CN100355500C - Method for preserving viii B group metal-organic phosphite complex catalyst liquid - Google Patents
Method for preserving viii B group metal-organic phosphite complex catalyst liquid Download PDFInfo
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- CN100355500C CN100355500C CNB2003801054009A CN200380105400A CN100355500C CN 100355500 C CN100355500 C CN 100355500C CN B2003801054009 A CNB2003801054009 A CN B2003801054009A CN 200380105400 A CN200380105400 A CN 200380105400A CN 100355500 C CN100355500 C CN 100355500C
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- Prior art keywords
- phosphite
- organic phosphite
- viii
- oxygen
- ester
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- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000003054 catalyst Substances 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000007788 liquid Substances 0.000 title claims description 39
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000001301 oxygen Substances 0.000 claims abstract description 40
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 40
- 239000007789 gas Substances 0.000 claims abstract description 29
- 238000007037 hydroformylation reaction Methods 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims description 42
- 230000003197 catalytic effect Effects 0.000 claims description 28
- 102000040350 B family Human genes 0.000 claims description 22
- 108091072128 B family Proteins 0.000 claims description 22
- 238000004321 preservation Methods 0.000 claims description 15
- 239000010948 rhodium Substances 0.000 claims description 15
- 229910052703 rhodium Inorganic materials 0.000 claims description 10
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 10
- 238000006555 catalytic reaction Methods 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 150000008301 phosphite esters Chemical class 0.000 abstract description 16
- 239000003446 ligand Substances 0.000 abstract description 15
- -1 phosphite compound Chemical class 0.000 abstract description 14
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 230000006866 deterioration Effects 0.000 abstract 1
- 230000002035 prolonged effect Effects 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 27
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- 125000000217 alkyl group Chemical group 0.000 description 14
- 125000005461 organic phosphorous group Chemical group 0.000 description 9
- 125000003118 aryl group Chemical group 0.000 description 8
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 125000001118 alkylidene group Chemical group 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- NENDHUHGFRLXEN-UHFFFAOYSA-N acetic acid;rhodium Chemical compound [Rh].CC(O)=O NENDHUHGFRLXEN-UHFFFAOYSA-N 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 150000002829 nitrogen Chemical class 0.000 description 3
- VCAFTIGPOYBOIC-UHFFFAOYSA-N phenyl dihydrogen phosphite Chemical compound OP(O)OC1=CC=CC=C1 VCAFTIGPOYBOIC-UHFFFAOYSA-N 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 3
- 150000003284 rhodium compounds Chemical class 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000006315 carbonylation Effects 0.000 description 2
- 238000005810 carbonylation reaction Methods 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
- PJTDYILSADBVLX-UHFFFAOYSA-N (3,5-dimethylphenyl) dihydrogen phosphite Chemical compound P(O)(O)OC1=CC(=CC(=C1)C)C PJTDYILSADBVLX-UHFFFAOYSA-N 0.000 description 1
- WUEDQBKOWHOREX-UHFFFAOYSA-N CC(C)(C)C1=CC(=CC(=C1OP(O)O)C(C)(C)C)CN Chemical compound CC(C)(C)C1=CC(=CC(=C1OP(O)O)C(C)(C)C)CN WUEDQBKOWHOREX-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 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
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 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
- 239000007853 buffer solution Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- IDUSTNHRSGBKQU-UHFFFAOYSA-N diethyl phenyl phosphite Chemical compound CCOP(OCC)OC1=CC=CC=C1 IDUSTNHRSGBKQU-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- RSNDQTNQQQNXRN-UHFFFAOYSA-N dodecyl dihydrogen phosphite Chemical compound CCCCCCCCCCCCOP(O)O RSNDQTNQQQNXRN-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- COZDRCIGYRIREC-UHFFFAOYSA-N naphthalen-1-yl dihydrogen phosphite Chemical compound C1=CC=C2C(OP(O)O)=CC=CC2=C1 COZDRCIGYRIREC-UHFFFAOYSA-N 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000000047 product Substances 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
- 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 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- XTTGYFREQJCEML-UHFFFAOYSA-N tributyl phosphite Chemical compound CCCCOP(OCCCC)OCCCC XTTGYFREQJCEML-UHFFFAOYSA-N 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
- 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 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
- C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
- B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
-
- 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
- B01J33/00—Protection of catalysts, e.g. by coating
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A method of storing a catalyst solution containing a free phosphite ligand and a Group VIII metal-organophosphite complex catalyst, in which the deterioration of phosphite compound is inhibited to thereby enable stably storing the catalyst solution for a prolonged period of time. In particular, a method of storing a Group VIII metal-organophosphite complex catalyst solution, characterized in that a catalyst solution containing a free organophosphite ligand and a Group VIII metal-organophosphite complex catalyst is stored in an atmosphere wherein the partial pressure of oxygen is 10 Pa or below; and a method of storing a Group VIII metal-organophosphite complex catalyst solution, characterized in that a hydroformylation catalyst solution containing a free organophosphite ligand and a Group VIII metal-organophosphite complex catalyst is withdrawn from a reaction vessel and stored in a storage container wherein the partial pressure of oxygen in gas phase components is 10 Pa or below.
