CN111111774A - Organic phosphine-containing polymer carrier loaded rhodium and heteropoly acid catalyst, preparation and application thereof - Google Patents
Organic phosphine-containing polymer carrier loaded rhodium and heteropoly acid catalyst, preparation and application thereof Download PDFInfo
- Publication number
- CN111111774A CN111111774A CN201811293543.1A CN201811293543A CN111111774A CN 111111774 A CN111111774 A CN 111111774A CN 201811293543 A CN201811293543 A CN 201811293543A CN 111111774 A CN111111774 A CN 111111774A
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- CN
- China
- Prior art keywords
- catalyst
- rhodium
- heteropoly acid
- organic
- containing polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 239000010948 rhodium Substances 0.000 title claims abstract description 100
- 239000003054 catalyst Substances 0.000 title claims abstract description 92
- 229920000642 polymer Polymers 0.000 title claims abstract description 79
- 239000011964 heteropoly acid Substances 0.000 title claims abstract description 57
- 229910000073 phosphorus hydride Inorganic materials 0.000 title claims abstract description 52
- 229910052703 rhodium Inorganic materials 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 title claims description 49
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 118
- 238000000034 method Methods 0.000 claims abstract description 45
- 230000001588 bifunctional effect Effects 0.000 claims abstract description 32
- 238000005810 carbonylation reaction Methods 0.000 claims abstract description 23
- 230000006315 carbonylation Effects 0.000 claims abstract description 21
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims abstract description 18
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims abstract description 18
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims abstract description 14
- -1 rhodium metal complex Chemical class 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims description 51
- 239000012298 atmosphere Substances 0.000 claims description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 23
- 239000000178 monomer Substances 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 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 claims description 18
- 239000003999 initiator Substances 0.000 claims description 18
- 229920000620 organic polymer Polymers 0.000 claims description 18
- 239000003960 organic solvent Substances 0.000 claims description 18
- 150000003254 radicals Chemical class 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 14
- 239000002149 hierarchical pore Substances 0.000 claims description 13
- 239000011261 inert gas Substances 0.000 claims description 12
- 230000000379 polymerizing effect Effects 0.000 claims description 12
- 238000012719 thermal polymerization Methods 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- 239000011541 reaction mixture Substances 0.000 claims description 9
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 7
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 150000004714 phosphonium salts Chemical group 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 claims description 4
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical group [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 claims description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- RNLMWRAISTUVOB-UHFFFAOYSA-N 1,2,2-triphenylethenylphosphane Chemical compound C=1C=CC=CC=1C(P)=C(C=1C=CC=CC=1)C1=CC=CC=C1 RNLMWRAISTUVOB-UHFFFAOYSA-N 0.000 claims description 2
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 claims 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 claims description 2
- CIKIJXVINACKDK-UHFFFAOYSA-N CCP(C=C)(C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound CCP(C=C)(C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1 CIKIJXVINACKDK-UHFFFAOYSA-N 0.000 claims description 2
- MNAFWSMBNUXQEO-UHFFFAOYSA-N P.C=C.C=C.C=C Chemical compound P.C=C.C=C.C=C MNAFWSMBNUXQEO-UHFFFAOYSA-N 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 238000009826 distribution Methods 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 11
- 239000012752 auxiliary agent Substances 0.000 abstract description 5
- 230000009471 action Effects 0.000 abstract description 2
- 238000007334 copolymerization reaction Methods 0.000 abstract description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 abstract 1
- SCESWTHQFQXGMV-UHFFFAOYSA-N ethenylphosphane Chemical compound PC=C SCESWTHQFQXGMV-UHFFFAOYSA-N 0.000 abstract 1
- 229910052740 iodine Inorganic materials 0.000 abstract 1
- 239000011630 iodine Substances 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 65
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 42
- 230000001681 protective effect Effects 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- 239000007983 Tris buffer Substances 0.000 description 11
- 238000001816 cooling Methods 0.000 description 9
- 229910001873 dinitrogen Inorganic materials 0.000 description 9
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 9
- 238000011068 loading method Methods 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000000967 suction filtration Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000005086 pumping Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000013315 hypercross-linked polymer Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OZHUWVSXUOMDDU-UHFFFAOYSA-N tris(ethenyl)phosphane Chemical compound C=CP(C=C)C=C OZHUWVSXUOMDDU-UHFFFAOYSA-N 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- PPTXVXKCQZKFBN-UHFFFAOYSA-N (S)-(-)-1,1'-Bi-2-naphthol Chemical compound C1=CC=C2C(C3=C4C=CC=CC4=CC=C3O)=C(O)C=CC2=C1 PPTXVXKCQZKFBN-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 229930194076 Germanin Natural products 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- QKIUAMUSENSFQQ-UHFFFAOYSA-N dimethylazanide Chemical compound C[N-]C QKIUAMUSENSFQQ-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000007210 heterogeneous catalysis Methods 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- ULNFTUJQIGMSAY-UHFFFAOYSA-N iodomethane;triphenylphosphane Chemical compound IC.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 ULNFTUJQIGMSAY-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- FIAFUQMPZJWCLV-UHFFFAOYSA-N suramin Chemical compound OS(=O)(=O)C1=CC(S(O)(=O)=O)=C2C(NC(=O)C3=CC=C(C(=C3)NC(=O)C=3C=C(NC(=O)NC=4C=C(C=CC=4)C(=O)NC=4C(=CC=C(C=4)C(=O)NC=4C5=C(C=C(C=C5C(=CC=4)S(O)(=O)=O)S(O)(=O)=O)S(O)(=O)=O)C)C=CC=3)C)=CC=C(S(O)(=O)=O)C2=C1 FIAFUQMPZJWCLV-UHFFFAOYSA-N 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- SXWIAEOZZQADEY-UHFFFAOYSA-N 1,3,5-triphenylbenzene Chemical compound C1=CC=CC=C1C1=CC(C=2C=CC=CC=2)=CC(C=2C=CC=CC=2)=C1 SXWIAEOZZQADEY-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 241001233914 Chelidonium majus Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910001093 Zr alloy Inorganic materials 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003245 coal Substances 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
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 description 1
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002717 polyvinylpyridine Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- KXAHUXSHRWNTOD-UHFFFAOYSA-K rhodium(3+);triiodide Chemical class [Rh+3].[I-].[I-].[I-] KXAHUXSHRWNTOD-UHFFFAOYSA-K 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
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Abstract
The invention provides a large-surface-area multistage-pore-structure organic phosphine-containing polymer loaded Rh and heteropoly acid bifunctional catalyst for preparing methyl acetate by methanol heterogeneous carbonylation without methyl iodide auxiliary agent and a preparation method thereof. The catalyst mainly comprises two parts, namely a main active component and a carrier. The main active components are rhodium metal complex and heteropoly acid; the organic phosphine-containing polymer carrier is prepared by selecting organic salts containing vinyl phosphine, and adopting a solvothermal polymerization method to carry out self-polymerization orAnd (3) generating after copolymerization reaction. In a fixed bed reactor, under certain temperature and pressure and the action of the catalyst, CH can be reacted without iodine-containing auxiliary agents such as methyl iodide and the like3OH/CO is converted into methyl acetate with high selectivity.
