JPH0372048B2 - - Google Patents
Info
- Publication number
- JPH0372048B2 JPH0372048B2 JP57180504A JP18050482A JPH0372048B2 JP H0372048 B2 JPH0372048 B2 JP H0372048B2 JP 57180504 A JP57180504 A JP 57180504A JP 18050482 A JP18050482 A JP 18050482A JP H0372048 B2 JPH0372048 B2 JP H0372048B2
- Authority
- JP
- Japan
- Prior art keywords
- rhodium
- oxide
- carbon monoxide
- compound
- reaction
- 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 - Lifetime
Links
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 20
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 16
- 150000003284 rhodium compounds Chemical class 0.000 claims description 15
- 238000007037 hydroformylation reaction Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 150000002903 organophosphorus compounds Chemical class 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 150000001336 alkenes Chemical class 0.000 claims description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 17
- 239000010948 rhodium Substances 0.000 description 15
- 229910052703 rhodium Inorganic materials 0.000 description 14
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 10
- -1 Inorganic acid salts Chemical class 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 description 3
- GGQQNYXPYWCUHG-RMTFUQJTSA-N (3e,6e)-deca-3,6-diene Chemical compound CCC\C=C\C\C=C\CC GGQQNYXPYWCUHG-RMTFUQJTSA-N 0.000 description 2
- WWUVJRULCWHUSA-UHFFFAOYSA-N 2-methyl-1-pentene Chemical compound CCCC(C)=C WWUVJRULCWHUSA-UHFFFAOYSA-N 0.000 description 2
- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical compound CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 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 2
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- AOHZKGPNHXMRGN-UHFFFAOYSA-N 1,4-bis(diphenylphosphanyl)butane-2,3-diol Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CC(O)C(O)CP(C=1C=CC=CC=1)C1=CC=CC=C1 AOHZKGPNHXMRGN-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- MNZAKDODWSQONA-UHFFFAOYSA-N 1-dibutylphosphorylbutane Chemical compound CCCCP(=O)(CCCC)CCCC MNZAKDODWSQONA-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical group CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- OWWIWYDDISJUMY-UHFFFAOYSA-N 2,3-dimethylbut-1-ene Chemical compound CC(C)C(C)=C OWWIWYDDISJUMY-UHFFFAOYSA-N 0.000 description 1
- PKVDGQHNRICJLA-UHFFFAOYSA-N 2,4-dimethylhex-1-ene Chemical compound CCC(C)CC(C)=C PKVDGQHNRICJLA-UHFFFAOYSA-N 0.000 description 1
- ILPBINAXDRFYPL-UHFFFAOYSA-N 2-octene Chemical compound CCCCCC=CC ILPBINAXDRFYPL-UHFFFAOYSA-N 0.000 description 1
- MCIPQLOKVXSHTD-UHFFFAOYSA-N 3,3-diethoxyprop-1-ene Chemical compound CCOC(C=C)OCC MCIPQLOKVXSHTD-UHFFFAOYSA-N 0.000 description 1
- QDMFTFWKTYXBIW-UHFFFAOYSA-N 3-Methyl-1-heptene Chemical group CCCCC(C)C=C QDMFTFWKTYXBIW-UHFFFAOYSA-N 0.000 description 1
- QELBSMCWTZLTPK-UHFFFAOYSA-J C(C(=O)[O-])(=O)[O-].[Rh+3].[Na+].C(C(=O)[O-])(=O)[O-] Chemical compound C(C(=O)[O-])(=O)[O-].[Rh+3].[Na+].C(C(=O)[O-])(=O)[O-] QELBSMCWTZLTPK-UHFFFAOYSA-J 0.000 description 1
- GOIBNJZOBLPKGF-UHFFFAOYSA-K CO.C(C)(=O)[O-].[Rh+3].C(C)(=O)[O-].C(C)(=O)[O-] Chemical compound CO.C(C)(=O)[O-].[Rh+3].C(C)(=O)[O-].C(C)(=O)[O-] GOIBNJZOBLPKGF-UHFFFAOYSA-K 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- KMTTUERWIBEAEN-UHFFFAOYSA-N [2-(diphenylphosphanylmethyl)cyclobutyl]methyl-diphenylphosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CC1CCC1CP(C=1C=CC=CC=1)C1=CC=CC=C1 KMTTUERWIBEAEN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- WXMZPPIDLJRXNK-UHFFFAOYSA-N butyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(CCCC)C1=CC=CC=C1 WXMZPPIDLJRXNK-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007810 chemical reaction solvent 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
