CN114452988A - Supported heteropoly acid nano catalyst and preparation method thereof, and preparation method of aryl methyl stearate - Google Patents
Supported heteropoly acid 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 90
- 239000011943 nanocatalyst Substances 0.000 title claims abstract description 74
- 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 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 55
- 238000000034 method Methods 0.000 claims abstract description 34
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 14
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 114
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 108
- 238000003756 stirring Methods 0.000 claims description 98
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 75
- QYDYPVFESGNLHU-UHFFFAOYSA-N elaidic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCC(=O)OC QYDYPVFESGNLHU-UHFFFAOYSA-N 0.000 claims description 69
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 claims description 69
- 229940073769 methyl oleate Drugs 0.000 claims description 69
- 238000010438 heat treatment Methods 0.000 claims description 66
- 238000002156 mixing Methods 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 35
- 229910021485 fumed silica Inorganic materials 0.000 claims description 32
- 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
- 230000008929 regeneration Effects 0.000 claims description 14
- 238000011069 regeneration method Methods 0.000 claims description 14
- 238000005804 alkylation reaction Methods 0.000 claims description 11
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 10
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000000571 coke Substances 0.000 claims description 9
- 239000003599 detergent Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910020628 SiW12O40 Inorganic materials 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 6
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 5
- 230000001476 alcoholic effect Effects 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 230000029936 alkylation Effects 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- 238000000643 oven drying Methods 0.000 claims description 2
- -1 methyl enoate Chemical compound 0.000 claims 1
- 238000002791 soaking Methods 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000007789 sealing Methods 0.000 description 33
- 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
- 239000000203 mixture Substances 0.000 description 28
- 239000012074 organic phase Substances 0.000 description 20
- 239000002904 solvent Substances 0.000 description 17
- 229910052681 coesite Inorganic materials 0.000 description 16
- 229910052906 cristobalite Inorganic materials 0.000 description 16
- 238000003760 magnetic stirring Methods 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
- 238000005303 weighing Methods 0.000 description 14
- 238000012512 characterization method Methods 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000001228 spectrum 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
- 239000011521 glass Substances 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
- 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
- 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
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-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
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 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
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 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
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 238000003547 Friedel-Crafts alkylation reaction Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 1
- 150000001336 alkenes Chemical class 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
- 239000011218 binary composite Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000015784 hyperosmotic salinity response Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 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
- 229940098779 methanesulfonic acid Drugs 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
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 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
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- 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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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- 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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- 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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- 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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Abstract
The invention relates to a supported heteropoly acid nano catalyst, a preparation method thereof and a preparation method of methyl arylstearate. 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, the acid does not need to be neutralized, the used catalyst can be regenerated after simple treatment, the method is environment-friendly, the environmental protection property of the treatment after the reaction is improved, the production and manufacturing cost is reduced, and the method is easy to control and realize industrial production.
Description
Technical Field
The invention relates to the field of catalysts, and particularly relates to a supported heteropoly acid nano catalyst and a preparation method thereof, and a preparation method of aryl methyl stearate.
Background
The betaine surfactant is a surfactant with high salt tolerance, high salinity resistance and water resistance, and can be used in a binary composite oil displacement agent in tertiary oil recovery operation, so that the oil displacement agent can obtain high surface activity and ultralow interfacial tension at a low concentration. One key intermediate in the synthesis of this surfactant is methyl arylstearate. Methyl arylstearate is obtained mainly by friedel-crafts alkylation of methyl oleate with xylene. Methyl oleate belongs to internal olefin, is not active enough in chemical property, has larger molecular weight and has more active lipid groups, so that the alkylation reaction has more rigorous conditions, more side reactions and more difficult control of the reaction. Therefore, the development of green, environmentally friendly and highly efficient catalysts is the focus of research for realizing industrialization of this reaction.
At present, the alkylation reaction for synthesizing the methyl arylstearate is generally catalyzed by organic protonic acid, however, if liquid acid (such as methanesulfonic acid) is used as a catalyst in industrial scale-up production, a series of difficult problems of equipment corrosion, large one-time investment of reaction equipment, substandard discharge of waste liquid (material), 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 alkylation reaction is difficult to recycle, so the key for realizing the industrial production of the methyl arylstearate is to solve the problem.
Disclosure of Invention
One of the objects of the present invention is: provides a supported heteropoly acid nano catalyst.