Description
Technical field
The present invention relates to the store method of VIII B family metal-organic phosphite complex catalysis liquid.
Background technology
In the presence of VIII B family metal complex catalyst, with carbon monoxide and hydrogen the olefines unsaturated compound is carried out hydroformylation, thus the preparation aldehydes, this technology is by extensive industrialization.As the catalyst in this hydroformylation reaction, used the complex compound catalyst of rhodium grade in an imperial examination VIII B family metal being modified with the such part of trivalent phosphorous compound and obtaining in the past, for activity or the selectivity that improves hydroformylation reaction, multiple part is studied at present.Particularly brought into use in recent years show high activity and optionally bi-ester of phosphite replace the main in the past phosphine compound that uses.
Yet as record among WO97/20974 and the Te Kai 2001-342162 etc., bi-ester of phosphite is more apt to deteriorate than phosphine compound, and the price of bi-ester of phosphite is than the price height of phosphine compound, and how reducing the loss has in use become problem.
Disclose among WO97/20974 and the WO97/20797 a kind of by use buffer solution or water to the reaction product fluid handle remove become promote bi-ester of phosphite hydrolysis reason the phosphoric acid compound so that the stable method of phosphite ester ligand.
In addition, the spy opens and discloses following method among 2001-342162 and the Te Kai 2001-342164: initiatively remove moisture from the zone that catalyst exists, and rotten with what suppress that hydrolysis because of bi-ester of phosphite causes.But, though by these methods can the inhibitory reaction implementation process in phosphite ester rotten, preserve catalyst during, can not suppress that it is slowly rotten.
Patent documentation 1:WO97/20974 communique p.1 L.12～L.25, p.3.L.9～L.25
Patent documentation 2:WO97/20797 communique p.1 L.11～L.23, p.3.L.8～L.22
Patent documentation 3: the spy opens 2001-342162 communique [0002]～[0004], [0008]
Patent documentation 4: the spy opens 2001-342164 communique [0002]～[0004], [0008]
Summary of the invention
The purpose of this invention is to provide a kind ofly when preservation contains the catalytic liquid of free phosphite ester ligand and VIII B family metal-organic phosphite complex compound catalyst, suppress the rotten of bi-ester of phosphite, thus method of preserving steady in a long-term.
The inventor etc. have carried out concentrated research to above-mentioned problem, found that, untamed catalyst rotten mainly is that oxidation by catalyst causes when preserving catalyst by prior art, further find when preservation contains the catalytic liquid of free phosphite ester ligand and VIII B family metal-organic phosphite complex compound catalyst, preserve the micro amount of oxygen that exists in the container and not only make the phosphite ester ligand oxidation, and further promote its decomposition, thereby cause rotten, and then, the inventor finds, when preserving, can steady in a long-termly preserve, thereby finished the present invention by reducing partial pressure of oxygen.That is, main points of the present invention are following (1)～(4).
(1) store method of VIII B family metal-organic phosphite complex catalysis liquid, it is characterized by, to contain the catalytic liquid of free organic phosphite part and VIII B family metal-organic phosphite complex compound catalyst, be kept in the atmosphere gas of partial pressure of oxygen smaller or equal to 10Pa.
