CN114452988B - Supported heteropolyacid nano catalyst and preparation method thereof and preparation method of aryl methyl stearate - Google Patents
Supported heteropolyacid nano catalyst and preparation method thereof and preparation method of aryl methyl stearate Download PDFInfo
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- 239000011964 heteropoly acid Substances 0.000 title claims abstract description 82
- 239000011943 nanocatalyst Substances 0.000 title claims abstract description 65
- 125000005002 aryl methyl group Chemical group 0.000 title claims abstract description 37
- CAMHHLOGFDZBBG-UHFFFAOYSA-N epoxidized methyl oleate Natural products CCCCCCCCC1OC1CCCCCCCC(=O)OC CAMHHLOGFDZBBG-UHFFFAOYSA-N 0.000 title claims abstract description 37
- HPEUJPJOZXNMSJ-UHFFFAOYSA-N octadecanoic acid methyl ester Natural products CCCCCCCCCCCCCCCCCC(=O)OC HPEUJPJOZXNMSJ-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 55
- 238000000034 method Methods 0.000 claims abstract description 38
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 110
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 108
- 238000003756 stirring Methods 0.000 claims description 82
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 69
- QYDYPVFESGNLHU-UHFFFAOYSA-N elaidic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCC(=O)OC QYDYPVFESGNLHU-UHFFFAOYSA-N 0.000 claims description 65
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 claims description 65
- 229940073769 methyl oleate Drugs 0.000 claims description 65
- 238000010438 heat treatment Methods 0.000 claims description 54
- 239000000243 solution Substances 0.000 claims description 33
- 229910021485 fumed silica Inorganic materials 0.000 claims description 23
- 238000011068 loading method Methods 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 23
- 238000010992 reflux Methods 0.000 claims description 23
- 238000001816 cooling Methods 0.000 claims description 22
- 238000001914 filtration Methods 0.000 claims description 22
- 238000002390 rotary evaporation Methods 0.000 claims description 22
- 238000005470 impregnation Methods 0.000 claims description 16
- 125000003118 aryl group Chemical group 0.000 claims description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 15
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 230000001172 regenerating effect Effects 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 238000005804 alkylation reaction Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000003599 detergent Substances 0.000 claims description 7
- 230000008929 regeneration Effects 0.000 claims description 7
- 238000011069 regeneration method Methods 0.000 claims description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 230000029936 alkylation Effects 0.000 claims description 4
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 230000008595 infiltration Effects 0.000 claims description 2
- 238000001764 infiltration Methods 0.000 claims description 2
- 238000000643 oven drying Methods 0.000 claims description 2
- 239000002253 acid Substances 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000007867 post-reaction treatment Methods 0.000 abstract 1
- 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 32
- 239000012074 organic phase Substances 0.000 description 20
- 239000000203 mixture Substances 0.000 description 19
- 238000003760 magnetic stirring Methods 0.000 description 17
- 238000007789 sealing Methods 0.000 description 17
- 239000002904 solvent Substances 0.000 description 17
- 238000012360 testing method Methods 0.000 description 17
- 229910052681 coesite Inorganic materials 0.000 description 16
- 229910052906 cristobalite Inorganic materials 0.000 description 16
- 229910052682 stishovite Inorganic materials 0.000 description 16
- 229910052905 tridymite Inorganic materials 0.000 description 16
- 239000000377 silicon dioxide Substances 0.000 description 15
- 150000001335 aliphatic alkanes Chemical class 0.000 description 7
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 7
- 238000012512 characterization method Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 229910020628 SiW12O40 Inorganic materials 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 229910020881 PMo12O40 Inorganic materials 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- GGQQNYXPYWCUHG-RMTFUQJTSA-N (3e,6e)-deca-3,6-diene Chemical compound CCC\C=C\C\C=C\CC GGQQNYXPYWCUHG-RMTFUQJTSA-N 0.000 description 1
- 238000003547 Friedel-Crafts alkylation reaction Methods 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003473 lipid group Chemical group 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002539 nanocarrier Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
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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
- B01J27/14—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
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/90—Regeneration or reactivation
- B01J23/92—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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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
- B01J27/28—Regeneration or reactivation
- B01J27/285—Regeneration or reactivation of catalysts comprising compounds of phosphorus
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/02—Heat treatment
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/50—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids
- B01J38/56—Hydrocarbons
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C67/347—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to unsaturated carbon-to-carbon bonds
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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
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Abstract
The invention relates to a supported heteropolyacid nano catalyst, a preparation method thereof and a preparation method of aryl methyl stearate. Compared with the prior art, the catalyst has extremely high reaction activity, high catalytic efficiency and short time. When the method is used for preparing the aryl methyl stearate, after the reaction is finished, acid is not required to be neutralized, and the catalyst used by the method can be regenerated after simple treatment, so that the method is environment-friendly, improves the environment-friendly performance of post-reaction treatment, reduces the production and manufacturing cost, and is easy to control and realize industrial production.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a supported heteropolyacid nano catalyst and a preparation method thereof as well as a preparation method of aryl methyl stearate.
