WO2004091780A1 - Process for the preparation of a nickel/phosphorous ligand catalyst - Google Patents
Process for the preparation of a nickel/phosphorous ligand catalyst Download PDFInfo
- Publication number
- WO2004091780A1 WO2004091780A1 PCT/US2004/010472 US2004010472W WO2004091780A1 WO 2004091780 A1 WO2004091780 A1 WO 2004091780A1 US 2004010472 W US2004010472 W US 2004010472W WO 2004091780 A1 WO2004091780 A1 WO 2004091780A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- ligand
- nickel
- alkyl
- group
- vial
- Prior art date
Links
- 239000003446 ligand Substances 0.000 title claims abstract description 119
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims description 33
- 238000002360 preparation method Methods 0.000 title description 9
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 title description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 34
- 239000002184 metal Substances 0.000 claims abstract description 34
- 229920005989 resin Polymers 0.000 claims abstract description 34
- 239000011347 resin Substances 0.000 claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims abstract description 16
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims abstract description 16
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000010457 zeolite Substances 0.000 claims abstract description 9
- 239000002841 Lewis acid Substances 0.000 claims abstract description 7
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 7
- 150000007517 lewis acids Chemical class 0.000 claims abstract description 7
- 238000000622 liquid--liquid extraction Methods 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 150000002825 nitriles Chemical class 0.000 claims abstract description 7
- 238000000638 solvent extraction Methods 0.000 claims abstract description 7
- 230000002378 acidificating effect Effects 0.000 claims abstract description 6
- 229910000323 aluminium silicate Inorganic materials 0.000 claims abstract description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- 125000006539 C12 alkyl 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 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- 150000007530 organic bases Chemical class 0.000 claims description 14
- 239000007795 chemical reaction product Substances 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- FPPLREPCQJZDAQ-UHFFFAOYSA-N 2-methylpentanedinitrile Chemical compound N#CC(C)CCC#N FPPLREPCQJZDAQ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229920000620 organic polymer Polymers 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 125000004104 aryloxy group Chemical group 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- -1 acyclic hydrocarbons Chemical class 0.000 claims 1
- 125000003277 amino group Chemical group 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 125000004122 cyclic group Chemical group 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- 229920000642 polymer Polymers 0.000 claims 1
- 229920005553 polystyrene-acrylate Polymers 0.000 claims 1
- 239000000243 solution Substances 0.000 description 55
- 238000006243 chemical reaction Methods 0.000 description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 239000011701 zinc Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 14
- UVKXJAUUKPDDNW-NSCUHMNNSA-N (e)-pent-3-enenitrile Chemical compound C\C=C\CC#N UVKXJAUUKPDDNW-NSCUHMNNSA-N 0.000 description 13
- CFEYBLWMNFZOPB-UHFFFAOYSA-N Allylacetonitrile Natural products C=CCCC#N CFEYBLWMNFZOPB-UHFFFAOYSA-N 0.000 description 13
- 238000004458 analytical method Methods 0.000 description 13
- 229920001429 chelating resin Polymers 0.000 description 12
- 239000011550 stock solution Substances 0.000 description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 11
- 238000003760 magnetic stirring Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000007791 liquid phase Substances 0.000 description 6
- 239000002808 molecular sieve Substances 0.000 description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 6
- 238000011282 treatment Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000005669 hydrocyanation reaction Methods 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 229940093476 ethylene glycol Drugs 0.000 description 4
- 238000005755 formation reaction Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- VHILMKFSCRWWIJ-UHFFFAOYSA-N dimethyl acetylenedicarboxylate Chemical compound COC(=O)C#CC(=O)OC VHILMKFSCRWWIJ-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 150000002815 nickel Chemical class 0.000 description 3
