CN114849784B - 一种醛氧化制羧酸的非均相催化剂的制备方法 - Google Patents
一种醛氧化制羧酸的非均相催化剂的制备方法 Download PDFInfo
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- CN114849784B CN114849784B CN202210618268.6A CN202210618268A CN114849784B CN 114849784 B CN114849784 B CN 114849784B CN 202210618268 A CN202210618268 A CN 202210618268A CN 114849784 B CN114849784 B CN 114849784B
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- heterogeneous catalyst
- organic solid
- carboxylic acid
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- 239000002638 heterogeneous catalyst Substances 0.000 title claims abstract description 39
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 35
- 230000003647 oxidation Effects 0.000 title claims abstract description 31
- 150000001732 carboxylic acid derivatives Chemical class 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims description 15
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title claims 7
- 239000003054 catalyst Substances 0.000 claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- 239000011347 resin Substances 0.000 claims abstract description 34
- 229920005989 resin Polymers 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 23
- 150000003623 transition metal compounds Chemical class 0.000 claims abstract description 14
- 239000011148 porous material Substances 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 32
- 239000011973 solid acid Substances 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 26
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 230000000536 complexating effect Effects 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 16
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 14
- 235000019441 ethanol Nutrition 0.000 claims description 13
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 claims description 11
- 239000003208 petroleum Substances 0.000 claims description 10
- 238000005342 ion exchange Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 7
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 7
- 229910052723 transition metal Inorganic materials 0.000 claims description 7
- 230000003197 catalytic effect Effects 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 4
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 4
- 229940071125 manganese acetate Drugs 0.000 claims description 4
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 3
- 150000001735 carboxylic acids Chemical class 0.000 claims description 3
- RJYMRRJVDRJMJW-UHFFFAOYSA-L dibromomanganese Chemical compound Br[Mn]Br RJYMRRJVDRJMJW-UHFFFAOYSA-L 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 3