- 238000007796 conventional method Methods 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- KWKXNDCHNDYVRT-UHFFFAOYSA-N dodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1 KWKXNDCHNDYVRT-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- WUOIAOOSKMHJOV-UHFFFAOYSA-N ethyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(CC)C1=CC=CC=C1 WUOIAOOSKMHJOV-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- UJNZOIKQAUQOCN-UHFFFAOYSA-N methyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C)C1=CC=CC=C1 UJNZOIKQAUQOCN-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pentene-2 Natural products CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 description 1
- 235000011033 potassium malate Nutrition 0.000 description 1
- 239000001415 potassium malate Substances 0.000 description 1
- GCAKFSUPQDLXIL-UHFFFAOYSA-N potassium rhodium Chemical compound [K].[Rh] GCAKFSUPQDLXIL-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000002829 reductive effect Effects 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
- 150000003839 salts Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- ZMBHCYHQLYEYDV-UHFFFAOYSA-N trioctylphosphine oxide Chemical compound CCCCCCCCP(=O)(CCCCCCCC)CCCCCCCC ZMBHCYHQLYEYDV-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- RXPQRKFMDQNODS-UHFFFAOYSA-N tripropyl phosphate Chemical compound CCCOP(=O)(OCCC)OCCC RXPQRKFMDQNODS-UHFFFAOYSA-N 0.000 description 1
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 description 1
- UYUUAUOYLFIRJG-UHFFFAOYSA-N tris(4-methoxyphenyl)phosphane Chemical compound C1=CC(OC)=CC=C1P(C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 UYUUAUOYLFIRJG-UHFFFAOYSA-N 0.000 description 1
- FEVFLQDDNUQKRY-UHFFFAOYSA-N tris(4-methylphenyl) phosphite Chemical compound C1=CC(C)=CC=C1OP(OC=1C=CC(C)=CC=1)OC1=CC=C(C)C=C1 FEVFLQDDNUQKRY-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】
本発明はヒドロホルミル化方法に関するもので
あり、特に反応に使用する触媒の調製方法に関す
るものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a hydroformylation process, and more particularly to a process for preparing a catalyst used in the reaction.
オレフイン性化合物を触媒の存在下に水性ガス
と反応させて、アルデヒドまたはその水添物であ
るアルコールを製造する方法は、ヒドロホルミル
化方法として周知である。触媒としては通常、コ
バルトまたはロジウムのカルボニル錯体が用いら
れる。なかでもロジウムカルボニルを用いると、
高い活性とアルデヒドに対する高い選択率とが得
られるので好ましい。しかしロジウムカルボニル
は不安定なので、燐、砒素、アンチモン等を含む
配位子で修飾したロジウムカルボニルが用いられ
ることが多い。配位子としてはトリフエニルホス
フイン等の有機ホスフインが好んで用いられる
が、三価の有機燐化合物のオキサイドも用い得る
ことが知られている。 A method for producing an aldehyde or its hydrogenated alcohol by reacting an olefinic compound with a water gas in the presence of a catalyst is well known as a hydroformylation method. Carbonyl complexes of cobalt or rhodium are usually used as catalysts. Among them, when rhodium carbonyl is used,
This is preferred because it provides high activity and high selectivity for aldehydes. However, since rhodium carbonyl is unstable, rhodium carbonyl modified with a ligand containing phosphorus, arsenic, antimony, etc. is often used. As the ligand, organic phosphine such as triphenylphosphine is preferably used, but it is known that oxides of trivalent organic phosphorus compounds can also be used.
