EP1427695A1 - Procede de fabrication de composes nitriles - Google Patents
Procede de fabrication de composes nitrilesInfo
- Publication number
- EP1427695A1 EP1427695A1 EP02779637A EP02779637A EP1427695A1 EP 1427695 A1 EP1427695 A1 EP 1427695A1 EP 02779637 A EP02779637 A EP 02779637A EP 02779637 A EP02779637 A EP 02779637A EP 1427695 A1 EP1427695 A1 EP 1427695A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- group
- chosen
- reaction
- compounds
- nitrile
- 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.)
- Withdrawn
Links
- 238000000034 method Methods 0.000 title claims abstract description 48
- -1 nitrile compounds Chemical class 0.000 title claims abstract description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 49
- 150000001875 compounds Chemical class 0.000 claims abstract description 40
- 239000002608 ionic liquid Substances 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000003446 ligand Substances 0.000 claims abstract description 27
- 150000002825 nitriles Chemical group 0.000 claims abstract description 24
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- 239000012429 reaction media Substances 0.000 claims abstract description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 4
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 30
- 239000002841 Lewis acid Substances 0.000 claims description 19
- 239000003054 catalyst Substances 0.000 claims description 19
- 150000007517 lewis acids Chemical class 0.000 claims description 19
- 150000001450 anions Chemical class 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 17
- 150000001336 alkenes Chemical class 0.000 claims description 15
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 13
- 238000006317 isomerization reaction Methods 0.000 claims description 12
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 10
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 8
- 150000001768 cations Chemical class 0.000 claims description 8
- 239000002798 polar solvent Substances 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 150000007942 carboxylates Chemical class 0.000 claims description 6
- 125000003010 ionic group Chemical group 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 235000021317 phosphate Nutrition 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000007983 Tris buffer Substances 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 4
- 150000004820 halides Chemical class 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- XUAXVBUVQVRIIQ-UHFFFAOYSA-N 1-butyl-2,3-dimethylimidazol-3-ium Chemical compound CCCCN1C=C[N+](C)=C1C XUAXVBUVQVRIIQ-UHFFFAOYSA-N 0.000 claims description 3
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- VWPAKFDSXCXYJF-UHFFFAOYSA-N OS(C(C([Na])=CC=C1)=C1P(C1=CC=CC=C1)C1=CC=CC=C1)=O Chemical compound OS(C(C([Na])=CC=C1)=C1P(C1=CC=CC=C1)C1=CC=CC=C1)=O VWPAKFDSXCXYJF-UHFFFAOYSA-N 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- DOUHZFSGSXMPIE-UHFFFAOYSA-N hydroxidooxidosulfur(.) Chemical compound [O]SO DOUHZFSGSXMPIE-UHFFFAOYSA-N 0.000 claims description 3
- KYLUAQBYONVMCP-UHFFFAOYSA-N (2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P KYLUAQBYONVMCP-UHFFFAOYSA-N 0.000 claims description 2
- HVVRUQBMAZRKPJ-UHFFFAOYSA-N 1,3-dimethylimidazolium Chemical compound CN1C=C[N+](C)=C1 HVVRUQBMAZRKPJ-UHFFFAOYSA-N 0.000 claims description 2
- ZYVYEJXMYBUCMN-UHFFFAOYSA-N 1-methoxy-2-methylpropane Chemical compound COCC(C)C ZYVYEJXMYBUCMN-UHFFFAOYSA-N 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 claims description 2
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 2
- 229910018286 SbF 6 Inorganic materials 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 2
- NVIANCROYQGROD-UHFFFAOYSA-N bis(fluorosulfonyl)azanide Chemical compound FS(=O)(=O)[N-]S(F)(=O)=O NVIANCROYQGROD-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000002091 cationic group Chemical group 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- LFZKSOOXPOYSSJ-UHFFFAOYSA-N dimethyl(octyl)phosphane Chemical compound CCCCCCCCP(C)C LFZKSOOXPOYSSJ-UHFFFAOYSA-N 0.000 claims description 2
- HASCQPSFPAKVEK-UHFFFAOYSA-N dimethyl(phenyl)phosphine Chemical compound CP(C)C1=CC=CC=C1 HASCQPSFPAKVEK-UHFFFAOYSA-N 0.000 claims description 2
- KUMNEOGIHFCNQW-UHFFFAOYSA-N diphenyl phosphite Chemical compound C=1C=CC=CC=1OP([O-])OC1=CC=CC=C1 KUMNEOGIHFCNQW-UHFFFAOYSA-N 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-O guanidinium Chemical compound NC(N)=[NH2+] ZRALSGWEFCBTJO-UHFFFAOYSA-O 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 claims description 2
