CN114515597B - 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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- CN114515597B CN114515597B CN202011301852.6A CN202011301852A CN114515597B CN 114515597 B CN114515597 B CN 114515597B CN 202011301852 A CN202011301852 A CN 202011301852A CN 114515597 B CN114515597 B CN 114515597B
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- single crystal
- esterification catalyst
- mesoporous material
- alkyl sulfonate
- hexagonal single
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 title claims abstract description 129
- 239000003054 catalyst Substances 0.000 title claims abstract description 113
- 238000005886 esterification reaction Methods 0.000 title claims abstract description 91
- 230000032050 esterification Effects 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 239000013335 mesoporous material Substances 0.000 claims abstract description 78
- 239000013078 crystal Substances 0.000 claims abstract description 75
- 239000011148 porous material Substances 0.000 claims abstract description 71
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 150000008052 alkyl sulfonates Chemical class 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 23
- -1 sodium alkyl sulfonate Chemical class 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- 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 17
- 238000005406 washing Methods 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 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
- 238000002156 mixing Methods 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 8
- 238000001994 activation Methods 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 7
- 230000008025 crystallization Effects 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
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 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
- 238000004519 manufacturing process Methods 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
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical group [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 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
- 238000007725 thermal activation Methods 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 abstract description 26
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 239000012265 solid product Substances 0.000 description 20
- 239000008367 deionised water Substances 0.000 description 17
- 229910021641 deionized water Inorganic materials 0.000 description 17
- 230000003197 catalytic effect Effects 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- 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 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 238000001354 calcination Methods 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 238000010586 diagram Methods 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- 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 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- 239000003729 cation exchange resin Substances 0.000 description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000003756 stirring Methods 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
- 238000011156 evaluation Methods 0.000 description 5
- 150000007517 lewis acids Chemical class 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- 230000009257 reactivity Effects 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
- 239000011973 solid acid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 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
- 239000000919 ceramic Substances 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 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
- 229910052757 nitrogen 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
- 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
- 238000004458 analytical method Methods 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004587 chromatography analysis Methods 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
- 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
- 239000000463 material Substances 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 230000002194 synthesizing effect 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
- 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
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 238000013019 agitation Methods 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
- 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
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- PVGUQHABROGXFK-UHFFFAOYSA-K dodecyl sulfate lanthanum(3+) Chemical compound [La+3].CCCCCCCCCCCCOS([O-])(=O)=O.CCCCCCCCCCCCOS([O-])(=O)=O.CCCCCCCCCCCCOS([O-])(=O)=O PVGUQHABROGXFK-UHFFFAOYSA-K 0.000 description 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
- 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
- 229910052500 inorganic mineral Inorganic materials 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
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011707 mineral Substances 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
- 229920000620 organic polymer Polymers 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
- 239000002861 polymer material Substances 0.000 description 1
- 230000005855 radiation Effects 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
- 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
- 230000007847 structural defect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000008961 swelling 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
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/638—Pore volume more than 1.0 ml/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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)
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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- 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
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Abstract
The invention discloses an esterification catalyst, a preparation method thereof and application thereof in esterification synthesis reaction of acetic acid and alcohol in the field of fine chemical industry. The esterification catalyst comprises a carrier and alkyl sulfonate 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 canal structure is in a cubic cage shape, and the specific surface area is 300-1000m 2 Per gram, the pore volume is 0.4-1.6mL/g, and the average pore diameter is 3-13nm. The catalyst is used for the 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 an important organic chemical raw material, the industrial production level and the production capacity of the acetate have important influence on the development of chemical industry in China.
In recent years, the production process of acetate 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 catalyst is greatly developed and is 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, such 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 itself has poor heat resistance (generally, decomposition is carried out at a temperature of not higher than 250 ℃), a small specific surface area and a small pore volume, and the cation exchange resin is easily swelled, has poor reactivity as an esterification catalyst, and has low ester yield.
Compared with the resin catalyst, the inorganic mesoporous material has the structural advantages of large specific surface area and large pore volume and the performance advantages of high temperature resistance. However, the surface of the all-silicon mesoporous molecular sieve with a basic framework structure composed 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 has wide prospects for synthesizing acetate.
Therefore, it is an important working direction in the future for researchers to develop an acetate synthesis reaction catalyst having excellent performance, to improve the reaction efficiency, and to suppress the formation of by-products.
