CN115155557A - Catalyst for synthesizing tertiary alkyl ester, preparation method thereof and tertiary alkyl ester synthesis method - Google Patents
Catalyst for synthesizing tertiary alkyl ester, preparation method thereof and tertiary alkyl ester synthesis method Download PDFInfo
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- CN115155557A CN115155557A CN202210844409.6A CN202210844409A CN115155557A CN 115155557 A CN115155557 A CN 115155557A CN 202210844409 A CN202210844409 A CN 202210844409A CN 115155557 A CN115155557 A CN 115155557A
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- Prior art keywords
- catalyst
- tertiary alkyl
- alkyl ester
- carrier
- synthesizing
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- 239000003054 catalyst Substances 0.000 title claims abstract description 132
- 125000005907 alkyl ester group Chemical group 0.000 title claims abstract description 67
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 36
- 238000001308 synthesis method Methods 0.000 title claims abstract description 6
- 238000002360 preparation method Methods 0.000 title abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 67
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 27
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 16
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 15
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 15
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 14
- 230000008569 process Effects 0.000 claims abstract description 10
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 6
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 6
- 239000002808 molecular sieve Substances 0.000 claims abstract description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000004185 ester group Chemical group 0.000 claims abstract 3
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 43
- -1 halate Chemical compound 0.000 claims description 22
- 230000015572 biosynthetic process Effects 0.000 claims description 18
- 239000002243 precursor Substances 0.000 claims description 18
- 238000003786 synthesis reaction Methods 0.000 claims description 18
- 239000011949 solid catalyst Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 239000003426 co-catalyst Substances 0.000 claims description 9
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 8
- 238000005809 transesterification reaction Methods 0.000 claims description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 6
- 229940126062 Compound A Drugs 0.000 claims description 6
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 5
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 125000003107 substituted aryl group Chemical group 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- 150000001540 azides Chemical class 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 abstract description 9
- 230000035484 reaction time Effects 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000010924 continuous production Methods 0.000 abstract description 5
- 238000007086 side reaction Methods 0.000 abstract description 3
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 22
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 18
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 16
- 239000007787 solid Substances 0.000 description 8
- 150000002148 esters Chemical group 0.000 description 7
- 238000009210 therapy by ultrasound Methods 0.000 description 7
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 6
- PLXGRQSQSTVVQP-UHFFFAOYSA-N bis(2-methylbutan-2-yl) butanedioate Chemical compound CCC(C)(C)OC(=O)CCC(=O)OC(C)(C)CC PLXGRQSQSTVVQP-UHFFFAOYSA-N 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 238000002604 ultrasonography Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- GOORECODRBZTKF-UHFFFAOYSA-N ditert-butyl butanedioate Chemical compound CC(C)(C)OC(=O)CCC(=O)OC(C)(C)C GOORECODRBZTKF-UHFFFAOYSA-N 0.000 description 5
- 125000005233 alkylalcohol group Chemical group 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000003158 alcohol group Chemical group 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 125000004076 pyridyl group Chemical group 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 2
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 description 2
- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 125000000332 coumarinyl group Chemical group O1C(=O)C(=CC2=CC=CC=C12)* 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000002541 furyl group Chemical group 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 125000003373 pyrazinyl group Chemical group 0.000 description 2
- 125000000714 pyrimidinyl group Chemical group 0.000 description 2
- 125000000168 pyrrolyl group Chemical group 0.000 description 2
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 2
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000001544 thienyl group Chemical group 0.000 description 2
- 125000004306 triazinyl group Chemical group 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 description 1
- 125000000094 2-phenylethyl group Chemical class [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- DKMROQRQHGEIOW-UHFFFAOYSA-N Diethyl succinate Chemical compound CCOC(=O)CCC(=O)OCC DKMROQRQHGEIOW-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 125000000641 acridinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3C=C12)* 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 125000004604 benzisothiazolyl group Chemical group S1N=C(C2=C1C=CC=C2)* 0.000 description 1
- 125000004603 benzisoxazolyl group Chemical group O1N=C(C2=C1C=CC=C2)* 0.000 description 1
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000004618 benzofuryl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
- XSCHRSMBECNVNS-UHFFFAOYSA-N benzopyrazine Natural products N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 1
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000004935 benzoxazolinyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 125000001797 benzyl group Chemical class [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 125000000259 cinnolinyl group Chemical group N1=NC(=CC2=CC=CC=C12)* 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- GPWDPLKISXZVIE-UHFFFAOYSA-N cyclo[18]carbon Chemical class C1#CC#CC#CC#CC#CC#CC#CC#CC#C1 GPWDPLKISXZVIE-UHFFFAOYSA-N 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000002704 decyl 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])* 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000004987 dibenzofuryl group Chemical group C1(=CC=CC=2OC3=C(C21)C=CC=C3)* 0.000 description 1