Description
Technical Field
The invention belongs to the technical field of heterogeneous catalytic carbonylation, and particularly relates to a rhodium and heteropoly acid bifunctional catalyst loaded by an organic phosphine-containing polymer carrier and application thereof in a reaction for preparing methyl acetate by heterogeneous carbonylation of methanol.
Background
Methyl acetate is increasingly replacing acetone, butanone, ethyl acetate, cyclopentane, etc. internationally. Because it does not limit the discharge of organic pollutants, it can reach the new environmental standard of paint, printing ink, resin and adhesive factories. The synthesis of ethanol by methyl acetate hydrogenation is also one of the main ways for preparing ethanol by coal at present. The preparation method mainly comprises (1) directly carrying out esterification reaction on acetic acid and methanol by taking sulfuric acid as a catalyst to generate a methyl acetate crude product, then dehydrating by using calcium chloride, neutralizing by using sodium carbonate, and fractionating to obtain a methyl acetate finished product. (2) Dimethyl ether is synthesized by carbonylation on an H-MOR molecular sieve catalyst, but the carbon deposition of the molecular sieve is seriously inactivated, and the space-time yield is lower. (3) When the methanol is carbonylated to prepare the acetic acid, the methyl acetate exists as a byproduct, but the selectivity is low and the separation cost is high. The vast majority of the current commercially viable methyl acetate synthesis routes go through the intermediate step of acetic acid.
Currently, the methanol carbonylation process dominates in the industrial production of acetic acid, and the production capacity of the current acetic acid production device adopting the process accounts for 94 percent of the total production capacity of acetic acid. The industrial process for the carbonylation of methanol to produce acetic acid has gone through roughly three stages of development over the past 50 years:
the first stage is as follows: the BSAF company first achieved the commercial production of acetic acid by the methanol carbonylation process using a cobalt catalyst at relatively high reaction temperatures and pressures (250 ℃, 60MPa) in 1960. And a second stage: the company Monsanto developed rhodium-iodides (RhI) with higher activity and selectivity3) A catalytic system. The reaction temperature and pressure were also relatively low (about 195 ℃ C., 3.0MPa), and the selectivity of acetic acid based on methanol was 99% or more, and the selectivity based on CO was also 90% or more. The corrosion resistance of the device is very high, and a full zirconium alloy reaction kettle is needed. And a third stage: the industrialization of Ir catalysts is the methanol carbonylation process for the production of acetic acid. The process greatly improves the stability of the catalyst, the reaction is carried out under the condition of lower water content, the generation of liquid by-products is reduced, and the conversion rate of CO is improved.
The company Chiyoda, japan, and UOP jointly developed the acitica process based on a heterogeneous Rh catalyst in which an active Rh complex is chemically immobilized on a polyvinylpyridine resin. The coordination bond chelating polymer catalyst formed by the research and the combination of the Yuan national paniculate swallowwort root, a chemical research institute of Chinese academy of sciences, also forms an independent intellectual property system, has the characteristics of high stability, high activity and the like, and can improve the selectivity of CO.
However, since the homogeneous catalyst itself has the disadvantages of easy loss of active components, difficult separation, etc., some researchers have focused on the supported heterogeneous catalyst system. The heterogeneous catalysis system can achieve the characteristics that the catalyst and the product are convenient to separate, the concentration of the catalyst is not limited by solubility, and the like, and can improve the productivity and the like by increasing the concentration of the catalyst. The supported heterogeneous catalyst system can be roughly divided into a polymer carrier, an activated carbon carrier, an inorganic oxide carrier and other systems according to different carriers, but the supported catalyst system has the problems of lower activity than the homogeneous catalyst system, easy removal of active ingredients, higher requirement on the carrier and the like. And the methyl acetate preparation with high selectivity by methanol heterogeneous carbonylation directly skips the acetic acid synthesis route, thereby saving the mass production cost. Particularly, as the performance of polymer materials is continuously expanded and optimized, the methanol heterogeneous carbonylation has great potential in the direction of taking the methanol heterogeneous carbonylation as a carrier. Most of the methanol carbonylation systems are cyclic processes with methyl iodide additives, and the addition of methyl iodide causes the corrosion of the processes to equipment to be extremely serious, so that the equipment made of hastelloy or zirconium materials is required, and the investment cost is very high. Therefore, the development of the iodine-free carbonylation system can reduce the cost and the corrosion and has important significance.
