CN114515597A - Esterification catalyst, preparation method thereof and application thereof in esterification synthesis reaction of acetic acid and alcohol - Google Patents
Esterification catalyst, preparation method thereof and application thereof in esterification synthesis reaction of acetic acid and alcohol Download PDFInfo
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- CN114515597A CN114515597A CN202011301852.6A CN202011301852A CN114515597A CN 114515597 A CN114515597 A CN 114515597A CN 202011301852 A CN202011301852 A CN 202011301852A CN 114515597 A CN114515597 A CN 114515597A
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- Prior art keywords
- mesoporous material
- esterification catalyst
- hexagonal single
- alkyl sulfonate
- esterification
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 239000003054 catalyst Substances 0.000 title claims abstract description 112
- 238000005886 esterification reaction Methods 0.000 title claims abstract description 92
- 230000032050 esterification Effects 0.000 title claims abstract description 86
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 239000013335 mesoporous material Substances 0.000 claims abstract description 79
- 239000013078 crystal Substances 0.000 claims abstract description 76
- 239000011148 porous material Substances 0.000 claims abstract description 70
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- 150000008052 alkyl sulfonates Chemical class 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 21
- 229910052708 sodium Inorganic materials 0.000 claims description 19
- 239000011734 sodium Substances 0.000 claims description 19
- 239000007864 aqueous solution Substances 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 15
- -1 sodium alkyl sulfonate Chemical class 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 11
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 7
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 7
- 235000011151 potassium sulphates Nutrition 0.000 claims description 7
- 238000007725 thermal activation Methods 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound 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
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 5
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical group [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 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
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-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
- 150000002823 nitrates Chemical class 0.000 claims 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 abstract description 24
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 239000008367 deionised water Substances 0.000 description 17
- 229910021641 deionized water Inorganic materials 0.000 description 17
- 230000003197 catalytic effect Effects 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000012265 solid product Substances 0.000 description 12
- 230000008901 benefit Effects 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 10
- 238000009826 distribution Methods 0.000 description 10
- 238000001228 spectrum 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
- 238000001354 calcination Methods 0.000 description 8
- 239000003729 cation exchange resin Substances 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000002841 Lewis acid Substances 0.000 description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 150000007517 lewis acids Chemical class 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000011973 solid acid Substances 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- 229910052573 porcelain Inorganic materials 0.000 description 3
- 238000004445 quantitative analysis Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000001994 activation Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 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
- 230000007547 defect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- VQEHIYWBGOJJDM-UHFFFAOYSA-H lanthanum(3+);trisulfate Chemical compound [La+3].[La+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VQEHIYWBGOJJDM-UHFFFAOYSA-H 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 230000008961 swelling Effects 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
- 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
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 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 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000019439 ethyl acetate Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920001983 poloxamer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- REFMEZARFCPESH-UHFFFAOYSA-M sodium;heptane-1-sulfonate Chemical compound [Na+].CCCCCCCS([O-])(=O)=O REFMEZARFCPESH-UHFFFAOYSA-M 0.000 description 1
- AYFACLKQYVTXNS-UHFFFAOYSA-M sodium;tetradecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCCCS([O-])(=O)=O AYFACLKQYVTXNS-UHFFFAOYSA-M 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- POWFTOSLLWLEBN-UHFFFAOYSA-N tetrasodium;silicate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])[O-] POWFTOSLLWLEBN-UHFFFAOYSA-N 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- B01J35/615—
-
- B01J35/617—
-
- B01J35/635—
-
- B01J35/638—
-
- B01J35/647—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
-
- 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 belongs to the field of fine chemical engineering, and discloses an esterification catalyst, a preparation method thereof and application thereof in esterification synthesis reaction of acetic acid and alcohol. The esterification catalyst comprises a carrier and alkyl sulfonate loaded on the carrier, wherein the carrier is a hexagonal single-crystal mesoporous material, the hexagonal single-crystal mesoporous material has a cubic-centered Im3m crystal phase structure, a pore channel structure is in a cubic cage shape, and the specific surface area is 300-1000 m-2Per g, pore volume of 0.4-1.6mL/g, average pore diameter of 3-13 nm. The catalyst is used for synthesis reaction of acetate, and can obtain higher acetic acid conversion rate and acetate selectivity.
Description
Technical Field
The invention relates to the field of fine chemical engineering, in particular to an esterification catalyst, a preparation method thereof and application thereof in esterification synthesis reaction of acetic acid and alcohol.