- 125000005538 phosphinite group Chemical group 0.000 claims description 2
- 150000008301 phosphite esters Chemical class 0.000 claims description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 claims description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 claims description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 150000003871 sulfonates Chemical class 0.000 claims description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- 125000005497 tetraalkylphosphonium group Chemical group 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 claims description 2
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 claims description 2
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- KCUGPPHNMASOTE-UHFFFAOYSA-N 1,2,3-trimethylimidazol-1-ium Chemical compound CC=1N(C)C=C[N+]=1C KCUGPPHNMASOTE-UHFFFAOYSA-N 0.000 claims 1
- BCJVBDBJSMFBRW-UHFFFAOYSA-N 4-diphenylphosphanylbutyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCCP(C=1C=CC=CC=1)C1=CC=CC=C1 BCJVBDBJSMFBRW-UHFFFAOYSA-N 0.000 claims 1
- 150000001993 dienes Chemical class 0.000 claims 1
- 238000005669 hydrocyanation reaction Methods 0.000 abstract description 35
- 230000003197 catalytic effect Effects 0.000 abstract description 19
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 abstract description 9
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- 239000000203 mixture Substances 0.000 description 11
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 7
- 239000003638 chemical reducing agent Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- WBAXCOMEMKANRN-UHFFFAOYSA-N 2-methylbut-3-enenitrile Chemical compound C=CC(C)C#N WBAXCOMEMKANRN-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229910052723 transition metal Inorganic materials 0.000 description 6
- 150000003624 transition metals Chemical class 0.000 description 6
- 238000004587 chromatography analysis Methods 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 150000002816 nickel compounds Chemical class 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000011592 zinc chloride Substances 0.000 description 5
- 235000005074 zinc chloride Nutrition 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- NTUROZDXWLPVHB-UHFFFAOYSA-M sodium;3-diphenylphosphanylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 NTUROZDXWLPVHB-UHFFFAOYSA-M 0.000 description 4
- ZSUXOVNWDZTCFN-UHFFFAOYSA-L tin(ii) bromide Chemical compound Br[Sn]Br ZSUXOVNWDZTCFN-UHFFFAOYSA-L 0.000 description 4
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 4
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 3
- FPPLREPCQJZDAQ-UHFFFAOYSA-N 2-methylpentanedinitrile Chemical compound N#CC(C)CCC#N FPPLREPCQJZDAQ-UHFFFAOYSA-N 0.000 description 3
- CFEYBLWMNFZOPB-UHFFFAOYSA-N Allylacetonitrile Natural products C=CCCC#N CFEYBLWMNFZOPB-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000002051 biphasic effect Effects 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000001119 stannous chloride Substances 0.000 description 3
- 235000011150 stannous chloride Nutrition 0.000 description 3
- MXSVLWZRHLXFKH-UHFFFAOYSA-N triphenylborane Chemical compound C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1 MXSVLWZRHLXFKH-UHFFFAOYSA-N 0.000 description 3
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 2
- MWFMGBPGAXYFAR-UHFFFAOYSA-N 2-hydroxy-2-methylpropanenitrile Chemical compound CC(C)(O)C#N MWFMGBPGAXYFAR-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000001649 bromium compounds Chemical class 0.000 description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 150000002903 organophosphorus compounds Chemical class 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000010183 spectrum analysis Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000003623 transition metal compounds Chemical class 0.000 description 2
- 229940102001 zinc bromide Drugs 0.000 description 2
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 description 2
- YXTDAZMTQFUZHK-ZVGUSBNCSA-L (2r,3r)-2,3-dihydroxybutanedioate;tin(2+) Chemical compound [Sn+2].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O YXTDAZMTQFUZHK-ZVGUSBNCSA-L 0.000 description 1
- IHXNSHZBFXGOJM-HWKANZROSA-N (e)-2-methylbut-2-enenitrile Chemical compound C\C=C(/C)C#N IHXNSHZBFXGOJM-HWKANZROSA-N 0.000 description 1
- UVKXJAUUKPDDNW-NSCUHMNNSA-N (e)-pent-3-enenitrile Chemical compound C\C=C\CC#N UVKXJAUUKPDDNW-NSCUHMNNSA-N 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- XJKSTNDFUHDPQJ-UHFFFAOYSA-N 1,4-diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=C(C=2C=CC=CC=2)C=C1 XJKSTNDFUHDPQJ-UHFFFAOYSA-N 0.000 description 1