これらの修飾ロジウムカルボニル触媒は、通
常、ヒドロホルミル化反応帯域にロジウム化合物
および修飾剤である配位子を供給し、反応条件下
でロジウム化合物を還元カルボニル化することに
より、その場で調製されている。しかし、本発明
者の検討によれば、配位子として三価の有機燐化
合物のオキサイドを用いる場合には、、この方法
ではロジウムの触媒活性が十分に発現しない。こ
れはロジウム化合物が十分にロジウムカルボニル
に転化せず、その一部がロジウム金属になつてし
まうことによるものと考えられる。 These modified rhodium carbonyl catalysts are usually prepared in situ by feeding a rhodium compound and a modifier ligand into the hydroformylation reaction zone and reductive carbonylating the rhodium compound under the reaction conditions. . However, according to the studies of the present inventors, when the oxide of a trivalent organic phosphorus compound is used as a ligand, the catalytic activity of rhodium is not sufficiently expressed by this method. This is thought to be because the rhodium compound is not sufficiently converted to rhodium carbonyl, and a portion of it becomes rhodium metal.
本発明者らは三価の有機燐化合物のオキサイド
とロジウム化合物との混合物を水性ガスの代りに
一酸化炭素で処理すると、ロジウムが活性な修飾
ロジウムカルボニル触媒に転化することを見出
し、本発明を完成した。 The present inventors have discovered that when a mixture of a trivalent organophosphorus compound oxide and a rhodium compound is treated with carbon monoxide instead of water gas, the rhodium is converted into an active modified rhodium carbonyl catalyst, and the present invention has been developed based on this finding. completed.
すなわち本発明は、三価の有機燐化合物のオキ
サイドとロジウム化合物との混合物を一酸化炭素
で処理したものを触媒として、オレフイン性化合
物、一酸化炭素および水素を反応させることを特
徴とするヒドロホルミル化方法を要旨とするもの
である。 That is, the present invention is a hydroformylation process characterized by reacting an olefinic compound, carbon monoxide, and hydrogen using a mixture of a trivalent organic phosphorus compound oxide and a rhodium compound treated with carbon monoxide as a catalyst. The gist is the method.
本発明についてさらに詳細に説明すると、本発
明で触媒調製に用いるロジウム化合物としては、
硝酸ロジウム、硫酸ロジウム等の無機酸塩、酢酸
ロジウム、蓚酸ロジウムナトリウム、リンゴ酸ロ
ジウムカリウム等の有機酸塩、〔RhL6〕X3，
〔RhL3H2O〕X3，〔RhL3（OH）〕X2，〔RhL5
（NO2）〕X2，〔Rh（Py）3（NO3）2〕、（式中、Ｘは
NO3 -，OH-，１／２（SO4 -2）を表わし、ＬはNH3
を表わし、Pyはピリジンを表わす。）等のアミン
錯塩などがあげられる。なかでも硝酸ロジウムお
よび酢酸ロジウムが好んで用いられる。 To explain the present invention in more detail, the rhodium compounds used for catalyst preparation in the present invention include:
Inorganic acid salts such as rhodium nitrate and rhodium sulfate, organic acid salts such as rhodium acetate, rhodium sodium oxalate, rhodium potassium malate, [RhL 6 ]X 3 ,
[RhL 3 H 2 O] X 3 , [RhL 3 (OH)] X 2 , [RhL 5
(NO 2 )]X 2 , [Rh(Py) 3 (NO 3 ) 2 ], (where X is
NO 3 - , OH - , 1/2 (SO 4 -2 ), L represents NH 3 and Py represents pyridine. ) and other amine complex salts. Among them, rhodium nitrate and rhodium acetate are preferably used.
