CN1007246B - Process for preparing aldehydes - Google Patents
Process for preparing aldehydesInfo
- Publication number
- CN1007246B CN1007246B CN 85105102 CN85105102A CN1007246B CN 1007246 B CN1007246 B CN 1007246B CN 85105102 CN85105102 CN 85105102 CN 85105102 A CN85105102 A CN 85105102A CN 1007246 B CN1007246 B CN 1007246B
- Authority
- CN
- China
- Prior art keywords
- straight
- rhodium
- carbon atom
- branched alkyl
- catalyzer
- 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.)
- Expired
Links
- 150000001299 aldehydes Chemical class 0.000 title abstract 2
- 238000004519 manufacturing process Methods 0.000 title description 2
- 239000010948 rhodium Substances 0.000 claims abstract description 26
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 23
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- 150000001336 alkenes Chemical class 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- 239000007791 liquid phase Substances 0.000 claims abstract description 4
- 239000012429 reaction media Substances 0.000 claims abstract description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 18
- -1 sulfate radical Chemical class 0.000 claims description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims description 17
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 11
- 150000003003 phosphines Chemical class 0.000 claims description 10
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 10
- 238000006277 sulfonation reaction Methods 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 150000003284 rhodium compounds Chemical class 0.000 claims description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- WJIBZZVTNMAURL-UHFFFAOYSA-N phosphane;rhodium Chemical compound P.[Rh] WJIBZZVTNMAURL-UHFFFAOYSA-N 0.000 claims description 3
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 3
- KHBQMWCZKVMBLN-UHFFFAOYSA-N Benzenesulfonamide Chemical compound NS(=O)(=O)C1=CC=CC=C1 KHBQMWCZKVMBLN-UHFFFAOYSA-N 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- 241000370738 Chlorion Species 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052784 alkaline earth metal Chemical group 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical group 0.000 claims description 2
- 229910052728 basic metal Inorganic materials 0.000 claims description 2
- 150000003818 basic metals Chemical group 0.000 claims description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 2
- 230000000536 complexating effect Effects 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 claims description 2
- 229940006461 iodide ion Drugs 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 2
- 125000003107 substituted aryl group Chemical group 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Chemical group 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 15
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 14
- 238000007037 hydroformylation reaction Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 7
- 239000012074 organic phase Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 230000021523 carboxylation Effects 0.000 description 6
- 238000006473 carboxylation reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000009466 transformation Effects 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- VICYBMUVWHJEFT-UHFFFAOYSA-N dodecyltrimethylammonium ion Chemical compound CCCCCCCCCCCC[N+](C)(C)C VICYBMUVWHJEFT-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- UAQBAKXSESXNOU-UHFFFAOYSA-M hexadecyl(trimethyl)azanium trimethylazanium dibromide Chemical compound [Br-].C(CCCCCCCCCCCCCCC)[N+](C)(C)C.[Br-].C[NH+](C)C UAQBAKXSESXNOU-UHFFFAOYSA-M 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- GLFDLEXFOHUASB-UHFFFAOYSA-N trimethyl(tetradecyl)azanium Chemical compound CCCCCCCCCCCCCC[N+](C)(C)C GLFDLEXFOHUASB-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- OWQGBDSLJUVLKF-UHFFFAOYSA-N 2-dodecylpyridine Chemical compound CCCCCCCCCCCCC1=CC=CC=N1 OWQGBDSLJUVLKF-UHFFFAOYSA-N 0.000 description 1