- 150000002816 nickel compounds Chemical class 0.000 description 3
- 125000005538 phosphinite group Chemical group 0.000 description 3
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 125000004642 (C1-C12) alkoxy group Chemical group 0.000 description 2
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 229910052776 Thorium Inorganic materials 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000004687 hexahydrates Chemical class 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- MGSRCZKZVOBKFT-UHFFFAOYSA-N thymol Chemical compound CC(C)C1=CC=C(C)C=C1O MGSRCZKZVOBKFT-UHFFFAOYSA-N 0.000 description 2
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 2
- JRTIUDXYIUKIIE-KZUMESAESA-N (1z,5z)-cycloocta-1,5-diene;nickel Chemical compound [Ni].C\1C\C=C/CC\C=C/1.C\1C\C=C/CC\C=C/1 JRTIUDXYIUKIIE-KZUMESAESA-N 0.000 description 1
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 description 1
- DVWQNBIUTWDZMW-UHFFFAOYSA-N 1-naphthalen-1-ylnaphthalen-2-ol Chemical compound C1=CC=C2C(C3=C4C=CC=CC4=CC=C3O)=CC=CC2=C1 DVWQNBIUTWDZMW-UHFFFAOYSA-N 0.000 description 1
- GDCJAPJJFZWILF-UHFFFAOYSA-N 2-ethylbutanedinitrile Chemical compound CCC(C#N)CC#N GDCJAPJJFZWILF-UHFFFAOYSA-N 0.000 description 1
- IHXNSHZBFXGOJM-UHFFFAOYSA-N 2-methylbut-2-enenitrile Chemical compound CC=C(C)C#N IHXNSHZBFXGOJM-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910017717 NH4X Inorganic materials 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- NCYSTSFUYSFMEO-OBLTVXDOSA-N PGI3 Chemical compound O1\C(=C/CCCC(O)=O)C[C@@H]2[C@@H](/C=C/[C@@H](O)C\C=C/CC)[C@H](O)C[C@@H]21 NCYSTSFUYSFMEO-OBLTVXDOSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000005844 Thymol Substances 0.000 description 1
- NFGODEMQGQNUKK-UHFFFAOYSA-M [6-(diethylamino)-9-(2-octadecoxycarbonylphenyl)xanthen-3-ylidene]-diethylazanium;chloride Chemical group [Cl-].CCCCCCCCCCCCCCCCCCOC(=O)C1=CC=CC=C1C1=C2C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C21 NFGODEMQGQNUKK-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000003973 alkyl amines Chemical group 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- JYNZIOFUHBJABQ-UHFFFAOYSA-N allyl-{6-[3-(4-bromo-phenyl)-benzofuran-6-yloxy]-hexyl-}-methyl-amin Chemical group C=1OC2=CC(OCCCCCCN(C)CC=C)=CC=C2C=1C1=CC=C(Br)C=C1 JYNZIOFUHBJABQ-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- OHNJZIIDYQVMGK-UHFFFAOYSA-N chloro-bis(5-methyl-2-propan-2-ylphenoxy)phosphane Chemical compound CC(C)C1=CC=C(C)C=C1OP(Cl)OC1=CC(C)=CC=C1C(C)C OHNJZIIDYQVMGK-UHFFFAOYSA-N 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000012035 limiting reagent Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 229960004063 propylene glycol Drugs 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229960000790 thymol Drugs 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/141—Esters of phosphorous acids
- C07F9/145—Esters of phosphorous acids with hydroxyaryl compounds
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/323—Hydrometalation, e.g. bor-, alumin-, silyl-, zirconation or analoguous reactions like carbometalation, hydrocarbation
-
- 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
Definitions
- This invention relates to a process for the preparation of a catalyst which is a complex of nickel and a bidentate phosphorous compound.
- U.S. Patent 3,903,120 discloses a process for preparing zerovalent nickel complexes by reacting elemental nickel with a monodentate phosphorous ligand of the formula PZ 3 where Z is an alkyl or alkoxy group, preferably an aryloxy group.
- the process uses finely divided elemental nickel and is preferably carried out in the presence of a nitrile solvent.
- the reaction is taught to be carried out in the presence of excess ligand.
- U.S. Patent 3,846,461 discloses a process for preparing zerovalent nickel complexes of triorganophosphites by reacting triorganophosphite compounds with nickel chloride in the presence of a finely divided reducing metal which is more electropositive than nickel, and in the presence of a promoter selected from the group consisting of NH 3 , NH X, Zn(NH 3 ) 2 X 2 , and mixtures of NH 4 X and ZnX 2 , where X is a halide.
- Reducing metals include Na, Li, Mg, Ca, Ba, Sr, Ti, V, Fe, Co, Cu, Zn, Cd, Al, Ga, In, Sn, Pb, and Th, with Zn being preferred.
- U.S. Patent 5,523,453 discloses a method of preparing nickel hydrocyanation catalysts containing bidentate phosphorous ligands.
- Zero- valent nickel compounds that contain ligands that can be displaced by the bidentate phosphorous ligand are a preferred source of nickel.