Disclosure of Invention
The invention aims to solve the problems of excessive side reactions and serious environmental pollution of inorganic acid catalysts used in the existing 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. An esterification catalyst, its preparing process and its application in the esterifying synthesis reaction of acetic acid and alcohol are disclosed. The catalyst is used for the 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, characterized in that the esterification catalyst comprises a carrierAnd alkyl sulfonate 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 crystalline phase structure, the pore canal structure is cubic cage-shaped, and the specific surface area is 300-1000m 2 Per gram, the pore volume is 0.4-1.6mL/g, and the average pore diameter is 3-13nm.
The second aspect of the present invention provides a preparation method of the esterification catalyst, wherein the preparation method comprises the following steps:
(1) Mixing 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) Filtering, washing and drying the product to obtain the esterification catalyst.
In a third aspect, the present invention provides an application of the esterification catalyst in an esterification synthesis reaction of acetic acid and alcohol, wherein the esterification synthesis reaction comprises: acetic acid and alcohol are contacted with the esterification catalyst.
Through the technical scheme, the technical scheme of the invention has the following advantages:
(1) The esterification catalyst provided by the invention has stable structure, good high temperature resistance, and 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, easy control of 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 the acetate, and has mild process conditions and low requirements on reaction devices. The acetic acid conversion rate is high, and the selectivity of acetate 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 graph showing pore size distribution 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 an esterification catalyst A prepared in example 1 of the present invention;
FIG. 2 (a) is a pore size distribution diagram of a hexagonal single crystal mesoporous material A prepared in example 1 of the present invention;
FIG. 2 (b) is a pore size distribution diagram of the esterification catalyst A prepared in example 1 of the present invention.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the invention provides an esterification catalyst, which comprises a carrier and alkyl sulfonate 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 crystalline phase structure, the pore canal structure is in a cubic cage shape, and the specific surface area is 300-1000m 2 Per gram, the pore volume is 0.4-1.6mL/g, and the average pore diameter is 3-13nm.
The inventors of the present invention found that: in the prior art, esterification catalysts used to produce acetate are divided into two classes, homogeneous and heterogeneous. Wherein, the homogeneous catalyst mainly comprises inorganic acid solution and organic acid, and the heterogeneous catalyst mainly comprises solid acid and cation exchange resin. The homogeneous catalyst has the advantages of low cost and good catalytic activity, but the defects of difficult separation of products and the catalyst, more side reactions, easy corrosion to equipment and the like are eliminated. Although the solid acid esterification catalyst solves the problems of difficult product separation and serious equipment corrosion, the catalyst is rarely applied to industrial production due to the defects of poor catalytic activity, higher reaction temperature, lower product selectivity and the like. Compared with the above catalyst, the resin catalyst has the advantages of high selectivity, low cost, easy separation and the like, but has low ester yield and poor high temperature resistance in the process of synthesizing the acetate. The resin is an organic polymer material, is easy to swell in an organic solvent, is easy to deform and even decompose in a high-temperature environment, and is a main reason for poor temperature resistance of the resin catalyst. Lewis acid catalysts are valued for high activity, good selectivity and mild reaction conditions, but common Lewis acids are unstable in water and are easy to react with water to deactivate. The salt of a lewis acid in combination with a surfactant is called a green lewis acid because it is not easily hydrolyzed, and its catalytic effect in organic synthesis is receiving increasing attention. If a green Lewis acid which is not easily soluble in water is directly used as a catalyst in an acetate synthesis reaction, the catalytic efficiency may be lowered due to uneven dispersion.
The inventors of the present invention found that the above-mentioned problems can be solved and the efficiency of the catalyst can be improved by selecting an appropriate carrier to disperse the catalyst well. If the material used as the carrier has not only a larger specific surface area, a larger pore volume and a larger pore diameter, but also a stable framework structure, the structural defect that the resin catalyst is easy to expand and be heated and decomposed can be avoided, and the catalyst with excellent catalytic performance is hopeful to be obtained.
The inventor of the invention discovers that the hexagonal single crystal mesoporous molecular sieve has a cubic-centered Im3m crystalline phase structure, the pore canal structure is cubic cage-shaped, and the specific surface area is 300-1000m 2 The volume of the pores per gram is 0.4-1.6mL/g, the average pore diameter is 3-13nm, and the catalyst is very suitable for the catalytic reaction with macromolecules. In addition, the pore canal structure of the hexagonal single crystal mesoporous molecular sieve is composed of a silica basic structure, belongs to an inorganic structure, and can not only be swelled and deformed in an organic solvent, but also has better temperature resistance (can exist stably at 600 ℃). If hexagonal single crystal mesoporous material is used as a carrier, supported Lewis acid is used for preparing the catalyst with good dispersionCan be used for acetate synthesis reaction, and can show good catalytic activity and ester selectivity.