Background
The betaine type surfactant is a surfactant with higher salt resistance and high mineralization water resistance, and can be used in a binary compound oil displacement agent in tertiary oil recovery operation, so that the oil displacement agent can obtain higher surface activity and ultralow interfacial tension at a lower concentration. One key intermediate in the synthesis of this surfactant is methyl aryl stearate. Methyl aryl stearate is mainly obtained by friedel-crafts alkylation of methyl oleate and xylene. Methyl oleate belongs to internal olefins, is not active enough in chemical property, has a large molecular weight and has a relatively active lipid group, so that the alkylation reaction condition is more severe, side reactions are more and the reaction is more difficult to control. Therefore, the development of an environmentally friendly and efficient catalyst is the focus of research to realize industrialization of this reaction.
At present, the alkylation reaction for synthesizing methyl aryl stearate is usually catalyzed by organic protonic acid, however, if liquid acid (such as methylsulfonic acid) is used as a catalyst in industrial scale-up production, a series of difficult problems of corrosion equipment, large one-time investment of the reaction equipment, incapability of discharging waste liquid (materials) up to standard, high treatment cost and the like exist, and in addition, the conversion efficiency of the liquid acid catalyzed alkylation reaction is low and the liquid acid catalyzed waste liquid is difficult to recycle, so that the problem is the key for realizing the industrial production of methyl aryl stearate.
Disclosure of Invention
One of the objects of the present invention is: a supported heteropolyacid nanocatalyst is provided.
In order to achieve the above object, the present invention provides the following technical solutions:
a supported heteropolyacid nano catalyst is characterized in that the supported heteropolyacid nano catalyst is prepared by supporting heteropolyacid on a carrier;
Wherein the heteropolyacid is one of H3PW12O40、H4SiW12O40、H6P2W18O62、Cs2.5H0.5PW12O40; the carrier is one of fumed silica, nano titanium dioxide, nano zirconium dioxide and MCM-41.
Preferably, the loading of the heteropoly acid is 30-50%, and the above percentages are mass percentages.
Preferably, the supported heteropolyacid nano catalyst is used for catalyzing alkylation reaction of methyl oleate and m-xylene to prepare aryl methyl stearate.
The second object of the present invention is: provides a preparation method of a supported heteropolyacid nano catalyst.
In order to achieve the above object, the present invention provides the following technical solutions:
the supported heteropoly acid nano catalyst is prepared by adopting a balanced impregnation method or an isovolumetric impregnation method.
Preferably, the specific process of the equilibrium impregnation method is as follows: adding an alcohol solution into the carrier, and uniformly stirring and mixing; adding heteropoly acid, stirring for 22-26h, heating to 40-50deg.C, removing alcohol solution, and oven drying; wherein the alcohol solution is methanol or ethanol, and the drying condition is 55-65 ℃ for 12-24h.
Preferably, the specific process of the isovolumetric impregnation method is as follows: dissolving heteropoly acid in water to obtain heteropoly acid aqueous solution; uniformly dripping heteropolyacid aqueous solution on the surface of the carrier for infiltration; standing at room temperature to evaporate naturally.
The third object of the present invention is to: a method for preparing aryl methyl stearate is provided.
In order to achieve the above object, the present invention provides the following technical solutions:
A preparation method of aryl methyl stearate comprises the following specific steps:
the supported heteropolyacid nano catalyst is used as a catalyst, methyl oleate and m-xylene are used as raw materials, and the aryl methyl stearate is obtained through post-treatment.
Preferably, the preparation method of the methyl aryl stearate comprises the following specific steps:
Adding m-xylene and a supported heteropoly acid nano catalyst into a reaction vessel, stirring and mixing uniformly, heating to 130-170 ℃, then adding methyl oleate, heating and stirring for refluxing for 2-5 hours, cooling, and performing aftertreatment to obtain aryl methyl stearate;
the specific process of the post-treatment is as follows: the catalyst was removed by filtration, and unreacted m-xylene was removed by rotary evaporation to give methyl aryl stearate.
Preferably, the methyl oleate is linear methyl oleate, and the feeding speed of the methyl oleate is 0.1-0.2g/min; the mass ratio of the supported heteropolyacid nano catalyst to the methyl oleate is 1: (5-15), wherein the mass ratio of the methyl oleate to the m-xylene is 1: (1-5).
Preferably, the supported heteropolyacid nano catalyst is used for catalyzing alkylation synthesis of methyl oleate and m-xylene to obtain aryl methyl stearate, and then the supported heteropolyacid nano catalyst is regenerated through washing or burnt.
Preferably, the specific process of washing and regenerating is as follows: washing the catalyst for 2-60h by using a detergent at the temperature of 20-100 ℃;
Wherein the detergent is one or two of aromatic hydrocarbon and long-chain alkane, and when the detergent consists of the aromatic hydrocarbon and the long-chain alkane, the mass ratio of the aromatic hydrocarbon to the long-chain alkane is 1:10-10:1.
Preferably, the specific process of the scorching regeneration is as follows: in the air, the catalyst is recycled and put into a muffle furnace for burning and regenerating, the burning and regenerating speed is 0.2-5 ℃/min, the initial temperature is increased to 300-400 ℃ from the initial temperature of 25-100 ℃, and the final temperature is kept constant for burning and regenerating for 4-24 hours, thus the burning and regenerating of the catalyst is completed.