In order to achieve the above purpose, the invention provides the following technical scheme:
a supported heteropoly acid nano catalyst is prepared by supporting heteropoly acid on a carrier;
wherein the heteropoly acid is H3PW12O40、H4SiW12O40、H6P2W18O62、Cs2.5H0.5PW12O40One of (1); the carrier is one of fumed silica, nano titanium dioxide, nano zirconium dioxide and MCM-41.
Preferably, the loading amount of the heteropoly acid is 30-50%, and the percentage is mass percent.
Preferably, the supported heteropolyacid nano-catalyst is used for catalyzing the alkylation reaction of methyl oleate and m-xylene to prepare aryl methyl stearate.
The second purpose of the invention is: provides a preparation method of a supported heteropoly acid nano catalyst.
In order to achieve the above purpose, the invention provides the following technical scheme:
the preparation method of the supported heteropoly acid nano catalyst is characterized in that the supported heteropoly acid nano catalyst is prepared by adopting a balanced impregnation method or an isometric impregnation method.
Preferably, the equilibrium impregnation method comprises the following specific processes: adding an alcohol solution into the carrier, and uniformly stirring and mixing; adding heteropoly acid, stirring for 22-26h, heating to 40-50 deg.C to remove alcoholic solution, and oven drying; wherein the alcoholic solution is methanol or ethanol, and the drying condition is that the alcoholic solution is dried for 12-24h at 55-65 ℃.
Preferably, the specific process of the equal-volume impregnation method is as follows: dissolving heteropoly acid in water to obtain heteropoly acid water solution; uniformly dropwise adding a heteropoly acid aqueous solution to the surface of the carrier for infiltration; standing at room temperature to evaporate naturally.
The third purpose of the invention is that: provides a preparation method of aryl methyl stearate.
In order to achieve the above purpose, the invention provides the following technical scheme:
a preparation method of aryl methyl stearate comprises the following specific steps:
the aryl methyl stearate is obtained by post-treating the supported heteropoly acid nano catalyst which is used as a catalyst and methyl oleate and m-xylene which are used as raw materials.
Preferably, the preparation method of the methyl arylstearate 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 ℃, adding methyl oleate, heating, stirring and refluxing for 2-5h, cooling, and performing post-treatment to obtain aryl methyl stearate;
wherein the post-treatment comprises the following specific processes: filtering to remove the catalyst, and removing unreacted m-xylene by rotary evaporation to obtain the aryl methyl stearate.
Preferably, the methyl oleate is linear methyl oleate, and the feeding speed of the methyl oleate is 0.1-0.2 g/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, after the supported heteropolyacid nano-catalyst is used for catalyzing the alkylation synthesis of methyl oleate and m-xylene to obtain aryl methyl stearate, the supported heteropolyacid nano-catalyst is regenerated by washing or scorching.
Preferably, 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 ℃;
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 coke-burning regeneration is as follows: in the air, the catalyst is recovered and put into a muffle furnace for coke burning regeneration, the coke burning regeneration is raised from the initial temperature of 25-100 ℃ to the termination temperature of 300-400 ℃ at the heating rate of 0.2-5 ℃/min, and the final temperature is burnt for 4-24h at constant temperature, thus completing the coke burning regeneration of the catalyst.
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 the pure heteropoly acid is used for catalyzing the preparation process of aryl methyl stearate, so that the catalysis efficiency is low, and the stability and the dispersibility are poor. The catalyst is loaded on a nano carrier material, so that the catalytic efficiency, the stability and the dispersibility are improved. The catalyst has the advantages of mild reaction conditions, little pollution, simple preparation, little corrosion to equipment, environmental friendliness and no need of neutralization after the reaction of the solid acid catalyst, and is expected to replace liquid acid and be applied to industrial production.
2) The supported heteropolyacid nano catalyst provided by the invention has excellent alkylation catalytic reaction performance, is easy to separate and recover after catalytic reaction, and has stable activity after multiple times of catalysis. Meanwhile, the catalyst deactivation can be regenerated by washing or scorching.
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 will 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 in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and those skilled in the art can also obtain other drawings according to the drawings without creative efforts.
