CN112473736B - Supported polyacid catalyst and application thereof in preparation of levulinate - Google Patents
Supported polyacid catalyst and application thereof in preparation of levulinate Download PDFInfo
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- CN112473736B CN112473736B CN202011404624.1A CN202011404624A CN112473736B CN 112473736 B CN112473736 B CN 112473736B CN 202011404624 A CN202011404624 A CN 202011404624A CN 112473736 B CN112473736 B CN 112473736B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 71
- JOOXCMJARBKPKM-UHFFFAOYSA-M 4-oxopentanoate Chemical compound CC(=O)CCC([O-])=O JOOXCMJARBKPKM-UHFFFAOYSA-M 0.000 title claims abstract description 30
- 229940058352 levulinate Drugs 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000002808 molecular sieve Substances 0.000 claims abstract description 24
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000007787 solid Substances 0.000 claims abstract description 16
- 230000003197 catalytic effect Effects 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 22
- 239000002028 Biomass Substances 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 16
- UAGJVSRUFNSIHR-UHFFFAOYSA-N Methyl levulinate Chemical compound COC(=O)CCC(C)=O UAGJVSRUFNSIHR-UHFFFAOYSA-N 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 13
- 240000008042 Zea mays Species 0.000 claims description 12
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 12
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 12
- 235000005822 corn Nutrition 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000001913 cellulose Substances 0.000 claims description 7
- 229920002678 cellulose Polymers 0.000 claims description 7
- 238000005470 impregnation Methods 0.000 claims description 6
- 230000001376 precipitating effect Effects 0.000 claims description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 5
- 239000008103 glucose Substances 0.000 claims description 5
- 150000004730 levulinic acid derivatives Chemical class 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 229920000858 Cyclodextrin Polymers 0.000 claims description 2
- 239000001116 FEMA 4028 Substances 0.000 claims description 2
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims description 2
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims description 2
- 229960004853 betadex Drugs 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 239000012263 liquid product Substances 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims 1
- 239000010907 stover Substances 0.000 claims 1
- 239000007848 Bronsted acid Substances 0.000 abstract description 7
- 239000011964 heteropoly acid Substances 0.000 abstract description 7
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 239000002841 Lewis acid Substances 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 abstract description 2
- 150000007517 lewis acids Chemical class 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 description 10
- 238000006555 catalytic reaction Methods 0.000 description 5
- 229940040102 levulinic acid Drugs 0.000 description 5
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000006136 alcoholysis reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229930091371 Fructose Natural products 0.000 description 2
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 2
- 239000005715 Fructose Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- -1 etc.) Substances 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 239000003864 humus Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000002029 lignocellulosic biomass Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- KVBGVZZKJNLNJU-UHFFFAOYSA-N naphthalene-2-sulfonic acid Chemical compound C1=CC=CC2=CC(S(=O)(=O)O)=CC=C21 KVBGVZZKJNLNJU-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
Images
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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of catalyst preparation and application, and in particular relates to a solid supported heteropolyacid catalyst. The invention also relates to application of the supported catalyst in preparation of levulinate. The invention loads the molecular sieve and the heteropoly acid according to different proportions to prepare H 3 PW 12 O 40 The Sapo-18 catalyst can load strong Bronsted acid of heteropoly acid on the surface of a molecular sieve, enhances the Bronsted acid of the catalyst, and obtains the supported polyacid catalyst with the optimal ratio of Bronsted acid to Lewis acid by regulating and controlling the load of the polyacid, and the supported polyacid catalyst have a synergistic effect, so that the catalytic effect is greatly improved. Meanwhile, the polyacid catalyst is converted from homogeneous phase to heterogeneous phase, and the green and sustainable use of the catalyst is realized.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation and application, and in particular relates to a solid supported heteropolyacid catalyst. The invention also relates to application of the supported catalyst in preparation of levulinate.
Background
Biomass resources have the characteristics of low cost, renewable resources, wide resources, environmental friendliness and the like, and the utilization of biomass resources to produce related chemicals has important significance for realizing sustainable development. For example, an important platform chemical, levulinic acid, is primarily used to produce various biochemicals, such as solvents, resins, plasticizers, polymers, herbicides, pharmaceuticals, flavors, and biofuels, via esterification, substitution, and redox processes, from cellulose-rich biomass resources.