Compared with the prior art, the invention has the following advantages:
1) The heteropoly acid is an ionic metal oxygen cluster compound, has certain acidity and small specific surface area, and has low catalytic efficiency and poor stability and dispersibility when being used for catalyzing the preparation process of aryl methyl stearate. The catalyst is loaded on the nano carrier material, so that the catalytic efficiency, stability and dispersibility are improved. The catalyst has the advantages of mild reaction conditions, small pollution, simple preparation, small corrosiveness to equipment, environmental friendliness, no need of neutralization after the reaction of the solid acid catalyst, and hopefulness of replacing liquid acid and being applied to industrial production.
2) The supported heteropolyacid nano catalyst has excellent alkylation catalytic reaction performance, is easy to separate and recycle after catalytic reaction, and has stable catalyst activity after multiple times of catalysis. Meanwhile, the catalyst deactivation may be regenerated by washing or by burning.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention may be realized and attained by the structure particularly pointed out in the written description and claims hereof as well as the appended drawings.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions of the prior art, the following description will briefly explain the drawings used in the embodiments or the description of the prior art, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a FT-IR characterization diagram of fumed silica supported by phosphotungstic acid equilibrium impregnation in example 2;
FIG. 2 is a graph showing the Raman characterization of fumed silica supported by phosphotungstic acid equilibrium impregnation in example 2;
FIG. 3 is a graph showing adsorption and desorption isotherms of the phosphotungstic acid equilibrium impregnation method-supported fumed silica N 2 in example 2;
FIG. 4 is a GC-Mass characterization of reactants and products of the phosphotungstic acid equilibrium impregnation supported fumed silica catalyzed commercial methyl oleate and meta-xylene alkylation reaction of example 2;
FIG. 5 is a reaction equation for the preparation of methyl aryl stearate in the examples.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments of the present invention. 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.
Example 1
700Mg of fumed silica is weighed, added into 30mL of methanol, uniformly mixed under magnetic stirring, then 300mg of phosphotungstic acid is added under stirring, and the sealing film is sealed and stirred for 24 hours (the stirring time can be any time in the range of 22-26 hours). And heating the mixture solution to 40 ℃ (the temperature is selected to be any of 40-50 ℃ in the process) under stirring to remove the methanol solvent, then placing the sample into a vacuum oven 60 ℃ (the temperature is selected to be any of 55-65 ℃ in the process) and drying overnight (the drying time is controlled to be 12-24H), and finally obtaining the H 3PW12O40/SiO2 with the loading amount of 30 wt%. 2.531g of m-xylene and 225mg of supported heteropoly acid nano catalyst are added into a reaction vessel, stirred and mixed uniformly by a magnetic stirrer, heated to 170 ℃, then 1.509g of methyl oleate is added, the feeding speed is 0.13g/min (any speed in the feeding speed is selected to be 0.1-0.2 g/min), heated, stirred and refluxed for 5 hours, cooled and treated, the supported heteropoly acid nano catalyst in an organic phase is removed by filtration, and unreacted m-xylene is removed by rotary evaporation, so that aryl methyl stearate can be obtained, and the reaction equation is shown in figure 5. The methyl oleate conversion was 89.65% by GC-Mass test.
Example 2
500Mg of fumed silica is weighed, added into 30mL of methanol, uniformly mixed under magnetic stirring, then 500mg of phosphotungstic acid is added under stirring, and the sealing film is sealed and stirred for 24 hours. And the mixture solution was heated to 40 ℃ with stirring to remove the methanol solvent, and then the sample was dried overnight in a vacuum oven at 60 ℃ to obtain 50wt% loading of H 3PW12O40/SiO2. Adding 2.531g of m-xylene and 225mg of supported heteropoly acid nano catalyst into a reaction vessel, stirring and mixing uniformly by a magnetic stirrer, heating to 150 ℃, then adding 1.509g of methyl oleate, heating and stirring for reflux for 3 hours at the feeding speed of 0.13g/min, cooling and post-treatment, filtering to remove the supported heteropoly acid nano catalyst in an organic phase, and then removing unreacted m-xylene by rotary evaporation to obtain aryl methyl stearate. The conversion of methyl oleate was 99.39% by GC-Mass test.
In this example, the FT-IR characterization spectrum of the aerosil supported by phosphotungstic acid equilibrium impregnation method is shown in fig. 1, and it can be seen from fig. 1: 1079cm -1、979cm-1、881cm-1、788cm-1 is four characteristic peaks of phosphotungstic acid, which indicates that Keggin structure is not changed after phosphotungstic acid is loaded on fumed silica. (PW 12 in FIG. 1 means H 3PW12O40;PW12(50)@SiO2 means H 3PW12O40/SiO2 having a loading of 50% by weight)
In this embodiment, the Raman characterization spectrum of the aerosil supported by phosphotungstic acid equilibrium impregnation method is shown in fig. 2, and it can be seen from fig. 2: 990cm -1、990.6cm-1、1005.5cm-1 is the stretching vibration of W-O-W, W =o and P-O in phosphotungstic acid. After the phosphotungstic acid is loaded on the fumed silica, the Keggin structure of the phosphotungstic acid is not changed although the characteristic peak intensity of the phosphotungstic acid is reduced.
In this embodiment, a characterization chart of N 2 adsorption/desorption isotherms of the phosphotungstic acid equilibrium impregnation method loaded fumed silica is shown in fig. 3, and it can be seen from fig. 3: the nitrogen adsorption and desorption isotherm of the catalyst is of type IV, the back ring is of type H 3, and the mesopores are formed by stacking H 3PW12O40/SiO2 nano particles.