- YJLPJNLZCOKVAM-UHFFFAOYSA-N 2-ethylhexanoic acid;rhodium Chemical compound [Rh].CCCCC(CC)C(O)=O YJLPJNLZCOKVAM-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NXCKJKRCISDGDY-UHFFFAOYSA-M C1(=CC=CC=C1)S(=O)(=O)[O-].CC([N+](C)(C)CCCCCCCCCCCCCCCC)(CC)C Chemical compound C1(=CC=CC=C1)S(=O)(=O)[O-].CC([N+](C)(C)CCCCCCCCCCCCCCCC)(CC)C NXCKJKRCISDGDY-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N Lactic Acid Natural products CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- STGLJNCRNHEHQH-UHFFFAOYSA-H S(=O)(=O)([O-])C=1C=C(C=CC1)P(C1=CC(=CC=C1)S(=O)(=O)[O-])C1=CC(=CC=C1)S(=O)(=O)[O-].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].P.S(=O)(=O)([O-])C=1C=C(C=CC1)P(C1=CC(=CC=C1)S(=O)(=O)[O-])C1=CC(=CC=C1)S(=O)(=O)[O-] Chemical compound S(=O)(=O)([O-])C=1C=C(C=CC1)P(C1=CC(=CC=C1)S(=O)(=O)[O-])C1=CC(=CC=C1)S(=O)(=O)[O-].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].P.S(=O)(=O)([O-])C=1C=C(C=CC1)P(C1=CC(=CC=C1)S(=O)(=O)[O-])C1=CC(=CC=C1)S(=O)(=O)[O-] STGLJNCRNHEHQH-UHFFFAOYSA-H 0.000 description 1
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 1
- WPUMCTWIJONGLG-UHFFFAOYSA-M [Na]OS(=O)(=O)C1=CC=CC=C1P Chemical compound [Na]OS(=O)(=O)C1=CC=CC=C1P WPUMCTWIJONGLG-UHFFFAOYSA-M 0.000 description 1
- FSHNFAOXXJLGJE-UHFFFAOYSA-N [Rh].[P] Chemical compound [Rh].[P] FSHNFAOXXJLGJE-UHFFFAOYSA-N 0.000 description 1
- NENDHUHGFRLXEN-UHFFFAOYSA-N acetic acid;rhodium Chemical compound [Rh].CC(O)=O NENDHUHGFRLXEN-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- RLGQACBPNDBWTB-UHFFFAOYSA-N cetyltrimethylammonium ion Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)C RLGQACBPNDBWTB-UHFFFAOYSA-N 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- MIZBCDQFHMSKPN-UHFFFAOYSA-M dodecyl(trimethyl)azanium;methanesulfonate Chemical compound CS([O-])(=O)=O.CCCCCCCCCCCC[N+](C)(C)C MIZBCDQFHMSKPN-UHFFFAOYSA-M 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 235000019256 formaldehyde Nutrition 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- AEDIXYWIVPYNBI-UHFFFAOYSA-N heptanamide Chemical compound CCCCCCC(N)=O AEDIXYWIVPYNBI-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- GHLZUHZBBNDWHW-UHFFFAOYSA-N nonanamide Chemical compound CCCCCCCCC(N)=O GHLZUHZBBNDWHW-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- SJLOMQIUPFZJAN-UHFFFAOYSA-N oxorhodium Chemical compound [Rh]=O SJLOMQIUPFZJAN-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003283 rhodium Chemical class 0.000 description 1
- 229910003450 rhodium oxide Inorganic materials 0.000 description 1
- SVOOVMQUISJERI-UHFFFAOYSA-K rhodium(3+);triacetate Chemical compound [Rh+3].CC([O-])=O.CC([O-])=O.CC([O-])=O SVOOVMQUISJERI-UHFFFAOYSA-K 0.000 description 1
- YWFDDXXMOPZFFM-UHFFFAOYSA-H rhodium(3+);trisulfate Chemical compound [Rh+3].[Rh+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O YWFDDXXMOPZFFM-UHFFFAOYSA-H 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical group [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical group [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- PDSVZUAJOIQXRK-UHFFFAOYSA-N trimethyl(octadecyl)azanium Chemical compound CCCCCCCCCCCCCCCCCC[N+](C)(C)C PDSVZUAJOIQXRK-UHFFFAOYSA-N 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
According to the process of the present invention, aldehydes are prepared by reacting olefins with carbon monoxide and hydrogen. The reaction is carried out in the liquid phase in the presence of water, using a rhodium complex containing a trisulphonated triarylphosphine or a triscarboxylated triarylphosphine as catalyst and a solubilising agent in the reaction medium.
Description
The invention relates in the presence of the water-soluble rhodium complex compound catalyst, prepare a kind of method of aldehyde by hydroformylation of olefins.