(2) store method of VIII B family metal-organic phosphite complex catalysis liquid, it is characterized by, the hydroformylation catalytic liquid that will contain free organic phosphite part and VIII B family metal-organic phosphite complex compound catalyst, after from reactor, taking out, preserve smaller or equal to the preservation container of 10Pa with the partial pressure of oxygen of gas phase part.
(3) above-mentioned (1) or (2) described store method is characterized by, and keep the temperature of catalytic liquid at 0 ℃～50 ℃ in the preservation process in preserving container.
(4) any described store method in above-mentioned (1)～(3) is characterized by, and described VIIIB family metal is a rhodium.
The specific embodiment
First embodiment of VIII B of the present invention family metal-organic phosphite complex catalysis liquid store method is characterised in that, to contain the catalytic liquid of free organic phosphite part and VIII B family metal-organic phosphite complex compound catalyst, be kept in the atmosphere gas of partial pressure of oxygen smaller or equal to 10Pa.In addition, second embodiment of VIII B of the present invention family metal-organic phosphite complex catalysis liquid store method is characterised in that, the hydroformylation catalytic liquid that will contain free organic phosphite part and VIII B family metal-organic phosphite complex compound catalyst, after taking out from container, preserve smaller or equal to the preservation container of 10Pa with the partial pressure of oxygen of gas phase part.
Among the present invention, bi-ester of phosphite as the organic phosphite in free organic phosphite part and the VIII B family metal-organic phosphite complex compound catalyst, can be to have, specifically can enumerate the compound shown in for example following general formula (1)～(10) as the ability of monodentate ligand or as the bi-ester of phosphite any commonly used of the ability of multidentate ligand.
(in the above-mentioned general formula (1), R
1～R
3Expression is substituted or unsubstituted monovalence alkyl independently respectively.)
Describedly can enumerate alkyl, aryl and cycloalkyl etc. by substituted monovalence alkyl.The object lesson of compound shown in the formula (1) can be enumerated for example trialkyl phosphites such as Trimethyl phosphite, triethyl phosphite, phosphorous acid normal-butyl diethyl ester, tri-n-butylphosphite, tricresyl phosphite n-propyl, tricresyl phosphite n-octyl, tricresyl phosphite dodecyl ester; Triaryl phosphites such as tricresyl phosphite phenylester, tricresyl phosphite naphthyl ester; Phosphorous acid alkyl aryl esters such as phosphorous acid 3,5-dimethylphenyl ester, phosphorous acid diethyl phenyl ester, phosphorous acid ethyl diphenyl etc.In addition, phosphorous acid two (3,6, the 8-tri-tert-2-naphthyl) phenylester that can also use the spy to open to put down in writing in the flat 6-122642 communique, phosphorous acid two (3,6,8-tri-tert-2-naphthyl) (4-xenyl) phenylester etc.Tricresyl phosphite phenylester most preferably wherein.
(in the above-mentioned general formula (2), R
1Expression is substituted or unsubstituted bivalent hydrocarbon radical R
5Expression is substituted or unsubstituted monovalence alkyl.)
As can substituted bivalent hydrocarbon radical, can enumerate alkylidene, it can contain aerobic, nitrogen, sulphur atom etc. in the middle of carbochain; The ring alkylidene, it can contain aerobic, nitrogen, sulphur atom etc. in the middle of carbochain; Divalence such as phenylene and naphthylene aromatic group; Divalence aromatic rings Direct Bonding or middle divalence aromatic group by atom bondings such as alkylidene or oxygen, nitrogen, sulphur; Divalence aromatic group and alkylidene Direct Bonding or the middle divalent group that passes through atom bondings such as oxygen, nitrogen, sulphur etc.The monovalence alkyl can be enumerated alkyl, aryl and cycloalkyl etc.
Compound shown in the above-mentioned general formula (2) can be enumerated for example US3 such as neopentyl (2,4, the 6-tert-butyl group-phenyl) phosphite ester, ethylidene (2,4, the 6-tert-butyl group-phenyl) phosphite ester, disclosed compound etc. in 415, No. 906 communiques.
