CN114515607A - Short rod-shaped all-silicon mesoporous material supported catalyst, preparation method and application in esterification synthesis reaction of methacrylic acid and methanol - Google Patents
Short rod-shaped all-silicon mesoporous material supported catalyst, preparation method and application in esterification synthesis reaction of methacrylic acid and methanol Download PDFInfo
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- CN114515607A CN114515607A CN202011305784.0A CN202011305784A CN114515607A CN 114515607 A CN114515607 A CN 114515607A CN 202011305784 A CN202011305784 A CN 202011305784A CN 114515607 A CN114515607 A CN 114515607A
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- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 147
- 239000010703 silicon Substances 0.000 title claims abstract description 147
- 239000003054 catalyst Substances 0.000 title claims abstract description 135
- 239000013335 mesoporous material Substances 0.000 title claims abstract description 59
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 57
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000005886 esterification reaction Methods 0.000 title claims abstract description 35
- 230000032050 esterification Effects 0.000 title claims abstract description 21
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title abstract description 21
- 239000002808 molecular sieve Substances 0.000 claims abstract description 86
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 86
- 239000011148 porous material Substances 0.000 claims abstract description 67
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- 239000002184 metal Substances 0.000 claims description 18
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 13
- 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 claims description 13
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- 238000000926 separation method Methods 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 10
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims description 9
- 229910052700 potassium Inorganic materials 0.000 claims description 9
- 239000011591 potassium Substances 0.000 claims description 9
- 150000001340 alkali metals Chemical class 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
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- -1 alkali metal salt Chemical class 0.000 claims description 6
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- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 5
- 238000010304 firing Methods 0.000 claims description 5
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 5
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- 238000002156 mixing Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052792 caesium Inorganic materials 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 229910052701 rubidium Inorganic materials 0.000 claims description 3
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 abstract description 32
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 239000011964 heteropoly acid Substances 0.000 description 13
- 230000003197 catalytic effect Effects 0.000 description 12
- 238000009826 distribution Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000010586 diagram Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 8
- 239000003729 cation exchange resin Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
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- 238000001228 spectrum Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000011161 development Methods 0.000 description 6
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- 238000000967 suction filtration Methods 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
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- 239000012153 distilled water Substances 0.000 description 3
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- 239000000377 silicon dioxide Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
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- 238000004438 BET method Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
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- 239000004743 Polypropylene Substances 0.000 description 1
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- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
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- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
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- 150000007522 mineralic acids Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- 239000008031 plastic plasticizer Substances 0.000 description 1
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- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
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- 229920000642 polymer Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
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- 150000003297 rubidium Chemical class 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 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 1
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- 239000002023 wood Substances 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- B01J35/615—
-
- B01J35/617—
-
- B01J35/635—
-
- B01J35/638—
-
- B01J35/647—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to the field of fine chemical engineering, and discloses a short rod-shaped all-silicon mesoporous material supported catalyst, a preparation method and application thereof in esterification synthesis reaction of methacrylic acid and methanol. The short rod-shaped all-silicon mesoporous material supported catalyst comprises a carrier and phosphotungstate loaded on the carrier, wherein the carrier is a short rod-shaped all-silicon mesoporous molecular sieve, and the specific surface area of the short rod-shaped all-silicon mesoporous molecular sieve is 450-850m2Per g, pore volume of 1.4-1.9ml/g, average pore diameter of 10-15nm, rod length of 05-1 μm. The catalyst is used for the esterification reaction of methacrylic acid, and can obtain higher methacrylic acid conversion rate and methyl methacrylate selectivity.
Description
Technical Field
The invention relates to the field of fine chemical engineering, in particular to a short rod-shaped all-silicon mesoporous material supported catalyst, a preparation method and application thereof in esterification synthesis reaction of methacrylic acid and methanol.
Background
Methyl Methacrylate (MMA) is mainly used in the industries of organic glass (PMMA) coating, textile, adhesive, leather, papermaking, floor polishing, unsaturated resin modification, methacrylic acid high-grade esters, wood impregnating compound, printing and dyeing auxiliary agent, plastic plasticizer and the like. In recent years, the demands of domestic and foreign MMA polymers, profiles, plates, coatings, emulsions and the like are increased, the application fields are continuously widened, and the rapid development of the MMA industry is promoted. At present, the domestic methyl methacrylate production technology is still in the beginning stage. The development of a methacrylic acid esterification catalyst with independent intellectual property rights and a matched process are development requirements of the MMA production industry in China.
For the esterification reaction of methacrylic acid and methanol, currently, acidic cation exchange resin is generally used industrially for producing methyl methacrylate, and the cation exchange resin has the advantages of good stability, high selectivity, low cost, easy separation and the like in the esterification reaction. However, the cation exchange resin has poor heat resistance (generally, the cation exchange resin is decomposed at a temperature of not higher than 250 ℃), small specific surface area and pore volume, and the cation exchange resin is easy to swell, so that the cation exchange resin is poor in reaction activity as an esterification catalyst and low in ester yield. At present, for researchers of methacrylic esterification catalysts, the development of novel esterification catalysts and the improvement of catalytic activity, ester selectivity and stability thereof are urgent research efforts.
The heteropoly acid is a kind of oxygen-containing polyacid which is formed by coordination and bridging of heteroatoms and polyatomic atoms through oxygen atoms according to a certain structure. As a novel catalytic material, heteropoly acid is widely regarded by researchers in the field of catalytic research by virtue of unique acidity and structural advantages, and is also widely applied to esterification reaction. The heteropolyacid (including dodecaphosphotungstic acid, dodecasilicotungstic acid, dodecaphosphomolybdic acid and the like) with a Keggin structure has better catalytic esterification reaction performance. However, these heteropoly acids are easily soluble in water, methanol, ethanol, acetone and other small molecular solvents with strong polarity, can only be used as homogeneous catalysts in the esterification reaction of methacrylic acid and methanol, and are difficult to separate from the reaction system. The heteropolyacid salt of an alkali metal (for example, potassium salt, rubidium salt, cesium salt and the like) is not only high in acid strength but also insoluble in water, and is a relatively suitable catalyst for synthesizing methyl methacrylate. Although alkali metal heteropolyacid salts have excellent catalytic properties, their use is limited because they are difficult to prepare and are not suitable for fixed bed reactors because of their bed resistance after filling the reactor.