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 description 1
- FHDQNOXQSTVAIC-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;chloride Chemical compound [Cl-].CCCCN1C=C[N+](C)=C1 FHDQNOXQSTVAIC-UHFFFAOYSA-M 0.000 description 1
- YJJKYKYXZZCJEE-UHFFFAOYSA-N 2,2-diphenylethylphosphane Chemical compound C=1C=CC=CC=1C(CP)C1=CC=CC=C1 YJJKYKYXZZCJEE-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
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- TYOVSFHFYHSADG-UHFFFAOYSA-N 4,8-dichloro-2-methylquinoline Chemical compound C1=CC=C(Cl)C2=NC(C)=CC(Cl)=C21 TYOVSFHFYHSADG-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 101000693728 Homo sapiens S-acyl fatty acid synthase thioesterase, medium chain Proteins 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- HOIQMOFIONYARA-UHFFFAOYSA-N N=P(F)=O Chemical compound N=P(F)=O HOIQMOFIONYARA-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 102100025541 S-acyl fatty acid synthase thioesterase, medium chain Human genes 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000005228 aryl sulfonate group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- UCYRAEIHXSVXPV-UHFFFAOYSA-K bis(trifluoromethylsulfonyloxy)indiganyl trifluoromethanesulfonate Chemical compound [In+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F UCYRAEIHXSVXPV-UHFFFAOYSA-K 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- KPWJBEFBFLRCLH-UHFFFAOYSA-L cadmium bromide Chemical compound Br[Cd]Br KPWJBEFBFLRCLH-UHFFFAOYSA-L 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- RJYMRRJVDRJMJW-UHFFFAOYSA-L dibromomanganese Chemical compound Br[Mn]Br RJYMRRJVDRJMJW-UHFFFAOYSA-L 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- BYMZQQLCZDLNKW-UHFFFAOYSA-N nickel(2+);tetracyanide Chemical compound [Ni+2].N#[C-].N#[C-].N#[C-].N#[C-] BYMZQQLCZDLNKW-UHFFFAOYSA-N 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical group [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical class OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 1
- 229920005554 polynitrile Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- TXIMTWZYLXAHCQ-UHFFFAOYSA-N sodium;triphenyl phosphate Chemical compound [Na].C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 TXIMTWZYLXAHCQ-UHFFFAOYSA-N 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 description 1
- 229940007163 stannous tartrate Drugs 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- RVKZDIDATLDTNR-UHFFFAOYSA-N sulfanylideneeuropium Chemical compound [Eu]=S RVKZDIDATLDTNR-UHFFFAOYSA-N 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/08—Preparation of carboxylic acid nitriles by addition of hydrogen cyanide or salts thereof to unsaturated compounds
- C07C253/10—Preparation of carboxylic acid nitriles by addition of hydrogen cyanide or salts thereof to unsaturated compounds to compounds containing carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/04—Preparation of carboxylic acid nitriles by reaction of cyanogen halides, e.g. ClCN, with organic compounds
Definitions
- the present invention relates to the manufacture of nitrile compounds from unsaturated organic compounds by reaction with hydrogen cyanide. It relates more particularly to the manufacture of nitrile compounds used for the synthesis of adiponitrile, an important chemical intermediate for the manufacture of large chemical compounds such as hexamethylene diamine and ⁇ -caprolactam. These last two compounds are used, in particular, in the manufacture of polymers such as polyamides and more particularly polyamides 6 and 6-6, or other polymers such as polyurethanes.
- nitrile compounds have been proposed.
- the direct hydrocyanation of an olefin or polyolefin such as, for example, 1, 3-butadiene by reaction with hydrogen cyanide is a process developed industrially and which is the subject of numerous patents or publications.
- This process consists, roughly, in a first step to carry out the addition of a molecule of HCN on an ethylenic unsaturation to obtain an unsaturated nitrile compound.
- this step leads to the production of many isomers of unsaturated nitriles.
- the addition of a new HCN molecule leads, in a next step to a polynitrile, for example, to a dinitrile such as adiponitrile when the starting olefin is 1, 3-butadiene.
- the process comprises, after the first hydrocyanation step, a step called “isomerization step” consisting in transforming the major part of the branched nitrile isomers in linear nitrile isomers such as, in the case of the hydrocyanation of butadiene, in 3- and 4-pentenenitriles.