Known aldehyde and alcohol can be prepared by alkene and carbon monoxide and H-H reaction.This reacts available metallic carbonyls hydride and carries out catalysis, adopts the carbonyl hydride of VIII family metallic element in the periodic table of elements better.Except the industrial cobalt metal that has been widely used as catalyzer, rhodium also demonstrated its importance in recent years.Compare with cobalt, rhodium can make reaction under low pressure carry out, and can preferentially generate the positive aldehyde of straight chain and have only more a spot of different aldehyde.At last, when making catalyzer with rhodium, much less when hydrogenation of olefins becomes the amount of stable hydrocarbon to make catalyzer than with cobalt.
In existent method, used rhodium catalyst is to use with the improved form that contains the carbonyl hydrogenatedization rhodium of ligand, and in some cases, ligand is excessive.Verified three grades of phosphines or phosphite are particularly suitable as ligand.Use them can make reaction pressure drop to 300 crust (30 * 10
2KPa) below.Yet the problem that this method exists is the separation of reaction product and the recovery of catalyzer, because catalyzer is uniform dissolution in reaction product.Usually reaction product can steam from reaction mixture, but owing to the susceptibility of formed alcohols and aldehydes to heat, in fact this method can only be used for the hydroformylation of 5 carbon atoms with interior light alkene.And, have been found that the distillatory thermal load also causes the catalyzer considerable damage owing to the rhodium complex decomposes.
Above-mentioned shortcoming can for example be avoided at the catalyzer described in the Germany patent specification (DE-PS) 2627354 by using water-soluble catalyst system, and the solvability of rhodium complex can be by reaching as the complex compound component with the sulfonation triaryl phosphine.In this way, can simply organic phase and water be separated after aldehyde reaction is finished, catalyzer is just separated from reaction product, that is to say, without the distillatory method, thereby does not also just have heat-processed.Except using the sulfonation triaryl phosphine, the carboxylation triaryl phosphine also can be used as the complex compound branch of water-soluble rhodium complex compound.
Verified this method can be used for hydroformylation, particularly ethene and the propylene than light alkene admirably, and is used to resemble hexene, and during higher olefins such as octene and decene, transformation efficiency just descends significantly, this means for industrial-scale production just no longer suitable.
The reduction of transformation efficiency is because higher olefins solubleness in water is less, and the reaction between two kinds of reactants will be carried out at aqueous phase in this reaction.
Germany patent application (DE) 3135127A1 proposes olefin(e) compound in water and organic phase and leave and carry out hydroformylation, and reaction system or not miscible or slightly soluble only also have solubilizing agent.
In implementing this reaction, only be confined to single sulfonation triaryl phosphine and single carboxylation triaryl phosphine to show that particularly single sulfonation triaryl phosphine life-span is very short, thereby to be unsuitable for repeated use as the complexing component of rhodium complex.
Therefore task is to overcome above-mentioned shortcoming, and proposing one is suitable in the heterogeneous system of being made up of water-soluble catalytic agent solution and organic raw material, also has in the heterogeneous system of reaction product and gasiform reactant existence the method for higher hydroformylation in some cases.
According to the present invention, above-mentioned task is to solve like this, and by alkene and carbon monoxide and hydrogen prepared in reaction aldehyde in the liquid phase that is existed by water and water-soluble rhodium phosphine complex, temperature of reaction is 20～150 ℃, and pressure is 1～200 to cling to (100～20 * 10
8KPa) this method is characterised in that with the rhodium complex that contains three sulfonation triaryl phosphines and three carboxylation triaryl phosphines as catalyzer, and contains solubilizing agent in the reaction medium.
Be as the component of rhodium complex and have under the situation that solubilizing agent exists unexpectedly at three sulfonation triaryl phosphines or its phosphines of three hydroxylations three virtue, hydroformylation of olefins always reaches the selectivity of high conversion and height, and does not cause the reduction of transformation efficiency owing to the rapid decomposition of catalyzer.
