CN114515598A - 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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- CN114515598A CN114515598A CN202011305768.1A CN202011305768A CN114515598A CN 114515598 A CN114515598 A CN 114515598A CN 202011305768 A CN202011305768 A CN 202011305768A CN 114515598 A CN114515598 A CN 114515598A
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- catalyst
- silica gel
- alkyl sulfonate
- pore diameter
- methyl methacrylate
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- 239000003054 catalyst Substances 0.000 title claims abstract description 117
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000011148 porous material Substances 0.000 claims abstract description 107
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 84
- 239000000741 silica gel Substances 0.000 claims abstract description 68
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 68
- 238000005886 esterification reaction Methods 0.000 claims abstract description 38
- 150000008052 alkyl sulfonates Chemical class 0.000 claims abstract description 35
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 22
- 230000002902 bimodal effect Effects 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims description 40
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 230000032050 esterification Effects 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 229910052708 sodium Inorganic materials 0.000 claims description 19
- 239000011734 sodium Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- -1 sodium alkyl sulfonate Chemical class 0.000 claims description 16
- 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 14
- 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
- 238000009826 distribution Methods 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 8
- 229910052746 lanthanum Inorganic materials 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000012065 filter cake Substances 0.000 claims description 7
- 238000001694 spray drying Methods 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 238000001035 drying Methods 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
- 239000002253 acid Substances 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
- 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
- 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
- 150000002823 nitrates Chemical class 0.000 claims 1
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 125000005395 methacrylic acid group Chemical group 0.000 abstract 1
- 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
- 230000000052 comparative effect Effects 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
- 238000004519 manufacturing process Methods 0.000 description 9
- 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
- 239000000243 solution Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- 239000012265 solid product Substances 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- LDEQKGLOBJBYQW-UHFFFAOYSA-K dodecane-1-sulfonate lanthanum(3+) Chemical compound [La+3].C(CCCCCCCCCCC)S(=O)(=O)[O-].C(CCCCCCCCCCC)S(=O)(=O)[O-].C(CCCCCCCCCCC)S(=O)(=O)[O-] LDEQKGLOBJBYQW-UHFFFAOYSA-K 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 238000011161 development Methods 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
- 230000002378 acidificating effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- 239000011973 solid acid Substances 0.000 description 3
- 238000003756 stirring Methods 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
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 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
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 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
- 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
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 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
- 230000015572 biosynthetic process 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
- 239000013043 chemical agent Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003247 decreasing effect Effects 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
- 239000000499 gel 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
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 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
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing 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
- 239000007787 solid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000001179 sorption measurement Methods 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
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- B01J35/615—
-
- B01J35/635—
-
- B01J35/638—
-
- B01J35/647—
-
- 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
Abstract
The invention relates to the field of fine chemical engineering, and discloses a catalyst for methyl methacrylate synthesis reaction, and a preparation method and application thereof. The catalyst comprises a carrier and alkyl sulfonate loaded on the carrier, wherein the carrier is macroporous silica gel, and the specific surface area of the macroporous silica gel is 200-400m2The pore volume is 0.8-2mL/g, the pore diameter is bimodal, the first most probable pore diameter is 1-5nm, and the second most probable pore diameter is 20-50 nm. The catalyst is used for the esterification reaction of methacrylic acid, and can obtain higher methacrylic acidConversion 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 and a preparation method and application thereof.
Background
As an important organic chemical product and organic chemical raw material, the industrial production level and 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 widened continuously, 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.
Esterification catalysts are the core technology for MMA production. For esterification reaction of methacrylic acid and methanol, the traditional production process using inorganic acids such as sulfuric acid, phosphoric acid, boric acid and the like as catalysts is gradually eliminated, and the organic acids such as p-toluenesulfonic acid and the like as catalysts have the defects of serious environmental pollution, low selectivity and difficult product separation. In contrast, esterification catalysts for heterogeneous reactions are currently an active area of research. In recent reports, researchers have tried to use catalysts such as acidic resins, organic tin compounds, rare earth solid superacids, lewis acids, etc. in the synthesis of carboxylic esters, and all have obtained significant experimental results. At present, the production of methyl methacrylate is generally carried out by industrially using acidic cation exchange resin, and the cation exchange resin has the advantages of good stability, high selectivity, lower 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. Lewis acid catalysts are regarded as important because of their high activity, good selectivity and mild reaction conditions, but common lewis acids are unstable in water and are easily deactivated by reaction with water. Salts formed by combining lewis acids with surfactants are called green lewis acids because they are not easily hydrolyzed, and their catalytic action in organic synthesis is receiving increasing attention. With the increasing demand of MMA, the green and environment-friendly process is adopted to synthesize methyl methacrylate, which has a broad prospect.