- ligands are organophosphorus compounds such as phosphites, phosphinites, phosphonites or phosphines. They can be monodentates or polydentates. In the case of processes in a two-phase medium, these organophosphorus ligands advantageously comprise one or more ionizable groups such as the sulfonate, phosphate, carboxylate or ammonium groups, for example to make them soluble in the polar phase.
- French Patent No. 2,338,253 it also describes a process for the synthesis of adiponitrile by hydrocyanation of butadiene.
- the reaction is carried out in a two-phase liquid medium, the catalyst being contained in an aqueous phase.
- This process makes it possible to recover adiponitrile in the organic phase free of catalyst and therefore of metal.
- the catalyst described is also a catalyst based on a metal such as nickel associated with a phosphine type ligand.
- this ligand comprises sulfonate radicals making it possible to make the catalyst soluble or dispersible in water.
- promoters such as Lewis acids, such as, for example, zinc chloride, triphenylborane for the hydrocyanation of an unsaturated nitrile compound.
- Constant research is undertaken to improve the performance of the synthesis of nitriles by hydrocyanation, either by development of new catalytic systems, or by modification of the reaction conditions and compositions of the hydrocyanation medium.
- US Pat. No. 6,169,198 describes the use of new metallocene-phosphorus type ligands.
- US Pat. No. 5,773,637 describes the use, as Lewis acid, of the perfluoroalkylsulfonate compounds.
- One of the aims of the present invention is to propose a new process for the manufacture of nitriles by hydrocyanation of an olefin by reaction with hydrogen cyanide, making it possible to obtain high yields and selectivities of linear nitriles as well as system stability. improved catalytic.
- the invention provides a process for manufacturing organic compounds comprising at least one nitrile function by implementing a hydrocyanation reaction between hydrogen cyanide and an organic compound comprising at least one ethylenic unsaturation.
- This last compound will be called for more than simplicity in the present invention, an olefin or poiyolefin when it comprises several ethylenic unsaturations.
- organic compounds suitable for the invention should not be interpreted as a limitation of the organic compounds suitable for the invention to hydrocarbons, but it also relates to organic compounds comprising at least one ethylenic unsaturation, and which may comprise atoms other than carbon and hydrogen or mixtures of hydrocarbons such as the mixture obtained by distillation of petroleum called in the field of hydrocarbons cut C4.
- This cut is advantageously treated to remove or transform the impurities such as the compounds comprising an acetylenic unsaturation, for example by hydrogenation as described in US Pat. No. 6,197,992.
- olefin within the meaning of the present invention, a compound comprising an unsaturation and a nitrile function such as for example the unsaturated nitrile compounds obtained by the reaction of HCN on a polyolefin.
- the reaction is carried out in the presence of a catalytic system comprising a metallic element chosen from the group comprising nickel, platinum, palladium and an organophosphorus ligand, the reaction medium comprising, in addition an ionic liquid at least in the liquid state at the temperature for carrying out the hydrocyanation reaction.
- a catalytic system comprising a metallic element chosen from the group comprising nickel, platinum, palladium and an organophosphorus ligand, the reaction medium comprising, in addition an ionic liquid at least in the liquid state at the temperature for carrying out the hydrocyanation reaction.
- the ionic liquid and the compound to be hydrocyanated are completely miscible, at least at the reaction temperature.
- the hydrocyanation reaction is carried out in a homogeneous or monophasic medium.
- the ionic liquid and the compound to be hydrocyanated are not or only partially miscible at the reaction temperature.
- the reaction is carried out in a non-homogeneous or biphasic medium.
- the catalytic system is advantageously soluble in the ionic liquid.
- slightly polar solvent can be added at the start of the reaction, but also can be used only after the end of the reaction to thus promote the separation of hydrocyanated products and ionic liquid in particular to allow the extraction of the catalytic system.
- the function of the slightly polar solvent is to render the ionic liquid insoluble in the phase constituted by said solvent, the untransformed olefin and the nitrile compounds formed.
- the catalytic system is at least partially miscible in the ionic liquid.
- this miscibility can be obtained by the presence of at least one ionizable group in the molecule of the organophosphorus ligand.
- ionizable groups mention may be made of anionic type groups such as sulfonate, sulfinate, phosphonate, phosphinate, carboxylate, sulfinate, or cationic type such as guanidinium, ammonium, pyridinium, imidazolium, phosphonium, sulfonium, for example.
- the number and the nature of these ionic groups are preferably chosen to obtain a solubility of the ligand in the ionic liquid. It may be advantageous for the nature of the ionizable group to be identical to that of the anion or of the cation associated with the ionic liquid.