Background
As an important organic chemical product and organic chemical raw material, the industrial production level and the production capacity of acetate have important influence on the development of chemical industry in China.
In recent years, the acetate production process in China is continuously developed, the production capacity of acetate is continuously improved, solid acid or cation exchange resin is used as an acetate synthesis reaction catalyst, and the acetate synthesis reaction catalyst is greatly developed and widely applied to industrial production. The solid catalyst has the advantages of good stability, high selectivity, low cost, easy separation and the like in the esterification reaction. However, these catalysts have a relatively slow reaction rate and a relatively low ester yield. The cation exchange resin has the advantages of good stability, high selectivity, low cost, easy separation and the like in the esterification reaction. However, the cation exchange resin has poor heat resistance (generally, the cation exchange resin is decomposed at a temperature of not higher than 250 ℃), small specific surface area and pore volume, and the cation exchange resin is easy to swell, so that the cation exchange resin is poor in reaction activity as an esterification catalyst and low in ester yield.
Compared with resin catalysts, the inorganic mesoporous material has the structural advantages of large specific surface area and pore volume and the performance advantage of high temperature resistance. However, the surface of the all-silicon mesoporous molecular sieve with the basic framework structure consisting of silicon and oxygen does not contain functional groups, and does not show any activity in the esterification reaction. Therefore, it is not practical to directly apply the all-silicon mesoporous molecular sieve material to the synthesis reaction of acetate. With the increasing demand of acetate, the green and environment-friendly process for synthesizing acetate has wide prospect.
Therefore, it is an important work direction for researchers to develop a catalyst for acetate synthesis reaction having excellent performance, to improve reaction efficiency, and to suppress the formation of by-products.
Disclosure of Invention
The invention aims to solve the problems of excessive side reactions and serious environmental pollution of inorganic acid catalysts used in the prior acetate production process, and the problems of poor catalytic activity, low ester selectivity and the like of solid acid catalysts and acidic cation exchange resin catalysts. Provides an esterification catalyst, a preparation method thereof and application thereof in esterification synthesis reaction of acetic acid and alcohol. The catalyst is used for synthesis reaction of acetate, and can obtain higher acetic acid conversion rate and acetate selectivity.
In order to achieve the above object, the first aspect of the present invention provides an esterification catalyst, which is characterized in that the esterification catalyst comprises a carrier and an alkylsulfonate supported on the carrier, wherein the carrier is a hexagonal single-crystal mesoporous material, the hexagonal single-crystal mesoporous material has a cubic-centered Im3m crystal phase structure, the pore channel structure is a cubic cage, and the specific surface area is 300-2Per g, pore volume of 0.4-1.6mL/g, average pore diameter of 3-13 nm.
The second aspect of the present invention provides a preparation method of the esterification catalyst, wherein the preparation method comprises:
(1) mixing the hexagonal single-crystal mesoporous material 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 esterification catalyst in an esterification synthesis reaction of acetic acid and alcohol, wherein the esterification synthesis reaction comprises: and carrying out contact reaction on acetic acid and alcohol and the esterification catalyst.
Through the technical scheme, the technical scheme provided by the invention has the following advantages:
(1) the esterification catalyst provided by the invention has the advantages of stable structure, good high temperature resistance, no deformation and no swelling in the reaction process.
(2) The esterification catalyst provided by the invention has the advantages of easily available raw materials, simple preparation method and process, easily controlled conditions, good product repeatability and no pollutant emission in the preparation process.
(3) The esterification catalyst provided by the invention is used for the synthesis reaction of acetic ester, the process conditions are mild, and the requirements on reaction devices are not high. The acetic acid conversion rate is high, and the acetate selectivity is high.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
FIG. 1 is an XRD spectrum of a hexagonal single-crystal mesoporous material A and an esterification catalyst A prepared in example 1 of the present invention;
FIG. 2 is a distribution diagram of the pore diameters of the hexagonal single-crystal mesoporous material A and the esterification catalyst A prepared in example 1 of the present invention.
Description of the reference numerals
FIG. 1(a) is an XRD spectrum of a hexagonal single-crystal mesoporous material A prepared in example 1 of the present invention;
FIG. 1(b) is an XRD spectrum of esterification catalyst A prepared in example 1 of the present invention;
FIG. 2(a) is a diagram showing a distribution of the pore size of the hexagonal single-crystal mesoporous material A prepared in example 1 of the present invention;
FIG. 2(b) is a graph showing the pore size distribution of esterification catalyst A prepared in example 1 of the present invention.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides an esterification catalyst, wherein the esterification catalyst comprises a carrier and alkyl sulfonate loaded on the carrier, wherein the carrier is a hexagonal single-crystal mesoporous material, the hexagonal single-crystal mesoporous material has a cubic-centered Im3m crystal phase structure, the pore channel structure is cubic cage-shaped, and the specific surface area is 300-1000 m-2Per g, pore volume of 0.4-1.6mL/g, average pore diameter of 3-13 nm.