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 238000002386 leaching Methods 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 150000001299 aldehydes Chemical class 0.000 abstract description 26
- JRPPVSMCCSLJPL-UHFFFAOYSA-N 7-methyloctanal Chemical compound CC(C)CCCCCC=O JRPPVSMCCSLJPL-UHFFFAOYSA-N 0.000 abstract description 16
- 230000002378 acidificating effect Effects 0.000 abstract description 12
- 239000007787 solid Substances 0.000 abstract description 12
- 239000002815 homogeneous catalyst Substances 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 6
- 238000010668 complexation reaction Methods 0.000 abstract description 6
- 238000004064 recycling Methods 0.000 abstract description 5
- 238000011084 recovery Methods 0.000 abstract description 3
- 125000004122 cyclic group Chemical group 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract 1
- 230000007797 corrosion Effects 0.000 abstract 1
- 238000005886 esterification reaction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- XZOYHFBNQHPJRQ-UHFFFAOYSA-N 7-methyloctanoic acid Chemical compound CC(C)CCCCCC(O)=O XZOYHFBNQHPJRQ-UHFFFAOYSA-N 0.000 description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 16
- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 16
- 239000000072 sodium resin Substances 0.000 description 16
- 238000006116 polymerization reaction Methods 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 238000004364 calculation method Methods 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 229910021645 metal ion Inorganic materials 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 230000007935 neutral effect Effects 0.000 description 8
- 239000012255 powdered metal Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 230000001105 regulatory effect Effects 0.000 description 8
- 238000004587 chromatography analysis Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000007800 oxidant agent Substances 0.000 description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 6
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229910001429 cobalt ion Inorganic materials 0.000 description 3
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 3
- 229910001437 manganese ion Inorganic materials 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229940037003 alum Drugs 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- -1 transition metal salts Chemical class 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 229910004003 H5IO6 Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 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