- 125000004988 dibenzothienyl group Chemical group C1(=CC=CC=2SC3=C(C21)C=CC=C3)* 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- SZHZCPHKDJWHNG-UHFFFAOYSA-N dipropyl butanedioate Chemical compound CCCOC(=O)CCC(=O)OCCC SZHZCPHKDJWHNG-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 125000003453 indazolyl group Chemical group N1N=C(C2=C1C=CC=C2)* 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000005956 isoquinolyl group Chemical group 0.000 description 1
- 125000001786 isothiazolyl group Chemical group 0.000 description 1
- 125000000842 isoxazolyl group Chemical group 0.000 description 1
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004593 naphthyridinyl group Chemical group N1=C(C=CC2=CC=CN=C12)* 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010451 perlite Substances 0.000 description 1
- 235000019362 perlite Nutrition 0.000 description 1
- LFSXCDWNBUNEEM-UHFFFAOYSA-N phthalazine Chemical compound C1=NN=CC2=CC=CC=C21 LFSXCDWNBUNEEM-UHFFFAOYSA-N 0.000 description 1
- 125000005545 phthalimidyl group Chemical group 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 125000006168 tricyclic group Chemical group 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
- B01J23/04—Alkali metals
-
- 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
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Abstract
The invention provides a catalyst for synthesizing tertiary alkyl ester, a preparation method thereof and a tertiary alkyl ester synthesis method, and belongs to the technical field of fine chemical engineering. The catalyst for synthesizing the tertiary alkyl ester comprises a carrier and a main catalyst loaded on the carrier, wherein the main catalyst is selected from oxides of alkali metals or alkaline earth metals, and the carrier is selected from gamma-Al 2 O 3 One of active carbon, molecular sieve and ion exchange resin. The catalyst is applied to a process for synthesizing the tertiary alkyl ester by adopting an ester exchange process, on one hand, when the purity of the synthesized tertiary alkyl ester is more than or equal to 99.0 percent, the yield of the tertiary alkyl ester is more than or equal to 85 percent, and the catalytic selection is effectively improvedThe side reaction is reduced, and the yield of the tertiary alkyl ester is improved; on the other hand, the reaction time is shortened, the reaction efficiency is improved, and the yield are improved; meanwhile, the catalyst and the reaction product are easy to separate, so that the continuous production of the tertiary alkyl ester is convenient to realize, and the method is simple, environment-friendly, economical and energy-saving.
Description
Technical Field
The invention belongs to the technical field of fine chemical engineering, and particularly relates to a catalyst for synthesizing tertiary alkyl ester, a preparation method of the catalyst and a tertiary alkyl ester synthesis method.
Background
Tertiary alkyl esters are an important class of organic chemicals because, unlike primary or secondary alkyl esters which can generally be prepared directly by direct reaction of primary or secondary alcohols, tertiary alkyl alcohols result in lower yields of product or even failure of the reaction due to steric hindrance of the reaction and the occurrence of other side reactions.
The transesterification process is an important route for the synthesis of tertiary alkyl esters, and usually, the transesterification process for the synthesis of tertiary alkyl esters can employ either an acidic catalyst or a basic catalyst, but the efficiency of the basic catalyst is significantly faster than that of the acidic catalyst. The basic catalyst is usually a homogeneous catalyst which is soluble in the reaction system, such as alkali metal alkoxide, hydroxide, oxide, carbonate, etc. For example, patent CN103804190A discloses that a mixture of lithium hydroxide and cesium carbonate is used as a catalyst, and dimethyl succinate or diethyl succinate is reacted with alkyl tertiary alcohol; for another example, US4904814 uses metal lithium, metal sodium, lithium amide, sodium methoxide or sodium ethoxide as a catalyst, wherein the nature of the metal sodium and the metal lithium as the catalyst is also catalyzed by reacting with alkyl alcohol as a reaction solvent to form lithium alkoxide or sodium alkoxide. For another example, patent CN112295600A discloses the synthesis of tertiary alkyl esters using lithium alkoxide as catalyst.
However, when the homogeneous catalyst is used for synthesizing the tertiary alkyl ester, the product and the catalyst need to be separated by adopting a distillation or reduced pressure rectification mode, the equipment flow is longer, the energy consumption is higher, and the production efficiency and the yield of the tertiary alkyl ester are lower.
Disclosure of Invention
Based on the above, the invention provides a catalyst for synthesizing tertiary alkyl ester and a preparation method thereof, which are used for solving the technical problems that in the tertiary alkyl ester synthesis process in the prior art, a product and the catalyst are difficult to separate, the equipment flow is long, the energy consumption is high, and the production efficiency and yield of the tertiary alkyl ester are low.
The invention also provides a method for synthesizing the tertiary alkyl ester.
The technical scheme for solving the technical problems is as follows:
a catalyst for synthesizing tertiary alkyl ester comprises a carrier and a main catalyst loaded on the carrier; wherein the main catalyst is selected from at least one of oxides of alkali metals or alkaline earth metals; the carrier is selected from gamma-Al 2 O 3 One of active carbon, molecular sieve and ion exchange resin.
Preferably, the catalyst for synthesizing a tertiary alkyl ester further comprises a co-catalyst supported on the carrier, the co-catalyst being selected from at least one of transition metal oxides.