Therefore, it is an important work direction for researchers to develop an esterification catalyst having excellent performance, to improve reaction efficiency, and to suppress the generation of by-products.
Disclosure of Invention
The invention aims to overcome 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 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 catalyst for methyl methacrylate synthesis reaction, wherein the catalyst comprises a carrier and an alkyl sulfonate supported on the carrier, wherein the carrier is a super-macroporous silica gel, and the specific surface area of the super-macroporous silica gel is 200-400m2The pore volume is 0.8-2mL/g, the pore diameter is bimodal, the first most probable pore diameter is 1-5nm, and the second most probable pore diameter is 20-50 nm.
In a second aspect, the invention provides a preparation method of the catalyst, wherein the preparation method comprises:
(1) mixing the super-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) and filtering, washing and drying the product to obtain the esterification catalyst.
In a third aspect, the present invention provides a use of the aforementioned catalyst in an esterification reaction, wherein the esterification reaction comprises: and (3) carrying out contact reaction on methacrylic acid and methanol with the catalyst.
Through the technical scheme, the technical scheme provided by the invention has the following advantages:
(1) the catalyst for methyl methacrylate synthesis reaction provided by the invention has large pore diameter and large pore volume, and is helpful for the diffusion of raw material and product molecules in the esterification reaction process of methacrylic acid and methanol.
(2) The catalyst for methyl methacrylate synthesis reaction provided by the invention has the advantages that the supported active component is green Lewis acid, the esterification catalytic capability is strong, the methacrylic acid conversion rate is high, and the methyl methacrylate selectivity is high.
(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 esterification reaction of methacrylic acid, the process conditions are mild, and the requirements on reaction devices are not high.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
FIG. 1 is a graph showing the distribution of pore sizes of the ultra-large pore silica gel A prepared in example 1 of the present invention and the catalyst A used in the synthesis reaction of methyl methacrylate.
Description of the reference numerals
(a) Is the pore size distribution diagram of the ultra-macroporous silica gel A prepared in the embodiment 1 of the invention;
(b) is a pore size distribution diagram of the catalyst a for the synthesis reaction of methyl methacrylate 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 catalyst for methyl methacrylate synthesis reaction, wherein the catalyst comprises a carrier and alkyl sulfonate loaded on the carrier, wherein the carrier is macroporous silica gel,the specific surface area of the super-macroporous silica gel is 200-400m2The pore volume is 0.8-2mL/g, the pore diameter is bimodal, the first most probable pore diameter is 1-5nm, and the second most probable pore diameter is 20-50 nm.
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 solid acid esterification catalyst is rarely applied to industrial production due to the defects of poor catalytic activity, higher reaction temperature, lower product selectivity and the like. 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.
The Lewis acid catalyst has high activity, good selectivity and mild reaction conditions when used for catalyzing esterification reaction, but the catalyst is easy to be inactivated due to hydrolysis. The salt formed by combining the lewis acid with the surfactant is referred to as a green lewis acid because it is 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 decreased due to non-uniform dispersion.