三価の有機燐化合物のオキサイドとしては、ト
リフエニルホスフインオキサイド、トリトリルホ
スフインオキサイド、トリアニシルホスフインオ
キサイド等のアリールホスフインオキサイド、ト
リブチルホスフインオキサイド、トリオクチルホ
スフインオキサイド等のアルキルホスフインオキ
サイド、またはアルキル基とアリール基とを合せ
もつアルキルアリールホスフインオキサイドが用
いられる。また、トリフエニルホスフアイトオキ
サイド、トリトリルホスフアイトオキサイド等の
アリールホスフアイトオキサイド、トリエチルホ
スフアイトオキサイド、トリプロピルホスフアイ
トオキサイド、トリブチルホスフアイトオキサイ
ド等のアルキルホスフアイトオキサイド、アルキ
ル基とアリール基とを合せもつアルキルアリール
ホスフアイトオキサイドも用いられる。さらには
ジフエニルホスフイノメタンジオキサイド、ジフ
エニルホスフイノエタンジオキサイド、ジフエニ
ルホスフイノブタンジオキサイド、１，２−ビス
（ジフエニルホスフイノメチル）シクロブタンジ
オキサイド、２，３−Ｏ−イソプロピリデン−
２，３−ジヒドロキシ−１，４−ビス（ジフエニ
ルホスフイノ）ブタンジオキサイド等の多座ホス
フインのオキサイドも用いることができる。 Examples of oxides of trivalent organic phosphorus compounds include arylphosphine oxides such as triphenylphosphine oxide, tritolylphosphine oxide, and trianisylphosphine oxide, and alkylphosphines such as tributylphosphine oxide and trioctylphosphine oxide. An oxide or an alkylarylphosphine oxide having both an alkyl group and an aryl group is used. In addition, aryl phosphite oxides such as triphenyl phosphite oxide and tritolyl phosphite oxide, alkyl phosphite oxides such as triethyl phosphite oxide, tripropyl phosphite oxide, and tributyl phosphite oxide, and combinations of alkyl and aryl groups. Also used are alkylaryl phosphite oxides. Furthermore, diphenylphosphinomethane dioxide, diphenylphosphinoethane dioxide, diphenylphosphinobutane dioxide, 1,2-bis(diphenylphosphinomethyl)cyclobutane dioxide, 2,3-O-isopropylidene-
Polydentate phosphine oxides such as 2,3-dihydroxy-1,4-bis(diphenylphosphino)butane dioxide can also be used.
これらの三価の有機燐化合物のオキサイドは、
ロジウム１原子に対しオキサイドの状態の燐が10
〜50原子となるように用いるのが好ましい。オキ
サイドの状態の燐が少なすぎると触媒の安定性が
低下するし、逆に燐が多すぎるとヒドロホルミル
化反応の速度が低下する。 The oxides of these trivalent organophosphorus compounds are
For every 1 atom of rhodium, there is 10 phosphorus in the oxide state.
It is preferable to use it so that it becomes 50 atoms. Too little phosphorus in the oxide state will reduce the stability of the catalyst, while too much phosphorus will slow down the hydroformylation reaction.
本発明では、上述のロジウム化合物と三価の有
機燐化合物のオキサイドとを混合して一酸化炭素
で処理することにより触媒を調製する。通常はヒ
ドロホルミル化反応の反応溶媒に、ロジウム化合
物と三価の有機燐化合物のオキサイドとを溶解な
いし懸濁させ、これに一酸化炭素を吹込む方式が
用いられる。処理条件は通常、一酸化炭素分圧。 In the present invention, a catalyst is prepared by mixing the above rhodium compound and an oxide of a trivalent organic phosphorus compound and treating the mixture with carbon monoxide. Usually, a method is used in which a rhodium compound and an oxide of a trivalent organic phosphorus compound are dissolved or suspended in a reaction solvent for the hydroformylation reaction, and carbon monoxide is blown into the solution. The processing conditions are usually carbon monoxide partial pressure.