The GC-Mass characterization spectrum of the phosphotungstic acid equilibrium impregnation method supported fumed silica catalyzed reaction product of methyl oleate and m-xylene alkylation is shown in FIG. 4, and can be seen from FIG. 4: after the catalytic reaction, the residual amount of the effective reaction raw material methyl oleate is less, and the effective conversion rate of the reaction is 99.39%.
Example 3
500Mg of fumed silica was weighed and uniformly dispersed in a petri dish. Then 500mg of phosphotungstic acid was weighed and dissolved in 10mL of water, and stirred well. Then slowly dripping a phosphotungstic acid aqueous solution into a surface dish with silicon dioxide dispersed therein by a dropper to infiltrate the surface dish, standing the surface dish at room temperature to naturally evaporate the surface dish, and obtaining a solid which is H 3PW12O40/SiO2 with the loading capacity of 50 wt%. Adding 2.531g of m-xylene and 225mg of supported heteropoly acid nano catalyst into a reaction vessel, stirring and mixing uniformly by a magnetic stirrer, heating to 150 ℃, then adding 1.509g of methyl oleate, heating and stirring for reflux for 3 hours at the feeding speed of 0.13g/min, cooling and post-treatment, filtering to remove the supported heteropoly acid nano catalyst in an organic phase, and then removing unreacted m-xylene by rotary evaporation to obtain aryl methyl stearate. The methyl oleate conversion was 94.91% by GC-Mass test.
Example 4
4.38G of cetyltrimethylammonium bromide (CTAB) and 1.2g of NaOH were weighed out and dissolved in 200mL of distilled water, stirred magnetically until the solution was homogeneous, then 20.8g of tetraethyl silicate (TEOS) was slowly added dropwise and stirred for 5min. Then, 8.64g of 1,3, 5-trimethylbenzene and 3.1g of n-hexane were slowly added dropwise, and vigorously stirred for 10 minutes to give a thick mixture solution. Heated to 85℃and refluxed for two days. The solution was filtered under reduced pressure, washed with a large amount of distilled water, and dried overnight in a vacuum oven at 100℃to give a white powder. And (3) placing the white powder into a corundum crucible with a cover, heating to 550 ℃ at 10 ℃/min, maintaining for 5 hours to remove residual CTAB and organic matters, and naturally cooling to room temperature to obtain the product MCM-41.
500Mg of the prepared MCM-41 is weighed and added into 30mL of methanol, the mixture is uniformly mixed under magnetic stirring, then 500mg of phosphotungstic acid is added under stirring, and the sealing film is sealed and stirred for 24 hours. And heating the mixture solution to 40 ℃ with stirring to remove the methanol solvent, and then placing the sample in a vacuum oven for drying overnight at 60 ℃ to finally obtain H 3PW12O40/MCM-41 with the loading of 50 wt%. Adding 2.531g of m-xylene and 225mg of supported heteropoly acid nano catalyst into a reaction vessel, stirring and mixing uniformly by a magnetic stirrer, heating to 170 ℃, then adding 1.509g of methyl oleate, heating, stirring and refluxing for 5 hours, cooling and post-treating, filtering to remove the supported heteropoly acid nano catalyst in an organic phase, and then removing unreacted m-xylene by rotary evaporation to obtain aryl methyl stearate. The methyl oleate conversion was 96.66% by GC-Mass test.
Example 5
500Mg of nano titanium dioxide is weighed, added into 30mL of methanol, uniformly mixed under magnetic stirring, then 500mg of phosphotungstic acid is added under stirring, and the sealing film is sealed and stirred for 24 hours. And the mixture solution was heated to 40 ℃ with stirring to remove the methanol solvent, and then the sample was dried overnight in a vacuum oven at 60 ℃ to obtain 50wt% loading of H 3PW12O40/TiO2. Adding 2.531g of m-xylene and 225mg of supported heteropoly acid nano catalyst into a reaction vessel, stirring and mixing uniformly by a magnetic stirrer, heating to 170 ℃, then adding 1.509g of methyl oleate, heating, stirring and refluxing for 5 hours, cooling and post-treating, filtering to remove the supported heteropoly acid nano catalyst in an organic phase, and then removing unreacted m-xylene by rotary evaporation to obtain aryl methyl stearate. The conversion of methyl oleate by GC-Mass test was 91.81%.
Example 6
500Mg of fumed silica is weighed, added into 30mL of methanol, uniformly mixed under magnetic stirring, then 500mg of silicotungstic acid is added under stirring, and the sealing film is sealed and stirred for 24 hours. And the mixture solution was heated to 40 ℃ with stirring to remove the methanol solvent, and then the sample was dried overnight in a vacuum oven at 60 ℃ to obtain 50wt% loading of H 4SiW12O40@SiO2. Adding 2.531g of m-xylene and 225mg of supported heteropoly acid nano catalyst into a reaction vessel, stirring and mixing uniformly by a magnetic stirrer, heating to 150 ℃, then adding 1.509g of methyl oleate, heating and stirring for reflux for 3 hours at the feeding speed of 0.13g/min, cooling and post-treatment, filtering to remove the supported heteropoly acid nano catalyst in an organic phase, and then removing unreacted m-xylene by rotary evaporation to obtain aryl methyl stearate. The methyl oleate conversion was 95.72% by GC-Mass test.