On the other hand, in recent years, porous organic polymers have attracted extensive attention of researchers due to advantages such as controllable chemical and physical properties, simple functionalized synthesis strategies, large specific areas, and low raw material prices, and more porous organic polymers are used as carriers and applied to the field of heterogeneous catalysis, and organic functional groups in monomer components can be modulated, so that various polymer carriers can be purposefully synthesized according to different reaction requirements.
In 2007, germanin et al (chem. mater,2008,20,7069) also synthesized polyaniline-type supercrossesA bipolymer. They adopt Ullmann and Buherwald coupling reaction to carry out copolymerization and crosslinking on polyaniline and phenylenediamine so as to obtain the hypercrosslinked polymer taking nitrogen atoms as connecting points. In order to obtain higher specific surface area, germanin et al (j. mater. chem,2007,17,4989) generate post-crosslinking of polyaniline and diiodomethane or paraformaldehyde to form a methylene-linked network structure, a lewis acid catalyst is not needed in the whole reaction process, hydrogen chloride waste gas is not generated, and the specific surface area of the obtained polymer can reach 632m2(ii) in terms of/g. In 2011, Tan Bien professor group (Macromolecules,2011,44,2410) at university of science and technology in Huazhong adopts dimethoxymethane as a cross-linking agent to carry out one-step F-C alkylation on rigid aromatic ring molecules, so as to obtain a super cross-linked polymer with a high specific surface area and a mainly microporous structure. Rigid aromatic ring molecules may include benzene, toluene, chlorobenzene, phenol, biphenyl, triphenylbenzene, and the like. The method has the advantages of only methanol as a byproduct, mild reaction conditions, low raw material cost and suitability for large-scale production, and most importantly, diversified porous structures can be formed by different proportions of the framework precursor and the cross-linking agent, so that the method has potential application value. In 2012, the Copper group (j.am. chem.soc,2012,134,10741) successfully introduced chiral binaphthol monomers into hypercrosslinked polymers according to this synthetic approach. So far, porous polymers formed by chiral monomers are quite rare, and the development of the porous polymers is mainly limited by low specific surface area of formed materials and complicated synthetic steps, so that the porous polymers are difficult to be practically applied, and the Copper professor directly forms a hypercrosslinked polymer with the chiral binaphthol monomers by utilizing an external crosslinking method and one-step F-C alkylation.
In the current research of phosphine-containing polymers, the quaternary phosphonium salt polymer can support metal rhodium species and heteropoly acid on a carrier through ionic bonds, so that the catalyst forms Rh and heteropoly acid dual catalytic active centers under the action of electrostatic adsorption and can be used for a methanol carbonylation process without a methyl iodide auxiliary agent.
Disclosure of Invention
The invention aims to provide a rhodium and heteropoly acid bifunctional catalyst loaded by an organic phosphine-containing polymer carrier for preparing methyl acetate by heterogeneous carbonylation of methanol and a preparation method thereof. The phosphine-containing polymer supported Rh and heteropoly acid bifunctional catalyst shows good carbonylation activity and selectivity.
The technical scheme of the invention is as follows:
the rhodium-based catalyst consists of two parts, namely a main active component and a carrier, wherein the main active component is Rh and heteropoly acid, and the carrier is a polymer;
rh accounts for 0.01-5.0 wt% of the total mass of the catalyst, preferably accounts for 0.1-4.0 wt% of the total mass of the catalyst, and optimally accounts for 0.2-1.0 wt% of the total mass of the catalyst;
the heteropoly acid accounts for 0.1-50 wt% of the total mass of the catalyst, preferably 0.5-50.0 wt% of the total mass of the catalyst, and most preferably 5-30.0 wt% of the total mass of the catalyst.
The catalyst is characterized in that the organic polymer carrier has a hierarchical pore structure with macropores, mesopores and micropores, and the pore volume of the organic polymer carrier is 0.1-5.0 cm3The pore diameter is 0.2-60.0 nm, and the specific surface area is 300-3000 m2/g。
The carrier is a polymer formed by polymerizing a vinyl-containing quaternary phosphonium salt monomer, and the preparation method comprises the following steps:
(a) adding a free radical initiator into an organic solvent containing an organic phosphine monomer under the protection of 273-473K and inert gas, wherein the weight ratio of the phosphine monomer to the free radical initiator is 0.5: 1-100: 1; stirring the obtained mixture solution for 0.1-100 hours;
(b) transferring the mixture solution in the step (a) into a hydrothermal kettle under 273-473K and inert gas protection atmosphere, and standing for 1-100 hours under the condition of solvent thermal polymerization;
(c) and (c) evacuating the solvent from the reaction mixture obtained in step (b) at room temperature in vacuo to obtain an organic polymer support having a large surface area and a hierarchical pore structure.
The method, the organic solvent used in step (a) is one or more selected from dichloromethane, tetrahydrofuran and dimethylformamide; the free radical initiator is one or more selected from cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl hydroperoxide, azobisisobutyronitrile or azobisisoheptonitrile; the phosphine-containing monomer is one or more of triphenyl vinyl phosphine, corresponding quaternary phosphonium salt triphenyl vinyl methyl phosphorus iodide after quaternary phosphonation of triethylene phosphine, triphenyl vinyl ethyl phosphorus iodide and triethylene ethyl phosphorus iodide.