- Two such compounds are Ni(COD) 2 , where COD is 1 ,5-cyclooctadiene, and (oTTP) 2 Ni(C 2 H 4 ), where oTTP is P(O-ortho-C 6 H 4 CH 3 )3.
- divalent nickel compounds may be combined with reducing agents to produce a suitable nickel source. In the latter method of preparing catalyst, as the temperature of the catalyst preparation increases, the catalyst formation rate increases, but the amount of degradation product also increases.
- US Patent 6,069,267 describes a method for preparing a crude bidentate phosphorus-containing ligand suitable for use in the catalyst preparation.
- the resulting product is, however, not pure ligand, but rather a crude ligand mixture that contains byproducts of the reaction which may affect the rate of formation of the nickel-containing catalyst. That process does not provide for isolation and purification of the bidentate ligand.
- the present inventors observed that, compared to the use of purified ligand, such crude ligand mixtures do inhibit catalyst preparation reactions wherein divalent nickel compounds are contacted with reducing agents to produce the nickel catalyst.
- the present invention is a process for preparing a nickel/ligand catalyst, said process comprising:
- step (b) contacting the first reaction product at a temperature between about -25 deg C and about 35 deg C with about one half molar equivalent of HO-Z- OH, wherein Z is a substituted or unsubstituted aryl group different from R1 , to produce a second reaction product comprising a solids content, provided that if less than three molar equivalents of organic base are used in step (a), then sufficient organic base is used in step (b) to bring the total amount of organic base used in steps (a) and (b) combined to at least three molar equivalents of organic base relative to the PCI 3 ;
- step (c) separating the solids content from the second reaction product by filtration or extraction with water to produce a crude ligand mixture, said solids content comprising a salt formed from the organic base used in step (a) and optionally in step (b);
- step (e) recovering from the product of step (d) a solution containing a ligand of the formula
- step (f) contacting the solution of step (e) with nickel chloride in the presence of a nitrile solvent and a reducing metal which is more electropositive than nickel to produce the nickel/ligand catalyst.
- Suitable treatment methods include contacting the crude ligand mixture with the one or more of the following:
- a weakly acidic organic resin including organic polymers with carboxylic acid functional groups, such as Amberlyst CG-50 (Rohm & Haas),
- a weakly basic organic resin including organic polymers with alkylamine functional groups, such as Amberlyst® 21 (Rohm & Haas),
- a high-surface-area neutral organic resin including polystyrene adsorbent, such as Amberlite® XAD-4, and polyacrylate adsorbent, such as Amberlite® XAD-7 (Rohm & Haas),
- an aluminosilicate zeolite commonly referred to in the art as molecular sieves, such as 3A or 13X molecular sieves,
- (6) a two phase solvent system for liquid-liquid extraction where one phase is a non-polar aliphatic hydrocarbon such as hexane or cyclohexane and the other phase is a polar organic species such as adiponitrile, methylglutaronitrile, ethylsuccinonitrile, acetonitrile, ethyleneglycol or propyleneglycol, and (7) a Lewis acid.
- a non-polar aliphatic hydrocarbon such as hexane or cyclohexane
- a polar organic species such as adiponitrile, methylglutaronitrile, ethylsuccinonitrile, acetonitrile, ethyleneglycol or propyleneglycol
- Lewis acid a Lewis acid
- a solvent may be employed during the treatment to improve flowability and contact between the crude ligand and the treating agent.
- Suitable solvents include aliphatic hydrocarbons and nitriles. 3-Pentenenitrile is a preferred solvent.
- the material used for treatment is then separated from the crude ligand mixture to recover a treated ligand mixture that is then reacted with nickel chloride in the presence of a nitrile solvent and a reducing metal, to form a nickel/ligand catalyst at a higher reaction rate than that obtained by using a untreated crude ligand mixture.
- the reducing metal hereafter referred to as MET, can be any metal which is more electropositive than nickel.
- Such metals include Na, Li, K, Mg, Ca, Ba, Sr, Ti, V, Fe, Co, Cu, Zn, Cd, Al, Ga, In, Sn, Pb, and Th. Most preferred are Fe and Zn.
- the source of nickel for this invention is preferably nickel (II) chloride, NiCI 2 .
- NiCI 2 Either hydrated or anhydrous forms of NiCI 2 may be used.
- Anhydrous NiCI 2 is preferred in order to minimize the hydrolytic degradation of the ligand.