FIG. 1 is a FT-IR characterization spectrum of fumed silica supported by phosphotungstic acid equilibrium impregnation method in example 2;
FIG. 2 is a Raman characterization spectrum of fumed silica supported by phosphotungstic acid equilibrium impregnation method in example 2;
FIG. 3 is the N loading fumed silica by phosphotungstic acid equilibrium impregnation method in example 22Adsorption and desorption isotherm representation;
FIG. 4 is a GC-Mass characterization of reactants and products of the phosphotungstic acid equilibrium impregnation method loaded fumed silica catalyzed commercial methyl oleate and m-xylene alkylation reaction in example 2;
FIG. 5 is a reaction equation for the preparation of methyl arylstearate in the examples.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Weighing 700mg of fumed silica, adding the fumed silica into 30mL of methanol, uniformly mixing under magnetic stirring, then adding 300mg of phosphotungstic acid under stirring, and sealing and stirring a sealing film for 24 hours (the stirring time can be any time from 22 to 26 hours). Heating the mixture solution to 40 deg.C (any temperature of 40-50 deg.C) under stirring to remove methanol solvent, and drying in vacuum oven 60 deg.C (any temperature of 55-65 deg.C) overnightThe drying time is controlled to be 12-24H), and H with the load of 30 wt% is finally obtained3PW12O40/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 170 ℃, adding 1.509g of methyl oleate at a feeding speed of 0.13g/min (any speed of 0.1-0.2 g/min), heating, stirring and refluxing for 5 hours, cooling, performing post-treatment, filtering to remove the supported heteropoly acid nano catalyst in an organic phase, and performing rotary evaporation to remove unreacted m-xylene to obtain aryl methyl stearate, wherein the reaction equation is shown in figure 5. The conversion of methyl oleate measured by GC-Mass was 89.65%.
Example 2
Weighing 500mg of fumed silica, adding the fumed silica into 30mL of methanol, uniformly mixing under magnetic stirring, then adding 500mg of phosphotungstic acid under stirring, and sealing and stirring by using a sealing film for 24 hours. Heating the mixture solution to 40 ℃ under stirring to remove the methanol solvent, then putting the sample into a vacuum oven to dry at 60 ℃ overnight, and finally obtaining H with the load of 50 wt%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 ℃, adding 1.509g of methyl oleate, feeding at the speed of 0.13g/min, heating, stirring and refluxing for 3h, cooling, performing post-treatment, filtering to remove the supported heteropoly acid nano catalyst in an organic phase, and performing rotary evaporation to remove unreacted m-xylene to obtain aryl methyl stearate. The conversion of methyl oleate measured by GC-Mass was 99.39%.
The FT-IR characterization spectrum of the phosphotungstic acid equilibrium impregnation method loaded fumed silica in the embodiment is shown in FIG. 1, and can be seen from FIG. 1: 1079cm-1、979cm-1、881cm-1、788cm-1The four characteristic peaks of the phosphotungstic acid show that the Keggin structure is not changed after the phosphotungstic acid is loaded on the fumed silica. (PW in FIG. 1)12Refers to H3PW12O40；PW12(50)@SiO2Is referred to as negativeH loading of 50 wt%3PW12O40/SiO2)
The Raman characterization spectrum of the phosphotungstic acid equilibrium impregnation method loaded fumed silica in the present example is shown in fig. 2, and it can be seen from fig. 2 that: 990cm-1、990.6cm-1、1005.5cm-1The stretching vibration of W-O-W, W ═ O and P-O in phosphotungstic acid is shown. After the phosphotungstic acid is loaded on the fumed silica, although the characteristic peak intensity of the phosphotungstic acid is reduced, the Keggin structure of the phosphotungstic acid is not changed.
In this example, the phosphotungstic acid equilibrium impregnation method is used to load fumed silica N2The adsorption-desorption isotherm characterization graph is shown in fig. 3, and it can be seen from fig. 3 that: the nitrogen adsorption and desorption isotherm of the catalyst is IV type, and the rear ring is H3Type, mesoporous is made of H3PW12O40/SiO2The nano particles are piled up.
The GC-Mass characterization spectrum of the product of the phosphotungstic acid equilibrium impregnation method loaded fumed silica catalyzed methyl oleate and m-xylene alkylation reaction in the embodiment is shown in FIG. 4, and it can be seen from FIG. 4 that: 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 out and uniformly dispersed in a watch glass. Then 500mg of phosphotungstic acid is weighed and dissolved in 10mL of water, and the mixture is stirred uniformly. Then, a dropper is used for slowly dripping phosphotungstic acid aqueous solution into the surface dish dispersed with the silicon dioxide for wetting, standing at room temperature for natural evaporation, and the obtained solid is H with the load of 50 wt%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 ℃, adding 1.509g of methyl oleate, feeding at the speed of 0.13g/min, heating, stirring and refluxing for 3h, cooling, performing post-treatment, filtering to remove the supported heteropoly acid nano catalyst in an organic phase, and performing rotary evaporation to remove unreacted m-xylene to obtain aryl methyl stearate. The conversion of methyl oleate measured by GC-Mass was 94.91%.