The inventors of the present invention have found that the catalyst can be divided well by selecting a suitable supportThe problems can be solved and the efficiency of the catalyst is improved. Certain silica materials have structural advantages of large specific surface area, large pore volume, and performance advantages of high temperature resistance 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, the silica with proper structure is not suitable for being directly applied to the synthesis reaction of MMA as a catalyst, but is suitable for being used as a carrier to load green Lewis acid, and further an esterification catalyst with excellent catalytic performance is obtained. The specific surface area of the super-macroporous silica gel is 200-400m2The pore volume is 0.8-2mL/g, the pore diameter is in bimodal distribution, the first most probable pore diameter is 1-5nm, and the second most probable pore diameter is 20-50nm, so that the catalyst is very suitable for catalytic reaction with macromolecules. The basic structure of the ultra-macroporous silica gel is composed of a silica basic structure, belongs to an inorganic structure, and not only can not swell and deform in an organic solvent, but also has better temperature resistance. In addition, alkylsulfonates having good esterification catalytic properties, e.g., lanthanum alkylsulfonates, are not commercially available and can only be prepared in the laboratory. The obtained alkylsulfonate (lanthanum) is insoluble in water and cannot be supported on a carrier by a conventional impregnation method.
Based on the above, the inventor of the present invention creatively adopts a method of in-situ generation of alkyl sulfonate on the surface of a carrier, uses the super-macroporous silica gel as the carrier, and loads the alkyl sulfonate to prepare a catalyst with good dispersion, so that the catalyst 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 super-macroporous silica gel is preferably 210-390m2(ii)/g, the pore volume is from 1.1 to 1.9mL/g, the first mode pore size is from 1.5 to 4nm, and the second mode pore size is from 22 to 40 nm; more preferably, the specific surface area of the super-macroporous silica gel is 220-372m2The pore volume is 1.2-1.8mL/g, the first mode pore diameter is 2-3.4nm, and the second mode pore diameter is 25-35 nm. In the invention, the structural parameters of the ultra-macroporous silica gel are limited to be within the range, which is more beneficial to being on a carrier tableThe alkyl sulfonate is generated in situ, and the loaded alkyl sulfonate is well dispersed, so that the catalyst can show good catalytic activity and ester selectivity when being used for methyl methacrylate synthesis reaction.
According to the invention, the content of the super 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, based on the total weight of the catalyst, the content of the macroporous silica gel is 45-65 wt%, and the content of the alkyl sulfonate is 35-55 wt%; more preferably, the content of the super macroporous silica gel is 45.3-62.8 wt% and the content of the alkyl sulfonate is 37.2-54.7 wt% based on the total weight of the catalyst. In the invention, the contents of the super-macroporous silica gel and the alkyl sulfonate are controlled within the limited range, so that the prepared catalyst can be used for methyl methacrylate synthesis reaction, and can show good catalytic activity and ester selectivity.
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 group 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 super-macroporous silica gel comprises the following steps:
(I) in the presence of butanol and glycerol, contacting an inorganic silicon source with an acid agent to obtain a mixture;
(II) filtering and washing the mixture to obtain a silica gel filter cake;
and (III) carrying out ball milling and spray drying on the silica gel filter cake to obtain the super-macroporous silica gel.
According to the present invention, the acidic agent may be any of 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 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 said contacting comprise: the temperature is 15-40 ℃, and the time is 1-3 h; preferably, the temperature is 18-25 ℃ and the time is 1.5-2 h. The mixing contact may be carried out under stirring conditions in order to further facilitate uniform mixing between the substances.
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 number of washing times may be 2 to 10 times), and then subjected to suction filtration.
According to the present invention, in step (III), the ball milling conditions include: the rotation speed of the grinding ball can be 300-; preferably, the rotation speed of the grinding ball can be 350-450r/min, the temperature in the ball milling tank can be 50-70 ℃, and the ball milling time can be 4-6 h.
According to the present invention, in step (III), the spray-drying conditions include: the conditions of the spray drying may include: the temperature is 100-300 ℃, and the rotating speed can be 10000-15000 r/min; preferably, the spray drying conditions include: the temperature is 150-250 ℃, and the rotating speed is 11000-13000 r/min.
According to the invention, the specific surface area of the catalyst for the methyl methacrylate synthesis reaction is 150-400m2The pore volume is 0.5-2mL/g, the pore diameter is bimodal distribution, the first most probable pore diameter is 1-3nm, and the second most probable pore diameter is 15-40 nm; preferably, said catalysis for the synthesis reaction of methyl methacrylateThe specific surface area of the agent is 150-300m2(ii)/g, pore volume of 0.6-1.5mL/g, first mode pore diameter of 1.2-3nm, second mode pore diameter of 20-30 nm; more preferably, the specific surface area of the catalyst for the methyl methacrylate synthesis reaction is 171-283m2(ii)/g, pore volume of 0.8-1.4mL/g, first mode pore diameter of 1.6-2.9nm, second mode pore diameter of 22-28 nm.