Therefore, the study of supported heteropolyacid salt catalysts is of particular importance.
Disclosure of Invention
The invention aims to overcome the problems of low methacrylic acid conversion rate and low methyl methacrylate yield in the current methyl methacrylate production process, and provides a short rod-shaped all-silicon mesoporous material supported catalyst, a preparation method and application in esterification synthesis reaction of methacrylic acid and methanol. The catalyst is used for the esterification reaction of methacrylic acid, and can obtain higher methacrylic acid conversion rate and methyl methacrylate selectivity.
In order to achieve the above object, the first aspect of the present invention provides a short rod-shaped all-silicon mesoporous material supported catalyst, wherein the short rod-shaped all-silicon mesoporous material supported catalyst comprises a carrier and phosphotungstate supported on the carrier, and the carrier is a short rod-shaped all-silicon mesoporous molecular sieve, wherein the specific surface area of the short rod-shaped all-silicon mesoporous molecular sieve is 450-2Per g, pore volume of 1.4-1.9ml/g, average pore diameter of 10-15nm, rod length of 0.5-1 μm.
In a second aspect, the invention provides a preparation method of the catalyst, wherein the preparation method comprises:
(1) the method comprises the steps of contacting a short rod-shaped full-silicon mesoporous molecular sieve with an aqueous solution of metal salt for a first reaction, separating for the first time to obtain a solid product, and drying and roasting the solid product for the first time to obtain a catalyst intermediate.
(2) And (3) contacting the catalyst intermediate with an aqueous solution of phosphotungstic acid for a second reaction, performing second separation to obtain a solid product, and washing, drying and roasting the solid product for a second time to obtain the short rod-shaped all-silicon mesoporous material supported catalyst.
In a third aspect, the present invention provides a use of the aforementioned catalyst in an esterification synthesis reaction of methacrylic acid and methanol, wherein the esterification synthesis reaction comprises: methacrylic acid and methanol are contacted with the catalyst.
Through the technical scheme, the technical scheme provided by the invention has the following advantages:
(1) the short rod-shaped all-silicon mesoporous material supported catalyst provided by the invention has large aperture and pore volume, and is beneficial to the diffusion of raw material and product molecules in the esterification reaction process of methacrylic acid and methanol.
(2) The active component loaded by the short rod-shaped all-silicon mesoporous material loaded catalyst provided by the invention is heteropolyacid salt of alkali metal, the catalytic capability of active central acid is strong, the conversion rate of methacrylic acid is high, and the selectivity of methyl methacrylate is high.
(3) The short rod-shaped all-silicon mesoporous material supported catalyst provided by the invention has the advantages of easily obtained raw materials, simple preparation method and process, easily controlled conditions and good product repeatability.
(4) The short rod-shaped all-silicon mesoporous material supported catalyst provided by the invention is used for the esterification reaction of methacrylic acid, and has mild technological conditions and low requirements on reaction devices.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
FIG. 1 is XRD spectra of a short rod-shaped all-silicon mesoporous molecular sieve A and a short rod-shaped all-silicon mesoporous material supported catalyst A prepared in example 1 of the present invention;
FIG. 2 is a diagram showing the pore size distribution of a short rod-shaped all-silicon mesoporous molecular sieve A and a short rod-shaped all-silicon mesoporous material supported catalyst A prepared in example 1 of the present invention;
FIG. 3 is a scanning electron microscope picture of a short rod-like all-silicon mesoporous molecular sieve A prepared in example 1 of the present invention.
Description of the reference numerals
FIG. 1(a) is the XRD spectrum of the short rod-like all-silicon mesoporous molecular sieve A prepared in example 1 of the present invention;
FIG. 1(b) is an XRD spectrum of catalyst A supported on a short rod-like all-silicon mesoporous material prepared in example 1 of the present invention'
FIG. 2(a) is a diagram showing the pore size distribution of a short rod-like all-silicon mesoporous molecular sieve A prepared in example 1 of the present invention;
fig. 2(b) is a pore size distribution diagram of the short rod-shaped all-silicon mesoporous material supported catalyst a prepared in example 1 of the present invention.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a short rod-shaped all-silicon mesoporous material supported catalyst, wherein the short rod-shaped all-silicon mesoporous material supported catalyst comprises a carrier and phosphotungstate loaded on the carrier, the carrier is a short rod-shaped all-silicon mesoporous molecular sieve, and the specific surface area of the short rod-shaped all-silicon mesoporous molecular sieve is 450-850m2Per g, pore volume of 1.4-1.9ml/g, average pore diameter of 10-15nm, rod length of 0.5-1 μm.