Example 4
4.38g of cetyltrimethylammonium bromide (CTAB) and 1.2g of NaOH were weighed out and dissolved in 200mL of distilled water, the solution was stirred magnetically until homogeneous, and then 20.8g of tetraethyl silicate (TEOS) was slowly added dropwise and stirred for 5 min. Then, 8.64g of 1, 3, 5-trimethylbenzene and 3.1g of n-hexane were slowly added dropwise thereto, and vigorously stirred for 10 minutes to obtain a thick mixture solution. The mixture was 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 in a vacuum oven overnight at 100 ℃ to give a white powder. Putting the white powder into a corundum crucible with a cover, heating to 550 ℃ at the speed of 10 ℃/min, keeping for 5 hours to remove residual CTAB and organic matters, and naturally cooling to room temperature to obtain a product MCM-41.
Weighing 500mg of MCM-41 prepared above, adding into 30mL of methanol, uniformly mixing under magnetic stirring, then adding 500mg of phosphotungstic acid under stirring, sealing and stirring by a sealing film for 24 hours. Heating the mixture solution to 40 ℃ under stirring to remove the methanol solvent, then putting the sample into a vacuum oven to dry at 60 ℃ overnight, and finally obtaining H with the load of 50 wt%3PW12O40/MCM-41. 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 ℃, adding 1.509g of methyl oleate, feeding at the speed of 0.13g/min, heating, stirring and refluxing for 5 hours, cooling, performing post-treatment, filtering to remove the supported heteropoly acid nano catalyst in an organic phase, and performing rotary evaporation to remove unreacted m-xylene to obtain aryl methyl stearate. The conversion of methyl oleate measured by GC-Mass was 96.66%.
Example 5
Weighing 500mg of nano titanium dioxide, adding the nano titanium dioxide into 30mL of methanol, uniformly mixing under magnetic stirring, then adding 500mg of phosphotungstic acid under stirring, and sealing and stirring the mixture by a sealing film for 24 hours. Heating the mixture solution to 40 ℃ under stirring to remove the methanol solvent, then putting the sample into a vacuum oven to dry at 60 ℃ overnight, and finally obtaining H with the load of 50 wt%3PW12O40/TiO2. 2.531g of m-xylene and 225mg of supported heteropolyacid nano-catalyst are added to the reactionStirring and mixing uniformly in a magnetic stirrer in a container, heating to 170 ℃, adding 1.509g of methyl oleate at the feeding speed of 0.13g/min, heating, stirring and refluxing for 5h, cooling, performing post-treatment, filtering to remove the supported heteropoly acid nano catalyst in the organic phase, and performing rotary evaporation to remove unreacted m-xylene to obtain the aryl methyl stearate. The conversion of methyl oleate measured by GC-Mass was 91.81%.
Example 6
Weighing 500mg of fumed silica, adding the fumed silica into 30mL of methanol, uniformly mixing under magnetic stirring, then adding 500mg of silicotungstic acid under stirring, and sealing and stirring by using a sealing film for 24 hours. Heating the mixture solution to 40 ℃ under stirring to remove the methanol solvent, then putting the sample into a vacuum oven to dry at 60 ℃ overnight, and finally obtaining H with the load of 50 wt%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 ℃, adding 1.509g of methyl oleate, feeding at the speed of 0.13g/min, heating, stirring and refluxing for 3h, cooling, performing post-treatment, filtering to remove the supported heteropoly acid nano catalyst in an organic phase, and performing rotary evaporation to remove unreacted m-xylene to obtain aryl methyl stearate. The conversion of methyl oleate measured by GC-Mass was 95.72%.