１〜200Kg／cm2、好ましくは１〜10Kg／cm2、温
度10〜200℃、好ましくは20〜150℃、時間１〜
100分、好ましくは２〜50分に範囲から選択され
る。。この処理により、可溶性となつたロジウム
化合物は容易に還元カルボニル化され、同時に三
価の有機燐化合物のオキサイドがこれにゆるく配
位して、ロジウムに〔CO〕ないしは〔CO〕と
〔オキサイド〕が共に錯結合した錯体が生成し、
これが触媒としての安定で高い活性を発揮するも
のと考えられる。 1 to 200 Kg/cm 2 , preferably 1 to 10 Kg/cm 2 , temperature 10 to 200°C, preferably 20 to 150°C, time 1 to
100 minutes, preferably from 2 to 50 minutes. . Through this treatment, the rhodium compound that has become soluble is easily reductively carbonylated, and at the same time, the oxide of the trivalent organic phosphorus compound is loosely coordinated to the rhodium compound, and rhodium becomes [CO] or [CO] and [oxide]. A complex is formed, which is bound together.
It is thought that this provides stability and high activity as a catalyst.
なお、一酸化炭素は窒素等の不活性ガスを含ん
でいてもよいが、水素の共存は好ましくない。水
素を含む一酸化炭素を用いると、ロジウム化合物
の一部が金属ロジウムとして析出することもあつ
て、得られる触媒液の活性が低下する。従つて水
素の存在量は一酸化炭素に対し５モル％以下、好
ましくは１モル％以下に止めるべきである。ま
た、一酸化炭素処理はヒドロホルミル化反応の原
料であるオレフイン性化合物の存在下に実施する
こともでき、所望ならばこのオレフイン性化合物
を溶媒としてこれにロジウム化合物および三価の
有機燐化合物のオキサイドを溶解ないし懸濁させ
て処理に供することもできる。 Note that carbon monoxide may contain an inert gas such as nitrogen, but the coexistence of hydrogen is not preferred. When carbon monoxide containing hydrogen is used, a portion of the rhodium compound may be precipitated as metal rhodium, resulting in a decrease in the activity of the resulting catalyst solution. Therefore, the amount of hydrogen present should be kept at 5 mol % or less, preferably 1 mol % or less, based on carbon monoxide. Further, the carbon monoxide treatment can also be carried out in the presence of an olefinic compound which is a raw material for the hydroformylation reaction, and if desired, a rhodium compound and a trivalent organic phosphorus compound oxide can be added to this olefinic compound using the olefinic compound as a solvent. It is also possible to dissolve or suspend the solution and subject it to the treatment.
一酸化炭素処理の装置としては攬拌槽や気泡塔
を用いることができるが、簡便にはロジウム化合
物と三価の有機燐化合物のオキサイドを含む溶液
を一酸化炭素と共に気液混合状態でパイプ中を流
通させる方式が採用される。 Although a stirring tank or a bubble column can be used as a carbon monoxide treatment device, it is convenient to pour a solution containing a rhodium compound and a trivalent organic phosphorus compound oxide together with carbon monoxide in a gas-liquid mixture into a pipe. A method of distributing the materials will be adopted.
