses solvent of table
Embodiment 21-24
In the pressure pipe of 15ml, 0.1g fructose or glucose, 4.7ml γ-penta lactones, 0.3ml water, catalyst A is added
Dosage is respectively 0.06g, 0.03g, in the case where revolving speed is 500r/min, reacts 30min at a temperature of 130 DEG C of fructose, and 180 DEG C of glucose
At a temperature of react 30min, after filtering reacting liquid, use HPLC detection sugar and HMF product.Concrete outcome such as table 5.
Sugared conversion ratio, the yield and selectivity of HMF under 5. different catalysts dosage of table
| Catalytic amount (g) | Sugar | Conversion ratio (%) | Yield (%) | Selectivity (%) |
| 0.06 | Fructose | 99.96 | 91.62 | 91.66 |
| 0.03 | Fructose | 98.63 | 87.87 | 89.09 |
| 0.06 | Glucose | 96.79 | 43.05 | 44.48 |
| 0.03 | Glucose | 89.41 | 38.55 | 43.11 |
Embodiment 25-29
By 0.1g fructose, 4.7ml γ-penta lactones, 0.3ml water, 0.05g catalyst is added in the pressure pipe of 15ml,
Revolving speed be 500r/min under, react 30min at 130 DEG C of temperature, after filtering reacting liquid, use HPLC detection sugar and HMF produce
Object.It after solid product filtering, repeats to rinse using ethyl alcohol, the dry 2h at 110 DEG C, is directly used in reaction later.Concrete outcome
Such as table 6.
The conversion ratio of fructose under 6. catalyst circulation of table, the yield and selectivity of HMF
| Cycle-index | Conversion ratio (%) | Yield (%) | Selectivity (%) |
| 1 | 99.95 | 93.69 | 93.73 |
| 2 | 99.83 | 92.82 | 92.98 |
| 3 | 99.22 | 90.33 | 91.04 |
| 4 | 98.87 | 89.47 | 90.49 |
| 5 | 98.13 | 86.62 | 88.27 |
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of biomass carbon based solid acid catalyst, comprising:
A the biomass of nitrogenous compound is impregnated in acid solution), solid product is obtained by filtration；
B) solid product is carbonized to obtain porous carbon support；
C) porous carbon support is reacted with p-aminobenzene sulfonic acid and nitrous acid isoamyl rouge, sulfonation obtains catalyst.
2. preparation method according to claim 1, which is characterized in that step A) biomass of the nitrogenous compound is cigarette
Stalk, eggplant straw or beanstalk stalk；The acid solution is the phosphoric acid or pyrophosphate solution of 10%~50% mass concentration.
3. preparation method according to claim 1, which is characterized in that step A) dip time is 1~for 24 hours；It is described
The biomass of nitrogenous compound and the mass ratio of acid solution are as follows: 1:(0.4~2)；The p-aminobenzene sulfonic acid and nitrous acid isoamyl
The mass ratio of rouge is 1:3~3:1.
4. preparation method according to claim 1, which is characterized in that step B) it is described reaction under inert gas protection into
Row；The carbonization temperature is 300~700 DEG C；The carbonization time is 1~10h.
5. preparation method according to claim 1, which is characterized in that step C) reaction temperature is 60~100 DEG C；Institute
State the reaction time be 4~for 24 hours.
6. a kind of biomass carbon based solid acid catalyst, which is characterized in that the preparation as described in Claims 1 to 5 any one
Method is prepared.
7. a kind of preparation method of 5 hydroxymethyl furfural, comprising:
Catalyst is prepared in preparation method described in glucose or fructose, solvent and Claims 1 to 5 any one to mix
It is stirred to react, obtains 5 hydroxymethyl furfural.
8. preparation method according to claim 7, which is characterized in that the reaction temperature is 80~250 DEG C, catalytic dehydration
Time is 1~600min.
9. a kind of preparation method of furfural, comprising:
Catalyst is prepared in preparation method described in xylose, solvent and Claims 1 to 5 any one to be mixed instead
It answers, obtains furfural.
10. preparation method as claimed in any one of claims 1 to 5, wherein be prepared catalyst prepare 5 hydroxymethyl furfural or
Application in furfural.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201810783996.6A CN108940313B (en) | 2018-07-17 | 2018-07-17 | Biomass carbon-based solid acid catalyst and preparation method and application thereof |
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| CN201810783996.6A CN108940313B (en) | 2018-07-17 | 2018-07-17 | Biomass carbon-based solid acid catalyst and preparation method and application thereof |
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| Publication Number | Publication Date |
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| CN108940313A true CN108940313A (en) | 2018-12-07 |
| CN108940313B CN108940313B (en) | 2020-08-25 |
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| CN115155616A (en) * | 2022-07-22 | 2022-10-11 | 华南理工大学 | Nano cellulose base porous solid acid catalyst and preparation method and application thereof |
| CN115155616B (en) * | 2022-07-22 | 2023-10-20 | 华南理工大学 | Nanocellulose-based porous solid acid catalyst and preparation method and application thereof |
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