Example 7
Weighing 500mg of nano titanium dioxide, adding the nano titanium dioxide into 30mL of methanol, uniformly mixing under magnetic stirring, then adding 500mg of silicotungstic acid under stirring, sealing and stirring by a sealing film for 24 hours. Heating the mixture solution to 40 ℃ under stirring to remove the methanol solvent, then putting the sample into a vacuum oven to dry at 60 ℃ overnight, and finally obtaining H with the load of 50 wt%4SiW12O40@TiO2. Adding 2.531g of m-xylene and 225mg of supported heteropolyacid nano catalyst into a reaction vessel, stirring and mixing uniformly by a magnetic stirrer, heating to 170 ℃, adding 1.509g of methyl oleate, feeding at the speed of 0.13g/min, heating, stirring and refluxing for 5 hours, cooling, performing post-treatment, filtering to remove the supported heteropolyacid nano catalyst in an organic phase, and then removing the supported heteropolyacid nano catalyst in the organic phaseAnd (4) removing unreacted m-xylene by rotary evaporation to obtain the aryl methyl stearate. The conversion of methyl oleate measured by GC-Mass was 98.46%.
Example 8
Weighing 500mg of prepared MCM-41, adding into 30mL of methanol, uniformly mixing under magnetic stirring, then adding 500mg of silicotungstic acid under stirring, sealing and stirring by a sealing film for 24 hours. Heating the mixture solution to 40 ℃ under stirring to remove the methanol solvent, then putting the sample into a vacuum oven to dry at 60 ℃ overnight, and finally obtaining H with the load of 50 wt%4SiW12O40@ MCM-41. 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 ℃, adding 1.509g of methyl oleate, feeding at the speed of 0.13g/min, heating, stirring and refluxing for 5 hours, cooling, performing post-treatment, filtering to remove the supported heteropoly acid nano catalyst in an organic phase, and performing rotary evaporation to remove unreacted m-xylene to obtain aryl methyl stearate. The conversion of methyl oleate determined by GC-Mass was 82.70%.
Example 9
Weighing 700mg of nano zirconium dioxide, adding the nano zirconium dioxide into 30mL of methanol, uniformly mixing under magnetic stirring, then adding 300mg of phosphotungstic acid under stirring, sealing and stirring a sealing film for 24 hours. Heating the mixture solution to 40 ℃ under stirring to remove the methanol solvent, then putting the sample into a vacuum oven to dry at 60 ℃ overnight, and finally obtaining H with the load of 30 wt%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 ℃, adding 1.509g of methyl oleate, feeding at the speed of 0.13g/min, heating, stirring and refluxing for 5 hours, cooling, performing post-treatment, filtering to remove the supported heteropoly acid nano catalyst in an organic phase, and performing rotary evaporation to remove unreacted m-xylene to obtain aryl methyl stearate. The conversion of methyl oleate measured by GC-Mass was 73.22%.
Example 10
Weighing 500mg MCM-41, adding into 30mL methanol, stirring under magnetic forceMixing uniformly, adding 500mg of phosphotungstic acid while stirring, sealing and stirring by a sealing film for 24 hours. Heating the mixture solution to 40 ℃ under stirring to remove the methanol solvent, then putting the sample into a vacuum oven to dry at 60 ℃ overnight, and finally obtaining H with the load of 50 wt%3PW12O40/MCM-41. 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 ℃, adding 1.509g of methyl oleate, feeding at the speed of 0.13g/min, heating, stirring and refluxing for 3h, cooling, performing post-treatment, filtering to remove the supported heteropoly acid nano catalyst in an organic phase, and performing rotary evaporation to remove unreacted m-xylene to obtain aryl methyl stearate. The conversion of methyl oleate measured by GC-Mass was 68.80%.
Example 11
Weighing 500mg MCM-41, adding into 30mL methanol, uniformly mixing under magnetic stirring, then adding 500mg phosphotungstic acid under stirring, sealing and stirring by a sealing film for 24 h. Heating the mixture solution to 40 ℃ under stirring to remove the methanol solvent, then putting the sample into a vacuum oven to dry at 60 ℃ overnight, and finally obtaining H with the load of 50 wt%3PW12O40/MCM-41. 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 ℃, adding 1.509g of methyl oleate, feeding at the speed of 0.13g/min, heating, stirring and refluxing for 2 hours, cooling, performing post-treatment, filtering to remove the supported heteropoly acid nano catalyst in an organic phase, and performing rotary evaporation to remove unreacted m-xylene to obtain aryl methyl stearate. The conversion of methyl oleate measured by GC-Mass was 80.02%.