The inventors of the present invention found that: in the prior art, esterification catalysts for the production of methyl methacrylate are divided into homogeneous and heterogeneous categories. Wherein, the homogeneous catalyst mainly comprises inorganic acid solution and organic acid, and the heterogeneous catalyst mainly comprises solid acid and cation exchange resin. The homogeneous catalyst has the advantages of low price and good catalytic activity, but the defects of difficult separation of products and the catalyst, more side reactions, easy corrosion of equipment and the like are gradually eliminated. Although the solid acid esterification catalyst solves the problems of difficult product separation and serious equipment corrosion, the product has poor catalytic activity and higher reaction temperatureThe defects of low selectivity and the like are rarely applied to industrial production. Compared with the above catalysts, the production of methyl methacrylate by using acidic cation exchange resin as an esterification catalyst is the main process in industrial application at present. The resin catalyst has the advantages of high selectivity, low cost, easy separation and the like, but the yield of the methyl methacrylate is low in the esterification reaction process of the methacrylic acid, and the high-temperature resistance is poor. The resin is an organic high molecular material, is easy to swell in an organic solvent, and is easy to deform or even decompose in a high-temperature environment, which is the main reason of poor temperature resistance of the resin catalyst. The development of new solid catalyst systems to compensate for the performance deficiencies of resin catalysts is a good solution to the problem. Heteropolyacids having a Keggin structure such as phosphotungstic acid, silicotungstic acid, phosphomolybdic acid and the like are good esterification catalysts, but the catalysts are easily soluble in water and methanol and are not suitable for esterification reaction of methacrylic acid and methanol. The corresponding alkali metal heteropolyacid salts are not suitable for use in fixed bed reactors because of their difficult shaping and preparation. Therefore, the heteropoly acid salt is loaded by selecting a proper carrier to prepare the novel catalyst which can be used for the synthesis reaction of methyl methacrylate. The inorganic mesoporous material has the structural advantages of large specific surface area and large pore volume, and is relatively suitable to be used as a carrier for loading heteropoly acid salts. The specific surface area of the short rod-shaped all-silicon mesoporous molecular sieve is 450-850m2Per g, a pore volume of 1.4 to 1.9ml/g, an average pore diameter of 10 to 15nm, a rod length of 0.5 to 1 μm, and is suitable for supporting heteropolyacid salts. In addition, since the alkali metal heteropolyacid salt is hardly soluble in water, it cannot be supported on a carrier by a conventional impregnation method.
Based on the above, the inventor of the present invention found that, in the development process of the esterification catalyst, if a two-step loading method is adopted, the heteropolyacid salt can be introduced into the surface and the pore channel of the short rod-shaped all-silicon mesoporous molecular sieve to prepare the esterification catalyst. The catalyst is used as a methacrylic acid esterification reaction catalyst, and can show good catalytic activity and ester selectivity.
According to the invention, the specific surface area of the short rod-shaped all-silicon mesoporous molecular sieve is 500-650m2G, pore volume of 1.5-1.8ml/g, average pore diameter of 11-13 nm; preference is given toThe specific surface area of the short rod-shaped full-silicon mesoporous molecular sieve is 571-609m2G, pore volume of 1.5-1.7ml/g, average pore diameter of 11-12 nm. In the present invention, the parameters of the short rod-like all-silicon mesoporous molecular sieve are defined within the above-mentioned ranges,
according to the invention, based on the total weight of the catalyst, the content of the short rod-shaped all-silicon mesoporous molecular sieve is 40-80 wt%, and the content of the phosphotungstate is 20-60 wt%; preferably, the content of the short rod-shaped all-silicon mesoporous molecular sieve is 50-65 wt%, and the content of the phosphotungstate is 35-50 wt%; more preferably, the content of the short rod-shaped all-silicon mesoporous molecular sieve is 53.2-62.1 wt% and the content of the phosphotungstate is 37.9-46.8 wt% based on the total weight of the catalyst. In the invention, the content of the short rod-shaped all-silicon mesoporous molecular sieve and the content of the phosphotungstate are limited to be within the ranges, so that the prepared catalyst can be used for the esterification reaction of methacrylic acid, and higher methacrylic acid conversion rate and methyl methacrylate selectivity can be obtained.
According to the invention, the phosphotungstate is an alkali metal salt of phosphotungstic acid, preferably one or more of potassium phosphotungstate, rubidium phosphotungstate or cesium phosphotungstate.
According to the invention, the preparation method of the short rod-shaped all-silicon mesoporous molecular sieve comprises the following steps:
(I) mixing a silicon source and an acidic aqueous solution in the presence of a template agent, ammonium fluoride and heptane to obtain a mixture;
(II) crystallizing, washing, filtering, drying and removing the template agent to obtain the short rod-shaped full-silicon mesoporous molecular sieve.
According to the invention, the templating agent is polyoxyethylene-polyoxypropylene-polyoxyethylene, preferably P123.
Preferably, the molar ratio of the template agent, ammonium fluoride, heptane, silicon source, water and hydrogen chloride is 1: (0.5-5): (10-200): (50-500): (3000-30000): (200-2000), preferably 1: (1-3): (20-100): (100-400): (4000-20000): (400-1600).
According to the invention, the acidic aqueous solution is preferably an aqueous hydrochloric acid solution.
According to the invention, the contact conditions are preferably: the contact temperature is 15-60 ℃, and the contact time is 5-40 hours; preferably, the contacting may be carried out under stirring conditions, wherein the stirring conditions include: the stirring rate is 200-900 rpm.
According to the invention, the crystallization conditions are preferably: the crystallization temperature is 80-130 ℃, and the crystallization time is 10-40 hours.
According to the present invention, the washing method is not particularly limited, and may be a method well known to those skilled in the art. Preferably: and mixing the solid obtained by separation with deionized water, stirring and pulping for 2 hours, standing for 3 hours, and separating. The above washing process was repeated 6-10 times.
According to the invention, the suction filtration separation is a well-known way of separating liquid from solid particles, which is to separate liquid from solid particles or a mixture of liquid and liquid by using air pressure.
According to the invention, the drying conditions are preferably: the drying temperature is 70-150 ℃, and the drying time is 3-20 h.
According to the invention, the template removal conditions are preferably: roasting in air atmosphere at 400-600 deg.c for 6-50 hr.
According to the invention, the specific surface area of the catalyst is 300-700m2Per g, pore volume of 0.8-1.6mL/g, average pore diameter of 8-13 nm; preferably, the specific surface area of the catalyst is 350-500m2Per g, the pore volume is 1-1.5mL/g, and the average pore diameter is 9-12 nm; more preferably, the specific surface area of the catalyst is 403-464m2Per g, pore volume of 1.1-1.3mL/g, average pore diameter of 9-10 nm. In the present invention, the catalyst with the above-mentioned specific parameters can be used for the esterification reaction of methacrylic acid, and higher methacrylic acid conversion rate and methyl methacrylate selectivity can be obtained.