Cellulose is the most abundant high molecular carbohydrate in lignocellulosic biomass and is therefore an attractive feedstock for the production of levulinic acid. To produce levulinic acid, it is first necessary that the cellulose be hydrolyzed to glucose, which is then converted to 5-Hydroxymethylfurfural (HMF), and then to levulinic acid and formic acid. Is widely used in the fields of medicine, food, chemical industry, energy and the like. Therefore, there is a great prospect in developing and utilizing levulinic acid esters and their high value downstream chemicals. However, at present, the industrial production of levulinate has the problems of low yield, serious environmental pollution and the like, and can not meet the requirements of the industrial development of levulinate in a new period. Therefore, the development of efficient and green levulinate preparation technology, the development of downstream levulinate products with high added value and the expansion of the levulinate application field have important practical significance for promoting the development of levulinate industry in China.
Acid-catalyzed alcoholysis is currently the main method for producing levulinate esters, and the reaction systems commonly used in recent years are: inorganic acid (such as concentrated sulfuric acid, etc.), metal salt catalyst (such as SnCl4, indium (OtF) 3, 2-naphthalene sulfonic acid (2-NSA), etc.), ionic liquid: 1- (1-sulfopropyl) -3-methylimidazole chloride salt, and the like. However, inorganic acids can cause corrosion to equipment, and increase the amount of alcohol, and inevitably produce a large amount of humus in the catalytic process; the catalytic effect of the metal salt catalyst is not particularly desirable; the ionic liquid is difficult to prepare and the cost is high. The polyacid-supported zeolite molecular sieve is a catalyst with excellent properties because it has advantages not found in other conventional catalysts, mainly in the following aspects:
(1) The catalytic activity is high, and the levulinate can be prepared by catalyzing biomass with high efficiency.
(2) Is nontoxic, pollution-free, convenient to recycle, and is a green and environment-friendly solid catalyst.
Heteropolyacids (HPAs) have unique acid properties and are higher than concentrated H 2 SO 4 The acid strength of hundreds of times or more is becoming more interesting as a green acid catalyst. Meanwhile, the molecular sieve catalyst, especially zeolite molecular sieve, has the characteristics of solid acidity, good hydrothermal stability, shape-selective catalysis of pore diameter and the like, and is widely used for levulinic acidAnd (3) preparing acid ester. There have been reports of preparing levulinate esters by using heteropolyacid as a catalyst, and reports of using molecular sieves, particularly zeolite molecular sieves, for preparing levulinate esters, but there are no reports of technical schemes for preparing levulinate esters by using heteropolyacid-supported molecular sieves as biomass conversion. Heteropoly acid-H of Keggin structure 3 PW 12 O 40 The catalyst has strong Bronsted acidity, plays a great role in catalyzing biomass alcoholysis, fructose dehydration and alcoholysis HMF, but is a homogeneous catalyst in a medium, and is unfavorable for separation of products and catalyst recovery. Zeolite molecular sieve Sapo-18 has Bronsted and stronger Lewis acidity which can catalyze the isomerization of glucose to fructose, but the single molecular sieve is not ideal in the reaction of preparing levulinate from biomass as a raw material. However, H prepared by loading molecular sieve and heteropolyacid according to different ratios 3 PW 12 O 40 The Sapo-18 catalyst can load strong Bronsted acid of heteropoly acid on the surface of a molecular sieve, enhances the Bronsted acid of the catalyst, and obtains the supported polyacid catalyst with the optimal ratio of Bronsted acid to Lewis acid by regulating and controlling the load of the polyacid, and the supported polyacid catalyst have a synergistic effect, so that the catalytic effect is greatly improved. Meanwhile, the polyacid catalyst is converted from homogeneous phase to heterogeneous phase, and the green and sustainable use of the catalyst is realized.
Disclosure of Invention
The invention provides a supported polyacid catalyst, a preparation method thereof and application thereof in preparation of levulinate.
To achieve this object, the following means are used.
The supported polyacid catalyst is characterized in that the catalyst is a polyacid compound with a Keggin structure, and the polyacid compound with the Keggin structure has the general formula:
xH 3 PW 12 O 40 sapo-18; x is H 3 PW 12 O 40 The mass ratio of the beta-cyclodextrin to the Sapo-18 is 0.05-0.5.