本発明によるヒドロホルミル化反応は、上述の
処理により調製した触媒を用いる以外は常法に従
つて実施される。反応原料のオレフイン性化合物
としては、エチレン、プロピレン、ブテン−１、
ペンテン−１、ヘキセン−１、オフテン−１、デ
セン−１等の直鎖α−オレフイン類の外にブテン
−２、ペンテン２、ヘキセン２、ヘキセン−３、
オクテン−２、オクテン−３等の直鎖内部オレフ
イン類、イソブチレン、２−メチルブテン−１、
２−メチルペンテン−１、３−メチルペンテン−
１、２−メチルヘキセン−１、３−メチルヘキセ
ン−１、２−メチルヘプテン−１、３−メチルヘ
プテン−１、４−メチルヘプテン−１等の分岐α
−オレフイン類、２，３−ジメチルブテン−１、
２，３−ジメチルペンテン−１、２，４−ジメチ
ルペンテン−１、２，３−ジメチルヘキセン−
１、２，４−ジメチルヘキセン−１、２，５−ジ
メチルヘキセン−１、３，４−ジメチルヘキセン
−１等の多分岐αオレフイン類やこれらの二重結
合異性体があげられる。また、プロピレン、ブテ
ン、イソブチレン等の二〜四量体のような異性体
混合物、さらにはアリルアルコール、アクロレイ
ンアセタール、ビニルアセテート、スチレン、ア
ルキルビニルエーテル等の置換基を有するオレフ
イン等も用いることができる。特に本発明は、プ
ロピレン、ブテン、イソブチレン等の二〜四量体
のような異性体混合物のヒドロホルミル化に有利
に適用される。何故ならば、これらは分岐を有す
る内部オレフインないしこれを手体とする混合物
であるが、有機ホスフインで修飾したロジウム触
媒を用いる場合と異なり、本発明によれば、これ
らの異性体混合物を原料とする場合でも、反応が
すみやかに進行するからである。 The hydroformylation reaction according to the present invention is carried out according to a conventional method except that the catalyst prepared by the above-mentioned treatment is used. The olefinic compounds used as reaction raw materials include ethylene, propylene, butene-1,
In addition to linear α-olefins such as pentene-1, hexene-1, oftene-1, and decene-1, butene-2, pentene-2, hexene-2, hexene-3,
Linear internal olefins such as octene-2 and octene-3, isobutylene, 2-methylbutene-1,
2-methylpentene-1, 3-methylpentene-
Branched α of 1,2-methylhexene-1, 3-methylhexene-1, 2-methylheptene-1, 3-methylheptene-1, 4-methylheptene-1, etc.
-Olefins, 2,3-dimethylbutene-1,
2,3-dimethylpentene-1, 2,4-dimethylpentene-1, 2,3-dimethylhexene-
Examples include hyperbranched α-olefins such as 1,2,4-dimethylhexene-1, 2,5-dimethylhexene-1, and 3,4-dimethylhexene-1, and double bond isomers thereof. Further, isomer mixtures such as dimers to tetramers of propylene, butene, isobutylene, etc., and olefins having substituents such as allyl alcohol, acrolein acetal, vinyl acetate, styrene, and alkyl vinyl ether can also be used. In particular, the present invention is advantageously applied to the hydroformylation of isomer mixtures such as dimers to tetramers of propylene, butene, isobutylene, etc. This is because these are branched internal olefins or mixtures using them as a hand body, but unlike the case of using a rhodium catalyst modified with an organic phosphine, according to the present invention, a mixture of these isomers can be used as a raw material. This is because the reaction proceeds quickly even when the reaction is carried out.
ヒドロホルミル化反応は通常、溶媒の存在下に
行なわれるが、溶媒の使用は不可欠ではない。溶
媒としては、触媒を溶解し、かつ反応に悪影響を
与えないものであれば、任意のものを用いること
ができる。 The hydroformylation reaction is usually carried out in the presence of a solvent, although the use of a solvent is not essential. Any solvent can be used as long as it dissolves the catalyst and does not adversely affect the reaction.
例えばベンゼン、トルエン、キシレン、ドデシ
ルベンゼン等の芳香族炭化水素、シクロヘキサン
等の脂環式炭化水素、ジブチルエーテル、エチレ
ングリコールジメチルエーテル、ジエチレングリ
コールジエチルエーテル、トリエチレングリコー
ルジメチルエーテル、テトラヒドロフラン等のエ
ーテル類、ジエチルフタレート、ジオクチルフタ
レート等のエステル類などが用いられる。また、
ヒドロホルミル化反応により生成したアルデヒド
アルコール、さらには副生する高沸点物等を溶媒
とすることもできる。 For example, aromatic hydrocarbons such as benzene, toluene, xylene, and dodecylbenzene, alicyclic hydrocarbons such as cyclohexane, ethers such as dibutyl ether, ethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, and tetrahydrofuran, diethyl phthalate, Esters such as dioctyl phthalate are used. Also,
Aldehyde alcohol produced by the hydroformylation reaction, or even by-product high-boiling substances, etc. can also be used as a solvent.
