CN116408125A - Catalyst for preparing ethyl levulinate by catalytic conversion of cellulose and preparation method and application thereof - Google Patents
Catalyst for preparing ethyl levulinate by catalytic conversion of cellulose and preparation method and application thereof Download PDFInfo
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- CN116408125A CN116408125A CN202310364308.3A CN202310364308A CN116408125A CN 116408125 A CN116408125 A CN 116408125A CN 202310364308 A CN202310364308 A CN 202310364308A CN 116408125 A CN116408125 A CN 116408125A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 74
- 229920002678 cellulose Polymers 0.000 title claims abstract description 56
- 239000001913 cellulose Substances 0.000 title claims abstract description 56
- GMEONFUTDYJSNV-UHFFFAOYSA-N Ethyl levulinate Chemical compound CCOC(=O)CCC(C)=O GMEONFUTDYJSNV-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 38
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title abstract description 11
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 31
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 31
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000011574 phosphorus Substances 0.000 claims abstract description 29
- 239000010937 tungsten Substances 0.000 claims abstract description 29
- 229920000767 polyaniline Polymers 0.000 claims abstract description 23
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 17
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 7
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000000542 sulfonic acid group Chemical group 0.000 claims abstract description 7
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 40
- 238000010438 heat treatment Methods 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 10
- 238000006277 sulfonation reaction Methods 0.000 claims description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 9
- 238000011282 treatment Methods 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- 239000012018 catalyst precursor Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000007810 chemical reaction solvent Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000002051 biphasic effect Effects 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 4
- 238000005303 weighing Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 239000004809 Teflon Substances 0.000 description 5
- 229920006362 Teflon® Polymers 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 4
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 4
- 235000019838 diammonium phosphate Nutrition 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000007848 Bronsted acid Substances 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000005539 carbonized material Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical group 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 239000003864 humus Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 125000004151 quinonyl group Chemical group 0.000 description 1
- 150000003336 secondary aromatic amines Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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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
- B01J27/24—Nitrogen compounds
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
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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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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Abstract
The invention discloses a catalyst for preparing ethyl levulinate by catalytic conversion of cellulose, a preparation method and application thereof. The catalyst comprises a carrier and an active component loaded on the carrier, wherein the carrier is a nitrogen-containing carbon-based carrier prepared by taking polyaniline as a carbon material precursor, and the active component is a phosphorus, tungsten and sulfonic acid group. The catalyst is applied to the field of preparing ethyl levulinate by catalytically converting cellulose, can realize 100% conversion rate of cellulose and selectivity of ethyl levulinate of more than 80% under a water-ethanol biphasic solvent, and can produce more than 400mg of ethyl levulinate per gram of cellulose.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a catalyst for preparing ethyl levulinate by catalytic conversion of cellulose, a preparation method and application thereof.
Background
Compared with fossil energy, biomass energy has the characteristics of less pollution, reproducibility, low cost, neutrality, relatively short growth period, rich raw materials and the like. In various biomasses, the cellulose content is most abundant, and the efficient utilization of lignocellulose biomass for producing biofuel is a way for effectively solving the energy crisis and environmental pollution.
The cellulose is used as the most abundant component of biomass, the addition of acid is often involved in the prior depolymerization process, and the method is difficult to avoid, so that not only can the undesirable product of humus be formed, thereby influencing the selectivity and yield of the target product, but also causing the corrosion and environmental problems of equipment, and the subsequent separation can increase the cost. Therefore, there is a need to develop a mild and efficient catalytic system to achieve efficient conversion of cellulose to ethyl levulinate.
Disclosure of Invention
The invention mainly aims to provide a catalyst for preparing ethyl levulinate by using catalytic conversion cellulose, which does not need acid, has high conversion rate and high selectivity of ethyl levulinate, and a preparation method and application thereof.
