CN114515598B - Catalyst for methyl methacrylate synthesis reaction, and preparation method and application thereof - Google Patents
Catalyst for methyl methacrylate synthesis reaction, and preparation method and application thereof Download PDFInfo
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- CN114515598B CN114515598B CN202011305768.1A CN202011305768A CN114515598B CN 114515598 B CN114515598 B CN 114515598B CN 202011305768 A CN202011305768 A CN 202011305768A CN 114515598 B CN114515598 B CN 114515598B
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- alkyl sulfonate
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- 239000003054 catalyst Substances 0.000 title claims abstract description 119
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000011148 porous material Substances 0.000 claims abstract description 112
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 87
- 239000000741 silica gel Substances 0.000 claims abstract description 69
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 69
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 150000008052 alkyl sulfonates Chemical class 0.000 claims abstract description 32
- 238000009826 distribution Methods 0.000 claims abstract description 20
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 19
- 230000002902 bimodal effect Effects 0.000 claims abstract description 11
- 238000005886 esterification reaction Methods 0.000 claims description 33
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 24
- -1 sodium alkyl sulfonate Chemical class 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 22
- 230000032050 esterification Effects 0.000 claims description 21
- 239000011734 sodium Substances 0.000 claims description 20
- 229910052708 sodium Inorganic materials 0.000 claims description 20
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 15
- 238000000498 ball milling Methods 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 14
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 229910052746 lanthanum Inorganic materials 0.000 claims description 8
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 8
- 238000001694 spray drying Methods 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000012065 filter cake Substances 0.000 claims description 6
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical group [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 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
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 abstract description 5
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 239000002841 Lewis acid Substances 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 150000007517 lewis acids Chemical class 0.000 description 9
- 239000000377 silicon dioxide Substances 0.000 description 8
- PVGUQHABROGXFK-UHFFFAOYSA-K dodecyl sulfate lanthanum(3+) Chemical compound [La+3].CCCCCCCCCCCCOS([O-])(=O)=O.CCCCCCCCCCCCOS([O-])(=O)=O.CCCCCCCCCCCCOS([O-])(=O)=O PVGUQHABROGXFK-UHFFFAOYSA-K 0.000 description 7
- 239000012265 solid product Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000003729 cation exchange resin Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 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 5
- 238000011161 development Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 2
- 239000011968 lewis acid catalyst Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000010701 ester synthesis reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 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
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000003930 superacid Substances 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
Images
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
- B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/638—Pore volume more than 1.0 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
-
- 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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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
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- 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 catalyst for methyl methacrylate synthesis reaction, a preparation method and application thereof. The catalyst comprises a carrier and alkyl sulfonate supported on the carrier, wherein the carrier is ultra-macroporous silica gel, and the specific surface area of the ultra-macroporous silica gel is 200-400m 2 And/g, wherein the pore volume is 0.8-2mL/g, the pore diameters are in bimodal distribution, the first most probable pore diameter is 1-5nm, and the second most probable pore diameter is 20-50nm. The catalyst is used for the methacrylate reaction, 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 catalyst for methyl methacrylate synthesis reaction, a preparation method and application thereof.
Background
As an important organic chemical product and an important organic chemical raw material, the industrial production level and the production capacity of Methyl Methacrylate (MMA) have important influence on the development of chemical industry in China. In recent years, the demand of MMA at home and abroad is increased, the application field is continuously widened, and the rapid development of MMA industry is promoted. At present, the domestic methyl methacrylate production technology is still in the starting stage. The development of the methacrylate catalyst with independent intellectual property rights and the matched process are the development demands of MMA production industry in China.
Esterification catalysts are the core technology for MMA production. For the esterification reaction of methacrylic acid and methanol, the traditional production process using inorganic acid such as sulfuric acid, phosphoric acid, boric acid and the like as a catalyst is gradually eliminated, and the organic acid such as p-toluenesulfonic acid and the like as a catalyst has the defects of serious environmental pollution, low selectivity and difficult separation of products. In comparison, esterification catalysts for heterogeneous reactions are currently a relatively active area of research. In the recent report, researchers have tried to use acid resin, organic tin compound, rare earth solid super acid, lewis acid and other catalysts in the synthesis of carboxylic ester, and have all obtained meaningful experimental results. At present, acid cation exchange resin is widely used in industry for producing methyl methacrylate, and the cation exchange resin has the advantages of good stability, high selectivity, lower cost, easy separation and the like in esterification reaction. However, the cation exchange resin itself has poor heat resistance (generally, decomposition is carried out at a temperature of not higher than 250 ℃), a small specific surface area and a small pore volume, and the cation exchange resin is easily swelled, has poor reactivity as an esterification catalyst, and has low ester yield. Lewis acid catalysts are valued for high activity, good selectivity and mild reaction conditions, but common Lewis acid is unstable in water and is easy to react with water to deactivate. The salt of a lewis acid in combination with a surfactant is called a green lewis acid because it is not easily hydrolyzed, and its catalytic effect in organic synthesis is receiving increasing attention. Along with the increasing demand of MMA, the synthesis of methyl methacrylate by adopting the green environment-friendly process has wide prospect.