In the invention, the catalyst defined by the specific parameters can show good catalytic activity and ester selectivity when being used for methyl methacrylate synthesis reaction.
In a second aspect, the invention provides a preparation method of the catalyst, wherein the preparation method comprises:
(1) mixing the super-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) and filtering, washing and drying the product to obtain the esterification catalyst.
According to the invention, the sodium alkyl sulfonate is linear alkyl sodium sulfonate and/or branched alkyl sodium sulfonate; preferably, the sodium alkyl sulfonate is sodium linear 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 the step (1), the weight ratio of the super-macroporous silica gel to the sodium alkyl sulfonate to the water is 1: (0.1-5): (5-100), preferably 1: (0.2-3): (10-60); among them, the water is preferably deionized water.
According to the invention, in the step (1), the mixing conditions of the ultra-large pore silica gel, the sodium alkyl sulfonate and the water comprise: the temperature can be 40-100 ℃, preferably 60-90 ℃; the time can be 1 to 50h, preferably 5 to 30 h. Preferably, in order to achieve a better mixing effect, the mixing efficiency can be improved by rapid stirring or ultrasonic means in the process of mixing the ultra-macroporous silica gel, the sodium alkylsulfonate and the deionized water.
According to the present invention, in the step (2), preferably, an aqueous solution of a metal salt is dropwise added to the mixture to carry out the contact reaction, wherein the dropwise addition rate is 0.5 to 2 mL/min.
According to the invention, in the step (2), the metal salt is selected from one or more of chloride, sulfate and nitrate of the metal; preferably, the metal is lanthanum and/or cerium.
According to the invention, the concentration of the aqueous solution of the metal salt is between 0.02 and 1.0mol/L, preferably between 0.05 and 0.6 mol/L.
According to the invention, the reaction conditions of the contact of the mixture with the aqueous solution of the metal salt comprise: the reaction temperature can be 40-100 ℃, and preferably 60-90 ℃; the time can be from 0.1 to 20 hours, preferably from 0.5 to 10 hours. Preferably, in order to achieve better contact reaction effect, the mixture can be rapidly stirred during the contact reaction with the aqueous solution of the metal salt.
According to the present invention, 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. Preferably, the deionized water is rapidly stirred during the mixing with the solid product for better washing effect.
According to the invention, the drying conditions comprise: the temperature can be 120-230 ℃, and preferably 150-200 ℃; the time can be 1 to 30h, preferably 3 to 20 h.
In a third aspect, the present invention provides a use of the aforementioned catalyst in an esterification synthesis reaction, wherein the esterification synthesis reaction comprises: and (3) carrying out contact reaction on methacrylic acid and methanol 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 0.1-3 MPa; the mass space velocity of the methacrylic acid is 0.01-30h-1Preferably 0.1 to 10h-1(ii) a The mass space velocity of the methanol is 0.01-50h-1Preferably 0.1 to 30h-1。
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples:
the pore structure parameter analysis of the samples was performed on an adsorption apparatus model ASAP2020-M + C, available from Micromeritics, USA. The sample was degassed at 350 ℃ for 4 hours under vacuum before measurement, and the specific surface area of the sample was calculated by the BET method and the pore volume was calculated by the BJH model. The elemental analysis experiments of 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 reagents used in the 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 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 subjected to a contact reaction for 1.5 hours. The solid material obtained by filtration was then washed 8 times with distilled water to obtain a silica gel filter cake. And (3) putting 10g of the silica gel filter cake 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 400 r/min. Sealing the ball milling tank, and ball milling for 5h in the ball milling tank at the temperature of 60 ℃. And (3) spray drying the silica gel filter cake subjected to ball milling at the temperature of 200 ℃ at the rotating speed of 12000r/min to obtain the super-macroporous silica gel A.