The preparation method of the rhodium and heteropoly acid bifunctional catalyst loaded on the organic phosphine-containing polymer carrier comprises any one of the following steps:
the method comprises the following steps:
(a) adding a required amount of polymer carrier into an Rh precursor-containing organic solvent under the protection of 273-473K and inert gas, wherein the weight ratio of Rh content to carrier is 0.01: 1-0.05: 1; stirring the obtained mixture solution for 0.1-100 hours;
(b) washing and filtering the reaction mixture obtained in the step (a) at room temperature by using the same solvent as that used in the system, and then removing the solvent in vacuum to obtain the organic phosphine-containing polymer carrier-supported rhodium-based catalyst;
(c) adding an organic phosphine-containing polymer carrier-loaded rhodium-based catalyst into an organic solvent containing heteropoly acid under 273-473K and inert gas protection atmosphere; stirring the obtained mixture solution for 0.1-100 hours;
(d) washing and filtering the reaction mixture obtained in the step (c) at room temperature by using the same solvent as that used in the system, and then removing the solvent in vacuum, thereby obtaining the rhodium and heteropoly acid bifunctional catalyst loaded by the organic phosphine-containing polymer carrier;
(e) roasting the rhodium heteropoly acid bifunctional catalyst loaded by the organic phosphine-containing polymer carrier obtained in the step (d) for 1-20 hours at 200-400 ℃ in an inert atmosphere to obtain a roasted rhodium heteropoly acid bifunctional catalyst loaded by the organic phosphine-containing polymer carrier;
or, the method two:
(a) adding a polymer carrier into an organic solvent containing an Rh precursor and heteropoly acid under 273-473K and inert gas protection atmosphere; stirring the obtained mixture solution for 0.1-100 hours;
(b) washing and filtering the reaction mixture obtained in the step (a) at room temperature by using a solvent which is the same as that used in the system, and then removing the solvent in vacuum, thereby obtaining the rhodium and heteropoly acid bifunctional catalyst loaded on the organic phosphine-containing polymer carrier;
(c) and (c) roasting the rhodium heteropoly acid bifunctional catalyst loaded by the organic phosphine-containing polymer carrier obtained in the step (b) for 1-20 hours at 200-400 ℃ in an inert atmosphere to obtain the roasted rhodium heteropoly acid bifunctional catalyst loaded by the organic phosphine-containing polymer carrier.
The method, in the first method, the organic solvent used in the step (a) is one or more selected from benzene, dichloromethane, tetrahydrofuran, methanol and dimethylformamide; the Rh precursor is selected from RhCl3、Rh2(CO)4Cl2And Rh (PPh)3)3One or more of Cl; the heteropoly acid is one or more selected from phosphotungstic acid, phosphomolybdic acid, silicotungstic acid and silicomolybdic acid, and the organic solvent used in the step (c) is one or two selected from methanol or ethanol;
in the second method, the organic solvent used in the step (a) is one or two of methanol or ethanol; the Rh precursor is selected from RhCl3、Rh2(CO)4Cl2And Rh (PPh)3)3One or more of Cl; the heteropoly acid is one or more selected from phosphotungstic acid, phosphomolybdic acid, silicotungstic acid and silicomolybdic acid.
In the first method, the content of an active component Rh is 0.1-20.0% of the weight of the catalyst; the content of the active component heteropoly acid is 5-30.0% of the weight of the catalyst; in the second method, the content of an active component Rh is 0.1-20.0% of the weight of the catalyst; the content of the active component heteropoly acid is 5-30.0% of the weight of the catalyst.
The rhodium and heteropoly acid bifunctional catalyst loaded by the organic phosphine-containing polymer carrier is applied to the reaction of preparing methyl acetate by heterogeneous methanol carbonylation. The catalyst is used for the preparation of the catalyst,
according to the preparation method, reactants such as CO and pumped methanol enter a fixed bed reactor filled with the catalyst provided by the invention to carry out methanol carbonylation reaction, and the main product is methyl acetate.
According to the method, the volume ratio of hydrogen to CO in the reaction gas is 0.1-2.
In the application, the material of the main reactor is stainless steel 316L; the reaction temperature is 130-250 ℃, the reaction pressure is 0.5-3.5 MPa, and the liquid volume space velocity is 0.1-15 h-1。
The application is that the volume airspeed of the reaction liquid is 0.1-15 h-1The molar ratio of CO to methanol is 1-2.
In the application, the reaction raw material is free of a cocatalyst, namely methyl iodide.
The organic polymer is preferably prepared by the following method:
firstly, under the protection of 273-473K and inert gas such as nitrogen or argon, adding a free radical initiator into an alkenyl functionalized quaternary phosphonium salt organic monomer, such as an organic solvent containing vinyl functionalized triphenylphosphine methyl iodide, in a three-neck round-bottom flask equipped with a stirring and temperature control device, wherein the weight ratio of the phosphine-containing monomer to the free radical initiator is 0.5: 1-100: 1. The obtained mixture solution is stirred for 0.1 to 100 hours. Wherein, preferably, the organic solvent used can adopt dichloromethane and one of tetrahydrofuran or dimethylformamide; the radical initiator may be one of azobisisobutyronitrile and azobisisoheptonitrile. And then, transferring the mixture solution into a closed reactor such as a hydrothermal kettle, and standing the solution for 1-100 hours under the protection of 293-473K and inert gas such as nitrogen or argon by using a solvent thermal polymerization method to polymerize the organic monomer such as vinyl functionalized triphenylphosphine methyl iodide quaternary phosphonium salt, thereby generating the required polymer carrier with high surface area and multi-polar pore structure. And finally, vacuum-pumping the solvent from the polymerized reaction mixture at room temperature to obtain the P-containing organic polymer carrier with the multipolar pore structure and high surface area. The specific surface area and pore size distribution of the sample were measured on an Autosorb-1 adsorption analyzer from Quantachrome Instruments. Samples were pretreated at 373K for 20 hours prior to testing.