- the expression “anhydrous” means that the nickel chloride contains less than
- Nickel chloride containing 1 % or less water is preferred. Processes for producing anhydrous nickel chloride have been described in co-pending application no. 09/994,102.
- the expression "hydrated NiCI 2 " means NiCI 2 containing 2% or more water by weight. Examples of hydrated NiCb include the dihydrate, the hexahydrate and aqueous solutions of NiCb. Preferred sources for producing anhydrous NiCI 2 are the hexahydrate product and an aqueous solution. NiCl2 as an aqueous solution is particularly preferred. The aqueous solution is available commercially as an approximately 29 weight percent NiCI 2 aqueous solution.
- the catalyst formation reaction is carried out in the presence of a nitrile solvent, preferably 3-pentenenitrile or 2-methyl-butenenitrile.
- concentration of ligand may range from about 1 % to 90% by weight. For practical reasons the preferred range of ligand concentration is 5% to 50%.
- the amount of reducing metal (MET) will generally fall in the range of 0.1% to 5% of the reaction mass.
- the molar ratio of NiCb to MET ranges from 0.1:1 to 100:1.
- the preferred ratio of NiCI 2 :MET ranges from 2:1 to 50:1.
- the reaction temperature may range from 0°C to 120°C. The preferred temperature range is dependent on the NiCI 2 form. Hydrated forms of NiCb react rapidly at lower temperatures than anhydrous NiCI 2 .
- the preferred temperature range is 0°C to 60°C, and the most preferred range is 25°C to 50°C.
- the preferred temperature range is 30°C to 110°C, and the most preferred range is 50°C to 100°C.
- the reaction may be run within a wide pressure range. For practical reasons, the preferred pressure ranges from about 5 psia to 50 psia (34 to 340 kPa). The reaction may be run in batch or continuous mode.
- Suitable ligands for the present invention are bidentate phosphorous- containing ligands selected from the group consisting of bidentate phosphites and bidentate phosphinites.
- Preferred ligands are bidentate phosphite ligands.
- the preferred bidentate phosphite ligands are of the following structural formulae:
- R 1 is phenyl, unsubstituted or substituted with one or more Ci to C 12 alkyl or C 1 to C 12 alkoxy groups; or naphthyl, unsubstituted or substituted with one or more C 1 to C 12 alkyl or C 1 to C 12 alkoxy groups; and Z is independently selected from the group consisting of structural formulae II, III, IV, V, and VI:
- R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 are independently selected from the group consisting of H, Ci to C12 alkyl, and Ci to C 12 alkoxy;
- X is O, S, or CH(R 10 );
- R 10 is H or d to C 12 alkyl
- R 11 and R 2 are independently selected from the group consisting of H, Ci to C12 alkyl, and Ci to C12 alkoxy; and CO 2 R 13 , R 13 is Ci to C 12 alkyl or C 6 to C 10 aryl, unsubstituted or substituted, with C to C 4 alkyl ; Y is O, S, or CH(R 14 ); R 14 is H or Ci to C 12 alkyl;
- R 15 is selected from the group consisting of H, Ci to C 12 alkyl, and Ci to
- R 16 is Ci to C 12 alkyl or C 6 to C 10 aryl, unsubstituted or substituted with
- Ci to C 4 alkyl In the structural formulae I through VIII, the Ci to C 12 alkyl, and Ci to C 12 alkoxy groups may be straight chains or branched.
- bidentate phosphite ligands that are useful in the present process include those having the formulae VII to XXIV, shown below wherein for each formula, R 17 is selected from the group consisting of methyl, ethyl or isopropyl, and R 18 and R 19 are independently selected from H or methyl:
- bidentate phosphites are of the type disclosed in atents 5,512,695; 5,512,696; 5,663,369; 5,688,986; 5,723,641; 5,847,101 ; 5,959,135; 6,120,700; 6,171 ,996; 6,171 ,997 and 6,399,534; the disclosures of which are incorporated herein by reference.
- Suitable bidentate phosphinites are of the type disclosed in U. S. Patents 5,523,453 and 5,693,843, the disclosures of which are incorporated herein by reference.
- the reaction may be carried out in a manner such that unreacted NiCb and MET may be separated from the reaction product by filtration or centrifugation. The collected excess nickel chloride can then be recycled back to a catalyst preparation reactor.
- the reducing metal is the limiting reagent in each reaction, and therefore the extent of reaction (conversion) is expressed as the percentage of the reducing metal reacted.