A catalyst for synthesizing a tertiary alkyl ester, the catalyst for synthesizing a tertiary alkyl ester selected from the group consisting of:
the main catalyst is Li 2 O, the carrier is gamma-Al 2 O 3 Or activated carbon; or
The main catalyst is Li 2 O and CaO, and the carrier is gamma-Al 2 O 3 Or activated carbon; or
The main catalyst is Li 2 O and MgO, and the carrier is gamma-Al 2 O 3 Or a catalyst of activated carbon; or
The main catalyst is Li 2 O, cuO as cocatalyst and gamma-Al as carrier 2 O 3 Or activated carbon; or
The main catalyst is Li 2 O and CaO, cuO as cocatalyst, and gamma-Al as carrier 2 O 3 Or activated carbon.
Preferably, the sum of the mass of the main catalyst and the mass of the auxiliary catalyst is 0.1-50% of the mass of the carrier.
Preferably, in the main catalyst, li 2 The content of O is 50-100%.
Preferably, the content of the cocatalyst is 0.1-10% of the content of the main catalyst.
A method for preparing a catalyst for synthesizing a tertiary alkyl ester as described above, comprising the steps of:
contacting a support with a precursor to produce a first product; the precursor is at least one of nitrate, sulfate, halate, phosphate, carbonate, bicarbonate and organic acid salt of alkali metal or alkaline earth metal, or at least one of hydroxide, oxide, amide and azide of alkali metal or alkaline earth metal;
converting the precursor in the first product to an oxide of an alkali metal or an alkaline earth metal.
A method for synthesizing tertiary alkyl ester takes a compound A with a molecular formula shown as a general formula I as a raw material, and the compound A and alcohol with a general formula ROH are subjected to ester exchange reaction under the action of a solid catalyst to prepare the tertiary alkyl ester shown as a general formula II;
wherein R1 independently represents a C1-C10 linear or partially linear alkyl group; r independently represents a C4-C12 tertiary alkyl group; m represents 1 or 2; if m =1, X is an unsubstituted or halogen-substituted alkyl group, a cycloalkyl group, an unsubstituted or substituted aryl or aralkyl group, or an aromatic heterocyclic group; (ii) a straight chain (-CH 2-) n if m =2, wherein n is an integer from 1 to 8;
wherein the solid catalyst is a catalyst for synthesizing tertiary alkyl ester as described above.
Preferably, the molar ratio of compound a to alcohol of formula ROH is 1.
Preferably, when the transesterification reaction is a batch reaction, the addition amount of the solid catalyst is 0.2 to 20 percent of the mass of the compound A; when the ester exchange reaction is a continuous reaction, the reaction space velocity is 1.0h -1 -0.02h -1 。
Preferably, when the transesterification reaction is a continuous reaction, the solid catalyst is separated and then repeatedly used.
Compared with the prior art, the invention has at least the following advantages:
the invention provides a catalyst for synthesizing tertiary alkyl ester, which comprises a carrier and a main catalyst loaded on the carrier, wherein the main catalyst is selected from oxides of alkali metals or alkaline earth metals, and the carrier is selected from gamma-Al 2 O 3 One of active carbon, molecular sieve and ion exchange resin. The catalyst is applied to a process for synthesizing the tertiary alkyl ester by adopting an ester exchange process, on one hand, when the purity of the synthesized tertiary alkyl ester is more than or equal to 99.0 percent, the yield of the tertiary alkyl ester is more than or equal to 85 percent, the catalytic selectivity is effectively improved, the occurrence of side reactions is reduced, and the yield of the tertiary alkyl ester is improved; on the other hand, the reaction time is shortened, the reaction efficiency is improved, and the yield and the output are improved; meanwhile, the catalyst and the reaction product are easy to separate, the continuous production of the tertiary alkyl ester is convenient to realize, and the method is simple, environment-friendly, economical and energy-saving.
Drawings
FIG. 1 is a process flow diagram of a continuous process for the synthesis of tertiary alkyl esters in one embodiment.
Detailed Description
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict. The technical solutions of the present invention will be further described below with reference to the following embodiments of the present invention, and the present invention is not limited to the following specific embodiments.
In one embodiment of the present invention, a catalyst for synthesizing a tertiary alkyl ester includes a support and a main catalyst supported on the support; wherein the main catalyst is selected from at least one of oxides of alkali metals or alkaline earth metals; the carrier is selected from gamma-Al 2 O 3 One of active carbon, molecular sieve and ion exchange resin.
It will be understood by those skilled in the art that the catalyst for synthesizing tertiary alkyl ester provided by the present invention is a solid catalyst, and the carrier is one of the components of the catalyst, is a framework of the active component of the catalyst, supports the active component (i.e. the main catalyst), allows the active component to be dispersed, and can increase the activityStrength of the added catalyst. In the present invention, the carrier itself may or may not have catalytic activity in whole or in part. In some cases, the support may be selected from SiO 2 、γ-Al 2 O 3 Glass fiber mesh (cloth), hollow ceramic ball, sea sand, layered graphite, hollow glass bead, quartz glass tube (sheet), common (conductive) glass sheet, organic glass, optical fiber, natural clay, foamed plastic, resin, wood chip, expanded perlite, activated carbon, etc., or may be a high molecular compound such as ion exchange resin, etc.