According to the present invention, the hexagonal single crystal mesoporous material preferably has a specific surface area of 650-800m 2 Per gram, the pore volume is 1.1-1.5mL/g, and the average pore diameter is 8-10nm; more preferably, the specific surface area of the hexagonal single crystal mesoporous material is 708-736m 2 Per gram, the pore volume is 1.2-1.3mL/g, and the average pore diameter is 9-9.2nm. In the invention, the structural parameters of the hexagonal single crystal mesoporous material are limited to be within the above 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 content of the hexagonal single crystal mesoporous material is 40-80 wt% and the content of the alkyl sulfonate is 20-60 wt% based on the total weight of the catalyst; 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 hexagonal single crystal mesoporous material is contained in an amount of 51.9 to 64.6 wt% and the alkyl sulfonate is contained in an amount of 35.4 to 48.1 wt% based on the total weight of the catalyst. In the invention, the content of the hexagonal single crystal mesoporous material and the content of the alkyl sulfonate are limited to be within the above ranges, and the prepared catalyst can show good catalytic activity and ester selectivity when being used for an 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 in the alkyl sulfonate is selected from one or more of heptane, dodecyl and tetradecyl; 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 template agent removal treatment and thermal activation treatment on the hexagonal single crystal mesoporous material raw powder to obtain the hexagonal single crystal mesoporous material.
The templating agent according to the present invention may be various templating agents conventional in the art. For example, the templating agent may be a triblock copolymer polyoxyethylene-polyoxypropylene-polyoxyethylene, which can be prepared by methods known to those skilled in the art, or can be obtained commercially, for example, from Fuka, under the trade name Synpronic F108, molecular formula EO132PO60EO132, average molecular weight Mn=14600.
According to the present invention, the acidic aqueous solution is preferably an aqueous solution of a mineral acid, including an aqueous solution of sulfuric acid, an aqueous solution of hydrochloric acid, an aqueous solution of hydrobromic acid and an aqueous solution of nitric acid, more preferably an aqueous solution of hydrochloric acid.
According to the present invention, the silicon source is preferably at least one of ethyl orthosilicate, methyl orthosilicate, propyl orthosilicate, sodium orthosilicate, and silica sol, more preferably ethyl orthosilicate.
According to the invention, in step (I), the molar ratio of the template, potassium sulfate, silicon source, water and 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 25-60deg.C, and the time is 10-200min. In order to further facilitate uniform mixing of the substances, according to a preferred embodiment of the invention, the mixing contact is carried out under stirring.
According to the present invention, in step (II), the crystallization conditions may include: the temperature is 25-60deg.C, preferably 30-55deg.C; the time is 10-72 hours, preferably 10-40 hours. According to a preferred embodiment, the crystallization is performed by a hydrothermal crystallization method.
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 washing times can be 2-10), and then suction filtration is performed.
According to the invention, in step (III), the template removal treatment is typically a calcination process. The template agent removal treatment process comprises the following steps: calcining the hexagonal single crystal mesoporous material raw powder in an air atmosphere; the template removal temperature is preferably 400-700 ℃, and the template removal time is preferably 8-20h.
According to the present invention, the heat activation treatment process includes: roasting in nitrogen atmosphere to remove the template agent to obtain a product; the thermal activation temperature is preferably 450-800 ℃, and the thermal activation time is preferably 8-20h.
According to the present invention, the drying conditions are not particularly limited, and include, for example: the drying temperature is 70-150 ℃ and the drying time is 3-20h.
According to the invention, the specific surface area of the esterification catalyst is 500-650m 2 Per gram, the pore volume is 0.8-1.2mL/g, and the average pore diameter is 6-8nm; preferably, the specific surface area of the esterification catalyst is 542-604m 2 Per gram, the pore volume is 0.9-1.1mL/g, and the average pore diameter is 6.8-7.4nm.
The second aspect of the present invention provides a preparation method of the esterification catalyst, wherein the preparation method comprises the following steps:
(1) Mixing 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) Filtering, washing and drying the product to obtain the esterification catalyst.
According to the invention, the sodium alkyl sulfonate is linear sodium alkyl sulfonate and/or branched sodium alkyl sulfonate; preferably, the sodium alkyl sulfonate is linear sodium alkyl sulfonate; preferably, the alkyl group in the sodium alkyl sulfonate is selected from one or more of heptane, dodecyl and tetradecyl.