Example 7
500Mg of nano titanium dioxide is weighed, added into 30mL of methanol, uniformly mixed under magnetic stirring, then 500mg of silicotungstic acid is added under stirring, and the sealing film is sealed and stirred for 24 hours. And the mixture solution was heated to 40 ℃ with stirring to remove the methanol solvent, and then the sample was dried overnight in a vacuum oven at 60 ℃ to obtain 50wt% loading of H 4SiW12O40@TiO2. Adding 2.531g of m-xylene and 225mg of supported heteropoly acid nano catalyst into a reaction vessel, stirring and mixing uniformly by a magnetic stirrer, heating to 170 ℃, then adding 1.509g of methyl oleate, heating, stirring and refluxing for 5 hours, cooling and post-treating, filtering to remove the supported heteropoly acid nano catalyst in an organic phase, and then removing unreacted m-xylene by rotary evaporation to obtain aryl methyl stearate. The conversion of methyl oleate was 98.46% by GC-Mass.
Example 8
500Mg of prepared MCM-41 is weighed, added into 30mL of methanol, uniformly mixed under magnetic stirring, then 500mg of silicotungstic acid is added under stirring, and the sealing film is sealed and stirred for 24 hours. And heating the mixture solution to 40 ℃ with stirring to remove the methanol solvent, and then placing the sample in a vacuum oven for drying overnight at 60 ℃ to finally obtain the H 4SiW12O40 @MCM-41 with the loading amount of 50 wt%. Adding 2.531g of m-xylene and 225mg of supported heteropoly acid nano catalyst into a reaction vessel, stirring and mixing uniformly by a magnetic stirrer, heating to 170 ℃, then adding 1.509g of methyl oleate, heating, stirring and refluxing for 5 hours, cooling and post-treating, filtering to remove the supported heteropoly acid nano catalyst in an organic phase, and then removing unreacted m-xylene by rotary evaporation to obtain aryl methyl stearate. The methyl oleate conversion was 82.70% by GC-Mass test.
Example 9
700Mg of nano zirconium dioxide is weighed, added into 30mL of methanol, uniformly mixed under magnetic stirring, then 300mg of phosphotungstic acid is added under stirring, and the sealing film is sealed and stirred for 24 hours. And the mixture solution was heated to 40 ℃ with stirring to remove the methanol solvent, and then the sample was dried overnight in a vacuum oven at 60 ℃ to obtain 30wt% loading of H 3PW12O40@ZrO2. Adding 2.531g of m-xylene and 225mg of supported heteropoly acid nano catalyst into a reaction vessel, stirring and mixing uniformly by a magnetic stirrer, heating to 170 ℃, then adding 1.509g of methyl oleate, heating, stirring and refluxing for 5 hours, cooling and post-treating, filtering to remove the supported heteropoly acid nano catalyst in an organic phase, and then removing unreacted m-xylene by rotary evaporation to obtain aryl methyl stearate. The methyl oleate conversion was 73.22% by GC-Mass test.
Example 10
500Mg of MCM-41 is weighed, added into 30mL of methanol, uniformly mixed under magnetic stirring, then 500mg of phosphotungstic acid is added under stirring, and the sealing film is sealed and stirred for 24 hours. And heating the mixture solution to 40 ℃ with stirring to remove the methanol solvent, and then placing the sample in a vacuum oven for drying overnight at 60 ℃ to finally obtain H 3PW12O40/MCM-41 with the loading of 50 wt%. Adding 2.531g of m-xylene and 225mg of supported heteropoly acid nano catalyst into a reaction vessel, stirring and mixing uniformly by a magnetic stirrer, heating to 130 ℃, then adding 1.509g of methyl oleate, heating and stirring for reflux for 3 hours at the feeding speed of 0.13g/min, cooling and post-treatment, filtering to remove the supported heteropoly acid nano catalyst in an organic phase, and then removing unreacted m-xylene by rotary evaporation to obtain aryl methyl stearate. The methyl oleate conversion was 68.80% by GC-Mass test.
Example 11
500Mg of MCM-41 is weighed, added into 30mL of methanol, uniformly mixed under magnetic stirring, then 500mg of phosphotungstic acid is added under stirring, and the sealing film is sealed and stirred for 24 hours. And heating the mixture solution to 40 ℃ with stirring to remove the methanol solvent, and then placing the sample in a vacuum oven for drying overnight at 60 ℃ to finally obtain H 3PW12O40/MCM-41 with the loading of 50 wt%. Adding 2.531g of m-xylene and 225mg of supported heteropoly acid nano catalyst into a reaction vessel, stirring and mixing uniformly by a magnetic stirrer, heating to 150 ℃, then adding 1.509g of methyl oleate, heating and stirring for refluxing for 2 hours at the feeding speed of 0.13g/min, cooling and post-treatment, filtering to remove the supported heteropoly acid nano catalyst in an organic phase, and then removing unreacted m-xylene by rotary evaporation to obtain aryl methyl stearate. The conversion of methyl oleate was 80.02% by GC-Mass.