Therefore, it is an important working direction for researchers to develop esterification catalysts with excellent performance, to improve the reaction efficiency and to suppress the formation of by-products.
Disclosure of Invention
The invention aims to solve the problems of low methacrylic acid conversion rate and low methyl methacrylate yield in the existing methyl methacrylate production process, and provides a catalyst for methyl methacrylate synthesis reaction, and a preparation method and application thereof. The catalyst is used for the methacrylate reaction, 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 catalyst for methyl methacrylate synthesis reaction, wherein the catalyst comprises a carrier and an alkyl sulfonate supported on the carrier, wherein the carrier is ultra-macroporous silica gel, and the specific surface area of the ultra-macroporous silica gel is 200-400m 2 And/g, wherein the pore volume is 0.8-2mL/g, the pore diameters are in bimodal distribution, the first most probable pore diameter is 1-5nm, and the second most probable pore diameter is 20-50nm.
The second aspect of the present invention provides a method for preparing the catalyst, wherein the method comprises the following steps:
(1) Mixing ultra-macroporous silica gel with sodium alkyl sulfonate and water to obtain a mixture;
(2) Carrying out contact reaction on the aqueous solution of the metal salt and the mixture to obtain a product;
(3) Filtering, washing and drying the product to obtain the esterification catalyst.
In a third aspect, the present invention provides an application of the catalyst in an esterification synthesis reaction, wherein the esterification synthesis reaction includes: methacrylic acid and methanol are contacted with the catalyst.
Through the technical scheme, the technical scheme of the invention has the following advantages:
(1) The catalyst for the methyl methacrylate synthesis reaction provided by the invention has large pore diameter and large pore volume, and is beneficial to the diffusion of raw materials and product molecules in the esterification reaction process of methacrylic acid and methanol.
(2) The catalyst for the methyl methacrylate synthesis reaction provided by the invention has the active components of green Lewis acid, strong esterification catalytic capability, high conversion rate of methacrylic acid and high selectivity of methyl methacrylate.
(3) The catalyst provided by the invention has the advantages of easily available raw materials, simple preparation method and process, easily controlled conditions and good product repeatability.
(4) The catalyst provided by the invention is used for the methacrylate reaction, and has mild process 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 a graph showing pore size distribution of ultra-large pore silica gel A prepared in example 1 of the present invention and catalyst A for methyl methacrylate synthesis reaction.
Description of the reference numerals
(a) Is the pore size distribution diagram of the ultra-large pore silica gel A prepared in the embodiment 1 of the invention;
(b) Is the pore size distribution diagram of catalyst A for methyl methacrylate synthesis prepared in example 1 of the present invention.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the invention provides a catalyst for methyl methacrylate synthesis reaction, wherein the catalyst comprises a carrier and alkyl sulfonate supported on the carrier, wherein the carrier is ultra-macroporous silica gel, and the specific surface area of the ultra-macroporous silica gel is 200-400m 2 And/g, wherein the pore volume is 0.8-2mL/g, the pore diameters are in bimodal distribution, the first most probable pore diameter is 1-5nm, and the second most probable pore diameter is 20-50nm.
The inventors of the present invention found that: in the prior art, esterification catalysts used to produce methyl methacrylate are classified into two types, homogeneous and heterogeneous. 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 cost and good catalytic activity, but the defects of difficult separation of products and the catalyst, more side reactions, easy corrosion to equipment and the like are eliminated. Although the solid acid esterification catalyst solves the problems of difficult product separation and serious equipment corrosion, the catalyst is rarely applied to industrial production due to the defects of poor catalytic activity, higher reaction temperature, lower product selectivity and the like. In contrast to the above catalysts, the production of methyl methacrylate using acidic cation exchange resins as esterification catalysts is currently the main process for industrial application. The resin catalyst has the advantages of high selectivity, low cost, easy separation and the like, but the yield of methyl methacrylate is low in the process of the methacrylate esterification reaction, and the high temperature resistance is poor. The resin is an organic polymer material, is easy to swell in an organic solvent, is easy to deform and even decompose in a high-temperature environment, and is a main reason for 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.