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- AHXGRMIPHCAXFP-UHFFFAOYSA-L chromyl dichloride Chemical compound Cl[Cr](Cl)(=O)=O AHXGRMIPHCAXFP-UHFFFAOYSA-L 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000007037 hydroformylation reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229940094933 n-dodecane Drugs 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- TWLXDPFBEPBAQB-UHFFFAOYSA-N orthoperiodic acid Chemical compound OI(O)(O)(O)(O)=O TWLXDPFBEPBAQB-UHFFFAOYSA-N 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- OKBMCNHOEMXPTM-UHFFFAOYSA-M potassium peroxymonosulfate Chemical compound [K+].OOS([O-])(=O)=O OKBMCNHOEMXPTM-UHFFFAOYSA-M 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001631 strontium chloride Inorganic materials 0.000 description 1
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- 229910001432 tin ion Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/2252—Sulfonate ligands
-
- 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
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Abstract
本发明公开了一种醛氧化制羧酸的非均相催化剂制备及应用的方法。其中的醛高效氧化反应的非均相催化剂,由均相催化剂过渡金属化合物负载于大孔有机固体酸性树脂上络合反应得到。本技术方案提供的非均相催化剂作为醛氧化反应制备羧酸的催化剂,具有较大的孔结构、高比表面积及强酸度,其操作工艺简单,条件温和、性能稳定,易于循环利用,且回收过程中能耗消耗低。应用在异壬醛氧化反应中醛的转化率大于95%,产物选择性大于95%,而且该催化剂还适合做酯化反应的催化剂,解决了相应均相催化剂不易回收利用,对设备腐蚀、三废污染的问题。
Description
技术领域
本发明涉及精细化工领域,尤其涉及一种醛氧化制羧酸的非均相催化剂制备及应用技术。
背景技术
有机羧酸是医药、农药和工业化学品制备重要的有机溶剂,通常采用醇或醛的氧化制备。传统上采用化学计量的氧化剂(如KMnO4、H5IO6、CrO3,KHSO5,NaClO2)或者过渡金属盐,硝酸银、二价铜盐等催化氧化,存在价格昂贵或环境污染的不足。近年来,随着烯烃氢甲酰化制备醛技术的快速发展与应用,直接采用醛氧化制酸具有工艺路线简单、生产控制方便、原料品种单一、产品得率高等优点。醛均相液相液化制备羧酸工艺是有机合成中重要的反应类型之一,在早期的工艺中,醛氧化多采用高锰酸钾,重铬酸钾等通用氧化剂。然而这些氧化剂氧化能力较弱,选择性相应较差,限制了其应用范围。尽管后来出现了二氧化锰、醋铬混合酐和铬酰氯等选择性较高的氧化剂,但由于存在着氧化成本高,用量大、三废严重等缺陷,所以在工业生产中缺乏竞争力。目前,以空气或氧气为氧化剂,Amoco(Co/Mn/Br)催化剂氧化制备羧酸是研究的主要方向。这一方法使用锰、钴、铜等过渡金属醋酸盐作为催化剂,反应条件温和,催化效率高,产品质量好。然而对于该催化体系而言,金属盐均匀溶解在反应体系中,分散度非常高,在后续产品分离过程中存在难度,对催化剂的回收利用带来困难。
近年针对均相催化剂难回收、利用率低的问题,许多专利授予了用于将醛氧化制备酸的非均相催化剂有关的发明,其中多数是以磷钼钒酸为基础的杂多酸类催化剂,或者负载钼、钯、铬、钨等贵金属元素,以无机二氧化硅、氧化铝、氧化钛、碳纳米材料或分子筛等为载体的复合型催化剂,比如专利US4803302A,CN112547131A,CN1031488A,CN110694687A,CN1031488A,CN1146438A,CN1583261A,CN1146439A和CN107282069A等,这些专利所描述的催化剂,其制备方法多为金属化合物在溶剂的存在下制成溶液,再加入不溶性氧化物在加热和搅拌下蒸发干,然后高温煅烧,粉碎和成型的制备方法。催化剂的改进主要是从催化剂的活性,选择性及稳定性方面进行的,如通过控制载体酸强度和孔结构来改善催化剂性能;在活性组分中加入过渡金属提高活性,增加产物的收率;加入稀土元素改善氧化还原能力,提高催化剂稳定性;加入Fe、Co、Ni等元素稳定催化剂活性组分,提高催化剂的使用寿命等。
现有公开醛氧化制备羧酸的技术中,或其均相催化剂难分离处理,不易回收利用、或负载型催化剂制备操作过程繁琐,工艺复杂,产物选择性不理想等缺陷。另外采用无机氧化铝和二氧化硅等为载体制备的非均相催化剂,存在比表面积小,毒性较大,催化剂重复性差,利用率低,同时所需要的贵金属含量比较大,生产成本依然较高。
发明内容