In order to achieve the aim, the invention provides a catalyst for preparing ethyl levulinate by catalytic conversion of cellulose, which comprises a carrier and an active component loaded on the carrier, wherein the carrier is a nitrogen-containing carbon-based carrier prepared by taking polyaniline as a carbon material precursor, and the active component is phosphorus, tungsten and sulfonic acid groups.
Further, the content of phosphorus is 0.04-0.15 wt%, the content of tungsten is 1-10 wt%, and the content of sulfur is 1-5 wt%.
The invention also provides a preparation method of the catalyst for preparing ethyl levulinate by catalytically converting cellulose, which comprises the following steps:
s1, adding citric acid into deionized water, heating to form citric acid gel, dispersing polyaniline into the deionized water to form polyaniline solution, mixing the citric acid gel and the polyaniline solution, stirring, adding precursor salt of phosphorus and precursor salt of tungsten, stirring again, evaporating to dryness, and finally drying to obtain a catalyst precursor;
s2, placing the catalyst precursor in a nitrogen atmosphere for calcination treatment, and then, performing sulfonation treatment by using concentrated sulfuric acid to obtain the catalyst for preparing ethyl levulinate by catalytic conversion of cellulose.
Further, in step S1, the mass ratio of citric acid to polyaniline is 1:1 to 2.
Further, in step S1, the conditions of the two stirring treatments are: the temperature is 20-60 ℃ and the time is 6-24 h.
Further, the precursor salt of phosphorus and the precursor salt of tungsten are phosphotungstic acid, or the precursor salt of phosphorus is diammonium hydrogen phosphate and the precursor salt of tungsten is ammonium tungstate.
Further, in step S1, the drying process conditions are: the temperature is 105 ℃ and the time is 8-12 hours.
Further, in step S2, the calcination treatment conditions are: heating to 600-800 ℃ at a heating rate of 2-6 ℃/min under nitrogen atmosphere, and calcining for 4h.
Further, in step S2, the sulfonation conditions are: sulfonation reflux reaction is carried out for 6-12 h by using 98% concentrated sulfuric acid, the sulfonation temperature is 120-180 ℃, and the volume mass ratio of the concentrated sulfuric acid to the calcined product is 10-20 mL:1g.
The invention also provides application of the catalyst in preparing ethyl levulinate by catalytic conversion of cellulose.
The invention also provides a method for preparing ethyl levulinate by catalytic conversion of cellulose, which comprises the following steps: taking cellulose as a raw material, adding the catalyst to react under the following reaction conditions: the catalyst dosage is 0.10-0.25 g, the cellulose dosage is 0.5g, the reaction temperature is 180-260 ℃, the reaction time is 1-5 h, and the reaction solvent is water-ethanol double compatilizer.
The beneficial effects of the invention are as follows:
the catalyst adopts phosphorus, tungsten and sulfonic acid groups as active components, so that the capability of the catalyst for cracking cellulose can be enhanced; phosphorus and metal tungsten form a transition metal gap compound structure, so that an interface charge transfer mechanism occurs on the surface of the catalyst, and the accessibility of the metal tungsten to electron-rich groups is improved; but also enhances the lewis acid strength; meanwhile, sulfonic acid groups are introduced to the carbon carrier, so that the strength of the Bronsted acid is increased, and the depolymerization capability of the catalyst is enhanced. Compared with other carbon-based catalysts, the catalyst provided by the invention has the advantages that the polyaniline-citric acid colloid is used for being impregnated and complexed with the phosphorus and tungsten precursors, and then the catalyst is calcined in an inert gas atmosphere, so that the phosphorus and tungsten active components can be anchored on the polyaniline carbon carrier, the leaching of the active components is weakened, and the service life of the catalyst is prolonged. And (3) sulfonating the calcined sample to obtain the catalyst.
The catalyst is applied to the field of preparing ethyl levulinate by catalytically converting cellulose, can realize 100% conversion rate of cellulose and selectivity of ethyl levulinate of more than 80% under a water-ethanol biphasic solvent, and can produce more than 400mg of ethyl levulinate per gram of cellulose.