- the catalytic systems suitable for the invention are those which preferably comprise the element nickel in the zero oxidation state or a complex with organophosphorus ligands which can comprise several ionizable groups described above or more generally the compounds containing phosphorus capable of giving a coordination compound with the transition metals and more particularly the catalytic metals mentioned above, in particular with nickel.
- These compounds can be mono, bi or polydentate and have a hydrophobic or hydrophilic character.
- organic phosphorus compounds suitable for the invention mention may be made of alkylphosphines, aryiphosphines, alkylarylphosphines, alkylphosphites, arylphosphites, alkylarylphosphites, alkyiphosphinites, arylphosphinites, alkylarylphosphinites, alkyiphosphonites, arylphosphonites, alkylarylphosphonites, the organic half of which is preferably up to 36 carbon atoms, substituted by one or more ionic groups described above.
- Examples of compounds that may be mentioned are tributylphosphine, dimethyl-n-octylphosphine, tricyclohexylphosphine, triphenylphosphine, tolylphosphine, tris (p-methoxyphenyl) phosphine, diphenylethylphosphine, dimethylphenylphosphine, 1, 4-phenyl-diphenyl , triethylphosphite, diphenylphosphite, said compounds preferably comprising at least one ionic group described above.
- the catalyst can be prepared before its introduction into the medium, ie in situ.
- the metals forming the catalytic element such as nickel, which are added in a medium in which the organophosphorus ligand is also soluble.
- a medium may be the ionic liquid.
- the catalytic system thus formed is added to the hydrocyanation medium.
- the preferred compounds are those of nickel, there may be mentioned as non-limiting examples:
- nickel at zero oxidation state
- potassium tetracyanonickelate K4 [Ni (CN) 4] bis (acrylonitrile) zero nickel, bis (cyclooctadiene-1, 5) 2 nickel and derivatives containing Group Va ligands such as tetrakis (triphenylphosphine) zero nickel
- CN CN
- Group Va ligands such as tetrakis (triphenylphosphine) zero nickel
- nickel compounds with a degree of oxidation greater than zero such as carboxylates (in particular acetate), carbonate, bicarbonate, borate, bromide, chloride, citrate, thiocyanate, cyanide, formate, hydroxide, hydrophosphite, phosphite, phosphate and derivatives , iodide, nitrate, sulfate, sulfite, aryl- and alkyl-sulfonates, allyl, acetylacetonate.
- the nickel compound itself it is not necessary for the nickel compound itself to be soluble in the preparation medium such as the ionic liquid. Indeed, it is sufficient that the complex is soluble, that is to say that the solubilization of nickel occurs during the addition of the ligand in the ionic liquid.
- a reducing agent for nickel reacting preferentially with the latter under the reaction conditions is added to the reaction medium.
- This reducing agent can be organic or mineral or hydrogen.
- This reducing agent is added in an amount such that the number of redox equivalents is between 1 and 10. However, values less than 1 and greater than 10 are not excluded.
- the nickel compound used corresponds to the oxidation state 0 of nickel, it is also possible to add a reducing agent of the type of those mentioned above, but this addition is not imperative.
- the same reducers are suitable.
- the reducing agents can also be elements of the reaction medium (phosphine, solvent, olefin).
- the reaction medium comprises an ionic liquid.
- This ionic liquid is an ionic compound whose cation is of onium type having at least one heteroatom such as N, P, S carrying the positive charge in conjugation with an aromatic cycle with 5 or 6 elements and an anion.
- Such compounds are for example described in the article by Yves Chauvin and Hélène Olivier - Bourbigou entitled "Non aqueous ionic liquids as reaction solvents" published in Chemtech 12, 1995, p 66, the article by T. Welton published in Chem. Rev. 1999, p 2071 or patents such as patent Ep 971 854.
- the ionic liquid comprises at least one cation chosen from the group comprising the structures tetraalkylammonium, N-alkylimidazolium, N-alkylpyridinium, N- aikylpicolinium, N-alkyltriazolium, N- alkylfluoropyrazolium, N-pyrrolidinium, alkylsulfonium, tetraalkylphosphonium, alkyloxonium.
- aikylimidazoliums such as 1,3-dimethylimidazolium, 1-butyl-2,3-dimethyl imidazolium, 1-butyl-3-methylimidazolium or 1,2, 3-triméthylimidazoiium.