According to the invention, the hexagonal single crystal mesoporous material, the sodium alkyl sulfonate and water have a weight ratio of 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 may be 40-100deg.C, preferably 60-90deg.C; the time may be 1 to 50 hours, preferably 5 to 30 hours. Preferably, in order to achieve better mixing effect, the mixing efficiency can be improved by rapid stirring or by means of ultrasonic means in the process of mixing the hexagonal single crystal mesoporous material, the sodium alkyl sulfonate and the deionized water. Wherein the water is preferably deionized water.
According to the present invention, in step (2), an aqueous solution of a metal salt is preferably added dropwise to the mixture at a dropping rate of 0.5 to 2.0mL/min for contact reaction.
According to the invention, the metal salt is selected from one or more of chloride, sulfate and nitrate of a metal; preferably, the metal is lanthanum and/or cerium; preferably, the concentration of the aqueous solution of the metal salt is 0.02 to 1.0mol/L, preferably 0.05 to 0.6mol/L.
According to the invention, the conditions of the contact reaction of said mixture with the aqueous metal salt solution include: the reaction temperature may be 40-100deg.C, preferably 60-90deg.C; the time may be 0.1 to 20 hours, preferably 0.5 to 10 hours. Preferably, in order to achieve a better contact reaction effect, the mixture may be rapidly stirred during the contact reaction with the aqueous metal salt solution.
The method for washing a solid product according to the present invention is not particularly limited, for example: the solid product may be washed with deionized water, the volume ratio of deionized water to solid product may be 5-20, and the number of washes may be 2-8. Preferably, to achieve better washing results, rapid agitation may be used during the mixing of deionized water with the solid product.
According to the present invention, the drying conditions include: the temperature may be 120-230 ℃, preferably 150-200 ℃; the time may be 1 to 30 hours, preferably 3 to 20 hours.
In a third aspect, the present invention provides an application of the esterification catalyst in an esterification synthesis reaction of acetic acid and alcohol, wherein the esterification synthesis reaction comprises: acetic acid and alcohol are contacted with the esterification catalyst.
According to the present 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 50-160deg.C, preferably 70-140deg.C; the pressure is 0.01-5.0MPa, preferably 0.1-3.0MPa; the mass space velocity of acetic acid is 0.01-30h -1 Preferably 0.1-10h -1 The method comprises the steps of carrying out a first treatment on the surface of the 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 by examples.
In the following examples and comparative examples:
the XRD pattern of the sample was obtained on an X' Pert MPD X-ray powder diffractometer manufactured by Philips company, cu ka radiation, λ= 0.154178nm, scan range 2θ=0.5 ° to 10 °.
The pore structure parameter analysis of the samples was performed on an ASAP2020-M+C type adsorber available from Micromeritics, inc. The sample was vacuum degassed at 350 ℃ for 4 hours prior to measurement, the specific surface area of the sample was calculated using the BET method, and the pore volume was calculated using the BJH model.
The drying oven is manufactured by Shanghai-Heng scientific instrument Co., ltd, and the model is DHG-9030A.
The muffle furnace is available from CARBOLITE company under the model CWF1100.
F108 used in examples and comparative examples was purchased from Fuka corporation. The other reagents used in the examples and comparative examples were purchased from national pharmaceutical chemicals, inc., and the purity of the reagents was analytically pure.
Example 1
(1) Preparation of hexagonal single crystal mesoporous material
20g (0.0014 mol) of template F108, 52.4g (0.3 mol) of potassium sulfate are mixed with 600g of aqueous hydrochloric acid (which contains 1.2mol of HCl) and stirred at 38℃until F108 is completely dissolved; 41.6g (0.2 mol) of ethyl orthosilicate is added into the solution, stirring is continued for 15min at 38 ℃, and standing and crystallization are carried out for 24h at 38 ℃; washing the solid product obtained by filtration with deionized water for 4 times, and drying at 110 ℃ for 10 hours after suction filtration to obtain the hexagonal mesoporous material raw powder. Calcining the hexagonal mesoporous material raw powder for 10 hours at 500 ℃ in an air atmosphere, and removing a template agent; and then calcining for 10 hours at 550 ℃ under the protection of nitrogen, and performing heat activation treatment to obtain the hexagonal single crystal mesoporous material A after heat activation.