FIG. 1(a) is a diagram showing the distribution of pore sizes of the ultra-large pore silica gel A. The pore size distribution diagram shows that the sample has wider pore size distribution and accords with the pore channel characteristics of amorphous silica gel. The pore diameter is in bimodal distribution, the first most probable pore diameter is 3.1nm, and the second most probable pore diameter is 33 nm.
The structural parameters of the ultra-macroporous silica gel a are listed in table 1.
(2) Preparation of the catalyst
10g of the ultra-macroporous silica gel A, 6g of sodium dodecyl sulfate and 400g of deionized water are mixed, stirred for 8 hours at 75 ℃ and mixed uniformly. Keeping the temperature of the mixture at 75 ℃, slowly dripping 180mL of lanthanum chloride aqueous solution with the concentration of 0.2mol/L into the mixture at the dripping speed of 1mL/min, stirring the mixture at 75 ℃ for reaction for 3h, and then cooling the mixture to room temperature. Standing at room temperature for 20 h. Filtering to obtain a solid product, washing with deionized water for 6 times, and drying at 180 ℃ for 20 hours to obtain the catalyst A.
Based on the total weight of the catalyst A, the content of the macroporous silica gel is 53.9 weight percent, and the content of the lanthanum dodecyl sulfonate is 46.1 weight percent.
FIG. 1(b) is a pore size distribution diagram of catalyst A. The pore size distribution diagram shows that the catalyst basically keeps the pore channel structure of the ultra-large pore silica gel A, the pore size distribution is wide, the catalyst is in a bimodal form, the first most probable pore size is 2.9nm, and the second most probable pore size is 28 nm. Because the lanthanum dodecyl sulfonate is loaded on the ultra-large pore silica gel, not only is dispersed on the outer surface of the silica gel, but also enters the pore canal to occupy a certain space, the specific surface area, the pore volume and the pore diameter of the catalyst are all smaller than those of the ultra-large pore 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 performance of the esterification reaction of the catalyst was evaluated on a fixed bed reactor. 5.0 g of the 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. The reaction evaluation results are shown in Table 3.
Examples 2 to 4
An ultra-large pore silica gel and a catalyst were prepared in the same manner as in example 1, except that:
changing various parameters in the preparation process of the super-macroporous silica gel in the step (1) of the embodiment 1, and carrying out the embodiments 2 to 4 to respectively obtain the super-macroporous silica gel B, C and D; the structural parameters of macroporous silica gel B, C, D are set forth in Table 1.
Carrying out examples 2-4 while varying the parameters during the preparation of the catalyst in step (2) of example 1, to obtain catalysts B, C and D, respectively; the composition and structural parameters of catalyst B, C, D are set forth in Table 2.
The esterification performance test of the catalyst B, C, D was carried out in the same manner as in the step (3) in example 1, and the reaction results are shown in Table 3.
Comparative example 1
An ultra-large pore silica gel and a catalyst were prepared in the same manner as in example 1, except that:
catalyst D1 was prepared by the method of example 1, step (2), eliminating step (1) from example 1, except that commercial silica was used instead of the extra large pore silica gel A.
The commercial silica content was 53.9 wt.% and the lanthanum dodecylsulfonate content was 46.1 wt.% based on the total weight of catalyst D1.
The esterification performance test of the catalyst D1 was carried out in the same manner as in the step (3) in example 1, and the reaction results are shown in Table 3.
Comparative example 2
An ultra-large pore silica gel and a catalyst were prepared in the same manner as in example 1, except that:
supermacroporous silica gel A was prepared as described in step (1) of example 1. Catalyst D2 was prepared in accordance with the procedure set forth in step (2) of example 1 so that the content of extra-large pore silica gel A was 75.5% by weight and the content of lanthanum dodecylsulfonate was 24.5% by weight, based on the total weight of catalyst D2.
The esterification performance test of the catalyst D2 was carried out in the same manner as in the step (3) in example 1, and the reaction results are shown in Table 3.