The procatalyst is selected from at least one of the oxides of alkali or alkaline earth metals, for example, the procatalyst is selected from Na 2 O、K 2 O、Li 2 O、ORb 2 、Cs 2 O, mgO, caO, baO. Preferably, the main catalyst contains Li 2 O, e.g. the procatalyst is Li 2 O or Li 2 O and MgO, or Li 2 O and CaO.
In some preferred embodiments, the catalyst for synthesizing a tertiary alkyl ester further comprises a co-catalyst supported on the carrier, the co-catalyst being selected from at least one of transition metal oxides. For example, the cocatalyst is selected from at least one of copper oxide, titanium dioxide, zirconium dioxide and bismuth oxide.
In some preferred embodiments provided herein, the catalyst for the synthesis of tertiary alkyl esters is selected from the group consisting of:
the main catalyst is Li 2 O, the carrier is gamma-Al 2 O 3 Or catalysts of activated carbon, i.e. Li 2 O-γ-Al 2 O 3 Catalysts or Li 2 An O-activated carbon catalyst; or the main catalyst is Li 2 O and CaO, and the carrier is gamma-Al 2 O 3 Or catalysts of activated carbon, i.e. Li 2 O@CaO-γ-Al 2 O 3 Catalysts or Li 2 O @ CaO-activated carbon catalyst; or the main catalyst is Li 2 O and MgO, and the carrier is gamma-Al 2 O 3 Or catalysts of activated carbon, i.e. Li 2 O@MgO-γ-Al 2 O 3 Catalysts or Li 2 O @ MgO-activated carbon catalyst; or the main catalyst is Li 2 O, cuO as cocatalyst and gamma-Al as carrier 2 O 3 Or catalysts of activated carbon, i.e. Li 2 O/CuO-γ-Al 2 O 3 Catalysts or Li 2 O/CuO-activated carbon catalyst; or the main catalyst is Li 2 O and CaO, cuO as cocatalyst, and gamma-Al as carrier 2 O 3 Or catalysts of activated carbon, i.e. Li 2 O@CaO/CuO-γ-Al 2 O 3 Catalysts or Li 2 O @ CaO/CuO-activated carbon catalyst.
In some embodiments of the invention, the sum of the mass of the procatalyst and the cocatalyst is from 0.1% to 50%, preferably from 0.5% to 20%, more preferably from 1% to 10% of the mass of the support.
In still other embodiments of the present invention, the main catalyst comprises Li 2 O content of 50% to 100%, preferably, li 2 The content of O is 60% to 90%, more preferably, li 2 The content of O is 70-80%.
In still other embodiments of the present invention, the content of the co-catalyst is 0.1% to 10% of the content of the main catalyst, and preferably, the content of the co-catalyst is 1% to 5% of the content of the main catalyst.
In still another embodiment provided by the present invention, a method for preparing a catalyst for synthesizing a tertiary alkyl ester as described above, includes the steps of:
contacting a support with a precursor to produce a first product; the precursor is at least one of nitrate, sulfate, halide, phosphate, carbonate, bicarbonate and organic acid salt of alkali metal or alkaline earth metal, or at least one of hydroxide, oxide, amide and azide of alkali metal or alkaline earth metal.
Converting the precursor in the first product to an oxide of an alkali metal or an alkaline earth metal.
In particular, the carrier and the precursor may be contacted in any way such that the precursor adheres to the surface or within the pores of the carrier. For example, the precursor may be contacted with the support by an impregnation method, a deposition precipitation method, an ion exchange method, a chemical vapor deposition method, or the like. After the precursor is contacted with the support, the precursor can be converted to the corresponding oxide by a suitable method such as oxidation, reduction, baking, high temperature calcination, and the like.
In one embodiment, the catalyst for synthesizing the tertiary alkyl ester is prepared by a precipitation method-high temperature roasting method. For example, the support is placed in a solution of the precursor and a precipitant is slowly added to convert the precursor to the corresponding carbonate or hydroxide (if the precursor itself is a carbonate or hydroxide, this step is omitted), resulting in a first product. And separating the first product from the solution, drying, and then roasting at high temperature to convert the precursor into corresponding oxide.
For example, liCl solution is prepared and gamma-Al is added 2 O 3 Or dispersing activated carbon in LiCl solution, adding NaCO into the solution 3 Solution, after a period of time, gamma-Al 2 O 3 Or the active carbon is fully infiltrated to obtain a first product. Separating and drying the first product, heating to 700 ℃ under reduced pressure to decompose the first product, and keeping the temperature for 50h until no gas is generated, thereby obtaining the catalyst for synthesizing the tertiary alkyl ester.
In another embodiment of the invention, a method for synthesizing tertiary alkyl ester, which takes a compound A with a general formula I as a raw material to perform transesterification reaction with alcohol with a general formula ROH under the action of a solid catalyst to prepare tertiary alkyl ester with a general formula II;
wherein R1 independently represents a C1-C10 linear or partially linear alkyl group; r independently represents a C4-C12 tertiary alkyl group; m represents 1 or 2; if m =1, X is an unsubstituted or halogen-substituted alkyl group, a cycloalkyl group, an unsubstituted or substituted aryl or aralkyl group, or an aromatic heterocyclic group; (ii) a straight chain (-CH 2-) n if m =2, wherein n is an integer from 1 to 8;
wherein the solid catalyst is a catalyst for synthesizing tertiary alkyl ester as described above.