- the extent of reaction (conversion) is determined by analyzing for the amount of active nickel produced by the catalyst synthesis reaction. The analysis is carried out by treating a solids- free aliquot of the reaction solution with dimethyl acetylenedicarboxylate (DMAD), which forms a stable nickel complex, (Ligand)Ni(DMAD), and analyzing quantitatively for this complex by High Pressure Liquid Chromatography (HPLC).
- DMAD dimethyl acetylenedicarboxylate
- HPLC High Pressure Liquid Chromatography
- the Comparative Example illustrates typical reaction behavior when the crude ligand mixture is not treated according to this invention.
- Examples 2, 3, and 5 illustrate that treating the crude ligand with various resins results in higher rates of reaction compared with reaction using no treatment of the ligand (Comparative Example).
- Example 6 illustrates the effect of treating the crude ligand with activated carbon.
- Examples 4 and 7 illustrate the positive effect of treatment with alumino silicate zeolites (molecular sieves).
- Examples 1 , 8, and 10 illustrate the benefits of utilizing liquid-liquid extraction to treat the crude ligand. mixture.
- Example 9 illustrates the benefits of treating the crude ligand mixture with small amount of a Lewis acid prior to the catalyst preparation.
- a "crude ligand VII" was prepared by a) treating a toluene solution of PCI 3 with two molar equivalents of thymol and three molar equivalents of triethylamine while maintaining a reaction temperature of about -5°C, to produce a first reaction product comprising di(2-isopropyl-5- methylphenoxy)phosphorus chloride, triethylammonium chloride (which is substantially insoluble in the mixture), unreacted triethylamine and toluene, b) adding one half molar equivalent of binaphthol (relative to PGI 3 ) to the reaction mixture while maintaining the reaction temperature at about -5°C, c) treating the product of step (b) with water to extract the triethylammonium hydrochloride and separating the resulting aqueous lower phase from the organic product solution, and subsequently distilling a portion of the toluene from the organic product solution to produce
- Ligand VII Stock Solution was prepared by: (1) dissolving 830 grams of "crude ligand VII” in 1000 grams of 3- pentenenitrile in an air-free 3 liter round bottom flask fitted with an over head stirrer, a heating mantel, a distillation head, a dip tube to draw off material out of the flask and an addition funnel,
- step (12) heating the solution from step (1 ) under vacuum to 45 to 60 deg C to distill off the toluene and then allowing the solution to cool to ambient temperature.
- Ligand VII Stock Solution (12.067 grams) was put into a dried 20 cc vial. Into this vial was also placed 0.493 grams of anhydrous NiCb and 0.096 grams of finely divided zinc metal. A small magnetic stirring bar was added to the vial. The vial was capped and placed into a heated aluminum block that had been pre-heated to 100 deg C. A stop watch was started when the vial was placed into the heated block. The contents of the vial were agitated using a rotating magnetic bar coupled to the magnetic bar inside the vial. At 1.5 hours a sample was taken of the solution. Analysis of this sample showed 425 ppm of Ni as catalyst in solution.
- This example shows the benefit of extracting crude ligand with adiponitrile.
- This example shows the benefit of treating crude ligand with Amberlyst® 21 base resin (Rohm & Haas), a weakly basic resin containing alkylamine groups.
- This example shows the benefit of treating crude ligand with Amberlite® CG-50 (Rohm & Haas), a weakly acidic resin containing carboxylic acid groups.
- This example shows the benefit of treating crude ligand with small pore zeolites.
- 5 cc of 3A Molecular Sieves (zeolite), which had been previously activated by drying overnight at 350 deg C was loaded into a 50 cc syringe body.
- 20 cc of 3-pentenenitrile was flushed through the resin and was disposed of.
- About 15 grams of "Ligand VII Stock Solution” was then allowed to drain through the sieves.
- the ligand solution was re-analyzed and found to have about 22 wt% ligand in it.
- This example shows the benefit of treating crude ligand with an adsorbent high-surface-area neutral organic resin.
- Example 6 This example shows the benefit of treating crude ligand with activated carbon.
- This example shows the benefit of treating crude ligand with a large pore zeolite.
- a small magnetic stirring bar was added to the vial.
- the vial was capped and placed into a heated aluminum block that had been pre-heated to 100 deg C.
- a stop watch was started when the vial was placed into the heated block.
- the contents of the vial were agitated using a rotating magnetic bar coupled to the magnetic bar inside the vial.