The inventors of the present invention found that: in the prior art, esterification catalysts for the production of acetate esters 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, high reaction temperature, low product selectivity and the like. Compared with the catalyst, the resin catalyst has the advantages of high selectivity, low cost, easy separation and the like, but the ester yield is low in the synthesis reaction process of the acetate ester, 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. 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. If a green Lewis acid, which is not easily soluble in water, is directly used as a catalyst in the acetate synthesis reaction, the catalytic efficiency may be decreased due to non-uniform dispersion.
The inventors of the present invention have found that the above problems can be solved and the catalyst efficiency can be improved by selecting a suitable carrier and dispersing the catalyst well. If the material used as the carrier not only has larger specific surface area, pore volume and pore diameter, but also has a stable framework structure, the structural defects that the resin catalyst is easy to swell and easy to be decomposed by heat can be avoided, and the acetic acid esterification catalyst with excellent catalytic performance is expected to be obtained.
The inventor of the invention finds that the hexagonal single-crystal mesoporous molecular sieve has a cubic-centered Im3m crystal phase structure, the pore structure is cubic cage-shaped, and the specific surface area is 300-1000m2Per g, pore volume of 0.4-1.6mL/g, average pore diameter of 3-13nmIs very suitable for catalytic reaction with macromolecules. In addition, the pore structure of the hexagonal single-crystal mesoporous molecular sieve is composed of a silica basic structure, belongs to an inorganic structure, and has the advantages of no swelling and deformation in an organic solvent and better temperature resistance (can exist stably at 600 ℃). If the hexagonal single-crystal mesoporous material is used as a carrier and the supported Lewis acid is used for preparing a catalyst with good dispersion, the catalyst can be used for acetate synthesis reaction and can show good catalytic activity and ester selectivity.
According to the invention, the specific surface area of the hexagonal single-crystal mesoporous material is preferably 650-800m2Per g, the pore volume is 1.1-1.5mL/g, and the average pore diameter is 8-10 nm; more preferably, the specific surface area of the hexagonal single-crystal mesoporous material is 708-736m2Per g, pore volume of 1.2-1.3mL/g, average pore diameter of 9-9.2 nm. In the invention, the structural parameters of the hexagonal single-crystal mesoporous material are limited within the range, and the prepared catalyst can show good catalytic activity and ester selectivity when used for acetate synthesis reaction.
According to the invention, based on the total weight of the catalyst, the content of the hexagonal single-crystal mesoporous material is 40-80 wt%, and the content of the alkyl sulfonate is 20-60 wt%; preferably, the content of the hexagonal single-crystal mesoporous material is 45-70 wt% and the content of the alkyl sulfonate is 30-55 wt% based on the total weight of the catalyst; more preferably, the content of the hexagonal single-crystal mesoporous material is 51.9 to 64.6 wt% and the content of the alkyl sulfonate is 35.4 to 48.1 wt% based on the total weight of the catalyst. In the invention, the contents of the hexagonal single-crystal mesoporous material and the alkyl sulfonate are limited to be within the ranges, and the prepared catalyst can show good catalytic activity and ester selectivity when being used for acetate 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 group in the alkyl sulfonate is selected from one or more of heptane, a decaalkyl group, a dodecyl group and a tetradecyl group; more preferably, the sulfonate in the alkyl sulfonate is lanthanum sulfonate and/or cerium sulfonate.
According to the invention, the preparation method of the hexagonal single-crystal mesoporous material comprises the following steps:
(I) mixing a template agent, potassium sulfate, an acidic aqueous solution and a silicon source to obtain a mixture;
(II) crystallizing, filtering, washing and drying the mixture to obtain hexagonal single-crystal mesoporous material raw powder;
(III) sequentially carrying out demoulding agent treatment and thermal activation treatment on the hexagonal single crystal mesoporous material raw powder to obtain the hexagonal single crystal mesoporous material.
According to the present invention, the templating agent may be various templating agents conventional in the art. For example, the templating agent may be a triblock copolymer polyoxyethylene-polyoxypropylene-polyoxyethylene, which may be prepared by methods known to those skilled in the art, or may be obtained commercially, for example, from Fuka under the trade name Synperonic F108, having the formula EO132PO60EO132 and an average molecular weight Mn of 14600.