Example 12
600mg of fumed silica is weighed and added into 30mL of methanol, the mixture is 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. Heating the mixture solution to 40 ℃ under stirring to remove the methanol solvent, then putting the sample into a vacuum oven to dry at 60 ℃ overnight, and finally obtaining H with the load of 40 wt%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 ℃, adding 1.509g of methyl oleate, feeding at the speed of 0.13g/min, heating, stirring and refluxing for 3h, cooling, performing post-treatment, filtering to remove the supported heteropoly acid nano catalyst in an organic phase, and performing rotary evaporation to remove unreacted m-xylene to obtain aryl methyl stearate. The conversion of methyl oleate measured by GC-Mass was 63.53%.
Example 13
Weighing 500mg of fumed silica, adding the fumed silica into 30mL of methanol, uniformly mixing under magnetic stirring, then adding 500mg of phosphotungstic acid under stirring, and sealing and stirring by using a sealing film for 24 hours. Heating the mixture solution to 40 ℃ under stirring to remove the methanol solvent, then putting the sample into a vacuum oven to dry at 60 ℃ overnight, and finally obtaining H with the load of 50 wt%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 ℃, adding 1.509g of methyl oleate, feeding at the speed of 0.13g/min, heating, stirring and refluxing for 4h, cooling, performing post-treatment, filtering to remove the supported heteropoly acid nano catalyst in an organic phase, and performing rotary evaporation to remove unreacted m-xylene to obtain aryl methyl stearate. The conversion of methyl oleate measured by GC-Mass was 72.82%.
Example 14
Weighing 500mg of fumed silica, adding the fumed silica into 30mL of methanol, uniformly mixing under magnetic stirring, then adding 500mg of phosphotungstic acid under stirring, and sealing and stirring by using a sealing film for 24 hours. Heating the mixture solution to 40 ℃ under stirring to remove the methanol solvent, then putting the sample into a vacuum oven to dry at 60 ℃ overnight, and finally obtaining H with the load of 50 wt%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 ℃, adding 1.509g of methyl oleate at the feeding speed of 0.13g/min, heating, stirring, refluxing and refluxingAnd 3h, cooling, performing post-treatment, filtering to remove the supported heteropolyacid nano catalyst in the organic phase, and performing rotary evaporation to remove unreacted m-xylene to obtain the methyl arylstearate. The conversion of methyl oleate measured by GC-Mass was 97.65%.
Example 15
Weighing 500mg of fumed silica, adding the fumed silica into 30mL of methanol, uniformly mixing under magnetic stirring, then adding 500mg of phosphotungstic acid under stirring, and sealing and stirring by using a sealing film for 24 hours. Heating the mixture solution to 40 ℃ under stirring to remove the methanol solvent, then putting the sample into a vacuum oven to dry at 60 ℃ overnight, and finally obtaining H with the load of 50 wt%3PW12O40/SiO2. Adding 1.510g of m-xylene and 225mg of supported heteropolyacid nano catalyst into a reaction vessel, stirring and mixing uniformly by a magnetic stirrer, heating to 150 ℃, adding 1.509g of methyl oleate, heating, stirring and refluxing for 3h at the feeding speed of 0.13g/min, cooling, performing post-treatment, filtering to remove the supported heteropolyacid nano catalyst in an organic phase, and performing rotary evaporation to remove unreacted m-xylene to obtain aryl methyl stearate. The conversion of methyl oleate measured by GC-Mass was 78.38%.
Example 16
Weighing 500mg of fumed silica, adding the fumed silica into 30mL of methanol, uniformly mixing under magnetic stirring, then adding 500mg of phosphotungstic acid under stirring, and sealing and stirring by using a sealing film for 24 hours. Heating the mixture solution to 40 ℃ under stirring to remove the methanol solvent, then putting the sample into a vacuum oven to dry at 60 ℃ overnight, and finally obtaining H with the load of 50 wt%3PW12O40/SiO2. 7.545g of m-xylene and 225mg of supported heteropoly acid nano catalyst are added into a reaction vessel, after being stirred and mixed uniformly by a magnetic stirrer, the mixture is heated to 130 ℃, 1.509g of methyl oleate is added, the feeding speed is 0.13g/min, the mixture is heated, stirred and refluxed for 3 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, thus obtaining the aryl methyl stearate. The conversion of methyl oleate measured by GC-Mass was 80.21%.