As catalyzer contain three strong sulfonation triaryl phosphines of coordination or the rhodium compound of three carboxylation triaryl phosphines has following general formula:
Ar in the formula
1, Ar
2And Ar
3Represent phenyl or naphthyl, Y
1, Y
2And Y
3Each representative contains the alkyl of the straight or branched of 1～4 carbon atom, alkoxyl group, halogen atom, OH-, CN-,-NO
2Or R
1R
2Groups such as N-, wherein R
1And R
2Each represents that one contains the straight chain of 1～4 carbon atom or removes alkyl group; x
1, x
2And x
3Each represents carboxylate group-(COO
-) and (or) sulfonate group-(SO
- 3); n
1, n
2And n
3Can be identical, also can be different, be 0～5 integer.M is that a kind of basic metal or alkaline-earth metal, zinc, ammonium or general formula are N(R
3R
4R
5R
6)
+Quaternary ammonium ion, R wherein
3, R
4, R
5And R
6Each represents a straight or branched alkyl that contains 1～4 carbon atom.
According to the embodiment that present method is recommended, rhodium compound is the complex-type compound that contains above-mentioned general formula, Ar in the formula
1, Ar
2And Ar
3Each represents a phenyl; x
1, x
2And x
3Each represents sulfonate group.
" solubilizing agent " can be understood as: both with water immiscible phase also with the miscible a kind of material of organic phase or the mixture of several materials, particularly better at the two-phase intermiscibility when elevated temperature.This material is known, is also referred to as consisting of phase-transferring agent, surface-active or amphipathic reactant or tensio-active agent.
Their effect mainly is the physical properties that changes interface between two liquid phases, thereby promotes organic reactant to change the water of catalyzer over to.
In this respect, particularly importantly solubilizing agent is not paid effect for the activity of the reactive metal that plays katalysis.Solubilizing agent can be divided into anionic, anionic and non-ionic type by its chemical structure.
The example that can be used for the anionic solubilizing agent of the inventive method is the carboxylate salt that contains 8～10 carbon atoms, particularly contains the saturated fatty acid of 12～18 carbon atoms, as lauric myristic and stearic salt.Also be negatively charged ion solubilizing agent as alkylsulfonates such as alkylbenzene sulfonate and sulfonated alkyl naphathalene and alkylaryl sulphonate in addition.
Neutrality and non-ionic solubilizer be the adducts of oxyethane especially; (addition makes to oxyethane by higher alcohol, alkyl phenyl polyoxyethylene glycol (addition makes to oxyethane by phenol) and acyl group polyoxyethylene glycol (addition makes to oxyethane by lipid acid) as the alkyl polyoxyethylene glycol.Particularly suitable positively charged ion solubilizing agent is level Four compounds, especially ammonium salt.The compound of verified at first, following general formula is valuable.
A represents the straight or branched alkyl in the formula, ω-hydroxyalkyl, and alkoxyl group or in some cases, representative contains the substituted aryl or the R of 6～25 carbon atoms
7-CONH-CH
2-CH
2-CH
2Group, R in the formula
7Representative contains the straight or branched alkyl of 5～11 carbon atoms; B, C and D can be the same or different, be a straight chain or branched-chain alkyl, or has a ω-hydroxyalkyl of 1～4 carbon atom, perhaps C and D with N form one five yuan or hexa-member heterocycle, E represents chlorion, bromide anion, iodide ion, particularly sulfate radical, tetrafluoroborate, acetate, first for sulfate radical, Phenylsulfonic acid root, benzene sulfonamide acid group, methylsulphonic acid root, lactate or citrate.First preferentially is recommended as this negatively charged ion for sulfate radical, sulfonate radical and lactate owing to its low-corrosiveness.
Meet above-mentioned general formula and suitable cationic example has the stearyl trimethyl ammonium, phenyltrimethyammonium, trimethylammonium-1-phenyl ammonium, benzyltrimethylammon.um, the dodecyl pyridine, amino four yl pyridines of stearyl, dodecyl trimethyl ammonium, its ammonium of benzyl three second, cetyltrimethyl ammonium, the tetradecyl trimethyl ammonium, N-(3-TMA (TriMethylAmine) propyl group) positive heptamide first is for sulfuric ester, dodecyl-three-beta-hydroxyethyl ammonium or N-(β-trimethyl ammonium propyl group) positive pelargonamide first is for sulfuric ester.