In addition, can also enumerate the compound shown in the following general formula (3),
(in the above-mentioned general formula (3), R
10Definition and above-mentioned general formula (2) in R
5Identical, Ar
1And Ar
2Expression is substituted or unsubstituted aryl independently respectively, and x and y represent 0 or 1 respectively independently, and Q represents to be selected from by-CR
11R
12-,-O-,-S-,-NR
13-,-SiR
11R
15-and-linking group in the group that CO-forms, R
11And R
12Represent hydrogen atom, C respectively independently
1～12Alkyl, phenyl, tolyl or anisyl, R
13, R
14And R
15Represent hydrogen atom or methyl respectively independently, n represents 0 or 1.), more specifically, can enumerate 1,1 '-biphenyl-2,2 '-two bases-US4 such as (2,6-di-t-butyl-4-aminomethyl phenyl) phosphite ester, 599, disclosed compound and 3 in No. 206 communiques, 3 '-di-t-butyl-5,5 '-dimethoxy-1,1 '-biphenyl-2,2 '-two bases-US4 such as (the 2-tert-butyl group-4-methoxyphenyl) phosphite ester, disclosed compound etc. in 717, No. 775 communiques.
(in the above-mentioned general formula (4), R
6Expression is substituted or unsubstituted ring-type or non-annularity trivalent hydrocarbon radical.)
Compound shown in the above-mentioned general formula (4) can be enumerated for example 4-ethyl-2,6,7-trioxy--1 phosphorus two ring-[2,2,2]-US4 such as octane, disclosed compound etc. in 567, No. 306 communiques.
(in the above-mentioned general formula (5), R
7Definition and the R in the above-mentioned general formula (3)
4Identical, R
8And R
9Expression is substituted or unsubstituted alkyl independently respectively, and a and b represent 0～6 integer respectively, and a and b sum be 2～6, and X represents the alkyl of (a+b) valency.)
In the compound shown in the above-mentioned general formula (5), preferably can enumerate the compound shown in for example following general formula (6).
(in the above-mentioned general formula (6), X represent to be selected from by alkylidene, arlydene and-Ar
1-(CH
2)
x-Q
n-(CH
2)
y-Ar
2Divalent group in the group of-composition, wherein Ar
1, Ar
2, Q, x, the definition of y, n and the Ar in the above-mentioned general formula (3)
1, Ar
2, Q, x, y, n be identical.)。In addition, comprise that also the spy opens the compound of putting down in writing in clear 62-116535 communique and the clear 62-116587 communique of Te Kai.
(in the above-mentioned general formula (7), X, Ar
1, Ar
2, Q, x, the definition of y, n and X, the Ar in the above-mentioned general formula (3)
1, Ar
2, Q, x, y, n be identical, R
18Definition and the R in the above-mentioned general formula (2)
1Identical).
(in the above-mentioned general formula (8), R
19And R
20Represent aromatic hydrocarbyl respectively independently, and wherein at least one side's aromatic hydrocarbyl has alkyl on the adjacent carbon atom of the carbon atom that combines with oxygen atom, m represents 2～4 integer, each-O-P (OR
19) (OR
20) base can differ from one another, X represents to be substituted or unsubstituted m valency alkyl).
In the compound shown in the above-mentioned general formula (8), preferred spy opens the compound of putting down in writing in the flat 5-178779 communique.
(in the above-mentioned general formula (9), R
21～R
24Expression is substituted or unsubstituted alkyl R independently respectively
21And R
22, R
23And R
24Can mutually combine forms ring, and W represents to have substituting group or do not have substituent divalence aromatic hydrocarbyl, and L represents to have substituting group or do not have substituent saturated or unsaturated divalence aliphatic alkyl).
As the compound shown in the above-mentioned general formula (9), for example use the special compound of putting down in writing in the flat 8-259578 communique of opening.
(in the above-mentioned general formula (10), R
25～R
28Expression is substituted or unsubstituted monovalence alkyl R independently respectively
25And R
26, R
27And R
28Can mutually combine forms ring, and A and B represent to have substituting group or do not have substituent bivalent hydrocarbon radical respectively independently, and n represents integer 0 or 1).
Described can enumerate alkyl, aryl and cycloalkyl etc. by substituted monovalence alkyl herein.As can substituted bivalent hydrocarbon radical, can be in aromatic series, aliphatic or the alicyclic bivalent hydrocarbon radical any one.
In addition, " free organic phosphite part " is meant the part that does not have with metal complex among the present invention.As free organic phosphite part, can use in the above-mentioned organic phosphorous acid ester compounds any one, but the organic phosphite part of preferred and used VIII B family metal-organic phosphite complex compound catalyst is identical.