Example 17
500mg of fumed silica was weighed out and uniformly dispersed in a watch glass. Then 500mg of phosphotungstic acid is weighed and dissolved in 10mL of water, and the mixture is stirred uniformly. Then, a dropper is used for slowly dripping phosphotungstic acid aqueous solution into the surface dish dispersed with the silicon dioxide to infiltrate the surface dish, the surface dish is kept at room temperature to be naturally evaporated, and the obtained solid is H with the load capacity of 50wt percent3PW12O40/SiO2. 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 ℃, adding 1.509g of methyl oleate, feeding at the speed of 0.13g/min, heating, stirring and refluxing for 5 hours, cooling, performing post-treatment, filtering to remove the supported heteropoly acid nano catalyst in an organic phase, and performing rotary evaporation to remove unreacted m-xylene to obtain aryl methyl stearate. The conversion of methyl oleate measured by GC-Mass was 62.52%.
Example 18
500mg of fumed silica was weighed out and uniformly dispersed in a watch glass. Then 500mg of phosphotungstic acid is weighed and dissolved in 10mL of water, and the mixture is stirred uniformly. Then, a dropper is used for slowly dripping phosphotungstic acid aqueous solution into the surface dish dispersed with the silicon dioxide for wetting, standing at room temperature for natural evaporation, and the obtained solid is H with the load of 50 wt%3PW12O40/SiO2. 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 ℃, adding 1.509g of methyl oleate, feeding at the speed of 0.13g/min, heating, stirring and refluxing for 3h, cooling, performing post-treatment, filtering to remove the supported heteropoly acid nano catalyst in an organic phase, and performing rotary evaporation to remove unreacted m-xylene to obtain aryl methyl stearate. The conversion of methyl oleate measured by GC-Mass was 78.79%.
Example 19
500mg of fumed silica is weighed, added to 30mL of methanol, mixed uniformly under magnetic stirring, and then 500mg of H is added under stirring6P2W18O62And sealing and stirring the mixture for 24 hours by using a sealing film. And under stirring willThe mixture solution was heated to 40 ℃ to remove the methanol solvent, and then the sample was placed in a vacuum oven to dry overnight at 60 ℃ to obtain a 50 wt% loading of H6P2W18O62@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 ℃, adding 1.509g of methyl oleate, feeding at the speed of 0.13g/min, heating, stirring and refluxing for 3h, cooling, performing post-treatment, filtering to remove the supported heteropoly acid nano catalyst in an organic phase, and performing rotary evaporation to remove unreacted m-xylene to obtain aryl methyl stearate. The conversion of methyl oleate determined by GC-Mass was 66.49%.
Example 20
500mg of fumed silica is weighed, added to 30mL of methanol, mixed uniformly under magnetic stirring, and then 500mg of Cs is added under stirring2.5H0.5PW12O40And sealing and stirring the mixture for 24 hours by using a sealing film. Heating the mixture solution to 40 ℃ under stirring to remove the methanol solvent, then putting the sample into a vacuum oven to dry at 60 ℃ overnight, and finally obtaining the Cs with the loading of 50 wt%2.5H0.5PW12O40@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 ℃, adding 1.509g of methyl oleate, feeding at the speed of 0.13g/min, heating, stirring and refluxing for 3h, cooling, performing post-treatment, filtering to remove the supported heteropoly acid nano catalyst in an organic phase, and performing rotary evaporation to remove unreacted m-xylene to obtain aryl methyl stearate. The conversion of methyl oleate measured by GC-Mass was 61.25%.
Example 21
The supported heteropolyacid nanocatalysts in examples 1-20 above were deactivated and then regenerated by washing or scorching.
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 aromatic hydrocarbon or long-chain alkaneWhen the detergent consists of aromatic hydrocarbon and long-chain alkane, the mass ratio of the aromatic hydrocarbon to the long-chain alkane is 1: 10-10: 1, preferably, the aromatic hydrocarbon can be benzene, and the long-chain alkane can be C10-14A normal alkane.
The specific process of coke burning regeneration is as follows: in the air, the catalyst is recovered and put into a muffle furnace for coke burning regeneration, the coke burning regeneration is increased from an initial temperature of 25-100 ℃ (preferably, the temperature can be selected as 25 ℃) to an end temperature of 300-.
It should be noted that:
in the embodiment of the invention, when the methyl arylstearate 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 h.
In the embodiment, methyl oleate involved in the preparation of aryl methyl stearate is linear methyl oleate, the feeding speed of the methyl oleate can be adjusted according to actual conditions and is controlled to be 0.1-0.2g/min, the specific dosage of the supported heteropolyacid nano catalyst, the methyl oleate and the m-xylene can be adjusted according to actual conditions, and the proportion relation between the supported heteropolyacid nano catalyst, the methyl oleate and the m-xylene can meet the following conditions: the mass ratio of the 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).