When the catalyst is applied to prepare ethyl levulinate by catalyzing cellulose to convert under a water-ethanol biphasic solvent, the complete conversion of cellulose can be realized, the selectivity of ethyl levulinate in a liquid product is more than 80%, and more than 400mg of ethyl levulinate can be produced per gram of cellulose. The catalyst has the advantages of low economic cost, small metal load and high cycle number, can improve the depolymerization capability of the catalyst on cellulose, meets the industrial requirement of preparing ethyl levulinate by catalyzing the conversion of cellulose, and has good industrial application prospect.
Drawings
FIG. 1 is a high resolution view of the catalyst # 1 prepared in example 1 of the present invention;
FIG. 2 is an EDS layered image of the catalyst # 1 prepared in example 1 of the present invention;
FIG. 3 is a high resolution view of the 3# catalyst prepared in example 3 of the present invention;
FIG. 4 is an EDS layered image of the 3# catalyst prepared in example 3 of the present invention;
FIG. 5 is XRD patterns of the catalyst # 1 and the catalyst # 3 prepared in the examples of the present invention;
FIG. 6 is a FTIR spectrum of a catalyst # 1 and a catalyst # 3 prepared in the examples of the present invention;
FIG. 7 is NH of catalyst # 1 and catalyst # 3 prepared in accordance with the example of the present invention 3 -TPD profile;
FIG. 8 is a Raman spectrum of the catalyst # 1 and the catalyst # 3 prepared in the example of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The various materials used in the examples below, unless otherwise specified, are commercially available products known in the art.
Example 1
The preparation method of the catalyst for preparing ethyl levulinate by catalytic conversion of cellulose comprises the following steps:
s1, weighing 5g of citric acid to be uniformly dispersed in 10mL of deionized water, heating at 120 ℃ to form a sol solution I, and weighing 5g of polyaniline to be dispersed in 40mL of deionized water to form a solution II. Solution II was slowly added to solution I to form solution III, which was stirred at 30℃for 12h. 0.55g of phosphotungstic acid is weighed and slowly added into the solution III, stirred at 30 ℃ for 12 hours, evaporated to dryness at 90 ℃, and then the obtained product is put into an oven for drying for 12 hours to obtain a carbon material loaded phosphorus and tungsten precursor.
And S2, after full grinding, heating to 700 ℃ at a heating rate of 4 ℃/min under a nitrogen atmosphere, and keeping for 4 hours to obtain the carbon material loaded phosphorus and tungsten samples. Then, taking 3.7g of phosphorus and tungsten samples loaded by carbon materials and 50mL of 98% concentrated sulfuric acid in mass fraction in a 100mL Teflon lining, sulfonating and refluxing for 6 hours at 150 ℃, cooling to room temperature, filtering and washing to neutrality by using deionized water, and drying for 12 hours to obtain the catalyst for preparing ethyl levulinate by catalyzing and converting cellulose, wherein the number is No. 1.
Example 2
The preparation method of the catalyst for preparing ethyl levulinate by catalytic conversion of cellulose comprises the following steps:
s1, weighing 4.5g of citric acid to be uniformly dispersed in 20mL of deionized water, heating at 120 ℃ to form a sol solution I, and weighing 4.5g of polyaniline to be dispersed in 30mL of deionized water to form a solution II. Solution II was slowly added to solution I to form solution III, which was stirred at 25℃for 6h. 0.50g of phosphotungstic acid is weighed and slowly added into the solution III, stirred at 25 ℃ for 12 hours, evaporated to dryness at 90 ℃, and then the obtained product is put into an oven for drying for 12 hours to obtain a carbon material loaded phosphorus and tungsten precursor.