According to the invention, the acidic aqueous solution is preferably an aqueous solution of an inorganic acid, including aqueous sulfuric acid, aqueous hydrochloric acid, aqueous hydrobromic acid and aqueous nitric acid, more preferably aqueous hydrochloric acid.
According to the invention, the silicon source is preferably at least one of tetraethoxysilane, methyl orthosilicate, propyl orthosilicate, sodium orthosilicate and silica sol, and is more preferably tetraethoxysilane.
According to the invention, in the step (I), the mole ratio of the template agent, the potassium sulfate, the silicon source, the water and the hydrogen chloride is 1: (50-500): (50-300): (5000-50000): (200-2000), preferably 1: (100-300): (100-200): (10000-30000): (500-1500).
According to the invention, in step (I), the mixing conditions comprise: the temperature is 25-60 deg.C, and the time is 10-200 min. In order to further facilitate uniform mixing between the substances, according to a preferred embodiment of the invention, the mixing contact is carried out under stirring conditions.
According to the present invention, in step (II), the crystallization conditions may include: the temperature is 25-60 ℃, preferably 30-55 ℃; the time is 10-72h, preferably 10-40 h. According to a preferred embodiment, the crystallization is carried out by hydrothermal crystallization.
According to the present invention, 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 deionized water (the number of washing times can be 2-10), and then subjected to suction filtration.
According to the invention, in step (III), the method of template removal treatment is typically a calcination method. The template agent removing treatment process comprises the following steps: calcining original powder of the hexagonal single-crystal mesoporous material in air atmosphere; the temperature of the template removal agent is preferably 400-700 ℃, and the time of the template removal agent is preferably 8-20 h.
According to the invention, the thermal activation treatment process comprises: roasting the product in nitrogen atmosphere to remove the template agent; the thermal activation temperature is preferably 450-800 ℃, and the thermal activation time is preferably 8-20 h.
According to the present invention, the drying conditions are not particularly limited, and for example, the drying conditions include: the drying temperature is 70-150 ℃, and the drying time is 3-20 h.
According to the invention, the specific surface area of the esterification catalyst is 500-650m2Per gram, pore volume of 0.8-1.2mL/g, average pore diameter of 6-8 nm; preferably, the specific surface area of the esterification catalyst is 542-604m2Per g, pore volume of 0.9-1.1mL/g, average pore diameter of 6.8-7.4 nm.
In a second aspect, the present invention provides a preparation method of the esterification catalyst, wherein the preparation method comprises:
(1) mixing the hexagonal single-crystal mesoporous material 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, the weight ratio of the hexagonal single-crystal mesoporous material to the sodium alkyl sulfonate to the water is 1: (0.1-5): (5-100), preferably 1: (0.2-3): (10-60).
According to the invention, the mixing conditions of the hexagonal single-crystal mesoporous material, 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 hexagonal single crystal mesoporous material, the sodium alkyl sulfonate and the deionized water can be rapidly stirred or the mixing efficiency can be improved by means of an ultrasonic method in the mixing process. Wherein the water is preferably 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 2.0 mL/min.
According to the invention, 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; preferably, the concentration of the aqueous solution of the metal salt is 0.02 to 1.0mol/L, preferably 0.05 to 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, the mixture is rapidly stirred during the contact reaction with the aqueous solution of the metal salt in order to achieve a better contact reaction effect.
The method for washing the solid product according to the present invention 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 esterification catalyst in an esterification synthesis reaction of acetic acid and alcohol, wherein the esterification synthesis reaction comprises: and carrying out contact reaction on acetic acid and alcohol and the esterification catalyst.
According to the invention, the alcohol is selected from one or more of n-butanol, isobutanol, propanol, isopropanol, methanol and ethanol.
According to the invention, the conditions of the contact reaction include: the temperature is 50-160 ℃, and the optimal temperature is 70-140 ℃; the pressure is 0.01-5.0MPa, preferably 0.1-3.0 MPa; the mass space velocity of the acetic acid is 0.01-30h-1Preferably 0.1 to 10 hours-1(ii) a The molar ratio of acetic acid to alcohol is 1:0.1-20, preferably 1: 0.5-10.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples:
the XRD spectrum of the sample was obtained on an X' Pert MPD type X-ray powder diffractometer manufactured by Philips, with Cu K α ray, λ 0.154178nm, and a scan range of 2 θ 0.5 ° to 10 °.