The Lewis acid catalyst has high activity, good selectivity and mild reaction condition when catalyzing esterification reaction, but the catalyst is easy to be deactivated due to hydrolysis. Salts formed by the combination of lewis acids with surfactants are known as green lewis acids because they are not susceptible to hydrolysis. If a green Lewis acid which is not easily soluble in water is directly used as a catalyst in the ester synthesis reaction, the catalytic efficiency may be lowered due to uneven dispersion.
The inventors of the present invention found that the above-mentioned problems can be solved and the efficiency of the catalyst can be improved by selecting an appropriate carrier to disperse the catalyst well. Certain silica materials have the structural and high temperature resistant performance advantages of large specific surface area, large pore volume, as compared to resin catalysts. However, the silica surface having a basic skeleton structure composed of silicon and oxygen does not contain a functional group, and does not exhibit any activity in the esterification reaction. Therefore, silica of suitable structure is not suitable as a catalystThe catalyst is suitable for being used in MMA synthesis reaction, but is suitable for being used as a carrier to load green Lewis acid, so as to obtain the esterification catalyst with excellent catalytic performance. The specific surface area of the ultra-macroporous silica gel is 200-400m 2 The pore volume per gram is 0.8-2mL/g, the pore diameters are in bimodal distribution, the first most probable pore diameter is 1-5nm, the second most probable pore diameter is 20-50nm, and the catalyst is very suitable for the catalytic reaction with the participation of macromolecules. The basic structure of the ultra-macroporous silica gel is composed of a silica basic structure, belongs to an inorganic structure, and can not be swelled and deformed in an organic solvent, but also has better temperature resistance. In addition, alkyl sulfonates having good esterification catalytic properties, for example, lanthanum alkyl sulfonate, are not commercially available and can only be prepared in the laboratory. The resulting alkyl sulfonate (lanthanum) is insoluble in water and cannot be supported on a carrier by conventional impregnation methods.
Based on the above, the inventor creatively adopts a method for generating alkyl sulfonate in situ on the surface of a carrier, takes ultra-macroporous silica gel as the carrier, loads the alkyl sulfonate to prepare a catalyst with good dispersion, can be used for methyl methacrylate synthesis reaction, and can show good catalytic activity and ester selectivity.
According to the invention, the specific surface area of the ultra-macroporous silica gel is preferably 210-390m 2 The pore volume is 1.1-1.9mL/g, the first most probable pore diameter is 1.5-4nm, and the second most probable pore diameter is 22-40nm; more preferably, the specific surface area of the ultra-macroporous silica gel is 220-372m 2 And/g, wherein the pore volume is 1.2-1.8mL/g, the first most probable pore diameter is 2-3.4nm, and the second most probable pore diameter is 25-35nm. In the invention, the structural parameters of the ultra-macroporous silica gel are limited to be within the above ranges, so that the in-situ generation of the alkyl sulfonate on the surface of the carrier is facilitated, the supported alkyl sulfonate is well dispersed, and the supported alkyl sulfonate can show good catalytic activity and ester selectivity when being used for the synthesis reaction of methyl methacrylate.
According to the invention, the content of the ultra-macroporous silica gel is 40-70 wt% and the content of the alkyl sulfonate is 30-60 wt%, based on the total weight of the catalyst; preferably, the content of the ultra-macroporous silica gel is 45-65 wt% and the content of the alkyl sulfonate is 35-55 wt%, based on the total weight of the catalyst; more preferably, the content of the ultra-macroporous silica gel is 45.3 to 62.8 wt% and the content of the alkyl sulfonate is 37.2 to 54.7 wt% based on the total weight of the catalyst. In the present invention, the contents of the ultra-large pore silica gel and the alkyl sulfonate are controlled to be within the above-defined ranges, so that the prepared catalyst can exhibit excellent catalytic activity and ester selectivity when used for methyl methacrylate synthesis reaction.
According to the invention, the alkyl sulfonate is a linear alkyl sulfonate and/or a branched alkyl sulfonate; preferably, the alkyl sulfonate is a linear alkyl sulfonate; preferably, the alkyl in the alkyl sulfonate is selected from one or more of heptane, dodecyl, tetradecyl and octadecyl; more preferably, the sulfonate in the alkyl sulfonate is lanthanum sulfonate and/or cerium sulfonate, and still more preferably, the sulfonate in the alkyl sulfonate is lanthanum sulfonate.
According to the invention, the preparation method of the ultra-macroporous silica gel comprises the following steps:
(I) Contacting an inorganic silicon source with an acid agent in the presence of butanol and glycerol to obtain a mixture;
(II) filtering and washing the mixture to obtain a silica gel filter cake;
(III) ball milling and spray drying the silica gel filter cake to obtain the ultra-large pore silica gel.