And S2, after full grinding, heating to 600 ℃ at a heating rate of 5 ℃/min under a nitrogen atmosphere, and keeping for 4 hours to obtain the carbon material loaded phosphorus and tungsten samples. Then, taking 4.0g of phosphorus and tungsten samples loaded by carbon materials and 60mL of 98% concentrated sulfuric acid in mass fraction in a 100mL Teflon lining, sulfonating and refluxing at 120 ℃ for 8 hours, cooling to room temperature, filtering and washing to neutrality by using deionized water, and drying for 12 hours to obtain the catalyst for preparing ethyl levulinate by catalyzing and converting cellulose, wherein the number is No. 2.
Example 3
The preparation method of the catalyst for preparing ethyl levulinate by catalytic conversion of cellulose comprises the following steps:
s1, weighing 9g of citric acid to be uniformly dispersed in 20mL of deionized water, heating at 120 ℃ to form a sol solution I, and weighing 4.5g of polyaniline to be dispersed in 30mL of deionized water to form a solution II. Solution II was slowly added to solution I to form solution III, which was stirred at 50℃for 12h. 0.50g of ammonium tungstate and 0.05g of diammonium hydrogen phosphate are weighed and slowly added into the solution III, stirred at 50 ℃ for 12 hours, evaporated to dryness at 90 ℃, and then the obtained product is put into an oven for drying for 12 hours to obtain a phosphorus and tungsten precursor loaded by a carbon material.
And S2, after full grinding, heating to 750 ℃ at a heating rate of 6 ℃/min under a nitrogen atmosphere, and keeping for 4 hours to obtain the carbon material loaded phosphorus and tungsten samples. Then, taking 3.5g of phosphorus and tungsten samples loaded by carbon materials and 70mL of 98% concentrated sulfuric acid in mass fraction in a 100mL Teflon lining, sulfonating and refluxing for 10 hours at 160 ℃, cooling to room temperature, filtering and washing to neutrality by using deionized water, and drying for 12 hours to obtain the catalyst for preparing ethyl levulinate by catalyzing and converting cellulose, wherein the number is 3#.
Example 4
The preparation method of the catalyst for preparing ethyl levulinate by catalytic conversion of cellulose comprises the following steps:
s1, weighing 10g of citric acid to be uniformly dispersed in 30mL of deionized water, heating at 120 ℃ to form a sol solution I, and weighing 6g of polyaniline to be dispersed in 30mL of deionized water to form a solution II. Solution II was slowly added to solution I to form solution III, which was stirred at 60℃for 12h. 0.68g of ammonium tungstate and 0.07g of diammonium hydrogen phosphate are weighed and slowly added into the solution III, stirred at 60 ℃ for 24 hours, evaporated to dryness at 90 ℃, and then the obtained product is placed in an oven for drying for 12 hours to obtain a phosphorus and tungsten precursor loaded by a carbon material.
And S2, after full grinding, heating to 700 ℃ at a heating rate of 6 ℃/min under a nitrogen atmosphere, and keeping for 4 hours to obtain the carbon material loaded phosphorus and tungsten samples. Then, taking 5.0g of phosphorus and tungsten samples loaded by carbon materials and 75mL of 98% concentrated sulfuric acid in mass fraction in a 100mL Teflon lining, sulfonating and refluxing for 12 hours at 180 ℃, cooling to room temperature, filtering and washing to neutrality by using deionized water, and drying for 12 hours to obtain the catalyst for preparing ethyl levulinate by catalyzing and converting cellulose, wherein the number is No. 4.
Example 5
The preparation method of the catalyst for preparing ethyl levulinate by catalytic conversion of cellulose comprises the following steps:
s1, weighing 10g of citric acid to be uniformly dispersed in 30mL of deionized water, heating at 120 ℃ to form a sol solution I, and weighing 5g of polyaniline to be dispersed in 30mL of deionized water to form a solution II. Solution II was slowly added to solution I to form solution III, which was stirred at 60℃for 24h. 0.58g of ammonium tungstate and 0.09g of diammonium hydrogen phosphate are weighed and slowly added into the solution III, stirred at 60 ℃ for 24 hours, evaporated to dryness at 90 ℃, and then the obtained product is placed in an oven for drying for 12 hours to obtain a phosphorus and tungsten precursor loaded by a carbon material.