Example 12
600Mg of fumed silica is weighed, added into 30mL of methanol, uniformly mixed under magnetic stirring, then 400mg of phosphotungstic acid is added under stirring, and the sealing film is sealed and stirred for 24 hours. And the mixture solution was heated to 40 ℃ with stirring to remove the methanol solvent, and then the sample was dried overnight in a vacuum oven at 60 ℃ to obtain 40wt% loading of H 3PW12O40/SiO2. Adding 2.531g of m-xylene and 225mg of supported heteropoly acid nano catalyst into a reaction vessel, stirring and mixing uniformly by a magnetic stirrer, heating to 150 ℃, then adding 1.509g of methyl oleate, heating and stirring for reflux for 3 hours at the feeding speed of 0.13g/min, cooling and post-treatment, filtering to remove the supported heteropoly acid nano catalyst in an organic phase, and then removing unreacted m-xylene by rotary evaporation to obtain aryl methyl stearate. The methyl oleate conversion was 63.53% by GC-Mass test.
Example 13
500Mg of fumed silica is weighed, added into 30mL of methanol, uniformly mixed under magnetic stirring, then 500mg of phosphotungstic acid is added under stirring, and the sealing film is sealed and stirred for 24 hours. And the mixture solution was heated to 40 ℃ with stirring to remove the methanol solvent, and then the sample was dried overnight in a vacuum oven at 60 ℃ to obtain 50wt% loading of H 3PW12O40/SiO2. Adding 2.531g of m-xylene and 225mg of supported heteropoly acid nano catalyst into a reaction vessel, stirring and mixing uniformly by a magnetic stirrer, heating to 140 ℃, then adding 1.509g of methyl oleate, heating and stirring for reflux for 4 hours, cooling and post-treatment, filtering to remove the supported heteropoly acid nano catalyst in an organic phase, and then removing unreacted m-xylene by rotary evaporation to obtain aryl methyl stearate. The methyl oleate conversion was 72.82% by GC-Mass test.
Example 14
500Mg of fumed silica is weighed, added into 30mL of methanol, uniformly mixed under magnetic stirring, then 500mg of phosphotungstic acid is added under stirring, and the sealing film is sealed and stirred for 24 hours. And the mixture solution was heated to 40 ℃ with stirring to remove the methanol solvent, and then the sample was dried overnight in a vacuum oven at 60 ℃ to obtain 50wt% loading of H 3PW12O40/SiO2. Adding 2.531g of m-xylene and 225mg of supported heteropoly acid nano catalyst into a reaction vessel, stirring and mixing uniformly by a magnetic stirrer, heating to 160 ℃, then adding 1.509g of methyl oleate, heating, stirring and refluxing for 3 hours, cooling and post-treating, filtering to remove the supported heteropoly acid nano catalyst in an organic phase, and then removing unreacted m-xylene by rotary evaporation to obtain aryl methyl stearate. The conversion of methyl oleate was 97.65% by GC-Mass test.
Example 15
500Mg of fumed silica is weighed, added into 30mL of methanol, uniformly mixed under magnetic stirring, then 500mg of phosphotungstic acid is added under stirring, and the sealing film is sealed and stirred for 24 hours. And the mixture solution was heated to 40 ℃ with stirring to remove the methanol solvent, and then the sample was dried overnight in a vacuum oven at 60 ℃ to obtain 50wt% loading of H 3PW12O40/SiO2. Adding 1.510g of m-xylene and 225mg of supported heteropoly acid nano catalyst into a reaction vessel, stirring and mixing uniformly by a magnetic stirrer, heating to 150 ℃, then adding 1.509g of methyl oleate, heating and stirring for refluxing for 3 hours at the feeding speed of 0.13g/min, cooling and post-treatment, filtering to remove the supported heteropoly acid nano catalyst in an organic phase, and then removing unreacted m-xylene by rotary evaporation to obtain aryl methyl stearate. The conversion of methyl oleate was 78.38% by GC-Mass.
Example 16
500Mg of fumed silica is weighed, added into 30mL of methanol, uniformly mixed under magnetic stirring, then 500mg of phosphotungstic acid is added under stirring, and the sealing film is sealed and stirred for 24 hours. And the mixture solution was heated to 40 ℃ with stirring to remove the methanol solvent, and then the sample was dried overnight in a vacuum oven at 60 ℃ to obtain 50wt% loading of H 3PW12O40/SiO2. Adding 7.545g of m-xylene and 225mg of supported heteropoly acid nano catalyst into a reaction vessel, stirring and mixing uniformly by a magnetic stirrer, heating to 130 ℃, then adding 1.509g of methyl oleate, heating and stirring for reflux for 3 hours at the feeding speed of 0.13g/min, cooling and post-treatment, filtering to remove the supported heteropoly acid nano catalyst in an organic phase, and then removing unreacted m-xylene by rotary evaporation to obtain aryl methyl stearate. The methyl oleate conversion was 80.21% by GC-Mass test.