Above-claimed cpd can also two or more mix the part that is used as VIII B family metal-organic phosphite complex compound catalyst.In addition, above-mentioned trivalent organic phosphorous acid ester compounds can also be mixed use with pentavalent organic phosphorus compound such as triphenyl phosphine oxide etc.
VIII B family metal is meant 8～10 row metals in the present periodic table of elements among the present invention, specifically can enumerate rhodium, palladium, cobalt, ruthenium and platinum etc., preferred rhodium.
" VIII B family metal-organic phosphite complex compound catalyst " can form in the reaction system of hydroformylation reaction etc. among the present invention, also can use the material for preparing in advance.Compound as supplying with metallic compound is not particularly limited, and can enumerate for example cobalt chloride, cobalt acetate, palladium bichloride, palladium nitrate, ruthenic chloride etc., rhodium compounds such as preferred acetic acid rhodium, rhodium chloride and rhodium nitrate, more preferably acetic acid rhodium etc.When preparing using rhodium complex catalysts in advance, can easily prepare by the following method: in the presence of solvent, make these rhodium compounds and above-mentioned trivalent organic phosphorous acid ester compounds and ozone gas under 60 ℃～200 ℃, the condition of normal pressure～20MPa, carry out carbonylation.As solvent, can from the aftermentioned reaction dissolvent, choose usually, in fact preferably identical with the solvent that is used as reaction dissolvent.Preparation is during catalyst, the ratio of rhodium compound and free trivalent organic phosphorous acid ester compounds normally the mol ratio of phosphorus and rhodium (phosphorus: be 0.1～500 rhodium), preferred 0.1～100, more preferably 1～30.
" catalytic liquid " is meant the material of described catalyst dissolution gained in reaction dissolvent among the present invention, also can contain reaction raw materials or product.
As the reaction dissolvent of hydroformylation reaction, need only the energy catalyst-solvent and reaction is not had harmful effect, then can use any solvent, for example can use aliphatic hydrocarbons such as hexane, octane and cyclohexane; Aromatic hydrocarbons such as toluene, dimethylbenzene; Alcohol such as butanols, octanol and polyethylene glycol; Ethers such as triglyme; Esters such as dioctyl phthalate etc.In addition, when carrying out hydroformylation reaction, the aldehyde or the aldehyde condensates such as its tripolymer or the tetramer that can also use reaction to generate.And then, also can use the alkane corresponding with raw material olefin.
When preserving catalyst, in atmosphere of inert gases such as nitrogen, preserve usually, but it is in the majority to contain the situation of oxygen of 100ppm～hundreds of ppm usually in the nitrogen of uses such as factory.Yet, when preserving catalytic liquid, use the inert gases such as nitrogen after oxygen concentration fully reduced according to the present invention, preserve after making partial pressure of oxygen in the gas be less than or equal to 10Pa.Partial pressure of oxygen during preservation preferably is less than or equal to 5Pa, is more preferably less than or equals 1Pa.If partial pressure of oxygen is too high, cause that then part is rotten.
As the assay method of partial pressure of oxygen in the gas phase, can followingly measure: at first measure the pressure of gas phase, then gas phase gas is sampled, utilize oxymeter etc. that it is analyzed, use oxygen concentration in the gas of above-mentioned analysis to calculate partial pressure of oxygen in the gas phase.
As making partial pressure of oxygen reach the method for described atmosphere gas, can be listed below method: inert gases such as nitrogen after fully reducing with oxygen concentration or argon, the method for airtight (seal) gas phase portion.At this moment, the oxygen concentration in the inert gas is 100ppm or lower, preferred 50ppm or lower, more preferably 5ppm or lower.Even this moment identical oxygen concentration, if the pressure height of gas phase portion, then partial pressure of oxygen uprises, so the pressure of gas phase portion is preferably 200kPaG or following, more preferably 50kPaG or following, further preferred 0.5kPaG or following.Other method also comprises the method with oxygen concentration in the reduction gas phases such as oxygen absorbent; Or the oxygen adsorbent equipment is set makes gas phase circulation, thereby make method that oxygen concentration reduces etc.