In addition, the heteropolyacids of the present invention are other than the H mentioned in the examples3PW12O40、H4SiW12O40、H6P2W18O62、Cs2.5H0.5PW12O40In addition, it may also be H3PMo12O40、H4PMo11VO40、H5PMo10V2O40、H6PMo9V3O40、H3SiMo12O40、Cs2.5H0.5PMo12O40The specific preparation thereof and the process for preparing methyl arylstearate are the same as the heteropolyacids mentioned in the examples of the present invention.
Although the present 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 solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (12)
1. A supported heteropoly acid nano catalyst is characterized in that the supported heteropoly acid nano catalyst is a carrier on which heteropoly acid is supported;
wherein the heteropoly acid is H3PW12O40、H4SiW12O40、H6P2W18O62、Cs2.5H0.5PW12O40One of (1); the carrier is one of fumed silica, nano titanium dioxide, nano zirconium dioxide and MCM-41.
2. The supported heteropolyacid nanocatalyst of claim 1, wherein the loading of the heteropolyacid is in the range of 30% to 50%, and the percentages are mass percentages.
3. The supported heteropolyacid nanocatalyst of claim 1, wherein the supported heteropolyacid nanocatalyst is used for catalyzing the alkylation synthesis of methyl oleate and m-xylene to prepare aryl methyl stearate.
4. A method for preparing the supported heteropolyacid nano-catalyst as claimed in any one of claims 1 to 3, wherein the supported heteropolyacid nano-catalyst is prepared by using a balanced impregnation method or an isovolumetric impregnation method.
5. The preparation method of the supported heteropolyacid nano-catalyst according to claim 4, wherein the equilibrium impregnation method comprises the following specific steps:
adding an alcohol solution into the carrier, and uniformly stirring and mixing; adding heteropoly acid, stirring for 22-26h, heating to 40-50 deg.C, removing alcohol solution, and oven drying;
wherein the alcoholic solution is methanol or ethanol, and the drying condition is that the alcoholic solution is dried for 12-24h at 55-65 ℃.
6. The preparation method of the supported heteropolyacid nano-catalyst according to claim 4, wherein the specific process of the isometric impregnation method is as follows:
dissolving heteropoly acid in water to obtain heteropoly acid water solution; uniformly dropwise adding a heteropoly acid aqueous solution on the surface of the carrier for soaking; standing at room temperature to evaporate naturally.
7. The preparation method of the aryl methyl stearate is characterized by comprising the following specific steps of: taking the supported heteropolyacid nano-catalyst as claimed in any one of claims 1-2 as a catalyst, taking methyl oleate and m-xylene as raw materials, and carrying out aftertreatment to obtain the aryl methyl stearate.
8. The method for preparing methyl arylstearate according to claim 7, characterized by comprising the following steps:
adding m-xylene and a supported heteropoly acid nano catalyst into a reaction vessel, stirring and mixing uniformly, heating to 130-170 ℃, adding methyl oleate, heating, stirring and refluxing for 2-5h, cooling, and performing post-treatment to obtain aryl methyl stearate;
wherein the post-treatment comprises the following specific processes: filtering to remove the catalyst, and removing unreacted m-xylene by rotary evaporation to obtain the aryl methyl stearate.
9. The method for preparing methyl arylstearate according to claim 7, wherein the methyl oleate is a linear methyl enoate, and the feeding speed of the methyl oleate is 0.1-0.2 g/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).
10. The preparation method of methyl arylstearate according to claim 7, wherein the supported heteropolyacid nanocatalyst is used for catalyzing the alkylation synthesis of methyl oleate and m-xylene to obtain methyl arylstearate, and then the supported heteropolyacid nanocatalyst is regenerated by washing or scorching.
11. The method of claim 10, wherein the washing regeneration comprises the following steps: washing the catalyst for 2-60h by using a detergent at the temperature of 20-100 ℃;
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.
12. The method of claim 10, wherein the specific process of scorch regeneration comprises: in the air, the catalyst is recovered and put into a muffle furnace for coke burning regeneration, the coke burning regeneration is raised from the initial temperature of 25-100 ℃ to the termination temperature of 300-400 ℃ at the heating rate of 0.2-5 ℃/min, and the final temperature is burnt for 4-24h at constant temperature, thus completing the coke burning regeneration of the catalyst.
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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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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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