反応温度は高い方が反応速度の点では有利であ
るが、高温に過ぎると触媒が分解する恐れがあ
る。従つて通常は50〜170℃、特に100〜150℃で
反応を行なうのが好ましい。 A higher reaction temperature is advantageous in terms of reaction rate, but if the temperature is too high, there is a risk that the catalyst will decompose. Therefore, it is usually preferable to carry out the reaction at a temperature of 50 to 170°C, particularly 100 to 150°C.
水性ガスとしては、水素と一酸化炭素のモル比
率が１／５〜５／１、特に１／２〜２／１のもの
が好ましい。水性ガスの分圧としては20Kg／cm2〜
500Kg／cm2の範囲が用いられるが、好ましくは50
Kg／cm2〜300Kg／cm2の範囲である。 The water gas preferably has a hydrogen to carbon monoxide molar ratio of 1/5 to 5/1, particularly 1/2 to 2/1. Partial pressure of water gas is 20Kg/cm 2 ~
A range of 500Kg/ cm2 is used, preferably 50Kg/cm2.
It is in the range of Kg/cm 2 to 300Kg/cm 2 .
反応は連続方式および回分方式のいずれでも行
なうことができる。 The reaction can be carried out either continuously or batchwise.
以下に実施例により本発明をさらに具体的に説
明するが、本発明はその要旨を超えない限り、以
下の実施例に限定されるものではない。 EXAMPLES The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to the following Examples unless it exceeds the gist thereof.
実施例
内容積200mlのSUS−316製の上下攬拌式オー
トクレーブに、ブテンダイマー（ｎ−オクテン、
３−メチルヘプテン、３，４−ジメチルヘキセン
の二重結合異性体混合物）50ml、酢酸ロジウムの
メタノール溶液（ロジウム金属として1.3mg／ｇ）
0.38ｇ、トリフエニルホスフインオキサイド14.6
mg（ロジウムに対し11倍モル）を加えた。オート
クレーブを窒素ガスで置換したのち、さらに一酸
化炭素ガスを20Kg／cm2Ｇまで圧入したのち常圧に
放圧する操作を三回反復し、さらに３Kg／cm2Ｇま
で一酸化炭素を圧入したのち約30分を要して130
℃に昇温した。130℃に到達後直ちに全圧が200
Kg／cm2Ｇとなるように水性ガス（H2／CO＝１）
を圧入し、130℃で４時間反応を行なわせた。Example: Butene dimer (n-octene,
3-methylheptene, 3,4-dimethylhexene double bond isomer mixture) 50ml, rhodium acetate methanol solution (1.3mg/g as rhodium metal)
0.38g, triphenylphosphine oxide 14.6
mg (11 times the mole relative to rhodium) was added. After purging the autoclave with nitrogen gas, carbon monoxide gas was further pressurized to 20 kg/cm 2 G, and the operation of releasing the pressure to normal pressure was repeated three times, and carbon monoxide was further pressurized to 3 kg/cm 2 G. 130 which takes about 30 minutes
The temperature was raised to ℃. Immediately after reaching 130℃, the total pressure is 200℃.
Water gas (H 2 /CO=1) so that Kg/cm 2 G
was injected under pressure, and the reaction was carried out at 130°C for 4 hours.