Comparative example 3
An ultra-large pore silica gel and a catalyst were prepared in the same manner as in example 1, except that:
the method of step (1) in example 1 was modified so that the prepared ultra large pore siliconThe specific surface area of the gel D3 was 300m2The pore volume is 1.0mL/g, the pore diameters are distributed in a bimodal manner, the first mode pore diameter is 5nm, and the second mode pore diameter is 70 nm.
Catalyst D3 was prepared in accordance with the procedure in step (2) of example 1, so that a catalyst having a specific surface area of 300m was prepared2The pore volume is 1.0mL/g, the pore diameters are distributed in a bimodal manner, the first mode pore diameter is 7nm, and the second mode pore diameter is 15 nm.
The esterification performance test of the catalyst D3 was carried out in the same manner as in the step (3) in example 1, and the reaction results are shown in Table 3.
Comparative example 4
An ultra-large pore silica gel and a catalyst were prepared in the same manner as in example 1, except that:
the method of step (1) in example 1 was modified, specifically:
(2) preparation of the catalyst
10g of the ultra-macroporous silica gel A, 6g of sodium dodecyl sulfate and 400g of deionized water are mixed, stirred for 8 hours at 75 ℃ and mixed uniformly. The mixture was immersed in 180mL of a 0.2mol/L aqueous lanthanum chloride solution while maintaining the mixture at 75 ℃, stirred at 75 ℃ for 3 hours, and then cooled to room temperature. Standing at room temperature for 20 h. The solid product is obtained by filtration, washed by deionized water for 6 times and dried for 20h at 180 ℃ to obtain the catalyst D4.
As a result, the content of the extra large pore silica gel was 20% by weight and the content of the lanthanum dodecylsulfonate was 10% by weight based on the total weight of the catalyst D4.
And the specific surface area of the prepared catalyst is 250m2The pore volume is 1.0mL/g, the pore diameters are distributed in a bimodal manner, the first mode pore diameter is 5nm, and the second mode pore diameter is 15 nm.
The esterification performance test of the catalyst D4 was carried out in the same manner as in the step (3) in example 1, and the reaction results are shown in Table 3.
TABLE 1
TABLE 2
TABLE 3
As can be seen from Table 3, the catalyst provided by the present invention can directly convert methacrylic acid and methanol into methyl methacrylate. The catalyst provided by the invention can obtain the methacrylic acid conversion rate of more than 92.7 percent and the methyl methacrylate selectivity of more than 98.5 percent.
Comparing the data of example 1 and comparative example 1, it can be seen that if commercially available silica is used instead of ultra large pore silica gel to prepare the esterification catalyst, the methacrylic acid conversion and methyl methacrylate selectivity are lower.
Comparing the data of example 1 and comparative example 2, it can be seen that the contents of the ultra-large pore silica gel a and the lanthanum dodecylsulfonate are not within the range defined by the present invention, resulting in lower methacrylic acid conversion and methyl methacrylate selectivity.
Comparing the data of example 1 and comparative example 3, it can be seen that 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, resulting in lower methacrylic acid conversion and methyl methacrylate selectivity.
Comparing the data of example 1 and comparative example 4, it can be seen that the conversion of methacrylic acid and the selectivity of methyl methacrylate are lower as a result of not preparing the catalyst by the method of the present invention.
The result shows that the esterification catalyst obtained by taking the ultra-macroporous silica gel as the carrier to load the lanthanum alkylsulfonate has excellent performance.
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 various technical features being combined 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 catalyst for the methyl methacrylate synthesis reaction is characterized by comprising a carrier and alkyl sulfonate loaded on the carrier, wherein the carrier is macroporous silica gel, and the specific surface area of the macroporous silica gel is 200-400m2The pore volume is 0.8-2mL/g, the pore diameter is bimodal, the first most probable pore diameter is 1-5nm, and the second most probable pore diameter is 20-50 nm.
2. The catalyst as claimed in claim 1, wherein the specific surface area of the super-macroporous silica gel is 210-390m2The pore volume is 1.1-1.9mL/g, the first mode pore diameter is 1.5-4nm, and the second mode pore diameter is 22-40 nm.