The specific surface area of the hexagonal single crystal mesoporous material A is 721m 2 Per gram, pore volume of 1.3cm 3 And/g, average pore diameter of 9.1nm.
Fig. 1 (a) is an XRD spectrum of hexagonal single crystal mesoporous material a. From the XRD spectrum, it is apparent that the hexagonal single-crystal mesoporous material a exhibits 1 diffraction peak (2θ=0.6°) at the (110) plane and a diffraction shoulder (2θ=1.2°) at the (200) plane corresponding to the cubic center Im3m crystal phase in the small angle region. (110) The diffraction peak intensity of the surface is high, the peak shape is narrow, and the hexagonal single crystal mesoporous material has a good ordered mesoporous structure.
FIG. 2 (a) is a pore size distribution diagram of a hexagonal single crystal mesoporous material A. As can be seen from the pore size distribution diagram, the hexagonal single crystal mesoporous material has the advantages of narrow pore size distribution, very uniform pore channels and most probable pore size of about 9nm.
(2) Preparation of esterification catalyst
10g of hexagonal single crystal mesoporous material, 5g of sodium dodecyl sulfate and 400g of deionized water are mixed, stirred for 8 hours at 75 ℃ and uniformly mixed. The temperature of the mixture is kept at 75 ℃,180 mL of lanthanum sulfate aqueous solution with the concentration of 0.2mol/L is slowly added into the mixture in a dropwise manner at the rate of 1.0mL/min, and the mixture is stirred at 75 ℃ for 3 hours and then cooled to room temperature. Standing at room temperature for 20h. Filtering to obtain a solid product, washing the solid product with deionized water for 6 times, and drying the solid product at 180 ℃ for 20 hours to obtain an esterification catalyst A.
The content of hexagonal single crystal mesoporous material was 58.4 wt% and the content of lanthanum dodecylsulfate was 41.6 wt% based on the total weight of the esterification catalyst a.
The specific surface area of the esterification catalyst A was 570m 2 Per gram, pore volume of 1.1cm 3 /g, average pore size of7.2nm。
FIG. 1 (b) is an XRD spectrum of esterification catalyst A. As is evident from the XRD spectrum, the hexagonal single crystal mesoporous material a still maintains a typical mesoporous structure after being loaded. Because the pore canal of the catalyst is narrowed after the catalyst is loaded, the positions of two characteristic diffraction peaks on the XRD spectrum are shifted to a large angle direction.
FIG. 2 (b) is a pore size distribution diagram of the esterification catalyst A. From the pore size distribution, the pore channels of the catalyst are still very uniform, and the most probable pore size is about 7nm.
(3) Evaluation of esterification catalyst reactivity
The catalytic performance of the esterification catalyst a in the esterification reaction of acetic acid with n-butanol was evaluated on a fixed bed reactor. 5.0 g of the catalyst was charged into a stainless steel fixed bed reactor having an inner diameter of 8mm, a reaction temperature of 120℃and a reaction pressure of 0.3MPa and a weight space velocity of acetic acid of 3.0h were adjusted by nitrogen gas -1 The molar ratio of n-butanol to acetic acid was 4:1 and the reaction time was 50 hours. After cooling the product was analyzed by Agilent 7890A gas chromatograph equipped with FFAP capillary chromatography column and hydrogen flame detector (FID), and quantitative analysis was performed using a calibration factor with programmed temperature. The acetic acid conversion was 96.5% and the selectivity to n-butyl acetate was 99.5%.
Example 2
(1) Preparation of hexagonal single crystal mesoporous material
20g (0.0014 mol) of template F108, 73.4g (0.42 mol) of potassium sulfate are mixed with 833g of aqueous hydrochloric acid (which contains 2.1mol of HCl) and stirred at 55℃until F108 is completely dissolved; 58.2g (0.28 mol) of ethyl orthosilicate is added into the solution, stirring is continued for 10min at 55 ℃, and standing and crystallization are carried out for 10h at 55 ℃; washing the solid product obtained by filtration with deionized water for 6 times, and drying at 150 ℃ for 3 hours after suction filtration to obtain the hexagonal mesoporous material raw powder. Calcining the hexagonal mesoporous material raw powder for 15 hours at 600 ℃ in an air atmosphere, and removing a template agent; and then calcining for 8 hours at 650 ℃ under the protection of nitrogen, and performing heat activation treatment to obtain the hexagonal single crystal mesoporous material B after heat activation.
The specific surface area of the hexagonal single crystal mesoporous material B is 708m 2 /g，Pore volume of 1.2cm 3 And/g, average pore diameter of 9.0nm.