The pore structure parameter analysis of the samples was performed on an adsorption apparatus model ASAP2020-M + C, available from Micromeritics, USA. The 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 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.
F108 used in the examples and comparative examples was purchased from Fuka corporation. Other reagents used in examples and comparative examples were purchased from national pharmaceutical group chemical agents, ltd, and the purity of the reagents was analytical grade.
Example 1
(1) Preparation of hexagonal single crystal mesoporous material
20g (0.0014mol) of template F108, 52.4g (0.3mol) of potassium sulfate and 600g of hydrochloric acid aqueous solution (containing 1.2mol of HCl) are mixed and stirred at 38 ℃ until F108 is completely dissolved; adding 41.6g (0.2mol) of tetraethoxysilane into the solution, continuously stirring for 15min at 38 ℃, and standing and crystallizing for 24h at 38 ℃; washing the solid product obtained by filtering with deionized water for 4 times, and drying at 110 ℃ for 10h after suction filtration to obtain the hexagonal mesoporous material raw powder. Calcining the hexagonal mesoporous material raw powder for 10 hours at 500 ℃ in air atmosphere, and removing the template agent; then calcining the mixture for 10 hours at 550 ℃ under the protection of nitrogen to carry out thermal activation treatment, thus obtaining the thermally activated hexagonal single crystal mesoporous material A.
The specific surface area of the hexagonal single-crystal mesoporous material A is 721m2Per g, pore volume 1.3cm3In terms of/g, the mean pore diameter is 9.1 nm.
FIG. 1(a) is an XRD spectrum of hexagonal single-crystal mesoporous material A. From the XRD spectrum, it is evident that the hexagonal single-crystal mesoporous material a has 1 diffraction peak (2 θ ═ 0.6 °) of the (110) plane and a diffraction shoulder (2 θ ═ 1.2 °) of the (200) plane corresponding to the crystalline phase of the cubic center Im3m in the small angular region. (110) The hexagonal single crystal mesoporous material has high diffraction peak intensity and narrow peak shape, and shows that the hexagonal single crystal mesoporous material has a good ordered mesoporous structure.
FIG. 2(a) is a diagram showing the distribution of the pore diameter of the hexagonal single-crystal mesoporous material A. As can be seen from the pore size distribution diagram, the hexagonal single-crystal mesoporous material has narrow pore size distribution and very uniform pore channels, and the most probable pore size is about 9 nm.
(2) Preparation of esterification catalyst
Mixing 10g of hexagonal single-crystal mesoporous material, 5g of sodium dodecyl sulfate and 400g of deionized water, stirring for 8 hours at 75 ℃, and uniformly mixing. Keeping the temperature of the mixture at 75 ℃, slowly dripping 180mL of lanthanum sulfate aqueous solution with the concentration of 0.2mol/L into the mixture at the dripping speed of 1.0mL/min, stirring at 75 ℃ for reaction for 3h, and cooling 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 esterification catalyst A.
Based on the total weight of the esterification catalyst a, the content of the hexagonal single-crystal mesoporous material is 58.4 wt%, and the content of the lanthanum dodecylsulfonate is 41.6 wt%.
The specific surface area of esterification catalyst A was 570m2Per g, pore volume 1.1cm3In terms of/g, the mean pore diameter is 7.2 nm.
FIG. 1(b) is an XRD spectrum of esterification catalyst A. It can be clearly seen from the XRD spectrogram that the hexagonal single-crystal mesoporous material a still maintains a typical mesoporous structure after being loaded. Because the pore channel of the catalyst is narrowed after loading, the positions of two characteristic diffraction peaks on an XRD spectrogram are shifted towards a large-angle direction.
FIG. 2(b) is a pore size distribution diagram of esterification catalyst A. As can be seen from the pore size distribution, the channels of the catalyst are still very uniform, with a maximum pore size of about 7 nm.
(3) Evaluation of reaction Performance of esterification catalyst
The catalytic performance of esterification catalyst a in the esterification reaction of acetic acid with n-butanol was evaluated on a fixed bed reaction apparatus. 5.0 g of catalyst is filled into a stainless steel fixed bed reactor with the inner diameter of 8mm, the reaction temperature is 120 ℃, the reaction pressure is adjusted to be 0.3MPa by nitrogen, and the weight space velocity of acetic acid is 3.0h-1The molar ratio of n-butanol to acetic acid was 4:1, and the 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 acetic acid conversion was 96.5% and the n-butyl acetate selectivity was 99.5%.