The acid agent according to the present invention may be various substances or mixtures (e.g., solutions) conventionally used for adjusting pH. Preferably, the inorganic acid solution is selected from at least one aqueous solution of hydrochloric acid, sulfuric acid, nitric acid and hydrobromic acid. More preferably, the acid agent is an aqueous sulfuric acid solution.
According to the present invention, in the step (I), the inorganic silicon source, the acid agent, butanol and glycerol may be used in a weight ratio of 1: (0.05-0.5): (0.02-0.6): (0.02-0.6), preferably 1: (0.1-0.3): (0.06-0.4): (0.06-0.4).
According to the invention, the pH of the mixture is between 1.5 and 4.5, preferably between 2 and 4.
According to the invention, in step (I), the conditions of the contacting include: the temperature is 15-40 ℃ and the time is 1-3h; preferably, the temperature is 18-25℃and the time is 1.5-2 hours. In order to further facilitate uniform mixing of the substances, the mixing contact may be carried out under stirring.
According to the present invention, in the step (II), the washing conditions are not particularly limited, and for example, the washing process may include: after filtration, a solid product is obtained, which is repeatedly washed with distilled water (the washing times may be 2 to 10 times), and then suction filtration is performed.
According to the present invention, in step (III), the ball milling conditions include: the rotating speed of the grinding balls can be 300-500r/min, the temperature in the ball milling tank can be 30-80 ℃, and the ball milling time can be 2-10h; preferably, the rotating speed of the grinding balls can be 350-450r/min, the temperature in the ball milling tank can be 50-70 ℃, and the ball milling time can be 4-6h.
According to the invention, in step (III), the spray drying conditions comprise: the spray drying conditions may include: the temperature is 100-300 ℃, and the rotating speed of the rotation can be 10000-15000r/min; preferably, the spray drying conditions include: the temperature is 150-250 ℃, and the rotating speed is 11000-13000r/min.
According to the invention, the specific surface area of the catalyst for methyl methacrylate synthesis reaction is 150-400m 2 The pore volume is 0.5-2mL/g, the pore diameters are in bimodal distribution, the first most probable pore diameter is 1-3nm, and the second most probable pore diameter is 15-40nm; preferably, the specific surface area of the catalyst for methyl methacrylate synthesis reaction is 150-300m 2 Per gram, the pore volume is 0.6-1.5mL/g, the first most probable pore diameter is 1.2-3nm, and the second most probable pore diameter is 20-30nm; more preferably, the catalyst for methyl methacrylate synthesis reaction has a specific surface area of 171-283m 2 And/g, the pore volume is 0.8-1.4mL/g, the first most probable pore diameter is 1.6-2.9nm, and the second most probable pore diameter is 22-28nm.
In the present invention, the catalyst defined by the above specific parameters can exhibit excellent catalytic activity and ester selectivity when used for methyl methacrylate synthesis reaction.
The second aspect of the present invention provides a method for preparing the catalyst, wherein the method comprises the following steps:
(1) Mixing ultra-macroporous silica gel with sodium alkyl sulfonate and water to obtain a mixture;
(2) Carrying out contact reaction on the aqueous solution of the metal salt and the mixture to obtain a product;
(3) Filtering, washing and drying the product to obtain the esterification catalyst.
According to the invention, the sodium alkyl sulfonate is linear sodium alkyl sulfonate and/or branched sodium alkyl sulfonate; preferably, the sodium alkyl sulfonate is linear sodium alkyl sulfonate; preferably, the alkyl group in the sodium alkyl sulfonate is selected from one or more of heptane, dodecyl and tetradecyl.
According to the invention, in step (1), the weight ratio of the ultra-macroporous silica gel, the sodium alkyl sulfonate and water is 1: (0.1-5): (5-100), preferably 1: (0.2-3): (10-60); wherein the water is preferably deionized water.
According to the present invention, in step (1), the mixing conditions of the ultra-large pore silica gel, sodium alkyl sulfonate and water include: the temperature may be 40-100deg.C, preferably 60-90deg.C; the time may be 1 to 50 hours, preferably 5 to 30 hours. Preferably, in order to achieve better mixing effect, the mixing efficiency can be improved by rapid stirring or by means of ultrasonic means in the process of mixing the ultra-large pore silica gel, the sodium alkyl sulfonate and the deionized water.
According to the present invention, in step (2), an aqueous solution of a metal salt is preferably added dropwise to the mixture at a dropping rate of 0.5 to 2mL/min for contact reaction.
According to the present invention, in step (2), the metal salt is selected from one or more of chloride, sulfate and nitrate of a metal; preferably, the metal is lanthanum and/or cerium.