The XRD spectrum of hexagonal single crystal mesoporous material B is similar to that of FIG. 1 (a). The pore size distribution diagram of the hexagonal single crystal mesoporous material B is similar to that of fig. 2 (a).
(2) Preparation of esterification catalyst
10g of hexagonal single crystal mesoporous material, 4g of sodium tetradecyl sulfonate and 200g of deionized water are mixed, stirred for 15 hours at 60 ℃ and uniformly mixed. The mixture temperature was kept at 60℃and 350mL of a cerium sulfate aqueous solution having a concentration of 0.1mol/L was slowly added dropwise to the above mixture, followed by stirring at 60℃for 10 hours and then cooling to room temperature. Standing at room temperature for 20h. Filtering to obtain a solid product, washing the solid product with deionized water for 6 times, and drying the solid product at 200 ℃ for 5 hours to obtain an esterification catalyst B.
The content of hexagonal single crystal mesoporous material was 64.6 wt% and the content of cerium tetradecyl sulfonate was 35.4 wt% based on the total weight of the esterification catalyst B.
The specific surface area of the esterification catalyst B is 604m 2 Per gram, pore volume of 1.0cm 3 And/g, average pore diameter of 7.4nm.
(3) Evaluation of esterification catalyst reactivity
The catalytic performance of esterification catalyst B in the esterification reaction of acetic acid with isobutanol was evaluated on a fixed bed reactor. 5.0 g of the catalyst was charged into a stainless steel fixed bed reactor having an inner diameter of 8mm, a reaction temperature of 120℃and a reaction pressure of 0.3MPa and a weight space velocity of acetic acid of 3.0h were adjusted by nitrogen gas -1 The molar ratio of isobutanol to acetic acid was 4:1 and the reaction time was 50 hours. After cooling the product was analyzed by Agilent 7890A gas chromatograph equipped with FFAP capillary chromatography column and hydrogen flame detector (FID), and quantitative analysis was performed using a calibration factor with programmed temperature. The acetic acid conversion was 95.8% and the isobutyl acetate selectivity was 99.4%.
Example 3
(1) Preparation of hexagonal single crystal mesoporous material
20g (0.0014 mol) of template F108, 24.5g (0.14 mol) of potassium sulfate are mixed with 278g of aqueous hydrochloric acid (containing 0.7mol of HCl) and stirred at 30℃until F108 is completely dissolved; 29.1g (0.14 mol) of ethyl orthosilicate is added into the solution, stirring is continued for 60min at 30 ℃, and standing and crystallization are carried out for 40h at 30 ℃; washing the solid product obtained by filtration 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 a template agent; and then calcining for 16 hours at 500 ℃ under the protection of nitrogen, and performing heat activation treatment to obtain the hexagonal single crystal mesoporous material C after heat activation.
The specific surface area of the hexagonal single crystal mesoporous material C is 736m 2 Per gram, pore volume of 1.3cm 3 And/g, average pore diameter of 9.2nm.
The XRD spectrum of hexagonal single crystal mesoporous material C is similar to that of FIG. 1 (a). The pore size distribution diagram of the hexagonal single crystal mesoporous material B is similar to that of fig. 2 (a).
(2) Preparation of esterification catalyst
10g of hexagonal single crystal mesoporous material, 5.5g of sodium heptylsulfonate and 500g of deionized water are mixed, stirred for 5 hours at 90 ℃ and uniformly mixed. The temperature of the mixture was kept at 90 ℃, 100mL of a lanthanum trichloride aqueous solution with a concentration of 0.4mol/L was slowly added dropwise to the above mixture, and the mixture was stirred at 90 ℃ for reaction for 1 hour and then cooled to room temperature. Standing at room temperature for 20h. Filtering to obtain a solid product, washing the solid product with deionized water for 6 times, and drying the solid product at 150 ℃ for 20 hours to obtain an esterification catalyst C.
The content of hexagonal single crystal mesoporous material was 51.9 wt% and the content of lanthanum heptanesulfonate was 48.1 wt% based on the total weight of the esterification catalyst C.
The specific surface area of the esterification catalyst C was 542m 2 Per gram, pore volume of 0.9cm 3 And/g, average pore diameter of 6.8nm.