In a second aspect, the invention provides a preparation method of the catalyst, wherein the preparation method comprises:
(1) the method comprises the steps of contacting a short rod-shaped full-silicon mesoporous molecular sieve with an aqueous solution of metal salt to carry out a first reaction, then carrying out first separation to obtain a solid product, and drying and first roasting the solid product to obtain a catalyst intermediate.
(2) And (3) contacting the catalyst intermediate with an aqueous solution of phosphotungstic acid for a second reaction, performing second separation to obtain a solid product, and washing, drying and roasting the solid product for a second time to obtain the short rod-shaped all-silicon mesoporous material supported catalyst.
According to the invention, in step (1), the metal salt is selected from one or more of metal carbonate, chloride, sulfate and nitrate; preferably, the metal is an alkali metal; more preferably, the metal is selected from one or more of potassium, rubidium and cesium.
According to the invention, the concentration of the aqueous solution of the metal salt is between 0.05 and 2.0mol/L, preferably between 0.1 and 1.0 mol/L.
According to the invention, the weight ratio of the short rod-shaped all-silicon mesoporous molecular sieve to the aqueous solution of the metal salt is 1: (2-100), preferably 1: (5-50).
According to the invention, the conditions for the first reaction by contacting the short rod-shaped all-silicon mesoporous molecular sieve with the aqueous solution of the metal salt comprise: the reaction temperature can be 30-120 ℃, and preferably 40-90 ℃; the time can be from 0.5 to 20h, preferably from 2 to 10 h. Preferably, in order to achieve better mixing effect, the short rod-shaped all-silicon mesoporous molecular sieve can be rapidly stirred or the reaction efficiency can be improved by ultrasonic means in the contact reaction process of the short rod-shaped all-silicon mesoporous molecular sieve and the aqueous solution of the metal salt.
According to the invention, the conditions of the first firing include: the temperature is 250 ℃ and 400 ℃, and the time is 3-10 h.
According to the present invention, in step (1), the first separation method is not particularly required, and may be a method known in the art, for example: water was removed by evaporation using a rotary evaporator or heating during stirring.
According to the invention, in step (2), the concentration of the aqueous solution of phosphotungstic acid is 1 to 30%, preferably 5 to 20%.
According to the invention, the weight ratio of the short rod-shaped all-silicon mesoporous molecular sieve to the aqueous solution of the phosphotungstic acid is 1: (5-50), preferably 1: (10-30).
According to the present invention, the contacting of the catalyst intermediate with the aqueous solution of the metal salt is carried out under conditions of the second reaction including: the reaction temperature can be 30-120 ℃, and preferably 40-90 ℃; the time can be from 0.5 to 20h, preferably from 2 to 10 h. Preferably, in order to achieve better contact reaction effect, the catalyst intermediate and the aqueous solution of the metal salt may be rapidly stirred or ultrasonically treated to improve the contact reaction efficiency.
According to the present invention, the separation method in the step (2) is not particularly required, for example: the liquid can be removed by filtration or suction filtration to give a solid product.
According to the present invention, in step (2), the method for washing the solid product is not particularly required, for example: the solid product can be washed by deionized water, the volume ratio of the deionized water to the solid product can be 5-20, and the washing times can be 2-8.
According to the present invention, in the step (1) and the step (2), the conditions for drying the solid product are preferably: the drying temperature is 80-130 ℃, and the drying time is 3-20 hours.
According to the invention, the conditions of the second firing include: the temperature is 250 ℃ and 400 ℃, and the time is 3-10 h; the first firing conditions and the second firing conditions may be the same or different.
In a third aspect, the present invention provides a use of the aforementioned catalyst in an esterification synthesis reaction of methacrylic acid and methanol, wherein the esterification synthesis reaction comprises: methacrylic acid and methanol are contacted with the catalyst.
According to the invention, the contact conditions comprise: the contact temperature is 50-160 ℃, preferably 70-140 ℃; the contact pressure is 0.01-5.0MPa, preferably 0.1-3.0 MPa; the mass space velocity of the acetic acid is 0.01-30h-1Preferably 0.1 to 10h-1(ii) a The molar ratio of acetic acid to alcohol is 1 (0.1-20), preferably 1 (0.5-10).
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples:
the XRD spectrum of the sample was obtained on an X' Pert MPD type X-ray powder diffractometer manufactured by Philips, with Cu K α ray, λ 0.154178nm, and a scan range of 2 θ 0.5 ° to 10 °.
The pore structure parameter analysis of the samples was performed on an adsorption apparatus model ASAP2020-M + C, available from Micromeritics, USA. The samples were degassed at 350 ℃ for 4 hours under vacuum prior to assay.
The BET method is adopted to calculate the specific surface area of the sample, and the BJH model is adopted to calculate the pore volume.
Scanning electron microscope pictures of the samples were obtained on an XL-30 type field emission environment scanning electron microscope manufactured by FEI corporation of America.
Elemental analysis experiments on the samples were performed on an Eagle III energy dispersive X-ray fluorescence spectrometer manufactured by EDAX, USA.
The drying box is produced by Shanghai-Hengchang scientific instruments Co., Ltd, and is of a type DHG-9030A.
The muffle furnace is manufactured by CARBOLITE corporation, model CWF 1100.
The polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123) used in the examples and comparative examples was purchased from Sigma-Aldrich Chemistry; other reagents used in examples and comparative examples were purchased from national pharmaceutical group chemical agents, ltd, and the purity of the reagents was analytical grade.