为了克服现有技术存在的醛氧化过程中均相催化剂回收难、催化剂活性低的不足,本发明提供一种适用于高效催化氧化醛制备羧酸,易与产品分离,产品选择性高,且能克服目前技术中均相催化剂难分离的困难,实现循环利用的一种醛氧化制羧酸的非均相催化剂及其制备方法及应用。本发明该方法制备的非均相催化剂具有大的比表面积、孔结构和强酸度,其制备工艺路线简单、反应条件温和、可重复性高,具有原料醛的转化率高,产物酸的选择性好,收率高的优点,且该方法制备的非均相催化剂可以通过简单的回收方式实现循环利用的效果,从而很好的解决了均相催化剂存在的不易回收,以及无机载体负载型催化剂能耗高,重复性差的问题,易于大规模生产。
本发明解决上述技术问题采用的技术方案是:
本发明提供了一种醛氧化制羧酸的非均相催化剂的制备方法,该方法包括:将预先干燥处理的大孔有机固体酸性树脂置于反应器中,加入过渡金属化合物的溶液,在60-120℃恒温条件下搅拌络合反应6-24h;冷却至室温后,经过滤、洗涤、干燥后得到过渡金属元素络合的非均相固体酸催化剂;
其中;所述的大孔有机固体酸性树脂由二乙烯苯和对苯乙烯磺酸钠在引发剂和致孔剂的共同作用下,在50-150℃下聚合反应8-24h得到,所述的大孔有机固体酸性树脂为三维介孔结构,其中氮吸附法测定的平均细孔直径为2-30nm,氮吸附法测定的总细孔容积为0.2-1.8cm3/g,BET比表面积为200-700m2/g;所述的过渡金属化合物为过渡金属元素的无机盐或者过渡金属元素的有机盐;所述的大孔有机固体酸性树脂与过渡金属化合物溶液的重量比为1:4-12。
本发明所述的醛氧化制羧酸的非均相催化剂的制备方法中,优选所述的大孔有机固体酸性树脂由二乙烯苯和对苯乙烯磺酸钠在引发剂和致孔剂的共同作用下,在50-150℃下聚合反应8-24h得到。
本发明所述的醛氧化制羧酸的非均相催化剂的制备方法中,优选所述的预先干燥处理为:将大孔有机固体酸性树脂使用前先经甲醇或者无水乙醇淋洗4-6h,于80-100℃温度中干燥,得到预先干燥处理的大孔有机固体酸性树脂。
本发明所述的醛氧化制羧酸的非均相催化剂的制备方法中,优选所述的过渡金属化合物选自乙酸锰、乙酸钴、乙酸铜、硫酸锰、硫酸铜、硫酸铁、硝酸钴、硝酸锰、硫酸铈、硫酸镍、溴化锰、氯化钴、氯化镍、氯化锶、氯化铈、氯化铜、氯化铁、氯化铝、氯化铯、氧氯化锆、氯化锡中的一种或多种。
本发明所述的醛氧化制羧酸的非均相催化剂的制备方法中,优选过渡金属化合物溶液由过渡金属化合物溶于甲醇、乙醇、丙醇、正丁醇、异戊醇、正己醇、丙酮或二硫化碳溶液中获得,过渡金属化合物溶液的质量浓度为10-60%。
本发明所述的醛氧化制羧酸的非均相催化剂的制备方法中,优选所述洗涤为依次采用乙醇、丙酮、石油醚洗涤,所述干燥的温度为80℃-100℃。
本发明还进一步提供了一种上述的制备方法制备得到的醛氧化制羧酸的非均相催化剂。更进一步,还提供了上述非均相催化剂在催化氧化醛制备羧酸中的应用。
本发明与现有技术相比,其有益效果是:
本发明提供了一种工艺路线简单、条件温和、实用的醛高效氧化的均相催化剂络合大孔有机固体酸性树脂制备非均相催化剂的方法,该催化剂为三维介孔结构,具有丰富的孔结构、大的孔体积、高比表面积以及强疏水性和酸度,活性组分更加均匀分散,得到的非均相催化剂用于醛的氧化反应,与相应的均相催化剂相比,具有同等的催化效果,且该催化剂稳定性高,通过简单操作即可回收循环利用,生产成本低,基本无三废产生,具有较大的实用价值和社会经济效益。
附图说明
下面结合附图和实施例对本发明进一步说明。
图1是本发明制备的非均相大孔有机固体酸性树脂催化剂的红外光谱图。
具体实施方式
下面结合具体实施例,对本发明方法技术方案的实施和效果做进一步描述,但本发明的保护范围不限于下属实施例。
本发明实施例所用的络合载体大孔有机固体酸性树脂,属于有机共价聚合物,通过水热合成得到,具有丰富的三维介孔结构、大的孔体积、高比表面积以及强疏水性。
实施例1
催化剂A
聚合:向装有回流冷凝装置的反应釜中加入300份水,200份DVB,270份四氢呋喃,420份正十二烷,430份对苯乙烯磺酸钠,5份过氧化苯甲酰,搅拌形成均匀的混合溶液,调节适当搅拌速度,升温至120℃搅拌反应20h。将得到的反应产物过滤,用去离子水洗涤,在100℃下烘干,得到钠型树脂。
离子交换:在玻璃反应器中,加入钠型树脂100份,加入0.5mol/L的硫酸溶液300份,搅拌反应12h,过滤,用去离子水洗涤至中性,干燥得到大孔有机固体酸性树脂。
负载:将树脂经甲醇淋洗4h,在90℃恒温干燥后,与质量浓度为20%的硝酸钴溶液以1g/40g硝酸钴溶液混合,在80℃下搅拌络合反应6h,降至室温后,过滤,依次用乙醇、丙酮、石油醚洗涤,在100℃温度中干燥12h,制得粉末状金属离子络合的非均相大孔固体酸催化剂A。取出冷却至室温,将催化剂A与浓盐酸以0.5g/50ml的比例在室温下完全洗脱钴离子,经计算分析得到金属组分的络合量为6.1%,本催化剂的物理指标见表1.
取上述的非均相催化剂A 0.5g,置于100ml高压釜反应器中,在温度50℃,反应压力0.5mpa,氧气流速100ml/min的条件下,进行非均相空气氧化异壬醛制备异壬酸的反应,结果经过气相色谱分析,异壬醛的转化率为99.8%,异壬酸的选择性为98.2%。
实施例2
催化剂B
聚合:向装有回流冷凝装置的反应釜中加入500份水,150份DVB,900份四氯化碳,210份对苯乙烯磺酸钠,7份过氧化苯甲酰,搅拌形成均匀的混合溶液,调节适当搅拌速度,升温至80℃搅拌反应20h。将得到的反应产物过滤,用去离子水洗涤,在100℃下烘干,得到钠型树脂。
离子交换:在玻璃反应器中,加入钠型树脂100份,加入0.5mol/L的硫酸溶液300份,搅拌反应12h,过滤,用去离子水洗涤至中性,干燥得到大孔有机固体酸性树脂。
负载:将树脂经甲醇淋洗4h,在90℃恒温干燥后,与质量浓度为30%的硝酸钴溶液以1g/40g硝酸钴溶液混合,在80℃下搅拌络合反应6h,降至室温后,过滤,依次用乙醇、丙酮、石油醚洗涤,在100℃温度中干燥12h,制得粉末状金属离子络合的非均相大孔固体酸催化剂B。取出冷却至室温,将催化剂A与浓盐酸以0.5g/50ml的比例在室温下完全洗脱钴离子,经计算分析得到金属组分的络合量为6.9%,本催化剂的物理指标见表1.