(3) Evaluation of esterification catalyst reactivity
The catalytic performance of the esterification catalyst C in the esterification reaction of acetic acid with n-propanol was evaluated on a fixed bed reactor. 5.0 g of the catalyst was charged into a stainless steel fixed bed reactor having an inner diameter of 8mm, a reaction temperature of 110℃and a reaction pressure of 0.3MPa and a weight space velocity of acetic acid of 4.0h were adjusted by nitrogen gas -1 The molar ratio of n-propanol to acetic acid was 4:1 and the reaction time was 50 hours. After cooling the product, a capillary tube equipped with FFAP was usedAgilent 7890A gas chromatograph analysis of the column and hydrogen flame detector (FID) was performed using temperature programming and quantitative analysis with correction factors. The acetic acid conversion was 96.0% and the selectivity to n-propyl acetate was 99.6%.
Comparative example 1
Hexagonal single crystal mesoporous material and esterification catalyst were prepared in the same manner as in example 1, except that:
step (1) and step (2) in example 1 were omitted, and the catalytic performance of the porcelain ball (non-catalyst) was tested according to the acetic acid esterification reaction performance evaluation method of step (3) in example 1. The ceramic ball is of a Denstone 99 low-silicon ceramic ball, and parameters of the ceramic ball comprise: the alumina content is more than 99% and the silica content is less than 0.2%, which are purchased from holy gobian (Guanghan) haydite Co.
As a result, the conversion of acetic acid was 8.7%, and the selectivity to n-butyl acetate was 1.6%.
Comparative example 2
Hexagonal single crystal mesoporous material and esterification catalyst were prepared in the same manner as in example 1, except that:
step (1) and step (2) in example 1 were omitted, and the catalytic performance of the resin catalyst was tested according to the acetic acid esterification reaction performance evaluation method of step (3) in example 1. Wherein, the resin catalyst is purchased from Kai environmental protection technology Co., ltd, model 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
Hexagonal single crystal mesoporous material and esterification catalyst were prepared in the same manner as in example 1, except that:
the method of step (1) in example 1 was changed so that the specific surface area of the prepared hexagonal single crystal mesoporous material was 287m 2 Per g, pore volume was 0.35mL/g and average pore diameter was 6.2nm.
Catalyst D3 was prepared in the same manner as in step (2) of example 1, and the specific surface area of the catalyst thus prepared was 216m 2 Per g, pore volume was 0.3mL/g and average pore diameter was 4.0nm.
As a result, the conversion of acetic acid was 86.4%, and the selectivity to n-butyl acetate was 92.1%.
Comparative example 4
Hexagonal single crystal mesoporous material and esterification catalyst were prepared in the same manner as in example 1, except that:
the procedure of step (1) in example 1 was modified, specifically:
(2) Preparation of esterification catalyst
10g of hexagonal single crystal mesoporous material, 5g of sodium dodecyl sulfate and 400g of deionized water are mixed, stirred for 8 hours at 75 ℃ and uniformly mixed. The mixture was kept at 75℃and immersed in 180mL of a 0.2mol/L aqueous lanthanum sulfate solution, and the mixture was stirred at 75℃for 3 hours and then cooled to room temperature. Standing at room temperature for 20h. Filtering to obtain a solid product, washing the solid product with deionized water for 6 times, and drying the solid product at 180 ℃ for 20 hours to obtain an esterification catalyst D4.
The specific surface area of the catalyst thus prepared was 492m 2 Per g, pore volume was 0.9mL/g and average pore diameter was 6.6nm.
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 invention can directly convert acetic acid and alcohol to form acetate.
As can be seen from the data of comparative example 1 and comparative example 1, if porcelain balls were used instead of the esterification catalyst to be charged into the reactor, the acetic acid conversion rate was extremely low and almost no acetate was produced.
As can be seen from the data of comparative example 1 and comparative example 2, the acetic acid conversion and the acetate selectivity of the esterification catalyst were both significantly improved compared to the resin catalyst.
As can be seen from the data of comparative examples 1 and 3, the structural parameters of the hexagonal single crystal mesoporous material and the prepared catalyst are not within the range defined in the present invention, resulting in lower acetic acid conversion and acetate selectivity.
As can be seen from the data of comparative examples 1 and 4, the acetic acid conversion and the acetate selectivity were lower as the catalyst was not prepared by the process of the present invention.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (17)
1. The esterification catalyst is characterized by comprising a carrier and alkyl sulfonate 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 crystalline phase structure, the pore canal structure is in a cubic cage shape, and the specific surface area is 300-1000m 2 Per gram, the pore volume is 0.4-1.6mL/g, and the average pore diameter is 3-13nm; the alkyl sulfonate is linear alkyl sulfonate and/or branched alkyl sulfonate; the alkyl in the alkyl sulfonate is selected from one or more of heptane, dodecyl and tetradecyl; the sulfonate in the alkyl sulfonate is lanthanum sulfonate and/or cerium sulfonate.