According to the invention, the concentration of the aqueous solution of the metal salt is 0.02 to 1.0mol/L, preferably 0.05 to 0.6mol/L.
According to the invention, the conditions of the contact reaction of said mixture with the aqueous metal salt solution include: the reaction temperature may be 40-100deg.C, preferably 60-90deg.C; the time may be 0.1 to 20 hours, preferably 0.5 to 10 hours. Preferably, in order to achieve a better contact reaction effect, the mixture may be rapidly stirred during the contact reaction with the aqueous metal salt solution.
According to the invention, the method of washing the solid product is not particularly required, for example: the solid product may be washed with deionized water, the volume ratio of deionized water to solid product may be 5-20, and the number of washes may be 2-8. Preferably, to achieve better washing results, rapid agitation may be used during the mixing of deionized water with the solid product.
According to the present invention, the drying conditions include: the temperature may be 120-230 ℃, preferably 150-200 ℃; the time may be 1 to 30 hours, preferably 3 to 20 hours.
In a third aspect, the present invention provides an application of the catalyst in an esterification synthesis reaction, wherein the esterification synthesis reaction includes: methacrylic acid and methanol are contacted with the catalyst.
According to the invention, the conditions of the contact reaction include: the contact temperature is 40-150 ℃, preferably 60-120 ℃; the contact pressure is 0.01-5MPa, preferably 0.1-3MPa; the mass airspeed of the methacrylic acid is 0.01 to 30h -1 Preferably 0.1-10h -1 The method comprises the steps of carrying out a first treatment on the surface of the The mass space velocity of the methanol is 0.01 to 50h -1 Preferably 0.1-30h -1 。
The present invention will be described in detail by examples.
In the following examples and comparative examples:
the pore structure parameter analysis of the samples was performed on an ASAP2020-M+C type adsorber available from Micromeritics, inc. The sample was vacuum degassed at 350 ℃ for 4 hours prior to measurement, the specific surface area of the sample was calculated using the BET method, and the pore volume was calculated using the BJH model. Elemental analysis experiments of the samples were performed on an Eagle III energy dispersive X-ray fluorescence spectrometer manufactured by EDAX, inc. of America.
The drying oven is manufactured by Shanghai-Heng scientific instrument Co., ltd, and the model is DHG-9030A.
The muffle furnace is available from CARBOLITE company under the model CWF1100.
The reagents used in examples and comparative examples were purchased from national pharmaceutical chemicals, inc., and the purity of the reagents was analytically pure.
Example 1
(1) Preparation of ultra-macroporous silica gel
50g of 15 wt% water glass, 10g of 12 wt% sulfuric acid solution, 10g of n-butanol and 10g of glycerol were mixed at 20℃and the pH was adjusted to 3 with 98 wt% sulfuric acid, and the mixture was allowed to react for 1.5 hours. The solid matter obtained by filtration was then washed with distilled water 8 times to obtain a silica gel cake. 10g of silica gel filter cake is put into a 100mL ball milling tank, wherein the ball milling tank is made of polytetrafluoroethylene, grinding balls are made of agate, the diameter of each grinding ball is 3mm, the number of the grinding balls is 1, and the rotating speed is 400r/min. The ball milling tank is closed, and ball milling is carried out for 5 hours at the temperature of 60 ℃ in the ball milling tank. And (3) spray-drying the ball-milled silica gel filter cake at the temperature of 200 ℃ at the rotating speed of 12000r/min to obtain the ultra-macroporous silica gel A.
FIG. 1 (a) is a pore size distribution diagram of ultra-large pore silica gel A. As can be seen from the pore size distribution diagram, the pore size distribution of the sample is wider, and accords with the pore channel characteristics of amorphous silica gel. The pore diameters are in bimodal distribution, the first most probable pore diameter is 3.1nm, and the second most probable pore diameter is 33nm.
The structural parameters of the ultra-macroporous silica gel a are listed in table 1.
(2) Preparation of the catalyst
10g of ultra-large pore silica gel A, 6g of sodium dodecyl sulfate and 400g of deionized water are mixed, stirred at 75 ℃ for 8 hours and uniformly mixed. 180mL of lanthanum chloride aqueous solution with the concentration of 0.2mol/L is slowly added into the mixture in a dropwise manner at the rate of 1mL/min, stirred at 75 ℃ for reaction for 3h, and cooled to room temperature. Standing at room temperature for 20h. The solid product is obtained by filtration, washed with deionized water for 6 times and dried at 180 ℃ for 20 hours to obtain the catalyst A.
The content of the ultra-large pore silica gel was 53.9% by weight and the content of lanthanum dodecylsulfate was 46.1% by weight, based on the total weight of the catalyst A.