Solubilizing agent is 0.5～10% with respect to the concentration expressed in percentage by weight of catalyst solution in the aqueous solution of catalyzer.
Reacted by alkene and oxygen and carbon monoxide, temperature of reaction is 20～150 ℃, and preferably 50～120 ℃, pressure is 1～200 crust (100～20 * 10
3KPa), preferably 10～100 cling to (1 * 10
3～10 * 10
3KPa).
Catalyzer can join in the reaction mixture by premixed type, but can be prepared under the reaction conditions of mixture itself by the aqueous solution of component rhodium or rhodium compound and sulfonation triaryl phosphine or carboxylation triaryl phosphine equally, i.e. preparation in the presence of alkene.Except finely divided metal rhodium, water-soluble rhodium salt is rhodium chloride, rhodium sulfate, rhodium acetate or the compound that is dissolved in organic medium 2 ethyl hexanoic acid rhodium for example for example, perhaps insoluble compound for example rhodium oxide etc. also can use.
The weight concentration of rhodium is 10～2000PPm in the aqueous solution of catalyzer.
The consumption of used sulfonated phosphine or carboxylation phosphine is to be 1～100 mole for 1 grammeatom rhodium phosphine thing, preferably 2～300 moles.
The pH value of aqueous catalyst solution should not be lower than 2, should be 2～13 usually, and preferably 4～10.
The composition of synthetic gas, just carbon monoxide can in very large range change the content ratio of hydrogen, in the common used synthetic gas, carbon monoxide to the volume ratio of hydrogen be 1: 1 or only therewith value deviation is arranged slightly.But but react also continuous production of periodical operation.
Method of the present invention has been successfully used to contain the particularly straight or branched hydroformylation of olefins of six or six above carbon atoms of four or more carbon atom.In these alkene, two keys can endways also can be in the centre.
Routine example is described in detail the present invention down, but the present invention is not limited to following embodiment.
For the efficient of catalyst system is described, except the ratio of positive aldehyde, also need use following term to aldehyde:
" activity " is defined as, and (aldehyde (mole))/(grammeatom * minute)
" productive rate " is defined as, (weight of aldehyde)/(volume (cm of catalyst solution
3) * hour)
Example 1 does not add the comparison example of solubilizing agent.
Example 1(comparison example)
A) prepare catalyzer in advance
345ml is contained 20.4% 3-(-sulfo group phenyl) phosphine trisodium salt trisodium-tri(m-sulfophenyl)-phosphine and the aqueous solution that is equivalent to the acetic acid rhodium of 400PPM rhodium joins in one liter the autoclave that is incorporated with a tubular stinger; With synthetic gas (volume ratio CO: H=1: 1) be compressed to 25 crust (2.5 * 10
3KPa), then under agitation, 125 ℃ with synthetic gas processing reaction solution three hours, during this period, form active catalyst.Mixture is cooled to after about 300 ℃, stops to stir, placed 15 minutes, then from arm extrusion excess solution (～10g) analyze, all the other solution are stayed in the autoclave.
B) hydroformylation
The 170g1-hexene is pumped into by in the solution that a) prepares, stirs the mixture, at 25 crust (2.5 * 10
3KPa) constant pressure under kept 3 hours mixture heating up to 125 ℃ and under this temperature, mixture is cooled to 30 ℃ then, allows its clarification, the upper strata organism extrudes from arm, weigh (seeing Table 1), and analyze with gas-chromatography.
Above-mentioned steps b) is total to triplicate, all obtains basically at every turn
The amount of organic phase and water is relevant in the identical result, the activity of listing in table 1 and productive rate data and autoclave.The proportion of water is 1.1304.
Example 2
Except by the present invention 9.75g tetradecyl trimethyl ammonium first being joined the aqueous catalyst solution China and foreign countries for vitriol (weight percent 2.5%), all the other proportions that repeat example 1. catalyst solutions are 1.171.
Table 2 is listed test-results.
Example 2 shows that its activity and productive rate have all had sizable raising owing to add solubilizing agent, and selectivity does not obviously descend.