Example 17
500Mg of fumed silica was weighed and uniformly dispersed in a petri dish. Then 500mg of phosphotungstic acid was weighed and dissolved in 10mL of water, and stirred well. Then slowly dripping a phosphotungstic acid aqueous solution into a surface dish with silicon dioxide dispersed therein by a dropper to infiltrate the surface dish, standing the surface dish at room temperature to naturally evaporate the surface dish, and obtaining a solid which is H 3PW12O40/SiO2 with the loading capacity of 50 wt%. Adding 2.531g of m-xylene and 75mg of supported heteropoly acid nano catalyst into a reaction vessel, stirring and mixing uniformly by a magnetic stirrer, heating to 170 ℃, then adding 1.509g of methyl oleate, heating, stirring and refluxing for 5 hours, cooling and post-treating, filtering to remove the supported heteropoly acid nano catalyst in an organic phase, and then removing unreacted m-xylene by rotary evaporation to obtain aryl methyl stearate. The methyl oleate conversion was 62.52% by GC-Mass test.
Example 18
500Mg of fumed silica was weighed and uniformly dispersed in a petri dish. Then 500mg of phosphotungstic acid was weighed and dissolved in 10mL of water, and stirred well. Then slowly dripping a phosphotungstic acid aqueous solution into a surface dish with silicon dioxide dispersed therein by a dropper to infiltrate the surface dish, standing the surface dish at room temperature to naturally evaporate the surface dish, and obtaining a solid which is H 3PW12O40/SiO2 with the loading capacity of 50 wt%. Adding 2.531g of m-xylene and 150mg of supported heteropoly acid nano catalyst into a reaction vessel, stirring and mixing uniformly by a magnetic stirrer, heating to 150 ℃, then adding 1.509g of methyl oleate, heating and stirring for reflux for 3 hours at the feeding speed of 0.13g/min, cooling and post-treatment, filtering to remove the supported heteropoly acid nano catalyst in an organic phase, and then removing unreacted m-xylene by rotary evaporation to obtain aryl methyl stearate. The methyl oleate conversion was 78.79% by GC-Mass test.
Example 19
500Mg of fumed silica is weighed, added into 30mL of methanol, uniformly mixed under magnetic stirring, then added with 500mg of H 6P2W18O62 under stirring, and sealed and stirred for 24 hours by a sealing film. And the mixture solution was heated to 40 ℃ with stirring to remove the methanol solvent, and then the sample was dried overnight in a vacuum oven at 60 ℃ to obtain 50wt% loading of H 6P2W18O62@SiO2. Adding 2.531g of m-xylene and 225mg of supported heteropoly acid nano catalyst into a reaction vessel, stirring and mixing uniformly by a magnetic stirrer, heating to 150 ℃, then adding 1.509g of methyl oleate, heating and stirring for reflux for 3 hours at the feeding speed of 0.13g/min, cooling and post-treatment, filtering to remove the supported heteropoly acid nano catalyst in an organic phase, and then removing unreacted m-xylene by rotary evaporation to obtain aryl methyl stearate. The methyl oleate conversion was 66.49% by GC-Mass test.
Example 20
500Mg of fumed silica is weighed, added into 30mL of methanol, uniformly mixed under magnetic stirring, then added with 500mg of Cs 2.5H0.5PW12O40 under stirring, and sealed and stirred for 24 hours by a sealing film. And the mixture solution was heated to 40 ℃ with stirring to remove the methanol solvent, and then the sample was dried overnight in a vacuum oven at 60 ℃ to obtain Cs 2.5H0.5PW12O40@SiO2 with a loading of 50 wt%. Adding 2.531g of m-xylene and 225mg of supported heteropoly acid nano catalyst into a reaction vessel, stirring and mixing uniformly by a magnetic stirrer, heating to 150 ℃, then adding 1.509g of methyl oleate, heating and stirring for reflux for 3 hours at the feeding speed of 0.13g/min, cooling and post-treatment, filtering to remove the supported heteropoly acid nano catalyst in an organic phase, and then removing unreacted m-xylene by rotary evaporation to obtain aryl methyl stearate. The methyl oleate conversion was 61.25% by GC-Mass test.
Example 21
The supported heteropolyacid nanocatalysts of examples 1-20 above were regenerated by washing or by coke burning after deactivation.
The specific process of washing regeneration is as follows: washing the catalyst for 2-60h by using a detergent at the temperature of 20-100 ℃;
Wherein, the detergent is one or two of arene and long-chain alkane, when the detergent consists of arene and long-chain alkane, the mass ratio of arene to long-chain alkane is 1:10-10:1, preferably, the arene can select benzene, and the long-chain alkane can select C 10-14 n-alkane.
The specific process of the scorching regeneration is as follows: in air, the catalyst is recovered and put into a muffle furnace for burning regeneration, the burning regeneration is increased from an initial temperature of 25-100 ℃ (preferably, the temperature can be selected to be 25 ℃) to a final temperature of 300-400 ℃ (preferably, the temperature can be selected to be 350 ℃) at a heating rate of 0.2-5 ℃/min, and the final temperature is burnt for 4-24 hours (preferably, the time can be selected to be 12 hours) at a constant temperature, so that the burning regeneration of the catalyst is completed.
It should be noted that:
In the embodiment of the invention, when the methyl aryl stearate is prepared, the heating temperature and the reflux time can be adjusted according to actual conditions, the heating temperature is controlled to be 130-170 ℃, and the heating stirring reflux time is controlled to be 2-5 hours.