FIG. 1 (b) is a pore size distribution diagram of catalyst A. As can be seen from the pore size distribution diagram, the catalyst basically maintains the pore canal structure of the ultra-large pore silica gel A, has wide pore size distribution and is in a double-peak form, wherein the first most probable pore diameter is 2.9nm, and the second most probable pore diameter is 28nm. Because the lanthanum dodecyl sulfate is loaded on the ultra-macroporous silica gel, not only is the lanthanum dodecyl sulfate dispersed on the outer surface of the silica gel, but also a certain space is occupied in the pore canal, and the specific surface area, the pore volume and the pore diameter of the catalyst are smaller than those of the ultra-macroporous silica gel carrier. The composition and structural parameters of catalyst a are listed in table 2.
(3) Evaluation of catalyst Performance in methyl methacrylate Synthesis reaction
The esterification reaction performance of the catalyst was evaluated on a fixed bed reactor. 5.0 g of catalyst A was charged into a stainless steel fixed bed reactor having an inner diameter of 8mm, a reaction temperature of 100℃and a reaction pressure of 0.3MPa, and a weight space velocity of methacrylic acid of 1.0h -1 The weight space velocity of methanol is 2.7h -1 The reaction time was 50 hours. After cooling the product was analyzed by Agilent 7890A gas chromatograph equipped with FFAP capillary chromatography column and hydrogen flame detector (FID), and quantitative analysis was performed using a calibration factor with programmed temperature. The results of the reaction evaluation are shown in Table 3.
Examples 2 to 4
Ultra-large pore silica gel and catalyst were prepared in the same manner as in example 1 except that:
changing each parameter in the preparation process of the ultra-macroporous silica gel in the step (1) of the example 1, and carrying out the examples 2-4 to obtain the ultra-macroporous silica gel B, C and D respectively; the structural parameters of the oversized silica B, C, D are listed in table 1.
By changing the parameters in the catalyst preparation process in the step (2) of the example 1, the catalysts B, C and D are obtained by carrying out the examples 2 to 4 respectively; the composition and structural parameters of catalyst B, C, D are listed in table 2.
The esterification reaction performance test of the catalyst B, C, D was performed in the same manner as in step (3) of example 1, and the reaction results are shown in table 3.
Comparative example 1
Ultra-large pore silica gel and catalyst were prepared in the same manner as in example 1 except that:
catalyst D1 was prepared by the method of step (2) in example 1, except that commercially available silica was used instead of the ultra-large pore silica gel A, omitting step (1) in example 1.
The commercially available silica content was 53.9% by weight and the lanthanum dodecylsulfate content was 46.1% by weight, based on the total weight of catalyst D1.
The esterification reaction performance test of catalyst D1 was conducted in the same manner as in step (3) of example 1, and the reaction results are shown in Table 3.
Comparative example 2
Ultra-large pore silica gel and catalyst were prepared in the same manner as in example 1 except that:
the oversized silica gel A was prepared by the method of step (1) in example 1. Catalyst D2 was prepared in the same manner as in step (2) in example 1 so that the content of ultra-large pore silica gel A was 75.5% by weight and the content of lanthanum dodecylsulfate was 24.5% by weight, based on the total weight of catalyst D2.
The esterification reaction performance test of catalyst D2 was conducted in the same manner as in step (3) of example 1, and the reaction results are shown in Table 3.
Comparative example 3
Ultra-large pore silica gel and catalyst were prepared in the same manner as in example 1 except that:
the procedure of step (1) in example 1 was changed so that the specific surface area of the prepared ultra-large pore silica gel D3 was 300m 2 The pore volume is 1.0mL/g, the pore diameters are in bimodal distribution, the first most probable pore diameter is 5nm, and the second most probable pore diameter is 70nm.
Catalyst D3 was prepared in the same manner as in step (2) of example 1, and the specific surface area of the catalyst thus prepared was 300m 2 Per g, pore volume of 1.0mL/g, pore diameter of bimodal distribution, first most probable pore diameter of 7nm, second most probable pore diameterThe pore size can be 15nm.
The esterification reaction performance test of catalyst D3 was conducted in the same manner as in step (3) of example 1, and the reaction results are shown in Table 3.
Comparative example 4
Ultra-large pore silica gel and catalyst were prepared in the same manner as in example 1 except that:
the procedure of step (1) in example 1 was modified, specifically:
(2) Preparation of the catalyst
10g of ultra-large pore silica gel A, 6g of sodium dodecyl sulfate and 400g of deionized water are mixed, stirred at 75 ℃ for 8 hours and uniformly mixed. The mixture was immersed in 180mL of a lanthanum chloride aqueous solution having a concentration of 0.2mol/L at 75℃while maintaining the temperature of the mixture at 75℃and stirred for 3 hours, followed by cooling to room temperature. Standing at room temperature for 20h. The solid product was obtained by filtration, washed 6 times with deionized water and dried at 180℃for 20h to give catalyst D4.