Example 2
(1) Preparation of hexagonal single crystal mesoporous material
20g (0.0014mol) of template F108, 73.4g (0.42mol) of potassium sulfate and 833g of hydrochloric acid aqueous solution (containing 2.1mol of HCl) are mixed and stirred at 55 ℃ until F108 is completely dissolved; adding 58.2g (0.28mol) of tetraethoxysilane into the solution, continuously stirring for 10min at 55 ℃, and standing and crystallizing for 10h at 55 ℃; washing the solid product obtained by filtering with deionized water for 6 times, and drying at 150 ℃ for 3h after suction filtration to obtain the hexagonal mesoporous material raw powder. Calcining the hexagonal mesoporous material raw powder for 15 hours at 600 ℃ in air atmosphere, and removing the template agent; then calcining for 8h at 650 ℃ under the protection of nitrogen for heat activation treatment to obtain the heat-activated hexagonal single-crystal mesoporous material B.
The specific surface area of the hexagonal single-crystal mesoporous material B is 708m2Per g, pore volume 1.2cm3(iv)/g, average pore diameter 9.0 nm.
The XRD spectrum of the hexagonal single-crystal mesoporous material B is similar to that of figure 1 (a). The distribution of the pore diameter of the hexagonal single-crystal mesoporous material B is similar to that of FIG. 2 (a).
(2) Preparation of esterification catalyst
Mixing 10g of hexagonal single-crystal mesoporous material, 4g of sodium tetradecyl sulfonate and 200g of deionized water, stirring for 15h at 60 ℃, and uniformly mixing. Keeping the temperature of the mixture at 60 ℃, slowly dripping 350mL of 0.1mol/L aqueous solution of cerium sulfate into the mixture, stirring at 60 ℃ for reaction for 10h, and then cooling 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 200 ℃ for 5 hours to obtain the esterification catalyst B.
Based on the total weight of the esterification catalyst B, the content of the hexagonal single-crystal mesoporous material is 64.6 weight percent, and the content of the cerium tetradecyl sulfonate is 35.4 weight percent.
The specific surface area of esterification catalyst B was 604m2Per g, pore volume 1.0cm3In terms of/g, the mean pore diameter is 7.4 nm.
(3) Evaluation of reaction Performance of esterification catalyst
The catalytic performance of esterification catalyst B in the esterification reaction of acetic acid with isobutanol was evaluated on a fixed bed reaction apparatus. 5.0 g of catalyst is filled into a stainless steel fixed bed reactor with the inner diameter of 8mm, the reaction temperature is 120 ℃, the reaction pressure is adjusted to be 0.3MPa by nitrogen, and the weight space velocity of acetic acid is 3.0h-1The molar ratio of isobutanol to acetic acid was 4:1, and the reaction time was 50 hours. The product was cooled and analyzed on an Agilent 7890A gas chromatograph equipped with an FFAP capillary column and a hydrogen flame detector (FID), using temperature programming and quantitative analysis with calibration factors. Acetic acid conversion95.8% and isobutyl acetate selectivity 99.4%.
Example 3
(1) Preparation of hexagonal single crystal mesoporous material
20g (0.0014mol) of template F108, 24.5g (0.14mol) of potassium sulfate and 278g of hydrochloric acid aqueous solution (containing 0.7mol of HCl) are mixed and stirred at 30 ℃ until F108 is completely dissolved; adding 29.1g (0.14mol) of tetraethoxysilane into the solution, continuously stirring for 60min at 30 ℃, and standing and crystallizing for 40h at 30 ℃; washing the solid product obtained by filtering with deionized water for 8 times, and drying at 70 ℃ for 20 hours after suction filtration to obtain the hexagonal mesoporous material raw powder. Calcining the hexagonal mesoporous material raw powder for 20 hours at 400 ℃ in an air atmosphere, and removing the template agent; then calcining for 16h at 500 ℃ under the protection of nitrogen for heat activation treatment to obtain the heat-activated hexagonal single-crystal mesoporous material C.
The specific surface area of the hexagonal single crystal mesoporous material C is 736m2Per g, pore volume 1.3cm3In terms of a/g, the mean pore diameter is 9.2 nm.
The XRD spectrum of the hexagonal single-crystal mesoporous material C is similar to that of figure 1 (a). The distribution of the pore diameter of the hexagonal single-crystal mesoporous material B is similar to that of FIG. 2 (a).