The invention has the beneficial effects that:
a rhodium and heteropoly acid bifunctional catalyst loaded by an organic phosphine-containing polymer carrier without a methyl iodide auxiliary agent methanol heterogeneous carbonylation process is developed, and the catalyst has certain activity and good selectivity, so that the corrosion problem of the carbonylation process, which troubles people for a long time, is avoided.
Detailed Description
The following examples illustrate but do not limit what is intended to be protected by the present invention.
Example 1
At 298K and N25g of tris (4-vinylphenyl) ylphosphine ethyl iodide and 5g of tris (4-vinylphenyl) ylphosphine methyl iodide as monomers were dissolved in 100.0ml of tetrahydrofuran solvent under a protective atmosphere, 0.25g of azobisisobutyronitrile as a radical initiator was added to the above solution, and stirring was carried out for 2 hours. And transferring the stirred solution into a hydrothermal kettle, and polymerizing for 24 hours by using a solvent thermal polymerization method under the atmosphere of 373K and nitrogen gas. And cooling the polymerized solution to room temperature, and vacuumizing the solution at room temperature to remove the solvent to obtain the organic polymer carrier with the large-surface-area hierarchical pore structure formed by polymerizing the tri (4-vinyl benzene) phosphine. Then, at 298K and N2Under a protective atmosphere, 0.0285g of Rh (PPh)3)3And dissolving Cl in 50ml of dimethyl amide, adding 5g of the polymer into the mixture, stirring the mixture at room temperature for 24 hours, washing and filtering the dimethyl amide, vacuumizing the mixture, and pumping away the solvent to obtain the organic phosphine-containing polymer carrier-supported rhodium-based catalyst. Then, at 298K and N2Under the protection atmosphere, 0.824g of silicomolybdic acid is dissolved in 10ml of methanol, 5g of rhodium-based catalyst is added into the solution, the solution is stirred for 24 hours at room temperature, the methanol is washed and filtered, and then the solvent is pumped out by vacuum pumping to obtain the organic phosphine-containing polymer carrier negativeThe supported rhodium and heteropoly acid bifunctional catalyst. The technical route of polymerization and loading of metal Rh and heteropoly acid on the polymer carrier in this example is shown below. (Rh content 0.05%, silicomolybdic acid content 14%)
Example 2
At 298K and N25g of tris (4-vinylbenzene) ylphosphine ethyl iodide and 5g of tris (4-vinylbenzene) ylphosphine methyl iodide were dissolved as monomers in 100.0ml of a methylene chloride solvent under a protective atmosphere, 0.25g of azobisisoheptonitrile as a radical initiator was added to the above solution, and stirred for 2 hours. And transferring the stirred solution into a hydrothermal kettle, and polymerizing for 24 hours by using a solvent thermal polymerization method under the atmosphere of 373K and nitrogen gas. And cooling the polymerized solution to room temperature, and vacuumizing the solution at room temperature to remove the solvent to obtain the organic polymer carrier with the large-surface-area hierarchical pore structure. Then, at 298K and N2Under protective atmosphere, 0.0285gRhCl is added3Dissolving in 50ml tetrahydrofuran, adding 5g of the polymer, stirring for 24h at room temperature, washing with tetrahydrofuran, filtering, vacuumizing, and removing the solvent to obtain the rhodium-based catalyst loaded by the organic phosphine-containing polymer carrier. Then, at 298K and N2Under the protection atmosphere, 1.300g of silicotungstic acid is dissolved in 10ml of methanol, 5g of the rhodium-based catalyst is added into the methanol, the mixture is stirred for 24 hours at room temperature, and after ethanol washing and suction filtration, the solvent is pumped out in a vacuum mode to obtain the rhodium and heteropoly acid bifunctional catalyst loaded on the organic phosphine-containing polymer carrier. The technical route of polymerization and loading of metal Rh and heteropoly acid on the polymer carrier in this example is shown below. (Rh content 0.17%, silicomolybdic acid content 21%)
Example 3
At 298K and N2Under a protective atmosphere, 10.0g of tris (4-vinylbenzene) ylphosphine methyl iodide as a monomer was dissolved in 100.0ml of a dimethylformamide solvent, and 0.25g of the above solution was addedAzobisisobutyronitrile, as a free radical initiator, was stirred for 2 hours. And transferring the stirred solution into a hydrothermal kettle, and polymerizing for 24 hours by using a solvent thermal polymerization method under the atmosphere of 373K and nitrogen gas. And cooling the polymerized solution to room temperature, and vacuumizing the solution at room temperature to remove the solvent to obtain the organic polymer carrier with the large-surface-area hierarchical pore structure. Then, at 298K and N2Under a protective atmosphere, 0.0285g of Rh is added2(CO)4Cl2Dissolved in 50ml CH2Cl2And adding 5g of the polymer into the mixed solution, stirring the mixture for 24 hours at room temperature, washing the mixture by using dichloromethane, performing suction filtration, and vacuumizing the mixture to remove the solvent to obtain the rhodium-based catalyst loaded by the organic phosphine-containing polymer carrier. Then, at 298K and N2Under the protection atmosphere, 1.300g of phosphotungstic acid is dissolved in 10ml of ethanol, 5g of the rhodium-based catalyst is added into the solution, the solution is stirred for 24 hours at room temperature, and after the ethanol is washed and filtered, the solution is pumped out in a vacuum mode, so that the rhodium and heteropoly acid bifunctional catalyst loaded on the organic phosphine-containing polymer carrier is obtained. Roasting for 3h at 250 ℃ under inert atmosphere to obtain the roasted rhodium and heteropoly acid bifunctional catalyst loaded by the organic phosphine-containing polymer carrier. The polymerization and loading of the polymeric carrier with metallic Rh and heteropolyacid and the calcination route in this example are shown below. (Rh content 0.24%, silicomolybdic acid content 21%)