取上述的非均相催化剂B 0.5g,置于100ml高压釜反应器中,在温度50℃,反应压力0.5mpa,氧气流速100ml/min的条件下,进行非均相空气氧化异壬醛制备异壬酸的反应,结果经过气相色谱分析,异壬醛的转化率为99.8%,异壬酸的选择性为97.7%。
实施例3
催化剂C
聚合:向装有回流冷凝装置的反应釜中加入300份水,100份DVB,200份四氢呋喃,100份对苯乙烯磺酸钠,6份AIBN,搅拌形成均匀的混合溶液,调节适当搅拌速度,升温至100℃搅拌反应20h。将得到的反应产物过滤,用去离子水洗涤,在100℃下烘干,得到钠型树脂。
离子交换:在玻璃反应器中,加入钠型树脂100份,加入0.5mol/L的硫酸溶液300份,搅拌反应12h,过滤,用去离子水洗涤至中性,干燥得到大孔有机固体酸性树脂。
负载:将大孔有机固体酸性树脂与质量浓度为40%的硝酸钴溶液以1g/40g硝酸钴溶液混合,在80℃下搅拌络合反应6h,降至室温后,过滤,依次用乙醇、丙酮、石油醚洗涤,在100℃温度中干燥12h,制得粉末状金属离子络合的非均相大孔固体酸催化剂E。取出冷却至室温,将催化剂E与浓盐酸以0.5g/50ml的比例在室温下完全洗脱钴离子,经计算分析得到金属组分的络合量为7.2%,本催化剂的物理指标见表1。
取上述的非均相催化剂E 0.5g,置于100ml高压釜反应器中,在温度50℃,反应压力0.5mpa,氧气流速100ml/min的条件下,进行非均相空气氧化异壬醛制备异壬酸的反应,结果经过气相色谱分析,异壬醛的转化率为99.2%,异壬酸的选择性为98.3%。
实施例4
催化剂D
聚合:向装有回流冷凝装置的反应釜中加入500份水,150份DVB,200份乙酸乙酯,330份对苯乙烯磺酸钠,6份AIBN,搅拌形成均匀的混合溶液,调节适当搅拌速度,升温至90℃搅拌反应20h。将得到的反应产物过滤,用去离子水洗涤,在100℃下烘干,得到钠型树脂。
离子交换:在玻璃反应器中,加入钠型树脂100份,加入0.5mol/L的硫酸溶液300份,搅拌反应12h,过滤,用去离子水洗涤至中性,干燥得到大孔有机固体酸性树脂。
负载:将大孔有机固体酸性树脂与质量浓度为40%的乙酸锰溶液以1g/40g乙酸锰溶液混合,在80℃下搅拌络合反应10h,降至室温后,过滤,依次用乙醇、丙酮、石油醚洗涤,在100℃温度中干燥12h,制得粉末状金属离子络合的非均相大孔固体酸催化剂D。取出冷却至室温,将催化剂D与浓盐酸以0.5g/50ml的比例在室温下完全洗脱锰离子,经计算分析得到金属组分的络合量为6.8%,本催化剂的物理指标见表1。
取上述的非均相催化剂D 0.5g,置于100ml高压釜反应器中,在温度50℃,反应压力0.5mpa,氧气流速100ml/min的条件下,进行非均相空气氧化异壬醛制备异壬酸的反应,结果经过气相色谱分析,异壬醛的转化率为99.2%,异壬酸的选择性为98.0%。
实施例5
催化剂E
聚合:向装有回流冷凝装置的反应釜中加入500份水,150份DVB,900份四氯化碳,210份对苯乙烯磺酸钠,4份AIBN,4份聚乙烯醇,搅拌形成均匀的混合溶液,调节适当搅拌速度,升温至80℃搅拌反应20h。将得到的反应产物过滤,用去离子水洗涤,在100℃下烘干,得到钠型树脂。
离子交换:在玻璃反应器中,加入钠型树脂100份,加入0.5mol/L的硫酸溶液300份,搅拌反应12h,过滤,用去离子水洗涤至中性,干燥得到大孔有机固体酸性树脂。