<xnotran> , C4-C12 R , ,1- -1- - ,1,1- - ,1,1- - ,1- -1- - ,1- - ,1- -1- - ,1,1- - ,1,1,3- - ,1,1- - ,1- -1- - ,1,1- - ,1- -1- - ,1- -1- - ,1,1- - ,1- -1- - ,1,1,3- - ,1,1- -4- - ,1,1- -3- - ,1,1- - ,1,1- - ,1,1- - ,1,1- - ,1,1- - ,1,1- - ,1,1- - 1,1- - . </xnotran> Preferably tert-butyl or tert-amyl.
Alkyl X is advantageously C4-C18 alkyl, such as n-butyl, sec-butyl, tert-butyl, n-pentyl, tert-pentyl, n-hexyl, 2-ethyl-hexyl, n-octyl, decyl, dodecyl, hexadecyl or octadecyl.
Halogen-substituted alkyl X is, for example, alkyl as defined above which is substituted by one or more chlorine or bromine atoms.
Cycloalkyl X is advantageously C5-C7 cycloalkyl, for example cyclopentyl, cycloheptyl and especially cyclohexyl.
Aryl X is, for example, phenyl or naphthyl, and substituted aryl X is, for example, phenyl, sec-butyl or tert-butyl substituted by one or two of chloro, bromo, C1-C4 alkyl (e.g. methyl, ethyl, propyl, isopropyl, n-butyl), C1-C4 alkoxy (e.g. methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy or tert-butoxy), cyano or nitro.
Aralkyl X is, for example, unsubstituted or C1-C4 alkyl-substituted benzyl or phenethyl.
The aromatic heterocyclic group X is advantageously a monocyclic, bicyclic or tricyclic group. This may be purely heterocyclic or may comprise a heterocyclic ring and one or more fused benzene rings, for example pyridyl, pyrimidinyl, pyrazinyl, triazinyl, furyl, pyrrolyl, thienyl, quinolyl, coumarinyl, benzofuryl, benzimidazolyl, benzoxazolyl, dibenzofuryl, benzothienyl, dibenzothienyl, indolyl, carbazolyl, pyrazolyl, imidazolyl, oxazolyl, isoxazolyl, thiazolyl, indazolyl, benzothiazolyl, pyridazinyl, cinnolinyl, quinazolinyl, quinoxalinyl, phthalazine, phthalimidyl, quinolonyl, maleimido, naphthyridinyl, benzimidazolonyl, benzothiazolyl, quinazolinyl, quinoxalinyl, phthalazolyl, dioxopyrimidinyl, pyridyl, isoquinolyl, isothiazolyl, benzisoxazolyl, benzisothiazolyl, indazolinyl, acridinyl, quinazolindiacyl, quinoxalindioyl, benzoxazinodiacyl, benzoxazolinyl and naphthalene. Preferred are pyridyl, pyrimidinyl, pyrazinyl, triazinyl, furanyl, pyrrolyl, thienyl, quinolinyl, coumarinyl, benzofuranyl, benzimidazolyl and benzoxazolyl.
Esters in which R1 in formula II is methyl are preferably used as starting materials.
In the present invention, the tertiary alkyl ester synthesis method may be performed by a batch or continuous process, and is preferably performed in a continuous process mode. The batch reaction process is to add the catalyst into the reaction system during the reaction, and filter the catalyst before the next operation is carried out when the reaction reaches the target conversion rate. The catalyst can be reused until the catalytic activity is not required. The continuous reaction process is that before reaction, catalyst is filled into a fixed bed, a fluidized bed or other types of continuous flow reactors, then reaction materials are introduced into the reactors at a specified reaction temperature and then flow out of an outlet to the next step, and partial products can be circulated into the reactors in the reaction process to achieve process optimization.
Specifically, the method for synthesizing tertiary alkyl ester provided by the invention mainly comprises the following steps: adding ester, tertiary alkyl alcohol and solid catalyst as raw materialsInto the reactor, the molar ratio of ester to tertiary alkyl alcohol as starting material is 1. For batch reactions, the catalyst is used in an amount of 0.2 to 20% by mass of the ester of the starting material, and for continuous reactions the space velocity is 1h -1 -1/50h -1 The reaction temperature is from room temperature to reflux, and the reflux temperature is preferred in view of the need to distill off the formed R1 OH. The pressure is normal pressure or reduced pressure, and the reduced pressure is favorable for removing the byproduct alcohol in production so as to be favorable for moving the reaction equilibrium to the direction of the product.
Although the longer the reaction time or residence time, the higher the conversion, the longer the time, the better the conversion, since the longer the time, the slower the reaction speed, the more difficult the equilibrium is to move, the lower the efficiency, the higher the operating cost, the unfavorable cost reduction, and the need for comprehensive consideration.
The reaction product contains solvent, raw material and by-product, and can be purified by normal pressure or reduced pressure rectification, and the raw material can be fed into the reactor for cyclic utilization.
The technical solutions and technical effects of the present invention are further described below by specific experimental examples.