In the embodiment, the methyl oleate involved in the preparation of the aryl methyl stearate is linear methyl acrylate, the feeding speed of the methyl oleate can be adjusted according to the actual situation and controlled to be 0.1-0.2g/min, the specific dosage of the supported heteropoly acid nano catalyst, the specific dosage of the methyl oleate and the specific dosage of the m-xylene can be adjusted according to the actual situation, and the following proportional relation can be ensured to be satisfied: the mass ratio of the catalyst to the methyl oleate is 1: (5-15), the mass ratio of methyl oleate to metaxylene is 1: (1-5).
In addition, the heteropolyacid of the present invention may be H3PMo12O40、H4PMo11VO40、H5PMo10V2O40、H6PMo9V3O40、H3SiMo12O40、Cs2.5H0.5PMo12O40,, its specific preparation and the method for preparing methyl aryl stearate are the same as those of the heteropolyacid of the present invention except for H3PW12O40、H4SiW12O40、H6P2W18O62、Cs2.5H0.5PW12O40 mentioned in the examples.
Although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (7)
1. A method for preparing aryl methyl stearate, which is characterized by comprising the following steps:
The method comprises the steps of taking a supported heteropoly acid nano catalyst as a catalyst, taking methyl oleate and m-xylene as raw materials, adding the m-xylene and the supported heteropoly acid nano catalyst into a reaction container, uniformly stirring and mixing, heating to 130-170 ℃, then adding the methyl oleate, heating and stirring for refluxing for 2-5 hours, cooling, and performing post-treatment to obtain the aryl methyl stearate;
wherein the supported heteropolyacid nano catalyst is prepared by supporting heteropolyacid on a carrier;
The heteropolyacid is one of H 3PW12O40 or Cs 2.5H0.5PW12O40; the carrier is one of fumed silica, nano titanium dioxide, nano zirconium dioxide and MCM-41; the supported heteropolyacid nano catalyst is prepared by adopting a balanced impregnation method or an equal volume impregnation method;
The specific process of the equilibrium impregnation method is as follows: adding an alcohol solution into the carrier, and uniformly stirring and mixing; adding heteropoly acid, stirring for 22-26h, heating to 40-50deg.C, removing alcohol solution, and oven drying; wherein the alcohol solution is methanol or ethanol, and the drying condition is 55-65 ℃ for 12-24h;
The specific process of the isovolumetric impregnation method is as follows: dissolving heteropoly acid in water to obtain heteropoly acid aqueous solution; uniformly dripping heteropolyacid aqueous solution on the surface of the carrier for infiltration; standing at room temperature to evaporate naturally.
2. The method for preparing methyl aryl stearate according to claim 1, wherein the loading of the heteropoly acid is 30% -50%, and the above percentages are mass percentages.
3. The process for preparing methyl aryl stearate according to claim 1, wherein,
The specific process of the post-treatment is as follows: the catalyst was removed by filtration, and unreacted m-xylene was removed by rotary evaporation to give methyl aryl stearate.
4. The method for preparing aryl methyl stearate according to claim 1, wherein the feeding speed of methyl oleate is 0.1-0.2g/min; the mass ratio of the supported heteropolyacid nano catalyst to the methyl oleate is 1: (5-15), wherein the mass ratio of the methyl oleate to the m-xylene is 1: (1-5).
5. The method for preparing methyl aryl stearate according to claim 1, wherein the supported heteropolyacid nano catalyst is used for catalyzing alkylation synthesis of methyl oleate and m-xylene to obtain methyl aryl stearate, and then the supported heteropolyacid nano catalyst is regenerated through washing or charring.
6. The method for preparing aryl methyl stearate according to claim 5, wherein the specific process of washing and regenerating is as follows: washing the catalyst by a detergent at 20-100 ℃ for 2-60 h.
7. The method for preparing methyl aryl stearate according to claim 5, wherein the specific process of the scorching regeneration is as follows: in the air, the catalyst is recycled and put into a muffle furnace for burning and regenerating, the burning and regenerating speed is 0.2-5 ℃/min, the initial temperature is increased to 300-400 ℃ from the initial temperature of 25-100 ℃, and the final temperature is kept constant for burning and regenerating for 4-24 hours, thus the burning and regenerating of the catalyst is completed.
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| CN102698809A (en) * | 2012-05-11 | 2012-10-03 | 沈阳化工大学 | Preparation method of H3PW12O40/ nanometer TiO2 composite photocatalyst |
| CN106000464A (en) * | 2016-06-01 | 2016-10-12 | 盐城工学院 | Supported heteropolyacid catalyst, preparation method and application thereof |
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2021
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| CN1277894A (en) * | 1999-06-16 | 2000-12-27 | 中国科学院大连化学物理研究所 | Loading type heteropoly acid catalyst used for prepn. of linear alkyl benzene by alkylation of straight chair olefin and benzene |
| KR20040087625A (en) * | 2003-04-08 | 2004-10-14 | 한국에너지기술연구원 | Removal method of free fatty acid in wasted edible oil |
| CN101733148A (en) * | 2008-11-21 | 2010-06-16 | 中国科学院化学研究所 | Magnetic heteropolyacid catalyst, preparing method and application thereof |
| CN102698809A (en) * | 2012-05-11 | 2012-10-03 | 沈阳化工大学 | Preparation method of H3PW12O40/ nanometer TiO2 composite photocatalyst |
| CN106000464A (en) * | 2016-06-01 | 2016-10-12 | 盐城工学院 | Supported heteropolyacid catalyst, preparation method and application thereof |
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