In order to measure the discharging amount of phosphorus and rhodium, the organic product in the example 2 is mixed, concentrate and analyze, find in organic products, to contain the rhodium of 0.3PPM and the phosphorus of 4PPM.
Following example 3 has clearly illustrated the influence of different solubilizing agent to example 9.Table 3 has been summed up the mean value that carries out five groups of experimental results of hydroformylation with same catalyst solution.
Test conditions is identical with example 1 and example 2.
3, has only alcohol (HD-Ocenol 150/170 manufactory: Henket KG)
4, dodecyl trimethyl ammonium muriate
5, dodecyl chlorination pyridine
6, benzyl three or four basic ammonium vitriol
7, dodecyl trimethyl ammonium mesylate
8, benzyltrimethylammon.um lactic acid salt
9, dimethyl ethyl cetyltrimethyl ammonium benzene sulfonate
Reduce the concentration of water-soluble three sulfonated phosphine in the following example, so that the content of three (sulfophenyl) phosphine sodium salt is 12.2%(weight), other all adopts example 1 to the identical method of example 2, adopts the mean value of experimental result of five groups of hydroformylations of same catalyst solution to be listed in the table 4.
A) 30 independent experiments
11. the poly-Hoechst AG of di-alcohol 200(manufactory)
12. trimethylammonium cetyltrimethyl ammonium bromide
13. trimethylammonium cetyltrimethyl ammonium bromide
14. triethylene glycol
15. Oleic acid sodium salt
16. tetramethylene sulfone
17. tributyl n-Hexadecane ammonium lactic acid salt
The influence of phosphorus rhodium content comparison transformation efficiency in aldehyde reaction as can be seen of comparison sheet 3 and table 4.Very clear, when lower Rh/P value was 1: 50, active Schwellenwert was about 2(table 4), active Schwellenwert is a 1(table 3 when the Rh/P value is 1: 100) the former is two times of the latter.The increase that transforms under low P/Rh value is especially because the adding of solubilizing agent.
Added the discharging amount of measuring phosphorus and rhodium, the organic product in the example 12 is mixed, concentrated and analyze, found that rhodium is 0.41PPM in the organic phase, phosphorus is 6.63PPM.
Table 1
1234 φ are numbered in aldehyde reaction
(% is by gas-chromatography 22 18 18 16 18 for transformation efficiency
Analyze)
Just/different content is than 9,8/2 9,8/2 9,8/2 9,8/2 98/2
Organic phase (g) 153 167 172 175 167
Water in the reactor (g) 346 344 343 342 344
Active: 1.22 1.09 1.13 1.02 1.11
(C
7Aldehyde (mole))/(the grammeatom number * minute)
Productive rate 0.037 0.033 0.034 0.031
(C7 aldehyde (g))/(catalyst solution (cm3) * hour) 0.033
Table 2
1 2 3 4 5 φ
(% is by gas phase 47 47 48 35 42 43 for transformation efficiency
Stratographic analysis)
Just/different content is than 9,5/5 9,6/4 9,6/4 9,6/4 9,6/4 96/4
Organic phase (g) 168 175 185 220 176 185
Water in the reactor (g) 374 352 341 336 306 342
Active
(C
7Aldehyde (mole))/(rhodium grammeatom number * minute) 2.31 2.93 3.23 2.87 3.02 2.87
Productive rate
(C
7Aldehyde (g))/(catalyst solution (cm
3) * hour) 0.072 0.091 0.102 0.089 0.094 0.090
Claims (4)
1, in the liquid phase of water and water-soluble rhodium-phosphine complex existence, in 20-150 ℃ temperature range and 1-200 crust (100-20 * 10
3KPa) pressure condition under, carry out the method for prepared in reaction aldehyde by alkene and carbon monoxide and hydrogen, it is characterized in that, the rhodium complex that employing contains three sulfonation triaryl phosphine classes is a catalyzer, contain solubilizing agent in the reaction medium, the rhodium compound that is used as catalyzer contains three sulfonation triaryl phosphines of complexing, and its general formula is as follows:
Ar in the formula
1, Ar
2And Ar
3Each represents phenyl or naphthyl; Y
1, Y
2And Y
3Each representative contains the straight or branched alkyl of 1-4 carbon atom, alkoxyl group halogen atom, OH-, CN-NO
2-or R
1R
2N-group, wherein R
1And R
2Each represents a straight or branched alkyl that contains 1-4 carbon atom; X
1, X
2And X
3Each represents sulfonate group (SO
3-); n
1, n
2And n
3Can be identical, also can be different, represent integer 0-5; M is basic metal or alkaline-earth metal, and zinc, ammonium or general formula are N (R
3R
4R
5R
6)+quaternary ammonium ion, R wherein
3, R
4, R
5And R
6Each representative contains the straight or branched alkyl of 1-4 carbon atom.