Example 4
At 298K and N25.0g of tris (4-vinylphenyl) ylphosphine ethyl iodide and 5.0g of trivinylphosphine ethyl iodide were dissolved in 100.0ml of dimethylformamide as a solvent under a protective atmosphere, 0.25g of azobisisobutyronitrile as a radical initiator was added to the above solution, and stirring was carried out for 2 hours. And transferring the stirred solution into a hydrothermal kettle, and polymerizing for 24 hours by using a solvent thermal polymerization method under the atmosphere of 373K and nitrogen gas. And cooling the polymerized solution to room temperature, and vacuumizing the solution at room temperature to remove the solvent to obtain the organic polymer carrier with the large-surface-area hierarchical pore structure. Then, at 298K and N2Under the protection atmosphere, 0.0285gRh is added2(CO)4Cl2Dissolved in 50ml CH2Cl2And adding 5g of the polymer into the mixed solution, stirring the mixture for 24 hours at room temperature, washing the mixture by using dichloromethane, performing suction filtration, and vacuumizing the mixture to remove the solvent to obtain the rhodium-based catalyst loaded by the organic phosphine-containing polymer carrier. Then, at 298K and N2Under the protection atmosphere, 0.824g of silicotungstic acid is dissolved in 10ml of ethanol, 5g of the rhodium-based catalyst is added into the solution, the solution is stirred for 24 hours at room temperature, and after the ethanol is washed and filtered, the solution is pumped out in a vacuum mode to obtain the rhodium and heteropoly acid bifunctional catalyst loaded by the organic phosphine-containing polymer carrier. The technical route of polymerization and loading of metallic Rh and heteropolyacid on the polymeric support in this example is shown below. (Rh content 0.26%, silicomolybdic acid content 14%)
Example 5
At 298K and N2Under a protective atmosphere, 10.0g of tris (4-vinylbenzene) ylphosphine ethyl iodide as a monomer was dissolved in 100.0ml of a dimethylformamide solvent, and 0.25g of azobisisobutyronitrile as a radical initiator was added to the above solution, followed by stirring for 2 hours. And transferring the stirred solution into a hydrothermal kettle, and polymerizing for 24 hours by using a solvent thermal polymerization method under the atmosphere of 373K and nitrogen gas. And cooling the polymerized solution to room temperature, and vacuumizing the solution at room temperature to remove the solvent to obtain the organic polymer carrier with the large-surface-area hierarchical pore structure. Then, at 298K and N2Under a protective atmosphere, 0.0285g of Rh is added2(CO)4Cl2And 0.824g of silicomolybdic acid is dissolved in 50ml of ethanol, 5g of polymer is added into the solution, the solution is stirred for 24 hours at room temperature, and after the ethanol is washed and filtered, the solvent is pumped out in vacuum, and the rhodium heteropoly acid bifunctional catalyst loaded by the organic phosphine-containing polymer carrier is obtained. The technical route of the polymerization and loading of the polymeric carrier with the metal Rh and silicotungstic acid in the present example is shown below. (Rh content 0.26%, silicomolybdic acid content 14%)
Example 6
At 298K and N2Under a protective atmosphere, 10.0g of tris (4-vinylbenzene) ylphosphine ethyl iodide as a monomer was dissolved in 100.0ml of a toluene solvent, 0.25g of azobisisobutyronitrile as a radical initiator was added to the above solution, and the mixture was stirred for 2 hours. And transferring the stirred solution into a hydrothermal kettle, and polymerizing for 24 hours by using a solvent thermal polymerization method under the atmosphere of 373K and nitrogen gas. And cooling the polymerized solution to room temperature, and vacuumizing the solution at room temperature to remove the solvent to obtain the organic polymer carrier with the large-surface-area hierarchical pore structure. Then, at 298K and N2Under a protective atmosphere, 0.0285g of Rh (PPh)3)3And dissolving Cl and 1.3g of silicomolybdic acid in 50ml of methanol, adding 5g of polymer into the solution, stirring the solution at room temperature for 24 hours, washing and filtering the solution by using the methanol, vacuumizing the solution, and obtaining the rhodium and heteropoly acid bifunctional catalyst loaded on the organic phosphine-containing polymer carrier. The technical route of polymerization of the polymer carrier and loading of metal Rh and silicomolybdic acid in this example is shown below. (Rh content 0.05%, silicomolybdic acid content 21%)
Example 7
At 298K and N2Under a protective atmosphere, 10.0g of trivinylphosphine ethyl iodide as a monomer was dissolved in 100.0ml of a dimethylformamide solvent, and 0.25g of azobisisobutyronitrile as a radical initiator was added to the above solution, followed by stirring for 2 hours. And transferring the stirred solution into a hydrothermal kettle, and polymerizing for 24 hours by using a solvent thermal polymerization method under the atmosphere of 373K and nitrogen gas. And cooling the polymerized solution to room temperature, and vacuumizing the solution at room temperature to remove the solvent to obtain the organic polymer carrier with the large-surface-area hierarchical pore structure. Then, at 298K and N2Under a protective atmosphere, 0.0285g of RhCl is added3And 0.824g of phosphomolybdic acid is dissolved in 50ml of methanol, 5g of polymer is added into the solution, the solution is stirred for 24 hours at room temperature, and after methanol washing and suction filtration, the solution is pumped out in vacuum, and the rhodium and heteropoly acid bifunctional catalyst loaded on the organic phosphine-containing polymer carrier is obtained. Roasting at 250 deg.C for 3 hr under inert atmosphere to obtain roasted organic phosphine-containing polymer carrierRhodium and heteropolyacid bifunctional catalysts. The polymerization and loading of the polymer carrier with metal Rh and phosphomolybdic acid and the baking technical route in this example are shown below. (Rh content 0.18%, silicomolybdic acid content 14%)