- a sample was taken of the solution. Analysis of this sample showed 2490 ppm of Ni as catalyst in solution. This is about 6 times the amount of catalyst made in the Comparative Example.
- This example shows the benefit of extracting crude ligand with methylglutaronitrile.
- the contents of the vial were agitated using a rotating magnetic bar coupled to the magnetic bar inside the vial. At 1.5 hours a sample was taken of the solution. Analysis of this sample showed 3990 ppm of Ni as catalyst in solution. This is about 9 times the amount of catalyst made in the Comparative Example.
- This example shows the benefit of adding a Lewis acid such as ZnCb to crude ligand.
- This example shows the benefit of extracting crude ligand with ethylene glycol.
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Abstract
Description
Claims
Priority Applications (3)
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EP04759127A EP1610894B1 (en) | 2003-04-08 | 2004-04-06 | Process for the preparation of a nickel/phosphorus ligand catalyst |
DE602004005580T DE602004005580T2 (en) | 2003-04-08 | 2004-04-06 | PROCESS FOR PREPARING A NICKEL / PHOSPHOR LIGAND CATALYST |
JP2006509713A JP2006523141A (en) | 2003-04-08 | 2004-04-06 | Method for producing nickel / phosphorus ligand catalyst |
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US10/409,482 | 2003-04-08 | ||
US10/409,482 US6844289B2 (en) | 2003-04-08 | 2003-04-08 | Process for the preparation of a nickel/phosphorous ligand catalyst |
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PCT/US2004/010472 WO2004091780A1 (en) | 2003-04-08 | 2004-04-06 | Process for the preparation of a nickel/phosphorous ligand catalyst |
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US (1) | US6844289B2 (en) |
EP (1) | EP1610894B1 (en) |
JP (1) | JP2006523141A (en) |
CN (1) | CN100496725C (en) |
AT (1) | ATE357972T1 (en) |
DE (1) | DE602004005580T2 (en) |
MY (1) | MY138457A (en) |
SA (1) | SA04250241B1 (en) |
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WO (1) | WO2004091780A1 (en) |
Cited By (5)
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WO2006040023A1 (en) * | 2004-10-08 | 2006-04-20 | Basf Aktiengesellschaft | Method for purifying chelate ligands containing phosphorus |
WO2007109005A2 (en) * | 2006-03-17 | 2007-09-27 | Invista Technologies S.A R.L. | Method for the purification of triorganophosphites by treatment with a basic additive |
JP2008539248A (en) * | 2005-04-27 | 2008-11-13 | カルゴン、カーボン、コーポレーション | Method for separating E and Z isomers of alkene alcohol and its derivatives |
WO2013076569A1 (en) | 2011-10-26 | 2013-05-30 | Invista Technologies S.A R.L. | Methods for producing organodi phosphites from phosphorochloridites characterized by measuring side- product levels to determine further additions |
US8609901B2 (en) | 2009-04-21 | 2013-12-17 | Invista North America S.A R.L. | Highly selective process for producing organodiphosphites |
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FR2849027B1 (en) * | 2002-12-23 | 2005-01-21 | Rhodia Polyamide Intermediates | PROCESS FOR THE SYNTHESIS OF COMPOUNDS COMPRISING NITRIL FUNCTIONS FROM ETHYLENE-UNSATURATED COMPOUNDS |
FR2850966B1 (en) | 2003-02-10 | 2005-03-18 | Rhodia Polyamide Intermediates | PROCESS FOR PRODUCING DINITRIL COMPOUNDS |
FR2854891B1 (en) | 2003-05-12 | 2006-07-07 | Rhodia Polyamide Intermediates | PROCESS FOR PREPARING DINITRILES |
FR2854892B1 (en) * | 2003-05-12 | 2005-06-24 | Rhodia Polyamide Intermediates | PROCESS FOR PRODUCING DINITRILES |
DE102004050935A1 (en) * | 2004-10-18 | 2006-04-20 | Basf Ag | Extraction of nickel (0) complexes from nitrile mixtures with reduced leaching |
US7709674B2 (en) * | 2006-07-14 | 2010-05-04 | Invista North America S.A R.L | Hydrocyanation process with reduced yield losses |
CN102380353B (en) * | 2011-09-19 | 2013-08-21 | 江苏大学 | Method for preparing magnetic magnesium oxide surface molecular imprinting solid phase extractant |