负载:将大孔有机固体酸性树脂与质量浓度为40%的乙酸锰溶液以1g/40g乙酸锰溶液混合,在80℃下搅拌络合反应6h,降至室温后,过滤,依次用乙醇、丙酮、石油醚洗涤,在100℃温度中干燥12h,制得粉末状金属离子络合的非均相大孔固体酸催化剂C。取出冷却至室温,将催化剂C与浓盐酸以0.5g/50ml的比例在室温下完全洗脱锰离子,经计算分析得到金属组分的络合量为7.2%,本催化剂的物理指标见表1。
取上述的非均相催化剂C 0.5g,置于100ml高压釜反应器中,在温度50℃,反应压力0.5mpa,氧气流速100ml/min的条件下,进行非均相空气氧化异壬醛制备异壬酸的反应,结果经过气相色谱分析,异壬醛的转化率为98.7%,异壬酸的选择性为97.4%。
实施例6
催化剂F
聚合:向装有回流冷凝装置的反应釜中加入800份水,120份DVB,180份四氢呋喃,100份对苯乙烯磺酸钠,6份AIBN,3份柠檬酸钠,7份羧丙基纤维素钠,搅拌形成均匀的混合溶液,调节适当搅拌速度,升温至100℃搅拌反应20h。将得到的反应产物过滤,用去离子水洗涤,在100℃下烘干,得到钠型树脂。
离子交换:在玻璃反应器中,加入钠型树脂100份,加入0.5mol/L的硫酸溶液300份,搅拌反应12h,过滤,用去离子水洗涤至中性,干燥得到大孔有机固体酸性树脂。
负载:将大孔有机固体酸性树脂与质量浓度为40%的四氯化锡溶液以1g/40g四氯化锡溶液混合,在80℃下搅拌络合反应6h,降至室温后,过滤,依次用乙醇、丙酮、石油醚洗涤,在100℃温度中干燥12h,制得粉末状金属离子络合的非均相大孔固体酸催化剂F。取出冷却至室温,将催化剂F与浓盐酸以0.5g/50ml的比例在室温下完全洗脱锡离子,经计算分析得到金属组分的络合量为8.2%,本催化剂的物理指标见表1。
取上述的非均相催化剂F 0.5g,置于100ml高压釜反应器中,在温度50℃,反应压力0.5mpa,氧气流速100ml/min的条件下,进行非均相空气氧化异壬醛制备异壬酸的反应,结果经过气相色谱分析,异壬醛的转化率为99.4%,异壬酸的选择性为98.7%。
实施例7
催化剂G
聚合:向装有回流冷凝装置的反应釜中加入800份水,120份DVB,80份四氢呋喃,70份对苯乙烯磺酸钠,6份AIBN,8份明矾,搅拌形成均匀的混合溶液,调节适当搅拌速度,升温至100℃搅拌反应20h。将得到的反应产物过滤,用去离子水洗涤,在100℃下烘干,得到钠型树脂。
离子交换:在玻璃反应器中,加入钠型树脂100份,加入0.5mol/L的硫酸溶液300份,搅拌反应12h,过滤,用去离子水洗涤至中性,干燥得到大孔有机固体酸性树脂。
负载:将大孔有机固体酸性树脂与质量浓度为30%的四水合溴化锰溶液以1g/40g溴化锰溶液混合,在80℃下搅拌络合反应6h,降至室温后,过滤,依次用乙醇、丙酮、石油醚洗涤,在100℃温度中干燥12h,制得粉末状金属离子络合的非均相大孔固体酸催化剂G。取出冷却至室温,将催化剂G与浓盐酸以0.5g/50ml的比例在室温下完全洗脱锰离子,经计算分析得到金属组分的络合量为7.8%,本催化剂的物理指标见表1。
取上述的非均相催化剂G 0.5g,置于100ml高压釜反应器中,在温度50℃,反应压力0.5mpa,氧气流速100ml/min的条件下,进行非均相空气氧化异壬醛制备异壬酸的反应,结果经过气相色谱分析,异壬醛的转化率为99.8%,异壬酸的选择性为98.4%。