Example 8
At 298K and N2Under a protective atmosphere, 3.3g of tris (4-vinylbenzene) ylphosphine ethyl iodide, 3.3g of trivinylphosphine ethyl iodide and 3.3g of tris (4-vinylbenzene) ylphosphine methyl iodide were dissolved as monomers in 100.0ml of a tetrahydrofuran solvent, 0.25g of azobisisoheptonitrile as a radical initiator was added to the above solution, and stirring was carried out for 2 hours. And transferring the stirred solution into a hydrothermal kettle, and polymerizing for 24 hours by using a solvent thermal polymerization method under the atmosphere of 373K and nitrogen gas. And cooling the polymerized solution to room temperature, and vacuumizing the solution at room temperature to remove the solvent to obtain the organic polymer carrier with the large-surface-area hierarchical pore structure. Then, at 298K and N2Under a protective atmosphere, 0.0285g of Rh (PPh)3)3And dissolving Cl and 1.3g of phosphotungstic acid in 50ml of ethanol, adding 5g of polymer into the solution, stirring the solution at room temperature for 24 hours, washing the solution with ethanol, carrying out suction filtration, vacuumizing the solution, and pumping away the solvent to obtain the rhodium and heteropoly acid bifunctional catalyst loaded on the organic phosphine-containing polymer carrier. Roasting for 3h at 250 ℃ under inert atmosphere to obtain the roasted rhodium and heteropoly acid bifunctional catalyst loaded by the organic phosphine-containing polymer carrier. The polymerization and loading of the polymer carrier with metal Rh and phosphomolybdic acid and the baking technical route in this example are shown below. (Rh content 0.05%, silicomolybdic acid content 21%)
Example 9
At 298K and N2Under a protective atmosphere, 10.0g of tris (4-vinylbenzene) ylphosphine methyl iodide as a monomer was dissolved in 100.0ml of a dimethylformamide solvent, and 0.25g of azobisisobutyronitrile as a radical initiator was added to the above solution, followed by stirring for 2 hours. Will be provided withAnd transferring the stirred solution into a hydrothermal kettle, and polymerizing for 24 hours by using a solvent thermal polymerization method under the atmosphere of 373K and nitrogen gas. And cooling the polymerized solution to room temperature, and vacuumizing the solution at room temperature to remove the solvent to obtain the organic polymer carrier with the large-surface-area hierarchical pore structure. Then, at 298K and N2Under a protective atmosphere, 0.0285g of Rh is added2(CO)4Cl2Dissolved in 50ml CH2Cl25g of polymer are added thereto and stirred at room temperature for 24h, CH2Cl2And after washing and suction filtration, vacuumizing and pumping away the solvent to obtain the rhodium-based catalyst loaded by the organic phosphine-containing polymer carrier. The technical route of polymerization of the polymer carrier and loading of metallic Rh in this example is shown below. (Rh content 0.3%, silicomolybdic acid content 0%)
Application example: the prepared catalyst is applied to the reaction for preparing methyl acetate by taking methanol/CO as a raw material.
The reaction conditions are as follows: 195 deg.C, 2.5MPa, CH3OH/CO ═ 1: 1.5 (molar ratio), no methyl iodide auxiliary agent, CH3The feed rate of the OH liquid was 0.05ml/min, and the mass of the catalyst was 0.1000 g. After the reaction tail gas is cooled by a cold trap, the gas product is analyzed on line, and the chromatographic instruments are Agilent 7890A GC, PQ packed columns and TCD detectors. Off-line analysis of liquid phase product, FFAP capillary chromatographic column, FID detector. And (4) performing internal standard analysis, wherein isobutanol is used as an internal standard substance.
Methyl acetate and acetic acid were prepared according to the above procedure using rhodium and heteropolyacid catalyst supported on the organic phosphine-containing polymer support prepared in examples 1 to 8, and carbonylation TOF, methyl acetate selectivity and acetic acid selectivity are shown in table 1.
TABLE 1 results of the methanol carbonylation reaction of the examples
| Examples | TOFacetyl/h-1 | Acetic acid selectivity (%) | Methyl acetate selectivity (%) |
| 1 | 15 | 0 | 100 |
| 2 | 20 | 0 | 100 |
| 3 | 10 | 0 | 100 |
| 4 | 6 | 0 | 100 |
| 5 | 7 | 0 | 100 |
| 6 | 8 | 0 | 100 |
| 7 | 7 | 0 | 100 |
| 8 | 10 | 0 | 100 |
| 9 | 1 | 0 | 100 |
。
The present invention has been described in detail above, but the present invention is not limited to the specific embodiments described herein. It will be understood by those skilled in the art that other modifications and variations may be made without departing from the scope of the invention. The scope of the invention is defined by the appended claims.
Claims (10)
1. The organic phosphine-containing polymer carrier loaded rhodium and heteropoly acid catalyst is characterized in that: the rhodium-based catalyst consists of two parts, namely a main active component and a carrier, wherein the main active component is Rh and heteropoly acid, and the carrier is a polymer;
rh accounts for 0.01-5.0 wt% of the total mass of the catalyst, preferably accounts for 0.1-4.0 wt% of the total mass of the catalyst, and optimally accounts for 0.2-1.0 wt% of the total mass of the catalyst;
the heteropoly acid accounts for 0.1-50 wt% of the total mass of the catalyst, preferably 0.5-50.0 wt% of the total mass of the catalyst, and most preferably 5-30.0 wt% of the total mass of the catalyst.