The preservation of catalyst also can be carried out under atmosphere of inert gases in instruments such as reactor, preserves in the container but be preferably kept in jar (tank) or drum (drum) etc., and importantly keeps partial pressure of oxygen not raise.
Preferably the catalytic liquid temperature is remained on 0 ℃～50 ℃ in the preservation process,, then promote the rotten of bi-ester of phosphite if reach the high temperature more than 50 ℃ or 50 ℃, and when reaching low temperature below 0 ℃ or 0 ℃, bi-ester of phosphite is separated out, and produces problems such as obstruction, so be not preferred.
Embodiment
Enumerate embodiment below and further describe the present invention.
[preparation of catalytic liquid]
The catalytic liquid of using in following examples and the comparative example is a following substances: will be dissolved in 2.7L methyl alcohol and the solution and the 570g bi-ester of phosphite that form by 37g acetic acid rhodium, be dissolved in the 29kg hutanal, at 85 ℃, 0.39MPaG condition under, at the composition gas that contains carbon monoxide and hydrogen (carbon monoxide: in atmosphere gas hydrogen=1: 1 (mol ratio)), carry out 2 hours carbonylations, with the material of gained at 70 ℃, 1.0MPaG condition under carry out hydroformylation reaction, what alkene wherein used is propylene, remove unreacted alkene behind the reaction terminating, the material that uses gained is as catalytic liquid.
[assay method of partial pressure of oxygen]
Gas in the gas phase is sampled, and measure oxygen concentration, obtain the partial pressure of oxygen of preserving in the container by oxygen concentration that records and gaseous pressure with oxymeter.
[mensuration that the organic phosphite part is rotten]
When preserving beginning and preserve the sample that takes a morsel in the liquid when finishing, measure and compare by liquid chromatogram, estimate thus and preserve the rotten of organic phosphite part in the container.
In addition, " the rotten ratio of organic phosphite part " in following embodiment and the comparative example is the ratio with respect to free organic phosphite part and rhodium-organic phosphite complex compound catalyst part total amount.
The preparation of sample
Hydroformylation catalytic liquid (Rh 197mg/L, phosphite ester ligand 0.9wt%, hutanal 47.5wt%, high boiling substance 51.5wt%) is packed into in the stainless steel behind the nitrogen replacement (SUS) drum, wherein this nitrogen has been 5ppm or lower by oxygen adsorbent equipment and oxygen concentration, and gaseous pressure is transferred to 16kPaG.Analyze the O in the gas phase
2Concentration, result are 4ppm (O
2Dividing potential drop is 0.5Pa).
This catalytic liquid is analyzed after 40 days in room temperature preservation, and its result is, 99% when preserving beginning in the organic phosphite part not have to go bad and exist with the form of original organic phosphorous acid ester compounds.Bi-ester of phosphite as free organic phosphite part and rhodium-organic phosphite complex compound catalyst part uses following compound (11).
(in the formula, tBu represents the tert-butyl group ,-expression methyl).
Embodiment 1
Hydroformylation catalytic liquid (Rh 250mg/L, phosphite ester ligand 0.9wt%, hutanal 47.5wt%, high boiling substance 51.5wt%) is packed in stainless steel (SUS) drum of using nitrogen replacement, wherein this nitrogen has been 100ppm or lower by oxygen adsorbent equipment and oxygen concentration, and gaseous pressure is transferred to 16kPaG.Analyze the O in the gas phase
2Concentration, result are 90ppm (O
2Dividing potential drop is 9.2Pa).Use and identical compound (11) during said sample prepares as the bi-ester of phosphite of free organic phosphite part and rhodium-organic phosphite complex compound catalyst part.
This catalytic liquid is analyzed after 40 days in room temperature preservation, and its result is that the organic phosphite part has 96% when preserving beginning not go bad and still existence.
Comparative example 1
Hydroformylation catalytic liquid (Rh 250mg/L, phosphite ester ligand 0.9wt%, hutanal 47.5wt%, high boiling substance 51.5wt%) is packed in stainless steel (SUS) drum of using nitrogen replacement, wherein this nitrogen is the nitrogen (the mensuration oxygen concentration is 200ppm) through cryogenic separation that is used for operation in the present factory, and gaseous pressure is transferred to 16kPaG.Analyze the O in the gas phase
2Concentration, result are 200ppm (O
2Dividing potential drop is 20.4Pa).Use and identical compound (11) during said sample prepares as the bi-ester of phosphite of free organic phosphite part and rhodium-organic phosphite complex compound catalyst part.