Example 1
(1) Preparation of short rod-shaped full-silicon mesoporous molecular sieve
58 g of P123(0.01 mol) and 0.74 g (0.02 mol) of ammonium fluoride are mixed with 2165 g of aqueous hydrochloric acid (containing 10 mol of HCl), and stirred at 20 ℃ until P123 and ammonium fluoride are completely dissolved; 60 g of n-heptane (0.6 mol) and 582 g of ethyl orthosilicate (2.8 mol) were added to the above solution, vigorously stirred at 20 ℃ for 4 minutes and then left to stand for 1 hour; transferring the obtained mixture into a reaction kettle with a polytetrafluoroethylene lining, and crystallizing for 24 hours at 100 ℃; washing the solid matter obtained after filtering with deionized water for 8 times, and drying at 110 ℃ for 12 hours to obtain short rod-like all-silicon mesoporous molecular sieve raw powder; calcining the raw powder of the short rod-shaped all-silicon mesoporous molecular sieve at 500 ℃ for 24 hours, and removing the template agent to obtain the short rod-shaped all-silicon mesoporous molecular sieve A.
The specific surface area of the short rod-shaped full-silicon mesoporous molecular sieve A is 594m2Pore volume 1.6ml/g, average pore diameter 12 nm.
FIG. 1(a) is the XRD spectrum of short rod-like all-silicon mesoporous molecular sieve A. The XRD spectrogram shows that the short rod-shaped all-silicon mesoporous molecular sieve has a typical mesoporous two-dimensional hexagonal pore channel structure.
FIG. 2(a) is a diagram showing the pore size distribution of a short rod-like all-silicon mesoporous molecular sieve A. As can be seen from the pore size distribution diagram, the material has narrow pore size distribution and very uniform pore channels, and the most probable pore size is about 12 nm.
FIG. 3 is a scanning electron microscope image of a short rod-like all-silicon mesoporous molecular sieve A. It can be seen that the microstructure of the short rod-shaped all-silicon mesoporous molecular sieve A is in a short rod shape, and the length of the rod is between 0.5 and 1 mu m.
(2) Preparation of short rod-shaped all-silicon mesoporous material supported catalyst
10g of short rod-like all-silicon mesoporous molecular sieve A and 300g of potassium carbonate aqueous solution with the concentration of 0.6mol/L are mixed and stirred for reaction for 6 hours at 70 ℃. After the reaction is finished, the stirring is stopped, and the solvent water is removed by using a rotary evaporator to obtain a solid product. And drying the solid product at 100 ℃ for 8h, and roasting at 320 ℃ for 6h to obtain a catalyst intermediate. Mixing the catalyst intermediate with 200g of 10% phosphotungstic acid aqueous solution, and stirring and reacting for 6h at 70 ℃. After the reaction is finished, removing liquid by suction filtration to obtain a solid product. Washing the solid product with distilled water for 4 times, drying the solid product at 100 ℃ for 12h, and roasting at 320 ℃ for 6h to obtain the short rod-shaped all-silicon mesoporous material supported catalyst A.
The specific surface area of the short rod-shaped all-silicon mesoporous material supported catalyst A is 437m2Pore volume 1.2ml/g, average pore diameter 10 nm.
FIG. 1(b) is an XRD spectrum of a short rod-like all-silicon mesoporous material supported catalyst A. It can be clearly seen from the XRD spectrogram that the short rod-like all-silicon mesoporous molecular sieve a still maintains a typical two-dimensional hexagonal structure after being supported, and the basic framework structure of the mesoporous molecular sieve is not destroyed in the supporting process.
FIG. 2(b) is a diagram showing the pore size distribution of the short rod-shaped catalyst A supported by the all-silicon mesoporous material. As can be seen from the pore size distribution diagram, the channels of the catalyst are still very uniform, the most probable pore size is about 10nm, and the pore size is smaller than that of the short rod-shaped all-silicon mesoporous molecular sieve A.
Based on the total weight of the short rod-shaped all-silicon mesoporous material supported catalyst A, the content of the short rod-shaped all-silicon mesoporous molecular sieve is 57.7 wt%, and the content of the potassium phosphotungstate is 42.3 wt%.
(3) Evaluation of the Properties of the methacrylation reaction
The performance of the catalyst in the methacrylation reaction was evaluated on a fixed bed reactor. 5.0 g of short rod-shaped all-silicon mesoporous material supported catalyst A is filled into a stainless steel fixed bed reactor with the inner diameter of 8mm, the reaction temperature is 100 ℃, the reaction pressure is 0.3MPa, and the weight space velocity of methacrylic acid is 1.0h-1The weight space velocity of the methanol is 2.7h-1The reaction time was 50 hours. The product was cooled and analyzed by Agilent 7890A gas chromatograph equipped with FFAP capillary chromatographic column and hydrogen flame detector (FID), using programmed temperature and quantitative analysis with calibration factors.
As a result, the conversion of methacrylic acid was 97.8%, and the selectivity for methyl methacrylate was 99.4%.
Example 2
(1) Preparation of short rod-shaped full-silicon mesoporous molecular sieve
58 g of P123(0.01 mol) and 1.11 g (0.03 mol) of ammonium fluoride are mixed with 4184 g of aqueous hydrochloric acid (containing 16 mol of HCl), and stirred at 50 ℃ until the P123 and ammonium fluoride are completely dissolved; 100 g of n-heptane (1.0 mol) and 832 g of ethyl orthosilicate (4.0 mol) were added to the above solution, vigorously stirred at 50 ℃ for 4 minutes and then allowed to stand for 2 hours; transferring the obtained mixture into a reaction kettle with a polytetrafluoroethylene lining, and crystallizing for 40 hours at 80 ℃; washing the solid matter obtained after filtering with deionized water for 8 times, and drying at 150 ℃ for 4 hours to obtain short rod-like all-silicon mesoporous molecular sieve raw powder; calcining the raw powder of the short rod-shaped all-silicon mesoporous molecular sieve at 600 ℃ for 6 hours, and removing the template agent to obtain the short rod-shaped all-silicon mesoporous molecular sieve B.
The specific surface area of the short rod-shaped full-silicon mesoporous molecular sieve B is 609m2Pore volume 1.7ml/g, average pore diameter 11 nm.