2. The catalyst according to claim 1, wherein the organic polymer support has a hierarchical pore structure of macropores, mesopores and micropores, and has a pore volume of 0.1 to 5.0cm3(g) pore size distribution of 0.2 to 60.0nm, ratioThe surface area is 300 to 3000m2/g。
3. The catalyst according to claim 1 or 2, wherein the carrier is a polymer obtained by polymerizing a vinyl group-containing quaternary phosphonium salt monomer, and the catalyst is prepared by the following method:
(a) adding a free radical initiator into an organic solvent containing an organic phosphine monomer under the protection of 273-473K and inert gas, wherein the weight ratio of the phosphine monomer to the free radical initiator is 0.5: 1-100: 1; stirring the obtained mixture solution for 0.1-100 hours;
(b) transferring the mixture solution in the step (a) into a hydrothermal kettle under 273-473K and inert gas protection atmosphere, and standing for 1-100 hours under the condition of solvent thermal polymerization;
(c) and (c) evacuating the solvent from the reaction mixture obtained in step (b) at room temperature in vacuo to obtain an organic polymer support having a large surface area and a hierarchical pore structure.
4. The method according to claim 3, wherein the organic solvent used in step (a) is one or more selected from the group consisting of dichloromethane, tetrahydrofuran and dimethylformamide; the free radical initiator is one or more selected from cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl hydroperoxide, azobisisobutyronitrile or azobisisoheptonitrile; the phosphine-containing monomer is one or more of triphenyl vinyl phosphine, corresponding quaternary phosphonium salt triphenyl vinyl methyl phosphorus iodide after quaternary phosphonation of triethylene phosphine, triphenyl vinyl ethyl phosphorus iodide and triethylene ethyl phosphorus iodide.
5. A process for the preparation of an organophosphine containing polymer supported rhodium and heteropolyacid bifunctional catalyst as claimed in any one of claims 1 to 4, said process comprising any one of:
the method comprises the following steps:
(a) adding a required amount of polymer carrier into an organic solvent containing Rh precursor under 273-473K and inert gas protection atmosphere; stirring the obtained mixture solution for 0.1-100 hours;
(b) washing and filtering the reaction mixture obtained in the step (a) at room temperature by using the same solvent as that used in the system, and then removing the solvent in vacuum to obtain the organic phosphine-containing polymer carrier-supported rhodium-based catalyst;
(c) adding an organic phosphine-containing polymer carrier-loaded rhodium-based catalyst into an organic solvent containing heteropoly acid under 273-473K and inert gas protection atmosphere; stirring the obtained mixture solution for 0.1-100 hours;
(d) washing and filtering the reaction mixture obtained in the step (c) at room temperature by using the same solvent as that used in the system, and then removing the solvent in vacuum, thereby obtaining the rhodium and heteropoly acid bifunctional catalyst loaded by the organic phosphine-containing polymer carrier;
(e) roasting the rhodium heteropoly acid bifunctional catalyst loaded by the organic phosphine-containing polymer carrier obtained in the step (d) for 1-20 hours at 200-400 ℃ in an inert atmosphere to obtain a roasted rhodium heteropoly acid bifunctional catalyst loaded by the organic phosphine-containing polymer carrier;
or, the method two:
(a) adding a polymer carrier into an organic solvent containing an Rh precursor and heteropoly acid under 273-473K and inert gas protection atmosphere; stirring the obtained mixture solution for 0.1-100 hours;
(b) washing and filtering the reaction mixture obtained in the step (a) at room temperature by using a solvent which is the same as that used in the system, and then removing the solvent in vacuum, thereby obtaining the rhodium and heteropoly acid bifunctional catalyst loaded on the organic phosphine-containing polymer carrier;
(c) and (c) roasting the rhodium heteropoly acid bifunctional catalyst loaded by the organic phosphine-containing polymer carrier obtained in the step (b) for 1-20 hours at 200-400 ℃ in an inert atmosphere to obtain the roasted rhodium heteropoly acid bifunctional catalyst loaded by the organic phosphine-containing polymer carrier.
6. The method of claim 5,
the organic solvent used in step (a) of the first process isOne or more selected from benzene, dichloromethane, tetrahydrofuran, methanol and dimethylformamide; the Rh precursor is selected from RhCl3、Rh2(CO)4Cl2And Rh (PPh)3)3One or more of Cl; the heteropoly acid is one or more selected from phosphotungstic acid, phosphomolybdic acid, silicotungstic acid and silicomolybdic acid, and the organic solvent used in the step (c) is one or two selected from methanol or ethanol;
in the second method, the organic solvent used in the step (a) is one or two of methanol or ethanol; the Rh precursor is selected from RhCl3、Rh2(CO)4Cl2And Rh (PPh)3)3One or more of Cl; the heteropoly acid is one or more selected from phosphotungstic acid, phosphomolybdic acid, silicotungstic acid and silicomolybdic acid.
7. Use of a bifunctional catalyst of rhodium and heteropolyacid supported on an organophosphine-containing polymer support as claimed in any one of claims 1 to 4 in the carbonylation of heterogeneous methanol to produce methyl acetate.
8. Use according to claim 7, characterized in that: the material of the main reactor is stainless steel 316L material; the reaction temperature is 130-250 ℃, and the reaction pressure is 0.5-3.5 MPa.
9. Use according to claim 7 or 8, characterized in that: the volume space velocity of the reaction liquid is 0.1-15 h-1The molar ratio of CO to methanol is 1-2.
10. Use according to claim 7 or 8, characterized in that: the reaction raw material contains no methyl iodide catalyst.
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