この間、反応により消費された水性ガスは定圧
装置を経て蓄圧器から補給し、オートクレーブを
200Kg／cm2Ｇに保つた。この間のガス吸収の比反
応速度を表−１に示す。なお、反応速度は下記式
により算出し、後記の比較例１の反応速度を100
として表わした。 During this time, the water gas consumed by the reaction is replenished from the pressure accumulator via a constant pressure device, and the autoclave is
It was maintained at 200Kg/cm 2 G. Table 1 shows the specific reaction rate of gas absorption during this period. The reaction rate was calculated using the following formula, and the reaction rate of Comparative Example 1 described later was calculated by 100
It was expressed as
dx／dt＝ｋ（ａ−ｘ）1/2
ａ：オレフイン初濃度 ｘ：転化オレフイン濃度
ｋ：速度定数
比較例 １
実施例１において、一酸化炭素ガスの代りに窒
素ガスを20Kg／cm2Ｇまで圧入したのち常圧に放圧
する操作を３回反復したのち130℃に昇温した以
外は実施例１と同様にしてヒドロホルミル化反応
を行なつた。結果を表−１に示す。 dx/dt=k(a-x) 1/2 a: Initial concentration of olefin x: Concentration of converted olefin k: Rate constant comparison example 1 In Example 1, nitrogen gas was substituted for carbon monoxide gas at 20 kg/cm 2 G. A hydroformylation reaction was carried out in the same manner as in Example 1, except that the operation of pressurizing the mixture to 130°C and then releasing the pressure to normal pressure was repeated three times, and then the temperature was raised to 130°C. The results are shown in Table-1.
比較例 ２
実施例１において、トリフエニルホスフインオ
キサイドを用いなかつた以外は、実施例１と全く
同様にして反応を行なつた。結果を表−１に示
す。Comparative Example 2 The reaction was carried out in exactly the same manner as in Example 1, except that triphenylphosphine oxide was not used. The results are shown in Table-1.
表−１ No. 比反応速度 実施例１ 139 比較例１ 100 〃 ２ 81 Table-1 No. Specific reaction rate Example 1 139 Comparative example 1 100 〃 2 81
Claims (1)
化合物との混合物を一酸化炭素で処理したものを
触媒として、オレフイン性化合物、一酸化炭素お
よび水素を反応させることを特徴とするヒドロホ
ルミル化方法。 ２ 三価の有機燐化合物のオキサイドとロジウム
化合物との混合物を、有機液体中に溶解ないし懸
濁させた状態で、一酸化炭素で処理することを特
徴とする特許請求の範囲第１項記載の方法。 ３ 水素の含有量が５モル％以下の一酸化炭素で
処理することを特徴とする特許請求の範囲第１項
または第２項記載の方法。 ４ オレフイン性化合物が分岐を有する内部オレ
フインないしはこれを主体とする混合物であるこ
とを特徴とする特許請求の範囲第１項ないし第３
項のいずれかに記載の方法。[Claims] 1. An olefinic compound, carbon monoxide, and hydrogen are reacted using a mixture of a trivalent organic phosphorus compound oxide and a rhodium compound treated with carbon monoxide as a catalyst. Hydroformylation method. 2. The method according to claim 1, characterized in that a mixture of a trivalent organic phosphorus compound oxide and a rhodium compound is treated with carbon monoxide while being dissolved or suspended in an organic liquid. Method. 3. The method according to claim 1 or 2, characterized in that the treatment is performed with carbon monoxide having a hydrogen content of 5 mol% or less. 4 Claims 1 to 3, characterized in that the olefinic compound is an internal olefin having a branch or a mixture mainly composed of this.
The method described in any of the paragraphs.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57180504A JPS5970629A (en) | 1982-10-14 | 1982-10-14 | Hydroformylation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57180504A JPS5970629A (en) | 1982-10-14 | 1982-10-14 | Hydroformylation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5970629A JPS5970629A (en) | 1984-04-21 |
| JPH0372048B2 true JPH0372048B2 (en) | 1991-11-15 |
Family
ID=16084393
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57180504A Granted JPS5970629A (en) | 1982-10-14 | 1982-10-14 | Hydroformylation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5970629A (en) |
-
1982
- 1982-10-14 JP JP57180504A patent/JPS5970629A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5970629A (en) | 1984-04-21 |
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