And S2, after full grinding, heating to 700 ℃ at a heating rate of 4 ℃/min under a nitrogen atmosphere, and keeping for 4 hours to obtain the carbon material loaded phosphorus and tungsten samples. Then, taking 5.0g of phosphorus and tungsten samples loaded by carbon materials and 75mL of 98% concentrated sulfuric acid in mass fraction in a 100mL Teflon lining, sulfonating and refluxing for 6 hours at 150 ℃, cooling to room temperature, filtering and washing to neutrality by using deionized water, and drying for 12 hours to obtain the catalyst for preparing ethyl levulinate by catalyzing and converting cellulose, wherein the number is 5#
Example 6
Structure determination of catalyst
The structural characteristics of the catalysts prepared in the above examples were studied by various characterization and the results were as follows:
the contents of phosphorus (P), tungsten (W) and sulfur (S) in the catalyst and the polyaniline raw material prepared in the above examples were analyzed by ICP analysis, and the results are shown in Table 1 below.
TABLE 1 composition of the catalyst components
ICP results demonstrate the presence of P, W, S in the catalyst. The images of the catalyst are shown in figures 1 to 4.
Referring to fig. 5, polyaniline has two weak characteristic peaks at 2θ=20.2° (020) and 2θ=25.5° (200), which are broad diffraction peaks of amorphous nature of polyaniline. After sulfonation, the relevant characteristic peaks of the catalyst disappear, and the concentrated sulfuric acid washes out a large amount of oxide clusters formed after load calcination, while the reserved P, W species have low content and high dispersity, so that a highly crystallized structure is difficult to form.
Referring to FIG. 6, 1575cm for polyaniline -1 And 1484cm -1 C=c stretching vibration of the characteristic peaks of (C) corresponding to the quinone ring and the benzene ring, which occurs at 1304cm -1 The absorption peaks of (2) are respectively from C-N stretching vibration in the secondary aromatic amine, 1142-1114 cm -1 Corresponding to aromatic ringsIn-plane C-H bending vibrations. 814cm -1 Is the C-H bending vibration of aromatic rings in the polyaniline backbone. For catalyst # 1 and catalyst # 3, 1032and 1174cm can be seen after sulfonation with concentrated sulfuric acid -1 Increased peak intensity at 1032cm -1 In relation to symmetrical telescopic vibration of (o=s=obond), 1174cm -1 Then corresponds to an anti-symmetrical vibration of the sulfonic acid group, which in combination indicates successful introduction of the sulfonic acid group.
Referring to fig. 7, it is apparent that the amounts of both weak acid and medium strong acid of the catalyst # 1 and the catalyst # 3 are significantly increased as compared to polyaniline, which is very advantageous for cellulose.
Referring to fig. 8, raman spectrum results are shown. Located at 1350cm -1 And 1590cm -1 The two specific diffraction peaks correspond to the D and G bands, respectively, with the D band generally being regarded as disordered, edge, etc. sp 3 A hybridized carbon atom. And G band and sp 2 E of hybridized carbon atoms 2g Mode vibration is related. Typically using the intensity ratio of the D band and the G band (I D :I G ) To measure the degree of graphitization and disorder of the material. D. The presence of the G band demonstrates that the material we prepared is a carbonized material with polycyclic aromatic carbon sheets. The results are consistent with XRD.