2, method according to claim 1 is characterized in that Ar
1, Ar
2And Ar
3Each represents phenyl; X
1, X
2And X
3Each represents sulfonate group.
3, method according to claim 1 and 2 is characterized in that, adopting the compound shown in the following formula is solubilizing agent,
A represents the straight or branched alkyl in the formula, ω-hydroxyalkyl, and alkoxyl group, perhaps in some cases, representative contains the substituted aryl or the radicals R of 6-25 carbon atom
7-CONH-CH
2-CH
2-CH
2, R wherein
7For containing the straight or branched alkyl of 5-11 carbon atom; B, C and D can be identical or different, represent the straight or branched alkyl, or have the ω-hydroxyalkyl of 1-4 carbon atom, perhaps the common formation of C and D and N one five yuan or hexa-member heterocycle; E represents chlorion, bromide anion, and iodide ion, particularly sulfate radical, tetrafluoroborate, acetate moiety, first is for sulfate radical, Phenylsulfonic acid root, benzene sulfonamide acid group, tosylate, lactate or citrate.
4, method according to claim 1 is characterized in that, in the aqueous solution of catalyzer, the concentration expressed in percentage by weight of solubilizing agent is 0.5-10%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85105102 CN1007246B (en) | 1985-07-04 | 1985-07-04 | Process for preparing aldehydes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85105102 CN1007246B (en) | 1985-07-04 | 1985-07-04 | Process for preparing aldehydes |
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| Publication Number | Publication Date |
|---|---|
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| CN1007246B true CN1007246B (en) | 1990-03-21 |
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ID=4794259
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|---|---|---|---|
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1060412C (en) * | 1997-10-24 | 2001-01-10 | 中国石油化工总公司 | Phosphine ligand with temp. controlled phase transfer function, and application thereof |
| CN1091089C (en) * | 1999-04-29 | 2002-09-18 | 中国石油化工集团公司 | Preparation method of aldehyde |
| CN1122012C (en) * | 1999-04-29 | 2003-09-24 | 中国石油化工集团公司 | Preparation method of aldehyde |
| EP2848604B1 (en) * | 2012-05-10 | 2016-11-23 | Mitsubishi Gas Chemical Company, Inc. | Method for producing branched chain aldehyde |
| CN111470958B (en) * | 2019-01-23 | 2023-03-14 | 中国石油化工股份有限公司 | Composition and method for preparing aldehyde by two-phase catalytic hydroformylation |
| CN111470960B (en) * | 2019-01-23 | 2023-01-17 | 中国石油化工股份有限公司 | Composition and method for preparing aldehyde by two-phase catalytic hydroformylation |
| CN111470957B (en) * | 2019-01-23 | 2023-02-28 | 中国石油化工股份有限公司 | Composition and method for preparing aldehyde by two-phase catalytic hydroformylation |
| CN111470956B (en) * | 2019-01-23 | 2023-02-28 | 中国石油化工股份有限公司 | Composition and method for preparing aldehyde by two-phase catalytic hydroformylation |
| CN113578393A (en) * | 2020-04-30 | 2021-11-02 | 中国石油化工股份有限公司 | Composition and method for preparing aldehyde by two-phase catalytic hydroformylation |
| CN116606197B (en) * | 2023-05-29 | 2025-05-06 | 国家能源集团宁夏煤业有限责任公司 | Method and product for preparing aldehyde by Fischer-Tropsch oil hydroformylation reaction |
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