(2) Preparation of esterification catalyst
Mixing 10g of hexagonal single-crystal mesoporous material, 5.5g of sodium heptanesulfonate and 500g of deionized water, stirring for 5 hours at 90 ℃, and uniformly mixing. Keeping the temperature of the mixture at 90 ℃, slowly dripping 100mL of 0.4mol/L lanthanum trichloride aqueous solution into the mixture, stirring at 90 ℃ for reaction for 1h, and then cooling 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 150 ℃ for 20 hours to obtain the esterification catalyst C.
Based on the total weight of the esterification catalyst C, the content of the hexagonal single-crystal mesoporous material is 51.9 wt%, and the content of the heptane-based lanthanum sulfonate is 48.1 wt%.
The specific surface area of esterification catalyst C was 542m2Per g, pore volume 0.9cm3In terms of a/g, the mean pore diameter is 6.8 nm.
(3) Evaluation of reaction Performance of esterification catalyst
In a fixed bed reaction deviceThe catalyst performance of esterification catalyst C in the esterification reaction of acetic acid and n-propanol was evaluated. 5.0 g of catalyst is filled into a stainless steel fixed bed reactor with the inner diameter of 8mm, the reaction temperature is 110 ℃, the reaction pressure is adjusted to be 0.3MPa by nitrogen, and the weight space velocity of acetic acid is 4.0h-1The molar ratio of n-propanol to acetic acid was 4:1 and the reaction time was 50 hours. The product was cooled and analyzed on an Agilent 7890A gas chromatograph equipped with an FFAP capillary column and a hydrogen flame detector (FID), using temperature programming and quantitative analysis with calibration factors. The acetic acid conversion was 96.0% and n-propyl acetate selectivity was 99.6%.
Comparative example 1
The hexagonal single-crystalline mesoporous material and the esterification catalyst were prepared in the same manner as in example 1, except that:
the steps (1) and (2) in example 1 were omitted, and the catalytic performance of the ceramic balls (non-catalyst) was tested according to the acetoesterification performance evaluation method of step (3) in example 1. Wherein, the model of porcelain ball is the low silicon porcelain ball of Denstone 99, and the parameter of porcelain ball includes: more than 99 percent of alumina and less than 0.2 percent of silicon oxide, which are purchased from saint gobain ceramsite limited company.
As a result, the conversion of acetic acid was 8.7% and the selectivity for n-butyl acetate was 1.6%.
Comparative example 2
The hexagonal single-crystal mesoporous material and the esterification catalyst were prepared in the same manner as in example 1, except that:
the catalytic performance of the resin catalyst was tested according to the acetic acid esterification performance evaluation method of step (3) in example 1, with step (1) and step (2) in example 1 being eliminated. Wherein the resin catalyst is available from Kaiser environmental protection science and technology Co., Ltd, model No. D009.
As a result, the conversion of acetic acid was 90.3% and the selectivity to n-butyl acetate was 95.7%.
Comparative example 3
The hexagonal single-crystal mesoporous material and the esterification catalyst were prepared in the same manner as in example 1, except that:
change ofThe method of the step (1) in the example 1 is to prepare the hexagonal single-crystal mesoporous material with the specific surface area of 287m2Pore volume 0.35mL/g, average pore diameter 6.2 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 216m was prepared2Pore volume 0.3mL/g, average pore diameter 4.0 nm.
As a result, the conversion of acetic acid was 86.4% and the selectivity to n-butyl acetate was 92.1%.
Comparative example 4
The hexagonal single-crystal mesoporous material and the esterification 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 esterification catalyst
Mixing 10g of hexagonal single-crystal mesoporous material, 5g of sodium dodecyl sulfate and 400g of deionized water, stirring for 8 hours at 75 ℃, and uniformly mixing. The mixture was immersed in 180mL of a 0.2mol/L aqueous lanthanum sulfate 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. Filtering to obtain a solid product, washing with deionized water for 6 times, and drying at 180 ℃ for 20 hours to obtain the esterification catalyst D4.
The resulting catalyst had a specific surface area of 492m2Pore volume of 0.9mL/g and average pore diameter of 6.6 nm.
As a result, the conversion of acetic acid was 91.8% and the selectivity to n-butyl acetate was 96.7%.
It can be seen that the esterification catalyst provided by the present invention can directly convert acetic acid and alcohol into acetate.
Comparing the data of example 1 and comparative example 1, it can be seen that if ceramic balls are used instead of the esterification catalyst to be charged into the reactor, the acetic acid conversion is extremely low and acetate is hardly formed.