Example 7
Catalyst-catalyzed conversion of cellulose to Ethyl levulinate Performance test
Taking 0.10-0.25 g of the No. 1-5 catalyst to perform performance test in a miniature high-temperature high-pressure reaction kettle, wherein the consumption of cellulose is 0.5g, the reaction temperature is 180-260 ℃, the reaction time is 1-5 h, and the reaction solvent is a water-ethanol biphasic solvent (water: 10mL, ethanol: 20 mL). The specific reaction conditions and results are shown in Table 2.
TABLE 2 test of the conversion of cellulose to ethyl levulinate
From the above results, it can be seen that the catalyst of the present invention can achieve complete conversion of cellulose with the use of a water-ethanol double-compatibilizer, the selectivity of ethyl levulinate in the liquid product is more than 80%, the ethyl levulinate per gram of cellulose can be produced by more than 400mg, and the service life is longer than 15 times.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (10)
1. The catalyst for preparing ethyl levulinate by catalytic conversion of cellulose is characterized by comprising a carrier and an active component loaded on the carrier, wherein the carrier is a nitrogen-containing carbon-based carrier prepared by taking polyaniline as a carbon material precursor, and the active component is a phosphorus, tungsten and sulfonic acid group.
2. The catalyst for the catalytic conversion of cellulose to ethyl levulinate according to claim 1, wherein the phosphorus content is 0.04-0.15 wt%, the tungsten content is 1-10 wt%, and the sulfur content is 1-5 wt%.
3. The method for preparing the catalyst for preparing ethyl levulinate by catalytically converting cellulose according to claim 1 or 2, comprising the following steps:
s1, adding citric acid into deionized water, heating to form citric acid gel, dispersing polyaniline into the deionized water to form polyaniline solution, mixing the citric acid gel and the polyaniline solution, stirring, adding precursor salt of phosphorus and precursor salt of tungsten, stirring again, evaporating to dryness, and finally drying to obtain a catalyst precursor;
s2, placing the catalyst precursor in a nitrogen atmosphere for calcination treatment, and then, performing sulfonation treatment by using concentrated sulfuric acid to obtain the catalyst for preparing ethyl levulinate by catalytic conversion of cellulose.
4. The method for preparing the catalyst for preparing ethyl levulinate by catalytically converting cellulose according to claim 3, wherein in the step S1, the mass ratio of citric acid to polyaniline is 1:1 to 2.
5. The method for preparing a catalyst for preparing ethyl levulinate by catalytically converting cellulose according to claim 3, wherein in step S1, the conditions of the two stirring treatments are: the temperature is 20-60 ℃ and the time is 6-24 h.
6. The method for preparing a catalyst for preparing ethyl levulinate by catalytically converting cellulose according to claim 3, wherein in step S1, the drying treatment conditions are as follows: the temperature is 105 ℃ and the time is 8-12 hours.
7. The method for preparing a catalyst for preparing ethyl levulinate by catalytically converting cellulose according to claim 3, wherein in step S2, the calcination treatment conditions are as follows: heating to 600-800 ℃ at a heating rate of 2-6 ℃/min under nitrogen atmosphere, and calcining for 4h.
8. The method for preparing a catalyst for preparing ethyl levulinate by catalytically converting cellulose according to claim 3, wherein in step S2, the sulfonation condition is: sulfonation reflux reaction is carried out for 6-12 h by using 98% concentrated sulfuric acid, the sulfonation temperature is 120-180 ℃, and the volume mass ratio of the concentrated sulfuric acid to the calcined product is 10-20 mL:1g.
9. Use of a catalyst according to claim 1 or 2 for the catalytic conversion of cellulose to ethyl levulinate.
10. A method for preparing ethyl levulinate by catalytic conversion of cellulose, which is characterized by comprising the following steps: taking cellulose as a raw material, adding the catalyst as claimed in claim 1 or 2 for reaction, wherein the reaction conditions are as follows: the catalyst dosage is 0.10-0.25 g, the cellulose dosage is 0.5g, the reaction temperature is 180-260 ℃, the reaction time is 1-5 h, and the reaction solvent is water-ethanol double compatilizer.
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