The XRD spectrogram of the short rod-shaped all-silicon mesoporous molecular sieve B is similar to that in figure 1(a), the pore size distribution diagram of the short rod-shaped all-silicon mesoporous molecular sieve B is similar to that in figure 2(a), and the scanning electron micrograph of the short rod-shaped all-silicon mesoporous molecular sieve B is similar to that in figure 3.
(2) Preparation of short rod-shaped all-silicon mesoporous material supported catalyst
10g of a short rod-like all-silicon mesoporous molecular sieve B and 500g of a 0.2mol/L cesium carbonate aqueous solution were mixed and reacted at 90 ℃ for 2 hours with stirring. After the reaction is finished, the stirring is stopped, and the solvent water is removed by using a rotary evaporator to obtain a solid product. And drying the solid product at 130 ℃ for 3h, and roasting at 280 ℃ for 8h to obtain a catalyst intermediate. The catalyst intermediate is mixed with 300g of phosphotungstic acid aqueous solution with the concentration of 5 percent, and stirred and reacted for 2 hours at the temperature of 90 ℃. After the reaction is finished, removing liquid by suction filtration to obtain a solid product. Washing the solid product with distilled water for 4 times, drying the solid product at 130 ℃ for 5h, and roasting at 380 ℃ for 4h to obtain the short rod-shaped all-silicon mesoporous material supported catalyst B.
The specific surface area of the short rod-shaped all-silicon mesoporous material supported catalyst B is 464m2Pore volume 1.3ml/g, average pore diameter 9 nm.
The XRD spectrum of the short rod-shaped all-silicon mesoporous material supported catalyst B is similar to that of figure 1 (B). The distribution diagram of the aperture of the short rod-shaped all-silicon mesoporous material supported catalyst B is similar to that in the figure 2(B)
Based on the total weight of the short rod-shaped all-silicon mesoporous material supported catalyst B, the content of the short rod-shaped all-silicon mesoporous molecular sieve is 62.1 weight percent, and the content of the cesium phosphotungstate is 37.9 weight percent.
(3) Evaluation of the Properties of the methacrylation reaction
The conditions for evaluating the reaction performance of the short rod-like all-silicon mesoporous material supported catalyst B were the same as in the step (3) of example 1.
As a result, the conversion of methacrylic acid was 97.2%, and the selectivity for methyl methacrylate was 99.5%.
Example 3
(1) Preparation of short rod-shaped full-silicon mesoporous molecular sieve
58 g of P123(0.01 mol) and 0.37 g (0.01 mol) of ammonium fluoride are mixed with 1048 g of aqueous hydrochloric acid (containing 4 mol of HCl), and stirred at 15 ℃ until the P123 and ammonium fluoride are completely dissolved; 20 g of n-heptane (0.2 mol) and 208 g of ethyl orthosilicate (1.0 mol) were added to the above solution, vigorously stirred at 15 ℃ for 20 minutes and then left to stand for 1 hour; transferring the obtained mixture into a reaction kettle with a polytetrafluoroethylene lining, and crystallizing for 10 hours at 120 ℃; washing the solid matter obtained after filtering with deionized water for 8 times, and drying at 70 ℃ for 20 hours to obtain short rod-like all-silicon mesoporous molecular sieve raw powder; calcining the raw powder of the short rod-shaped all-silicon mesoporous molecular sieve at 400 ℃ for 30 hours, and removing the template agent to obtain the short rod-shaped all-silicon mesoporous molecular sieve C.
The specific surface area of the short rod-shaped full-silicon mesoporous molecular sieve C is 571m2Pore volume 1.5ml/g, average pore diameter 12 nm.
The XRD spectrum of the short rod-shaped all-silicon mesoporous molecular sieve C is similar to that in figure 1(a), the pore size distribution diagram of the short rod-shaped all-silicon mesoporous molecular sieve C is similar to that in figure 2(a), and the scanning electron micrograph of the short rod-shaped all-silicon mesoporous molecular sieve C is similar to that in figure 3.
(2) Preparation of short rod-shaped all-silicon mesoporous material supported catalyst
10g of short rod-like all-silicon mesoporous molecular sieve C and 200g of potassium carbonate aqueous solution with the concentration of 1.0mol/L are mixed and stirred for reaction for 10 hours at 40 ℃. After the reaction is finished, the stirring is stopped, and the solvent water is removed by using a rotary evaporator to obtain a solid product. And drying the solid product at 80 ℃ for 20h, and roasting at 300 ℃ for 6h to obtain a catalyst intermediate. The catalyst intermediate is mixed with 130g of phosphotungstic acid aqueous solution with the concentration of 20 percent, and the mixture is stirred and reacted for 8 hours at the temperature of 60 ℃. After the reaction is finished, removing liquid by suction filtration to obtain a solid product. Washing the solid product with distilled water for 4 times, drying the solid product at 80 ℃ for 20h, and roasting at 350 ℃ for 4h to obtain the short rod-shaped all-silicon mesoporous material supported catalyst C.
The specific surface area of the short rod-shaped all-silicon mesoporous material supported catalyst C is 403m2G, pore bodyThe volume was 1.1ml/g and the average pore diameter was 10 nm.
The XRD spectrum of the short rod-shaped all-silicon mesoporous material supported catalyst C is similar to that of figure 1 (b). The distribution diagram of the aperture of the short rod-shaped all-silicon mesoporous material supported catalyst C is similar to that in the figure 2(b)
Based on the total weight of the short rod-shaped all-silicon mesoporous material supported catalyst C, the content of the short rod-shaped all-silicon mesoporous molecular sieve is 53.2 weight percent, and the content of the potassium phosphotungstate is 46.8 weight percent.
(3) Evaluation of the Properties of the methacrylation reaction
The conditions for evaluating the reaction performance of the short rod-like all-silicon mesoporous material supported catalyst C were the same as in the step (3) of example 1.
As a result, the conversion of methacrylic acid was 97.5%, and the selectivity for methyl methacrylate was 99.3%.