The result was that the content of the ultra-large pore silica gel was 20% by weight and the content of lanthanum dodecylsulfate was 10% by weight, based on the total weight of the catalyst D4.
The specific surface area of the catalyst prepared was 250m 2 The pore volume is 1.0mL/g, the pore diameters are in bimodal distribution, the first most probable pore diameter is 5nm, and the second most probable pore diameter is 15nm.
The esterification reaction performance test of catalyst D4 was conducted in the same manner as in step (3) of example 1, and the reaction results are shown in Table 3.
TABLE 1
TABLE 2
TABLE 3 Table 3
As can be seen from Table 3, the catalyst provided by the invention can directly convert methacrylic acid and methanol to methyl methacrylate. The catalyst provided by the invention can obtain the methacrylic acid conversion rate of more than 92.7% and the methyl methacrylate selectivity of more than 98.5%.
As can be seen from the data of comparative example 1 and comparative example 1, if the esterification catalyst was prepared using commercially available silica instead of ultra-large pore silica gel, the conversion of methacrylic acid and the selectivity to methyl methacrylate were low.
The data of comparative example 1 and comparative example 2 show that the contents of ultra-large pore silica gel a and lanthanum dodecylsulfate are not within the range defined by the present invention, resulting in lower methacrylic acid conversion and methyl methacrylate selectivity.
As can be seen from the data of comparative examples 1 and 3, the structural parameters of the ultra-large pore silica gel a and the prepared catalyst are not within the range defined by the present invention, and as a result, the conversion of methacrylic acid and the selectivity of methyl methacrylate are low.
As can be seen from the data of comparative examples 1 and 4, since the catalyst was not prepared by the method of the present invention, the conversion of methacrylic acid and the selectivity of methyl methacrylate were low.
The result shows that the esterification catalyst obtained by taking the ultra-macroporous silica gel as the carrier to load the lanthanum alkyl sulfonate has excellent performance.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (19)
1. A catalyst for synthesizing methyl methacrylate is characterized in thatThe catalyst comprises a carrier and alkyl sulfonate supported on the carrier, wherein the carrier is ultra-macroporous silica gel, and the specific surface area of the ultra-macroporous silica gel is 200-400m 2 The pore volume is 0.8-2mL/g, the pore diameters are in bimodal distribution, the first most probable pore diameter is 1-5nm, and the second most probable pore diameter is 20-50nm; the alkyl sulfonate is linear alkyl sulfonate and/or branched alkyl sulfonate; the alkyl in the alkyl sulfonate is selected from one or more of heptane, dodecyl, tetradecyl and octadecyl; the sulfonate in the alkyl sulfonate is lanthanum sulfonate and/or cerium sulfonate.
2. The catalyst according to claim 1, wherein the ultra-macroporous silica gel has a specific surface area of 210-390m 2 And/g, wherein the pore volume is 1.1-1.9mL/g, the first most probable pore diameter is 1.5-4nm, and the second most probable pore diameter is 22-40nm.
3. The catalyst of claim 1, wherein the ultra-large pore silica gel is present in an amount of 40-70 wt% and the alkyl sulfonate is present in an amount of 30-60 wt%, based on the total weight of the catalyst.
4. A catalyst according to claim 3, wherein the content of the ultra-macroporous silica gel is 45-65% by weight and the content of the alkyl sulfonate is 35-55% by weight, based on the total weight of the catalyst.
5. The catalyst of claim 1, wherein the alkyl sulfonate is a linear alkyl sulfonate.
6. The catalyst of claim 1 or 4, wherein the preparation method of the ultra-macroporous silica gel comprises:
(I) Contacting an inorganic silicon source with an acid agent in the presence of butanol and glycerol to obtain a mixture;
(II) filtering and washing the mixture to obtain a silica gel filter cake;
(III) ball milling and spray drying the silica gel filter cake to obtain the ultra-large pore silica gel.
7. The catalyst of claim 6, wherein in step (I), the inorganic silicon source, the acid agent, butanol and glycerol are used in an amount of 1 by weight: (0.05-0.5): (0.02-0.6): (0.02-0.6); the pH value of the mixture is 1.5-4.5;
in step (I), the contacting conditions include: the temperature is 15-40 ℃ and the time is 1-3h;
in step (III), the ball milling conditions include: the rotating speed is 300-500r/min, the temperature in the ball milling tank is 30-80 ℃, and the ball milling time is 2-10h;
in step (III), the spray drying conditions include: the rotation speed is 10000-15000r/min, and the temperature is 100-300 ℃.