1. Preparation of the catalyst
The first experimental example: li 2 O-γ-Al 2 O 3 Preparation of
To 50ml of a 0.1M LiCl solution was added 5g of gamma-Al 2 O 3 Slowly adding 0.1M NaCO under the ultrasonic state 3 And (5) carrying out ultrasonic treatment on the solution for 30min. The solid was separated, dried and then placed in a tube furnace and heated to 680 ℃ under vacuum of 30KPaA for 48h. Reducing the pressure and cooling to obtain Li 2 O-γ-Al 2 O 3 A catalyst.
Experiment example two: li 2 Preparation of O-activated carbon
Adding 5g of activated carbon into 50ml of 0.1M LiCl solution, and slowly adding 0.1M NaCO under the ultrasonic condition 3 And (5) carrying out ultrasonic treatment on the solution for 30min. The solid was separated, dried and then placed in a tube furnace under vacuum of 30KPaA, warmed to 680 deg.C and held for 48h. Reducing the pressure and cooling to obtain Li 2 An O-activated carbon catalyst.
Experiment example three: li 2 O@CaO-γ-Al 2 O 3 Preparation of
40ml of 0.1M LiCl solution and 10ml of 0.1M CaCl solution were taken 2 The solution is mixed by ultrasound, 5g of gamma-Al is added 2 O 3 Slowly adding 0.1M NaCO under the ultrasonic state 3 And (5) carrying out ultrasonic treatment on the solution for 30min. The solid was separated, dried and then placed in a tube furnace and heated to 680 ℃ under vacuum of 30KPaA for 48h. Reducing the pressure and cooling to obtain Li 2 O@CaO-γ-Al 2 O 3 A catalyst.
Experimental example four: li 2 Preparation of O @ CaO-activated carbon
40ml of 0.1M LiCl solution and 10ml of 0.1M CaCl solution were taken 2 Mixing the solution with ultrasound, adding 5g of activated carbon, slowly adding 0.1M NaCO under ultrasound 3 Solution, ultrasonic treatment for 30min. The solid was separated, dried and then placed in a tube furnace under vacuum of 30KPaA, warmed to 680 deg.C and held for 48h. Reducing the pressure and cooling to obtain Li 2 O @ CaO-activated carbon catalyst.
Experimental example five: li 2 O@MgO-γ-Al 2 O 3 Preparation of
40ml of 0.1M LiCl solution and 10ml of 0.1M MgCl were added 2 The solution is mixed by ultrasound, 5g of gamma-Al is added 2 O 3 Slowly adding 0.1M NaCO under the ultrasonic state 3 Solution, ultrasonic treatment for 30min. The solid was separated, dried and then placed in a tube furnace and heated to 680 ℃ under vacuum of 30KPaA for 48h. Reducing the pressure and the temperature to obtain Li 2 O@MgO-γ-Al 2 O 3 A catalyst.
Experimental example six: li 2 O/CuO-γ-Al 2 O 3 Preparation of (2)
45ml of 0.1M LiCl solution and 10ml of 0.01M CuCl solution were added 2 The solution is mixed by ultrasound, 5g of gamma-Al is added 2 O 3 Slowly adding 0.1M NaCO under the ultrasonic condition 3 Solution, ultrasonic treatment for 30min. Separating out solid, drying, and placing the solid in tubeThe temperature in the furnace was raised to 680 ℃ under vacuum of 30KPaA and maintained for 48 hours. Reducing the pressure and the temperature to obtain Li 2 O/CuO-γ-Al 2 O 3 A catalyst.
Example seven: li 2 O@CaO/CuO-γ-Al 2 O 3 Preparation of
40ml of 0.1M LiCl solution and 5ml of 0.1M CaCl are taken 2 Solution, 5ml of 0.01M CuCl 2 The solution is mixed by ultrasound, 5g of gamma-Al is added 2 O 3 Slowly adding 0.1M NaCO under the ultrasonic condition 3 Solution, ultrasonic treatment for 30min. The solid was separated, dried and then placed in a tube furnace under vacuum of 30KPaA, warmed to 680 deg.C and held for 48h. Reducing the pressure and cooling to obtain Li 2 O@CaO/CuO-γ-Al 2 O 3 A catalyst.
2. Synthesis of tertiary alkyl esters
Experimental example eight: synthesis of di-tert-amyl succinate
100g of dimethyl succinate are added to 600ml of anhydrous tert-amyl alcohol at room temperature in a three-necked flask with heating oil bath, temperature-controlled thermocouple, constant-pressure dropping funnel and equipped with a rectification column. Then 2g of Li were added separately 2 O-γ-Al 2 O 3 Catalyst, li 2 O-activated carbon catalyst, li 2 O@CaO-γ-Al 2 O 3 、Li 2 O @ CaO-activated carbon, li 2 O@MgO-γ-Al 2 O 3 Catalyst, li 2 O/CuO-γ-Al 2 O 3 Catalysis, li 2 O@CaO/CuO-γ-Al 2 O 3 A catalyst. The reaction mixture is reacted at reflux temperature, the methanol formed is mixed with tert-amyl alcohol and distilled off continuously on a rectification column, and fresh tert-amyl alcohol is replenished according to the distillation amount of the alcohol. Reacting for 10-20 h until the conversion rate of the raw materials is more than or equal to 95%, filtering and separating reaction products and a catalyst, rectifying the reaction products under reduced pressure to obtain products with the purity of more than or equal to 99%, and calculating the yield of the products.