Example 4
A short rod-shaped all-silicon mesoporous molecular sieve and a short rod-shaped all-silicon mesoporous material supported catalyst were prepared in the same manner as in example 1, except that:
the preparation conditions of the short rod-like all-silicon mesoporous material supported catalyst of the step (2) in example 1 were changed to obtain a short rod-like all-silicon mesoporous material supported catalyst D. Based on the total weight of the short rod-shaped all-silicon mesoporous material supported catalyst D, the content of the short rod-shaped all-silicon mesoporous molecular sieve A is 76.6 weight percent, and the content of the potassium phosphotungstate is 23.4 weight percent.
The catalyst performance of catalyst D was tested according to the method for evaluating the performance of the methacrylation reaction of step (3) in example 1.
As a result, the conversion of methacrylic acid was 93.1%, and the selectivity for methyl methacrylate was 98.8%.
Comparative example 1
A short rod-shaped all-silicon mesoporous molecular sieve and a short rod-shaped all-silicon mesoporous material supported catalyst were prepared in the same manner as in example 1, except that:
the preparation conditions of the short rod-like all-silicon mesoporous material supported catalyst of the step (2) in example 1 were changed to obtain a short rod-like all-silicon mesoporous material supported catalyst D1. Based on the total weight of the short rod-shaped all-silicon mesoporous material supported catalyst D1, the content of the short rod-shaped all-silicon mesoporous molecular sieve A is 86.4 wt%, and the content of the potassium phosphotungstate is 13.6 wt%.
The catalyst D1 was tested for its catalytic performance according to the method for evaluating the performance of the methacrylation reaction of step (3) in example 1.
As a result, the conversion of methacrylic acid was 87.2%, and the selectivity for methyl methacrylate was 96.3%.
Comparative example 2
A short rod-shaped all-silicon mesoporous molecular sieve and a short rod-shaped all-silicon mesoporous material supported catalyst were prepared in the same manner as in example 1, except that:
the procedure (1) in example 1 was omitted, and the short rod-like all-silicon mesoporous molecular sieve obtained in the procedure (2) in example 1 was replaced with commercial silica to obtain catalyst D2. Such that the commercial silica content was 57.7 wt.% and the potassium phosphotungstate content was 42.3 wt.% based on the total weight of catalyst D2.
The catalyst D2 was tested for its catalytic performance according to the method for evaluating the performance of the methacrylation reaction of step (3) in example 1.
As a result, the conversion of methacrylic acid was 88.4%, and the selectivity for methyl methacrylate was 96.7%.
Comparative example 3
A short rod-shaped all-silicon mesoporous molecular sieve and a short rod-shaped all-silicon mesoporous material supported catalyst were prepared in the same manner as in example 1, except that:
the catalytic performance of the resin catalyst was tested by the methacrylation reaction performance evaluation method of the step (3) in example 1, except for the steps (1) and (2) in example 1. Wherein the resin catalyst is available from Kaiser environmental protection science and technology Co., Ltd, model No. D009.
As a result, the conversion of methacrylic acid was 90.2%, and the selectivity for methyl methacrylate was 96.9%.
Comparative example 4
A short rod-shaped all-silicon mesoporous molecular sieve and a short rod-shaped all-silicon mesoporous material supported catalyst were prepared in the same manner as in example 1, except that:
the method of the step (1) in example 1 was changed so that the prepared short rod-like all-silicon mesoporous molecular sieve D4 had a specific surface area of 395m2Pore volume 1.2mL/g, average pore diameter 9.0 nm.
Catalyst D4 was prepared in accordance with the procedure in step (2) of example 1, so that a catalyst having a specific surface area of 281m was prepared2Pore volume of 0.9mL/g, and average pore diameter of 7.9 nm.
As a result, the conversion of methacrylic acid was 89.7%, and the selectivity for methyl methacrylate was 96.1%.
The results show that the short rod-shaped all-silicon mesoporous material supported catalyst provided by the invention can directly convert methacrylic acid and methanol into methyl methacrylate. The short rod-shaped all-silicon mesoporous material supported catalyst provided by the invention can obtain higher methacrylic acid conversion rate and methyl methacrylate selectivity.
Comparing the data of example 1 and comparative example 1, it can be seen that if the contents of the short rod-like all-silicon mesoporous molecular sieve a and potassium phosphotungstate are outside the range defined by the present invention, both the conversion of methacrylic acid and the selectivity of methyl methacrylate are low.
Comparing the data of example 1 and comparative example 2, it can be seen that both the methacrylic acid conversion and methyl methacrylate selectivity are low if the catalyst is prepared using commercially available silica instead of a short rod-like all-silicon mesoporous molecular sieve.
Comparing the data of example 1 and comparative example 3, it can be seen that the methacrylic acid conversion rate and the methyl methacrylate selectivity of the short rod-shaped all-silicon mesoporous material supported catalyst are both significantly improved compared with the resin catalyst.
Comparing the data of example 1 and comparative example 4, it can be seen that the structural parameters of the short rod-shaped all-silicon mesoporous molecular sieve and the prepared catalyst are not within the range defined by the present invention, and as a result, the methacrylic acid conversion rate and the methyl methacrylate selectivity of the short rod-shaped all-silicon mesoporous material supported catalyst are significantly improved.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (12)
1. The short rod-shaped all-silicon mesoporous material supported catalyst is characterized by comprising a carrier and phosphotungstate loaded on the carrier, wherein the carrier is a short rod-shaped all-silicon mesoporous molecular sieve, and the specific surface area of the short rod-shaped all-silicon mesoporous molecular sieve is 450-850m2Per g, pore volume of 1.4-1.9ml/g, average pore diameter of 10-15nm, rod length of 0.5-1 μm.
2. The catalyst as claimed in claim 1, wherein the short rod-shaped all-silicon mesoporous molecular sieve has a specific surface area of 500-650m2G, pore volume of 1.5-1.8ml/g, average pore diameter of 11-13 nm; preferably, the specific surface area of the short rod-shaped all-silicon mesoporous molecular sieve is 571-609m2G, pore volume of 1.5-1.7ml/g, average pore diameter of 11-12 nm.