This catalytic liquid is analyzed after 40 days in room temperature preservation, and the organic phosphite part only has 78% when preserving beginning still to exist as a result.
Comparative example 2
In hydroformylation catalytic liquid (Rh 250mg/L, phosphite ester ligand 1wt%, the hutanal 99wt%) glass beaker of packing into, and be open in (O in the air
2Dividing potential drop is 20.4Pa) room temperature preservation.Use and identical compound (11) during said sample prepares as the bi-ester of phosphite of free organic phosphite part and rhodium-organic phosphite complex compound catalyst part.
This catalytic liquid analyzed in second day, the organic phosphite part only has 66% when preserving beginning still to exist as a result.
[discussion]
Analyze as can be known by the embodiment of the invention, when being exposed in the high atmosphere gas of partial pressure of oxygen, rotten with the organic phosphorous acid ester compounds of the amount of rhodium coordination or the amount more than it, and be not only organic phosphorous acid ester compounds with the rhodium coordination, the free organic phosphorous acid ester compounds that is dissolved in the catalytic liquid is also rotten, and the form of original organic phosphorous acid ester compounds disappears.
Reference example
In hydroformylation catalytic liquid (Rh 250mg/L, phosphite ester ligand 30wt%, toluene 30wt%, the high boiling substance 40wt%) glass beaker of packing into, and preserve in air at room temperature.Bi-ester of phosphite as free organic phosphite part and rhodium-organic phosphite complex compound catalyst part uses the tricresyl phosphite phenylester.
This catalytic liquid analyzed in second day, found that the phosphine part of 98% when preserving beginning exists.
The specific embodiment of above reference describes the present invention in detail, but one skilled in the art will appreciate that various changes or correction in addition under the condition that does not break away from spirit and scope of the invention.
The application is based on the application of Japan's special permission application (the special 2002-357783 of hope) of submitting on December 10th, 2002, is incorporated herein its content as a reference.
Industrial applicability
According to the present invention, can provide a kind of and contain free phosphite ester ligand and VIII B in preservation During the catalytic liquid of family's metal-organic phosphite complex compound catalyst, suppress bi-ester of phosphite Rotten, thus method of preserving steady in a long-term.
Claims (4)
1, the store method of VIII B family metal-organic phosphite complex catalysis liquid, it is characterized by, to contain the catalytic liquid of free organic phosphite part and VIII B family metal-organic phosphite complex compound catalyst, be kept in the atmosphere gas of partial pressure of oxygen smaller or equal to 10Pa.
2, the store method of VIII B family metal-organic phosphite complex catalysis liquid, it is characterized by, the hydroformylation catalytic liquid that will contain free organic phosphite part and VIII B family metal-organic phosphite complex compound catalyst, after from reactor, taking out, preserve smaller or equal to the preservation container of 10Pa with the partial pressure of oxygen of gas phase part.
3, store method as claimed in claim 1 or 2 is characterized by, and keeps the temperature of catalytic liquid at 0 ℃～50 ℃ in the preservation process in preserving container.
4, as each described store method of claim 1～3, it is characterized by, VIII B family metal is a rhodium.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002357783 | 2002-12-10 | ||
| JP357783/2002 | 2002-12-10 |
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|---|---|
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|---|---|---|---|
| CNB2003801054009A Expired - Lifetime CN100355500C (en) | 2002-12-10 | 2003-11-20 | Method for preserving viii B group metal-organic phosphite complex catalyst liquid |
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| WO (1) | WO2004052539A1 (en) |
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| CN111318293B (en) * | 2018-12-13 | 2023-09-01 | 中国石油化工股份有限公司 | Hydrotreating catalyst for rapidly increasing content of monocyclic aromatic hydrocarbon and preparation method thereof |
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|---|---|---|---|---|
| JP2001163824A (en) * | 1999-12-13 | 2001-06-19 | Mitsubishi Gas Chem Co Inc | Method for recovering aldehyde from reaction product liquid |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001163824A (en) * | 1999-12-13 | 2001-06-19 | Mitsubishi Gas Chem Co Inc | Method for recovering aldehyde from reaction product liquid |
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