The separated catalyst was used repeatedly until the conversion of the raw material was < 80% in a given time, and the number of times the catalyst was used repeatedly was counted.
TABLE 1 Synthesis results of di-tert-amyl succinate
| Catalyst and process for preparing same | Reaction time/h | Conversion of feedstock | Product yield | Number of repeated use/time |
| Li 2 O-γ-Al 2 O 3 | 15 | ≥95％ | 79％ | 16 |
| Li 2 O-activated carbon | 18 | ≥95％ | 75％ | 12 |
| Li 2 O@CaO-γ-Al 2 O 3 | 15 | ≥95％ | 85％ | 17 |
| Li 2 O @ CaO-activated carbon | 18 | ≥95％ | 82％ | 12 |
| Li 2 O@MgO-γ-Al 2 O 3 | 16 | ≥95％ | 79％ | 16 |
| Li 2 O/CuO-γ-Al 2 O 3 | 10 | ≥95％ | 84％ | 21 |
| Li 2 O@CaO/CuO-γ-Al 2 O 3 | 10 | ≥95％ | 86％ | 20 |
Please refer to table 1, when the prepared catalyst is used for synthesizing di-tert-amyl succinate, the conversion rate of the raw materials is more than or equal to 95%, the used reaction time is 10h-18h, the product yield is 75% -86%, the catalyst can be reused for 12-21 times, and good catalytic efficiency, selectivity and catalytic stability are shown.
Example nine: synthesis of di-tert-butyl succinate
Mixing Li 2 O@CaO/CuO-γ-Al 2 O 3 For the synthesis of di-tert-butyl succinate, 80g of di-tert-butyl succinate were placed in a three-necked flask with a heating oil bath, a temperature-controlled thermocouple, a constant-pressure dropping funnel and an installed rectifying column at room temperatureThe ethyl ester was added to 500ml of anhydrous tert-butanol. Then 10g of Li were added 2 O@CaO/CuO-γ-Al 2 O 3 A catalyst. The reaction mixture is reacted at reflux temperature, the ethanol formed is mixed with tert-butanol and distilled off continuously on a rectification column, and fresh tert-butanol is added according to the distillation quantity of the alcohol. The conversion rate of the reaction raw materials is more than or equal to 95 percent, the reaction product and the catalyst are filtered and separated, the reaction product is rectified under reduced pressure to obtain a product with the purity of more than or equal to 99 percent, the yield of the di-tert-butyl succinate is 95 percent, and the reaction time is 12 hours.
Experimental example ten: synthesis of di-tert-amyl succinate
Mixing Li 2 O@CaO/CuO-γ-Al 2 O 3 For the synthesis of di-tert-amyl succinate, in particular, 90g of di-n-propyl succinate were added to 400ml of anhydrous tert-amyl alcohol at room temperature in a three-necked flask with a heated oil bath, a temperature-controlled thermocouple, a constant-pressure dropping funnel and an equipped rectifying column. Then Li is added 2 O@CaO/CuO-γ-Al 2 O 3 A catalyst. The reaction mixture is reacted at reflux temperature, the n-propanol formed is mixed with tert-amyl alcohol and distilled off continuously on a rectification column, and fresh tert-amyl alcohol is replenished according to the distillation amount of the alcohol. When the conversion rate of the reaction raw materials is more than or equal to 95 percent, filtering and separating the reaction product and the catalyst, and carrying out vacuum rectification on the reaction product to obtain a product with the purity of more than or equal to 99 percent, wherein the yield of the di-tert-butyl succinate is 90 percent, and the reaction time is 9 hours.
Experimental example eleven: synthesis of di-tert-amyl succinate by continuous reaction process
Referring to FIG. 1, a fluidized bed reactor containing Li is provided 2 O@CaO/CuO-γ-Al 2 O 3 Catalyst at reflux temperature for 0.1h -1 Is fed into the reactor and the product is withdrawn from the bottom of the rectifying tower. The other processes are the same as those in the eighth embodiment. The continuous operation is carried out for 1 week, and the yield of the product with the purity more than or equal to 99 percent reaches more than 85 percent.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (11)
1. A catalyst for synthesizing tertiary alkyl ester is characterized by comprising a carrier and a main catalyst loaded on the carrier;
wherein the main catalyst is selected from at least one of oxides of alkali metals or alkaline earth metals;
the carrier is selected from gamma-Al 2 O 3 One of active carbon, molecular sieve and ion exchange resin.
2. The catalyst for synthesizing a tertiary alkyl ester according to claim 1, further comprising a co-catalyst supported on the carrier, the co-catalyst being selected from at least one of transition metal oxides.