实施例8
催化剂H
聚合:向装有回流冷凝装置的反应釜中加入400份水,190份DVB,1400份1,4-二氧六环,180份对苯乙烯磺酸钠,6份AIBN,8份明矾,搅拌形成均匀的混合溶液,调节适当搅拌速度,升温至100℃搅拌反应20h。将得到的反应产物过滤,用去离子水洗涤,在100℃下烘干,得到钠型树脂。
离子交换:在玻璃反应器中,加入钠型树脂100份,加入0.5mol/L的硫酸溶液300份,搅拌反应12h,过滤,用去离子水洗涤至中性,干燥得到大孔有机固体酸性树脂。
负载:将大孔有机固体酸性树脂与质量浓度为40%的乙酸铜溶液以1g/40g乙酸铜溶液混合,在100℃下搅拌络合反应8h,降至室温后,过滤,依次用乙醇、丙酮、石油醚洗涤,在100℃温度中干燥12h,制得粉末状金属离子络合的非均相大孔固体酸催化剂H。取出冷却至室温,将催化剂H与浓盐酸以0.5g/50ml的比例在室温下完全洗脱铜离子,经计算分析得到金属组分的络合量为8.2%,本催化剂的物理指标见表1。
取上述的非均相催化剂H 0.5g,置于100ml高压釜反应器中,在温度50℃,反应压力0.5mpa,氧气流速100ml/min的条件下,进行非均相空气氧化异壬醛制备异壬酸的反应,结果经过气相色谱分析,异壬醛的转化率为99.7%,异壬酸的选择性为98.4%。
表1:催化剂物理指标
Claims (6)
1.一种醛氧化制羧酸的非均相催化剂的制备方法,其特征在于,包括:将预先干燥处理的大孔有机固体酸性树脂置于反应器中,加入过渡金属化合物的溶液,在60-120℃恒温条件下搅拌络合反应6-24h;冷却至室温后,经过滤、洗涤、干燥后得到粉末状过渡金属元素络合的非均相固体酸催化剂;
所述的大孔有机固体酸性树脂由二乙烯苯和对苯乙烯磺酸钠在引发剂和致孔剂的共同作用下,在50-150℃下聚合反应8-24h,然后进行离子交换得到大孔有机固体酸性树脂得到;所述的大孔有机固体酸性树脂为三维介孔结构,其中氮吸附法测定的平均细孔直径为2-30nm,氮吸附法测定的总细孔容积为0.2-1.8cm3/g,BET比表面积为200-700m2/g;所述的过渡金属化合物选自乙酸锰、乙酸钴、乙酸铜、硫酸锰、硫酸铜、硝酸钴、硝酸锰、溴化锰、氯化钴、氯化铜、氯化锡中的一种或多种;
所述的大孔有机固体酸性树脂与过渡金属化合物溶液的重量比为1:4-12。
2.根据权利要求1所述的一种醛氧化制羧酸的非均相催化剂的制备方法,其特征在于,所述的预先干燥处理为:将大孔有机固体酸性树脂使用前先经甲醇或者无水乙醇淋洗4-6h,于80-100℃温度中干燥,得到预先干燥处理的大孔有机固体酸性树脂。
3.根据权利要求1所述的一种醛氧化制羧酸的非均相催化剂的制备方法,其特征在于,过渡金属化合物溶液由过渡金属化合物溶于甲醇、乙醇、丙醇、正丁醇、异戊醇、正己醇、丙酮或二硫化碳溶液中获得,过渡金属化合物溶液的质量浓度为10-60%。
4.根据权利要求1所述的一种醛氧化制羧酸的非均相催化剂的制备方法,其特征在于,所述洗涤为依次采用乙醇、丙酮、石油醚洗涤,所述干燥的温度为80℃-100℃。
5.一种权利要求1~4任一项权利要求所述的制备方法制备得到的醛氧化制羧酸的非均相催化剂。
6.一种权利要求5所述的醛氧化制羧酸的非均相催化剂在催化氧化醛制备羧酸中的应用。
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