8. The catalyst according to claim 1, wherein the catalyst for methyl methacrylate synthesis reaction has a specific surface area of 150 to 400m 2 And/g, wherein the pore volume is 0.5-2mL/g, the pore diameters are in bimodal distribution, the first most probable pore diameter is 1-3nm, and the second most probable pore diameter is 15-40nm.
9. The catalyst according to claim 8, wherein the catalyst for methyl methacrylate synthesis reaction has a specific surface area of 150 to 300m 2 And/g, the pore volume is 0.6-1.5mL/g, the first most probable pore diameter is 1.2-3nm, and the second most probable pore diameter is 20-30nm.
10. The catalyst according to claim 9, wherein the catalyst for methyl methacrylate synthesis reaction has a specific surface area of 171-283m 2 And/g, the pore volume is 0.8-1.4mL/g, the first most probable pore diameter is 1.6-2.9nm, and the second most probable pore diameter is 22-28nm.
11. A process for preparing a catalyst as claimed in any one of claims 1 to 10, comprising:
(1) Mixing ultra-macroporous silica gel with sodium alkyl sulfonate and water to obtain a mixture; the sodium alkyl sulfonate is straight-chain sodium alkyl sulfonate and/or branched-chain sodium alkyl sulfonate; the alkyl in the sodium alkyl sulfonate is selected from one or more of heptane, dodecyl and tetradecyl;
(2) Carrying out contact reaction on the aqueous solution of the metal salt and the mixture to obtain a product; the metal salt is selected from one or more of chloride, sulfate and nitrate of metal; the metal is lanthanum and/or cerium;
(3) Filtering, washing and drying the product to obtain the esterification catalyst.
12. The method according to claim 11, wherein the sodium alkyl sulfonate is a linear sodium alkyl sulfonate.
13. The preparation method of claim 11, wherein in step (1), the weight ratio of the ultra-macroporous silica gel, the sodium alkyl sulfonate and water is 1: (0.1-5): (5-100).
14. The preparation method of claim 13, wherein the weight ratio of the ultra-macroporous silica gel, the sodium alkyl sulfonate and water is 1: (0.2-3): (10-60).
15. The production method according to claim 11, wherein the concentration of the aqueous solution of the metal salt is 0.02 to 1.0mol/L.
16. The method of claim 11, wherein the contacting conditions comprise: the temperature is 40-100deg.C, and the time is 0.1-20h.
17. Use of the catalyst of any one of claims 1-10 in an esterification synthesis reaction, wherein the esterification synthesis reaction comprises: methacrylic acid and methanol are contacted with the catalyst.
18. The use of claim 17, wherein the conditions of the contact reaction comprise: the contact temperature is 40-150 ℃; the contact pressure is 0.01-5MPa; the mass airspeed of the methacrylic acid is 0.01 to 30h -1 The method comprises the steps of carrying out a first treatment on the surface of the The mass space velocity of the methanol is 0.01 to 50h -1 。
19. The use of claim 18, wherein the conditions of the contact reaction comprise: the contact temperature is 60-120 ℃; the contact pressure is 0.1-3MPa; the mass airspeed of the methacrylic acid is 0.1 to 10h -1 The method comprises the steps of carrying out a first treatment on the surface of the The mass space velocity of the methanol is 0.1 to 30h -1 。
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| US8314045B1 (en) * | 2009-10-27 | 2012-11-20 | Entreprises Sinoncelli S.A.R.L. | Solid acid catalyst |
| WO2011108347A1 (en) * | 2010-03-05 | 2011-09-09 | Ｊｘ日鉱日石エネルギー株式会社 | Fischer-tropsch synthesis catalyst, manufacturing method therefor, and hydrocarbon manufacturing method |
| CN108722402A (en) * | 2017-04-20 | 2018-11-02 | 中国石油化工股份有限公司 | A kind of method of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane |
| CN108786897A (en) * | 2017-05-05 | 2018-11-13 | 中国石油化工股份有限公司 | The method of loaded catalyst and its preparation method and application and preparing propylene by dehydrogenating propane |
| CN108786864A (en) * | 2017-05-05 | 2018-11-13 | 中国石油化工股份有限公司 | The method of loaded catalyst and its preparation method and application and preparing propylene by dehydrogenating propane |
| CN108855201A (en) * | 2017-05-10 | 2018-11-23 | 中国石油化工股份有限公司 | The method of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane |
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