3. The catalyst of claim 1, wherein the ultra-large pore silica gel is present in an amount of 40 to 70 wt.%, and the alkyl sulfonate is present in an amount of 30 to 60 wt.%, based on the total weight of the catalyst; preferably, the content of the super 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.
4. The catalyst according to claim 1 or 3, wherein 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 group 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.
5. The catalyst of claim 1 or 3, wherein the preparation method of the ultra-large pore silica gel comprises the following steps:
(I) in the presence of butanol and glycerol, contacting an inorganic silicon source with an acid agent to obtain a mixture;
(II) filtering and washing the mixture to obtain a silica gel filter cake;
and (III) carrying out ball milling and spray drying on the silica gel filter cake to obtain the super-macroporous silica gel.
6. The catalyst of claim 5, wherein in step (I), the inorganic silicon source, the acid agent, butanol and glycerol are used in a weight ratio of 1: (0.05-0.5): (0.02-0.6): (0.02-0.6); the pH value of the mixture is 1.5-4.5; preferably, in step (I), the contacting conditions include: the temperature is 15-40 ℃, and the time is 1-3 h;
preferably, 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 2-10 h;
preferably, in step (III), the spray-drying conditions comprise: the rotation speed is 10000-15000r/min, and the temperature is 100-300 ℃.
7. The catalyst according to any one of claims 1 to 6, wherein the catalyst for the synthesis reaction of methyl methacrylate has a specific surface area of 150-400m2The pore volume is 0.5-2mL/g, the pore diameter is bimodal distribution, the first most probable pore diameter is 1-3nm, and the second most probable pore diameter is 15-40 nm;
preferably, the specific surface area of the catalyst for the methyl methacrylate synthesis reaction is 150-300m2(ii)/g, pore volume of 0.6-1.5mL/g, first mode pore diameter of 1.2-3nm, second mode pore diameter of 20-30 nm;
more preferably, the specific surface area of the catalyst for the methyl methacrylate synthesis reaction is 171-283m2Per g, pore volume of 0.8-1.4mL/g,the first mode pore size is 1.6-2.9nm, and the second mode pore size is 22-28 nm.
8. A method for preparing the catalyst according to any one of claims 1 to 7, comprising:
(1) mixing the super-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) and filtering, washing and drying the product to obtain the esterification catalyst.
9. The preparation method according to claim 8, wherein the sodium alkylsulfonate is sodium linear alkylsulfonate and/or sodium branched alkylsulfonate;
preferably, the sodium alkyl sulfonate is sodium linear alkyl sulfonate;
preferably, the alkyl group in the sodium alkyl sulfonate is selected from one or more of heptane, dodecyl and tetradecyl.
10. The preparation method according to claim 8, wherein in the step (1), the weight ratio of the ultra-large pore silica gel to the sodium alkylsulfonate to the water is 1: (0.1-5): (5-100), preferably 1: (0.2-3): (10-60);
preferably, in step (2), the metal salt is selected from one or more of chloride, sulfate and nitrate salts of the metal;
preferably, the metal is lanthanum and/or cerium;
preferably, the concentration of the aqueous solution of the metal salt is 0.02-1.0 mol/L;
preferably, the conditions of the contact reaction include: the temperature is 40-100 ℃ and the time is 0.1-20 h.
11. Use of a catalyst according to any one of claims 1 to 7 in an esterification synthesis reaction, wherein the esterification synthesis reaction comprises: and (3) carrying out contact reaction on methacrylic acid and methanol with the catalyst.
12. The use of claim 11, wherein the conditions of the contact reaction comprise: the contact temperature is 40-150 ℃, preferably 60-120 ℃; the contact pressure is 0.01-5MPa, preferably 0.1-3 MPa; the mass space velocity of the methacrylic acid is 0.01-30h-1Preferably 0.1 to 10h-1(ii) a The mass space velocity of the methanol is 0.01-50h-1Preferably 0.1 to 30 hours-1。
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US8314045B1 (en) * | 2009-10-27 | 2012-11-20 | Entreprises Sinoncelli S.A.R.L. | Solid acid catalyst |
| 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 |
-
2020
- 2020-11-19 CN CN202011305768.1A patent/CN114515598B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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