Further, the method comprises the steps of, x is preferably 0.1 to 0.3.
The supported polyacid catalyst is prepared by the following method:
according to the mass ratio of 1:0.05 to 0.5 of molecular sieve Sapo-18 and polyacid compound H are respectively weighed 3 PW 12 O 40 The method comprises the steps of carrying out a first treatment on the surface of the By reacting polyacid compounds H 3 PW 12 O 40 Pouring into a reactor, adding water according to an isovolumetric impregnation method, stirring and dissolving to obtain a polyacid solution, then dropwise adding the polyacid solution into molecular sieve Sapo-18 powder, stirring while dripping, continuously stirring after dissolving, standing a reaction system, precipitating a pale gray solid, drying, and calcining the solid in a muffle furnace to obtain the H for preparing levulinate 3 PW 12 O 40 A/Sapo-18 catalyst.
The stirring time is 60min; the standing time is 24 hours.
The drying temperature is 100 ℃ and the drying time is 12 hours.
The calcination temperature is 550 ℃ and the calcination time is 4 hours.
The method for preparing levulinate by catalyzing biomass (comprising corn stalk, cellulose and glucose) hydrolysis by using the supported polyacid catalyst for preparing levulinate provided by the invention comprises the following steps:
adding biomass powder, a supported catalyst and a methanol solution into a high-pressure reaction kettle, setting the reaction temperature to be 150-200 ℃ and the reaction time to be 4-8 hours, and hydrolyzing the biomass to obtain methyl levulinate. After the reaction is finished, the catalyst is filtered and separated, and can be reused for conversion. The liquid product was filtered to obtain a methanol solution of methyl levulinate. The product methyl levulinate is diluted by methanol for gas-phase detection, and the yield is 20-80%.
The ratio of the biomass powder to the supported polyacid catalyst to the methanol solution is 0.05-0.15g;0.1-0.5g;5-20ml.
Advantageous effects
The polyoxometallate with Keggin structure is used as a catalyst, so that a plurality of technical problems can be solved in the process of converting cellulose into levulinate:
1. on molecular sieve is introducedH 3 PW 12 O 40 And (3) Bronsted acid sites, the acidity and the recoverability of the catalyst are improved. The yield and the selectivity of the levulinate prepared by catalysis are higher than those of the levulinate prepared by singly using H 3 PW 12 O 40 And Sapo-18 as a catalyst. At the same time H 3 PW 12 O 40 The synergistic effect of Bronsted acidity and Sapo-18 Lewis acidity can better meet the requirement of converting biomass into levulinate.
2. The catalyst has higher catalytic activity in the process of converting corn stalk, cellulose and glucose into levulinate. Shows higher levulinate yield and selectivity during the conversion process.
3. The catalyst has stable property in the reaction process, and is convenient to recycle. The catalyst is suitable for producing levulinate by a one-pot method in an alcohol system, is environment-friendly, can reduce the separation and purification cost of target products due to high selectivity and high yield, and is a novel green sustainable method in biomass conversion of levulinate.
Drawings
FIG. 1 is 10% H 3 PW 12 O 40 Influence of the amount of the Sapo-18 catalyst on the catalysis of the corn stalks to produce methyl levulinate.
FIG. 2 is 20% H 3 PW 12 O 40 Influence of the amount of the Sapo-18 catalyst on the catalysis of the corn stalks to produce methyl levulinate.
FIG. 3 is 30% H 3 PW 12 O 40 Influence of the amount of the Sapo-18 catalyst on the catalysis of the corn stalks to produce methyl levulinate.
Detailed Description
The invention provides a polyacid supported catalyst which is used in the preparation of levulinate. To achieve this object, the following is implemented.
Example 1
The mass ratio is 10:1 respectively weighing a molecular sieve Sapo-18 and a polyacid compound H 3 PW 12 O 40 The method comprises the steps of carrying out a first treatment on the surface of the By equal volumeDetermination of adsorption saturation of molecular sieves by impregnation method to 20ml of water, polyacid Compound H 3 PW 12 O 40 Pouring into a reactor, adding 20ml of water, stirring for dissolving, then dropwise adding polyacid solution into Sapo-18 powder, stirring while dropwise adding, stirring for 60min after dissolving, standing the reaction system for 24h, precipitating light gray solid, filtering, drying, placing the solid into a muffle furnace, and calcining at 550 ℃ for 4h to obtain 10% H for preparing levulinate 3 PW 12 O 40 A/Sapo-18 catalyst.