Comparing the data of example 1 and comparative example 2, it can be seen that both the acetic acid conversion and acetate selectivity of the esterification catalyst are significantly improved compared to the resin catalyst.
Comparing the data of example 1 and comparative example 3, it can be seen that the structural parameters of the hexagonal single crystalline mesoporous material and the prepared catalyst are not within the range defined by the present invention, and as a result, the acetic acid conversion rate and the acetate selectivity are low.
Comparing the data of example 1 and comparative example 4, it can be seen that the acetic acid conversion and acetate selectivity are lower as a result of not preparing the catalyst by the method of the present invention.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (12)
1. The esterification catalyst is characterized by comprising a carrier and alkyl sulfonate loaded on the carrier, wherein the carrier is a hexagonal single-crystal mesoporous material, the hexagonal single-crystal mesoporous material has a cubic-centered Im3m crystal phase structure, the pore channel structure is in a cubic cage shape, and the specific surface area is 300-1000m2Per g, pore volume of 0.4-1.6mL/g, average pore diameter of 3-13 nm.
2. The esterification catalyst according to claim 1, wherein the hexagonal single-crystal mesoporous material has a specific surface area of 650-800m2Per g, the pore volume is 1.1-1.5mL/g, and the average pore diameter is 8-10 nm; preferably, the specific surface area of the hexagonal single-crystal mesoporous material is 708-736m2Per g, pore volume of 1.2-1.3mL/g, average pore diameter of 9-9.2 nm.
3. The esterification catalyst according to claim 1 or 2, wherein the hexagonal single-crystalline mesoporous material is contained in an amount of 40 to 80 wt% and the alkyl sulfonate is contained in an amount of 20 to 60 wt%, based on the total weight of the catalyst.
4. The esterification catalyst according to claim 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, a decaalkyl group, a dodecyl group and a tetradecyl group;
more preferably, the sulfonate in the alkyl sulfonate is lanthanum sulfonate and/or cerium sulfonate.
5. The esterification catalyst according to claim 1 or 2, wherein the preparation method of the hexagonal single-crystal mesoporous material comprises:
(I) mixing a template agent, potassium sulfate, an acidic aqueous solution and a silicon source to obtain a mixture;
(II) crystallizing, filtering, washing and drying the mixture to obtain hexagonal single-crystal mesoporous material raw powder;
(III) sequentially carrying out demoulding agent treatment and thermal activation treatment on the hexagonal single crystal mesoporous material raw powder to obtain the hexagonal single crystal mesoporous material.
6. The esterification catalyst according to claim 5, wherein in step (I), the molar ratio of the templating agent, potassium sulfate, silicon source, water, and hydrogen chloride is 1: (50-500): (50-300): (5000-50000): (200- & lt2000-);
preferably, in step (II), the crystallization conditions include: the temperature is 25-60 ℃, and the crystallization time is 10-72 h;
preferably, in step (III), the conditions of the stripper plate agent treatment include: the temperature is 400-700 ℃, and the time is 8-20 h; the conditions of the thermal activation treatment include: the temperature is 450 ℃ and 800 ℃, and the time is 8-20 h.
7. The esterification catalyst according to any one of claims 1 to 6, wherein the specific surface area of the esterification catalyst is 650m2Per g, pore volume of 0.8-1.2mL/g,the average pore diameter is 6-8 nm; preferably, the specific surface area of the esterification catalyst is 542-604m2Per g, pore volume of 0.9-1.1mL/g, average pore diameter of 6.8-7.4 nm.
8. A method for preparing the esterification catalyst according to any one of claims 1 to 7, wherein the method comprises:
(1) mixing the hexagonal single-crystal mesoporous material 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 a sodium linear alkylsulfonate and/or a 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 the weight ratio of the hexagonal single-crystal mesoporous material to the sodium alkyl sulfonate to the water is 1: (0.1-5): (5-100);
preferably, 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 an esterification catalyst according to any one of claims 1 to 7 in an esterification synthesis reaction of acetic acid and an alcohol, wherein the esterification synthesis reaction comprises: and carrying out contact reaction on acetic acid and alcohol and the esterification catalyst.
12. The use of claim 11, wherein the conditions of the contact reaction comprise: the temperature is 50-160 ℃, and the optimal temperature is 70-140 ℃; the pressure is 0.01-5.0MPa, preferably 0.1-3.0 MPa; the mass space velocity of the acetic acid is 0.01-30h-1Preferably 0.1 to 10 hours-1(ii) a The molar ratio of acetic acid to alcohol is 1:0.1-20, preferably 1: 0.5-10.
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