3. The catalyst of claim 1 or 2, wherein the short rod-like all-silicon mesoporous molecular sieve is present in an amount of 40 to 80 wt% and the phosphotungstate is present in an amount of 20 to 60 wt%, based on the total weight of the catalyst.
4. A catalyst as claimed in claim 1 or 3, wherein the phosphotungstate is an alkali metal salt of phosphotungstic acid, preferably one or more of potassium phosphotungstate, rubidium phosphotungstate or caesium phosphotungstate.
5. The catalyst of any one of claims 1-4, wherein the short rod-shaped all-silicon mesoporous molecular sieve is prepared by a method comprising:
(I) mixing a silicon source and an acidic aqueous solution in the presence of a template agent, ammonium fluoride and heptane to obtain a mixture;
(II) crystallizing, washing, filtering, drying and removing the template agent to obtain the short rod-shaped full-silicon mesoporous molecular sieve.
6. The catalyst of claim 5, wherein the templating agent is polyoxyethylene-polyoxypropylene-polyoxyethylene;
preferably, the molar ratio of the template agent, ammonium fluoride, heptane, silicon source, water and hydrogen chloride is 1: (0.5-5): (10-200): (50-500): (3000-30000): (200-2000).
7. The catalyst according to any one of claims 1 to 6, wherein the specific surface area of the catalyst is 300-700m2Per g, pore volume of 0.8-1.6mL/g, average pore diameter of 8-13 nm; preferably, the specific surface area of the catalyst is 350-500m2Per g, the pore volume is 1-1.5mL/g, and the average pore diameter is 9-12 nm; more preferably, the specific surface area of the catalyst is 403-464m2Per g, pore volume of 1.1-1.3mL/g, average pore diameter of 9-10 nm.
8. A method for preparing the catalyst according to any one of claims 1 to 7, comprising:
(1) the method comprises the steps of contacting a short rod-shaped full-silicon mesoporous molecular sieve with an aqueous solution of metal salt for a first reaction, separating for the first time to obtain a solid product, and drying and roasting the solid product for the first time to obtain a catalyst intermediate.
(2) And (3) contacting the catalyst intermediate with an aqueous solution of phosphotungstic acid for a second reaction, performing second separation to obtain a solid product, and washing, drying and roasting the solid product for a second time to obtain the short rod-shaped all-silicon mesoporous material supported catalyst.
9. The production method according to claim 8, wherein, in step (1), the metal salt is selected from one or more of a carbonate, a chloride, a sulfate and a nitrate of a metal;
preferably, the metal is an alkali metal;
preferably, the concentration of the aqueous solution of the metal salt is 0.05-2.0 mol/L;
preferably, the weight ratio of the short rod-shaped all-silicon mesoporous molecular sieve to the aqueous solution of the metal salt is 1: (2-100);
preferably, the conditions of the first reaction include: the temperature is 30-120 ℃, and the time is 0.5-20 h;
preferably, the conditions of the first firing include: the temperature is 250 ℃ and 400 ℃, and the time is 3-10 h.
10. The production process according to claim 8, wherein in step (2), the concentration of the aqueous solution of phosphotungstic acid is 1 to 30%;
preferably, the weight ratio of the short rod-shaped all-silicon mesoporous molecular sieve to the aqueous solution of the phosphotungstic acid is 1: (5-50);
preferably, the conditions of the second reaction include: the temperature is 30-120 ℃, and the time is 0.5-20 h;
preferably, the conditions of the second roasting include: the temperature is 250 ℃ and 400 ℃, and the time is 3-10 h.
11. Use of a catalyst according to any one of claims 1 to 7 in an esterification synthesis reaction of methacrylic acid and methanol, wherein the esterification synthesis reaction comprises: methacrylic acid and methanol are contacted with the catalyst.
12. The use of claim 11, wherein the contacting conditions comprise: the contact temperature is 50-160 ℃, preferably 70-140 ℃; the contact pressure is 0.01-5.0MPa, preferably 0.1-3.0 MPa; the mass space velocity of the acetic acid is 0.01-30h-1Preferably 0.1 to 10h-1(ii) a The molar ratio of acetic acid to alcohol is 1 (0.1-20), preferably 1 (0.5-10).
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102950023A (en) * | 2011-08-31 | 2013-03-06 | 中国石油化工股份有限公司 | Load-type phosphotungstic acid catalyst and preparation method thereof as well as n-butyl acrylate preparation method |
| CN102962084A (en) * | 2011-08-31 | 2013-03-13 | 中国石油化工股份有限公司 | Supported phosphotungstic acid catalyst and preparation thereof, and preparation method of methyl acetate |
| CN103586077A (en) * | 2012-08-14 | 2014-02-19 | 中国石油化工股份有限公司 | Supported phospho-tungstic acid catalyst, preparation method thereof, applications thereof and preparation method of ethyl acetate |
| CN103586056A (en) * | 2012-08-14 | 2014-02-19 | 中国石油化工股份有限公司 | Supported phosphotungstic acid catalyst, preparation method and application thereof, and ethyl acetate preparation method |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102950023A (en) * | 2011-08-31 | 2013-03-06 | 中国石油化工股份有限公司 | Load-type phosphotungstic acid catalyst and preparation method thereof as well as n-butyl acrylate preparation method |
| CN102962084A (en) * | 2011-08-31 | 2013-03-13 | 中国石油化工股份有限公司 | Supported phosphotungstic acid catalyst and preparation thereof, and preparation method of methyl acetate |
| CN103586077A (en) * | 2012-08-14 | 2014-02-19 | 中国石油化工股份有限公司 | Supported phospho-tungstic acid catalyst, preparation method thereof, applications thereof and preparation method of ethyl acetate |
| CN103586056A (en) * | 2012-08-14 | 2014-02-19 | 中国石油化工股份有限公司 | Supported phosphotungstic acid catalyst, preparation method and application thereof, and ethyl acetate preparation method |
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