Corn stalk powder 0.1g,0.4g10% H 3 PW 12 O 40 The catalyst of Sapo-18 was placed in a high-pressure reactor, and 15ml of methanol solution was added thereto, followed by stirring under heating. The reaction temperature was 190℃and the reaction time was 6h. After the reaction was completed, the reaction mixture was cooled and filtered, and the clear liquid contained methyl levulinate, the precipitate was the catalyst. The conversion rate of the corn stalk is 40.5%, and the yield of the methyl levulinate is 26.5%.
Example 2
The mass ratio is 10:2 respectively weighing a molecular sieve Sapo-18 and a polyacid compound H 3 PW 12 O 40 The method comprises the steps of carrying out a first treatment on the surface of the The adsorption saturation of the molecular sieve is 20ml of water according to the isovolumetric impregnation method, and the polyacid compound H is added 3 PW 12 O 40 Pouring into a reactor, adding 20ml of water, stirring for dissolving, then dropwise adding polyacid solution into Sapo-18 powder, stirring while dropwise adding, stirring for 60min after dissolving, standing the reaction system for 24h, precipitating light gray solid, filtering, drying, placing the solid into a muffle furnace, and calcining at 550 ℃ for 4h to obtain 20% H for preparing levulinate 3 PW 12 O 40 A/Sapo-18 catalyst.
Corn stalk powder 0.1g,0.3g20% H 3 PW 12 O 40 The catalyst of Sapo-18 was placed in a high-pressure reactor, and 15ml of methanol solution was added thereto, followed by stirring under heating. The reaction temperature was 190℃and the reaction time was 6h. After the reaction was completed, the reaction mixture was cooled and filtered, and the clear liquid contained methyl levulinate, the precipitate was the catalyst. The conversion rate of the corn straw is 70.8 percent, and the levulinic acid methyl is adoptedThe yield of ester was 42.7%.
Example 3
The mass ratio is 10:3 weighing the molecular sieve Sapo-18 and the polyacid compound H respectively 3 PW 12 O 40 The method comprises the steps of carrying out a first treatment on the surface of the By combining multiple calculated compounds H 3 PW 12 O 40 Pouring into a reactor, adding 20ml of water according to an isovolumetric impregnation method, stirring for dissolution, then dropwise adding a polyacid solution into the Sapo-18 powder, stirring while dropwise adding, stirring for 60min after dissolution, standing the reaction system for 24h, precipitating a pale gray solid, filtering and drying the solid, placing the solid into a muffle furnace, and calcining at 550 ℃ for 4h to obtain 30% H for preparing levulinate 3 PW 12 O 40 A/Sapo-18 catalyst.
Corn stalk powder 0.1g,0.4g20% H 3 PW 12 O 40 The catalyst of Sapo-18 was placed in a high-pressure reactor, and 15ml of methanol solution was added thereto, followed by stirring under heating. The reaction temperature was 190℃and the reaction time was 6h. After the reaction was completed, the reaction mixture was cooled and filtered, and the clear liquid contained methyl levulinate, the precipitate was the catalyst. The conversion rate of the corn stalk is 100%, and the yield of the methyl levulinate is 72.6%.
Claims (9)
1. The supported polyacid catalyst is characterized by being a polyacid compound with a Keggin structure, and the general formula of the polyacid compound with the Keggin structure is as follows:
xH 3 PW 12 O 40 /Sapo-18；
x is H 3 PW 12 O 40 The mass ratio of the beta-cyclodextrin to the Sapo-18 is 0.05-0.5;
the preparation method of the supported polyacid catalyst comprises the steps of weighing a molecular sieve Sapo-18 and a polyacid compound H according to a mass ratio of 1:0.05-0.5 respectively 3 PW 12 O 40 The method comprises the steps of carrying out a first treatment on the surface of the By reacting polyacid compounds H 3 PW 12 O 40 Pouring into a reactor, adding water according to an equal volume impregnation method, stirring and dissolving to obtain polyacid solution, then dropwise adding the polyacid solution into molecular sieve Sapo-18 powder, stirring while dropwise adding, and dissolvingStirring continuously after decomposition, standing the reaction system, precipitating light gray solid, drying, and calcining the solid in a muffle furnace to obtain the H for preparing levulinate 3 PW 12 O 40 A Sapo-18 catalyst;
the calcination temperature is 550 ℃, and the calcination time is 4 hours.