CN103547349B (en) * | 2011-12-21 | 2016-03-16 | 因温斯特北美公司 | Extractant for reducing stable emulsion controls |
JP2015503510A (en) * | 2011-12-21 | 2015-02-02 | インヴィスタ テクノロジーズ エスアエルエル | Extraction solvent control to reduce stable emulsions |
TWI709566B (en) * | 2015-09-30 | 2020-11-11 | 美商陶氏科技投資公司 | Processes for producing organophosphorous compounds |
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US5512695A (en) * | 1994-04-14 | 1996-04-30 | E. I. Du Pont De Nemours And Company | Bidentate phosphite and nickel catalyst compositions for hydrocyanation of monoolefins |
US6069267A (en) * | 1997-07-29 | 2000-05-30 | E. I. Du Pont De Nemours And Company | Selective synthesis of organodiphosphite compounds |
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- 2003-04-08 US US10/409,482 patent/US6844289B2/en not_active Expired - Lifetime
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2004
- 2004-04-06 EP EP04759127A patent/EP1610894B1/en not_active Expired - Lifetime
- 2004-04-06 CN CNB2004800157318A patent/CN100496725C/en not_active Expired - Lifetime
- 2004-04-06 AT AT04759127T patent/ATE357972T1/en not_active IP Right Cessation
- 2004-04-06 JP JP2006509713A patent/JP2006523141A/en not_active Ceased
- 2004-04-06 DE DE602004005580T patent/DE602004005580T2/en not_active Expired - Lifetime
- 2004-04-06 WO PCT/US2004/010472 patent/WO2004091780A1/en active IP Right Grant
- 2004-04-07 MY MYPI20041274A patent/MY138457A/en unknown
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US5512695A (en) * | 1994-04-14 | 1996-04-30 | E. I. Du Pont De Nemours And Company | Bidentate phosphite and nickel catalyst compositions for hydrocyanation of monoolefins |
US6069267A (en) * | 1997-07-29 | 2000-05-30 | E. I. Du Pont De Nemours And Company | Selective synthesis of organodiphosphite compounds |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2006040023A1 (en) * | 2004-10-08 | 2006-04-20 | Basf Aktiengesellschaft | Method for purifying chelate ligands containing phosphorus |
JP2008539248A (en) * | 2005-04-27 | 2008-11-13 | カルゴン、カーボン、コーポレーション | Method for separating E and Z isomers of alkene alcohol and its derivatives |
WO2007109005A2 (en) * | 2006-03-17 | 2007-09-27 | Invista Technologies S.A R.L. | Method for the purification of triorganophosphites by treatment with a basic additive |
WO2007109005A3 (en) * | 2006-03-17 | 2007-11-15 | Invista Tech Sarl | Method for the purification of triorganophosphites by treatment with a basic additive |
EP2395010A1 (en) * | 2006-03-17 | 2011-12-14 | Invista Technologies S.A R.L. | Method for the purification of triorganophosphites by treatment with a basic additive |
US8609901B2 (en) | 2009-04-21 | 2013-12-17 | Invista North America S.A R.L. | Highly selective process for producing organodiphosphites |
US8772549B2 (en) | 2009-04-21 | 2014-07-08 | INVISTA North America S.à r.l. | Highly selective process for producing organodiphosphites |
WO2013076569A1 (en) | 2011-10-26 | 2013-05-30 | Invista Technologies S.A R.L. | Methods for producing organodi phosphites from phosphorochloridites characterized by measuring side- product levels to determine further additions |
US9221852B2 (en) | 2011-10-26 | 2015-12-29 | Invista North America S.A.R.L. | Method for making organodiphosphites from phosphorochloridites characterized by measuring side-product levels to determine further additions |
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Publication number | Publication date |
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ATE357972T1 (en) | 2007-04-15 |
EP1610894A1 (en) | 2006-01-04 |
US20040204312A1 (en) | 2004-10-14 |
EP1610894B1 (en) | 2007-03-28 |
US6844289B2 (en) | 2005-01-18 |
MY138457A (en) | 2009-06-30 |
DE602004005580D1 (en) | 2007-05-10 |
TW200500372A (en) | 2005-01-01 |
JP2006523141A (en) | 2006-10-12 |
SA04250241B1 (en) | 2007-07-31 |
CN1802213A (en) | 2006-07-12 |
CN100496725C (en) | 2009-06-10 |
DE602004005580T2 (en) | 2008-01-24 |
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