2. The esterification catalyst according to claim 1, wherein the hexagonal single crystal mesoporous material has a specific surface area of 650-800m 2 Per gram, the pore volume is 1.1-1.5mL/g, and the average pore diameter is 8-10nm.
3. The esterification catalyst according to claim 2, wherein the hexagonal single crystal mesoporous material has a specific surface area of 708-736m 2 Per gram, the pore volume is 1.2-1.3mL/g, and the average pore diameter is 9-9.2nm.
4. An esterification catalyst according to claim 1 or 3, wherein the hexagonal single crystal mesoporous material is present in an amount of 40-80 wt% and the alkyl sulfonate is present in an amount of 20-60 wt%, based on the total weight of the catalyst.
5. The esterification catalyst of claim 1, wherein the alkyl sulfonate is a linear alkyl sulfonate.
6. The esterification catalyst according to claim 1 or 3, 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 template agent removal treatment and thermal activation treatment on the hexagonal single crystal mesoporous material raw powder to obtain the hexagonal single crystal mesoporous material.
7. The esterification catalyst of claim 6, wherein in step (I), the molar ratio of the template, potassium sulfate, silicon source, water, and hydrogen chloride is 1: (50-500): (50-300): (5000-50000): (200-2000);
in step (II), the crystallization conditions include: the temperature is 25-60 ℃, and the crystallization time is 10-72h;
in step (III), the conditions of the stripper treatment include: the temperature is 400-700 ℃ and the time is 8-20h; the conditions of the heat activation treatment include: the temperature is 450-800 ℃ and the time is 8-20h.
8. The esterification catalyst according to claim 1, wherein the specific surface area of the esterification catalyst is 500-650m 2 Per gram, the pore volume is 0.8-1.2mL/g, and the average pore diameter is 6-8nm.
9. The esterification catalyst according to claim 8, wherein the specific surface area of the esterification catalyst is 542-604m 2 Per gram, the pore volume is 0.9-1.1mL/g, and the average pore diameter is 6.8-7.4nm.
10. A process for the preparation of an esterification catalyst according to any one of claims 1 to 9, comprising:
(1) Mixing hexagonal single crystal mesoporous material with sodium alkyl sulfonate and water to obtain a mixture; the sodium alkyl sulfonate is straight-chain sodium alkyl sulfonate and/or branched-chain sodium alkyl sulfonate; the alkyl in the sodium alkyl sulfonate is selected from one or more of heptane, dodecyl and tetradecyl;
(2) Carrying out contact reaction on the aqueous solution of the metal salt and the mixture to obtain a product; the metal salt is selected from one or more of chloride, sulfate and nitrate of metal; the metal is lanthanum and/or cerium;
(3) Filtering, washing and drying the product to obtain the esterification catalyst.
11. The method according to claim 10, wherein the sodium alkyl sulfonate is a linear sodium alkyl sulfonate.
12. The preparation method of claim 10, wherein the hexagonal single crystal mesoporous material, the sodium alkyl sulfonate and water have a weight ratio of 1: (0.1-5): (5-100).
13. The production method according to claim 10, wherein the concentration of the aqueous solution of the metal salt is 0.02 to 1.0mol/L.
14. The method of claim 10, wherein the contacting conditions comprise: the temperature is 40-100deg.C, and the time is 0.1-20h.
15. Use of the esterification catalyst of any one of claims 1-9 in an esterification synthesis reaction of acetic acid and an alcohol, wherein the esterification synthesis reaction comprises: acetic acid and alcohol are contacted with the esterification catalyst.
16. The application according to claim 15And wherein the conditions of the contacting reaction include: the temperature is 50-160 ℃; the pressure is 0.01-5.0MPa; the mass space velocity of acetic acid is 0.01-30h -1 The method comprises the steps of carrying out a first treatment on the surface of the The molar ratio of acetic acid to alcohol is 1:0.1-20.
17. The use of claim 16, wherein the conditions of the contact reaction comprise: the temperature is 70-140 ℃; the pressure is 0.1-3.0Mpa; the mass space velocity of acetic acid is 0.1-10h -1 The method comprises the steps of carrying out a first treatment on the surface of the The molar ratio of acetic acid to alcohol is 1:0.5-10.
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