2. A supported polyacid catalyst according to claim 1, wherein x is from 0.1 to 0.3.
3. The method for preparing a supported polyacid catalyst according to claim 1, characterized in that the molecular sieve Sapo-18 and the polyacid compound H are respectively weighed according to a mass ratio of 1:0.05-0.5 3 PW 12 O 40 The method comprises the steps of carrying out a first treatment on the surface of the By reacting polyacid compounds H 3 PW 12 O 40 Pouring into a reactor, adding water according to an isovolumetric impregnation method, stirring and dissolving to obtain a polyacid solution, then dropwise adding the polyacid solution into molecular sieve Sapo-18 powder, stirring while dripping, continuously stirring after dissolving, standing a reaction system, precipitating a pale gray solid, drying, and calcining the solid in a muffle furnace to obtain the H for preparing levulinate 3 PW 12 O 40 A Sapo-18 catalyst;
the calcination temperature is 550 ℃ and the calcination time is 4 hours.
4. A process for the preparation of a supported polyacid catalyst as claimed in claim 3, wherein the time of continued stirring is 60min; the standing time is 24 hours.
5. A method of preparing a supported polyacid catalyst according to claim 3, wherein the drying temperature is 100 ℃ and the drying time is 12 hours.
6. Use of a supported polyacid catalyst according to claim 1 for the preparation of levulinate esters by catalytic hydrolysis of biomass.
7. The use of a supported polyacid catalyst according to claim 6, wherein the biomass comprises corn stover, cellulose and glucose.
8. The use of a supported polyacid catalyst according to claim 6, characterized in that biomass powder, the supported polyacid catalyst and a methanol solution are added into a high-pressure reaction kettle, the reaction temperature is set to be 150-200 ℃, and the reaction time is set to be 4-8 hours, so that methyl levulinate is obtained by hydrolyzing biomass; after the reaction is finished, the catalyst is filtered and separated, can be reused for conversion, and the liquid product is methyl levulinate methanol solution obtained by filtering.
9. The use of a supported polyacid catalyst according to claim 8, wherein the ratio of biomass powder, supported polyacid catalyst and methanol solution is 0.05-0.15g;0.1-0.5g;5-20ml.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103191782A (en) * | 2012-01-09 | 2013-07-10 | 爱普香料集团股份有限公司 | Supported solid acid catalyst, and method for preparing ester perfumes through applying it |
| CN104402712A (en) * | 2014-10-22 | 2015-03-11 | 中国科学院广州能源研究所 | Method for preparing levulinic acid ester through variable temperature method |
| CN107162899A (en) * | 2017-05-22 | 2017-09-15 | 中国农业大学 | A kind of microwave radiation technology phosphotungstic acid or and its salt catalysis biomass carbohydrate alcoholysis synthesis of acetyl propionic ester method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103191782A (en) * | 2012-01-09 | 2013-07-10 | 爱普香料集团股份有限公司 | Supported solid acid catalyst, and method for preparing ester perfumes through applying it |
| CN104402712A (en) * | 2014-10-22 | 2015-03-11 | 中国科学院广州能源研究所 | Method for preparing levulinic acid ester through variable temperature method |
| CN107162899A (en) * | 2017-05-22 | 2017-09-15 | 中国农业大学 | A kind of microwave radiation technology phosphotungstic acid or and its salt catalysis biomass carbohydrate alcoholysis synthesis of acetyl propionic ester method |
Non-Patent Citations (2)
| Title |
|---|
| Direct Production of Ethyl Levulinate from Carbohydrates Catalyzed by H-ZSM-5 Supported Phosphotungstic Acid;Shiqiang Zhao, et al;《bioresources》;20151231;第10卷(第2期);第2225页第1-3段 * |
| Valorization of corn stover into furfural and levulinic acid over SAPO-18zeolites: Effect of Bronsted to Lewis acid sites ratios;Xiaoyun Li, et al;《Industrial Crops & Products》;20190910;第141卷;第9页左栏最后1段至右栏第1段 * |
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