3. A catalyst for the synthesis of tertiary alkyl esters, wherein the catalyst for the synthesis of tertiary alkyl esters is selected from the group consisting of:
the main catalyst is Li 2 O, the carrier is gamma-Al 2 O 3 Or a catalyst of activated carbon; or
The main catalyst is Li 2 O and CaO, and the carrier is gamma-Al 2 O 3 Or activated carbon; or
The main catalyst is Li 2 O and MgO, and the carrier is gamma-Al 2 O 3 Or a catalyst of activated carbon; or
The main catalyst is Li 2 O, cuO as cocatalyst and gamma-Al as carrier 2 O 3 Or activated carbon; or
The main catalyst is Li 2 O and CaO, cuO as cocatalyst, and gamma-Al as carrier 2 O 3 Or activated carbon.
4. The catalyst for synthesizing tertiary alkyl esters according to claim 2 or 3, wherein the sum of the mass of the main catalyst and the mass of the cocatalyst is 0.1-50% of the mass of the carrier.
5. The catalyst for synthesizing a tertiary alkyl ester according to claim 3, wherein in the main catalyst, li 2 The content of O is 50-100%.
6. The catalyst for synthesizing a tertiary alkyl ester according to claim 3, wherein the content of the co-catalyst is 0.1% to 10% of the content of the main catalyst.
7. A method for preparing a catalyst for the synthesis of tertiary alkyl esters as claimed in any one of claims 1 to 6, comprising the steps of:
contacting a support with a precursor to produce a first product; the precursor is at least one of nitrate, sulfate, halate, phosphate, carbonate, bicarbonate and organic acid salt of alkali metal or alkaline earth metal, or at least one of hydroxide, oxide, amide and azide of alkali metal or alkaline earth metal;
converting the precursor in the first product to an oxide of an alkali metal or an alkaline earth metal.
8. A tertiary alkyl ester synthesis method takes a compound A with a molecular formula shown as a general formula I as a raw material, and the compound A and an alcohol with a general formula ROH are subjected to ester exchange reaction under the action of a solid catalyst to prepare a tertiary alkyl ester shown as a general formula II;
wherein, R1 independently represents a C1-C10 linear or partially linear alkyl group; r independently represents a C4-C12 tertiary alkyl group; m represents 1 or 2; if m =1, X is unsubstituted or halogen-substituted alkyl, cycloalkyl, unsubstitutedOr a substituted aryl or aralkyl group, or an aromatic heterocyclic group; if m =2, then it is straight chain (-CH) 2 -) n, where n is an integer from 1 to 8;
characterized in that the solid catalyst is the catalyst for synthesizing tertiary alkyl ester according to any one of claims 1 to 6.
9. The process for the synthesis of a tertiary alkyl ester according to claim 8, wherein the molar ratio of compound a to the alcohol of formula ROH is from 1.
10. The method for synthesizing a tertiary alkyl ester according to claim 8, wherein when the transesterification is a batch reaction, the amount of the solid catalyst added is 0.2 to 20% by mass of the compound a; when the ester exchange reaction is a continuous reaction, the reaction space velocity is 1.0h -1 -0.02h -1 。
11. The method of synthesizing a tertiary alkyl ester according to claim 10, wherein the solid catalyst is separated and reused when the transesterification reaction is a continuous reaction.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4904814A (en) * | 1987-02-13 | 1990-02-27 | Ciba-Geigy Corporation | Process for the preparation of tert-alkyl esters |
| CN1900047A (en) * | 2006-07-19 | 2007-01-24 | 浙江大学 | Process for preparing methyl ethyl carbonate by ester exchanging reaction |
| CN101704751A (en) * | 2009-11-24 | 2010-05-12 | 吉林大学 | Synthesis method of methyl ethyl carbonate |
| CN103804190A (en) * | 2014-03-11 | 2014-05-21 | 南通龙翔化工有限公司 | Synthetic method of succinic acid di-tert alkyl ester |
| CN112295600A (en) * | 2020-11-24 | 2021-02-02 | 先尼科化工（上海）有限公司 | Catalyst for preparing tertiary alkyl ester |
-
2022
- 2022-07-18 CN CN202210844409.6A patent/CN115155557A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4904814A (en) * | 1987-02-13 | 1990-02-27 | Ciba-Geigy Corporation | Process for the preparation of tert-alkyl esters |
| CN1900047A (en) * | 2006-07-19 | 2007-01-24 | 浙江大学 | Process for preparing methyl ethyl carbonate by ester exchanging reaction |
| CN101704751A (en) * | 2009-11-24 | 2010-05-12 | 吉林大学 | Synthesis method of methyl ethyl carbonate |
| CN103804190A (en) * | 2014-03-11 | 2014-05-21 | 南通龙翔化工有限公司 | Synthetic method of succinic acid di-tert alkyl ester |
| CN112295600A (en) * | 2020-11-24 | 2021-02-02 | 先尼科化工（上海）有限公司 | Catalyst for preparing tertiary alkyl ester |
Non-Patent Citations (2)
| Title |
|---|
| 冯裕发;周维友;刘洋;吴中;何明阳;陈群;: "K/γ-Al_2O_3催化丙酸甲酯合成甲基丙烯酸甲酯", 化工进展, no. 03, pages 798 * |
| 姜利寒;颜姝丽;梁斌;: "非均相固体碱催化剂(CaO体系)用于生物柴油的制备", 工业催化, no. 05, pages 35 * |
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