- an anion chosen from halides, nitrate, phosphate, hydrosulfate, perfluoroalkyisulfonates, bis (perfluoroalkylsulfonyl) amides, bis (fluorosulfonyl) amide, bis (fluorophosphoryl ) amide, tris (perfluoroalkylsulfonyl) methylides, boron, aluminum, gallium, iron tetrahalides, phosphorus, arsenic and antimony hexahalides, zinc and tin trihalides, dihalides copper.
- Preferred anions of the invention are Br “f, BF” 4, PF "6, SbF 6", IAAH 4l ZnCl "3,
- the ionic liquid to be suitable with the process of the invention must be at least in the liquid state at the temperature for carrying out the hydrocyanation reaction.
- ionic liquids which are in the liquid state at a temperature below 100 ° C. are preferred because they allow better separation and extraction of the catalyst from the reaction medium in the case of a two-phase system.
- the ionic liquid which becomes miscible or at least partially miscible in the reaction medium only at the temperature of the implementation of the hydrocyanation reaction, or in the vicinity thereof, is entirely compatible for carrying out the invention.
- the immiscibility of the ionic liquid is preferably obtained by adding a slightly polar solvent to the reaction medium.
- This solvent dissolves the olefins to be hydrocyanated as well as the nitriles produced and makes the ionic liquid insoluble in the olefins and nitriles produced.
- slightly polar solvent mention may be made of saturated hydrocarbons such as hexane, heptane, octane, toluene, ethers such as diethyl ether, diisopropyl ether, methylisobutyl ether.
- the quantity used of nickel compound or of another transition metal is chosen to obtain a concentration in mole of transition metal per mole of organic compounds to be hydrocyanated or isomerized between 10 ⁇ 4 and 1, and preferably " between 0.005 and 0.5 mole of nickel or of the other transition metal used.
- the amount of ligand used to form the catalyst is chosen so that the number of moles of this compound, based on 1 mole of transition metal, is between 0.5 and 50 and preferably between 2 and 10.
- the hydrocyanation reaction is generally carried out at a temperature between 10 ° C and 200 ° C and preferably between 30 ° C and 120 ° C.
- the process of the invention can be carried out continuously or discontinuously.
- the hydrogen cyanide used can be prepared from metallic cyanides, in particular sodium cyanide, or cyanhydrins, such as acetone cyanohydrin or by any other known synthesis process.
- the hydrogen cyanide is introduced into the reactor in gaseous form or in liquid form. It can also be previously dissolved in an organic solvent.
- an inert gas such as nitrogen, argon
- the reactor is then brought to the chosen temperature, then the compound to be hydrocyanated is introduced.
- the hydrogen cyanide is then itself introduced, preferably continuously and regularly.
- the reaction mixture is withdrawn after cooling and the reaction products are isolated, for example, by separation of the phase containing the catalytic system and of the phase formed by the weakly or non-polar solvent, the hydrocyanated products and those which have not been transformed in the case of a two-phase system.
- the products of this last phase can be separated by distillation, for example.
- other separation means can be used such as, for example, distillation, liquid / liquid extraction.
- the product to be hydrocyanated is an unsaturated compound comprising a nitrile function, it is advantageous to use with the catalytic system a cocatalyst consisting of at least one Lewis acid.
- This reaction consists in particular in converting the ethylenically unsaturated aliphatic nitriles, in particular the linear pentenenitriles such as pentene-3-nitrile, pentene-4-nitrile and their mixtures obtained by hydrocyanation of butadiene into dinitriles more precisely into adiponitrile.
- linear pentenenitriles such as pentene-3-nitrile, pentene-4-nitrile and their mixtures obtained by hydrocyanation of butadiene into dinitriles more precisely into adiponitrile.
- pentenenitriles may contain quantities, generally in the minority, of other compounds, such as methyl-2-butene-3-nitrite, methyl-2-butene-2-nitrile, pentene-2-nitrile, valeronitria, adiponitrile, methyl-2-glutaronitrile, ethyl-2-succinonitrile or butadiene, originating from the previous hydrocyanation reaction of butadiene and or from the isomerization of methyl-2-butene-3-nitrile into pentenenitriles.
- other compounds such as methyl-2-butene-3-nitrite, methyl-2-butene-2-nitrile, pentene-2-nitrile, valeronitria, adiponitrile, methyl-2-glutaronitrile, ethyl-2-succinonitrile or butadiene, originating from the previous hydrocyanation reaction of butadiene and or from the isomerization of methyl-2-butene
- the Lewis acid used as cocatalyst allows in particular, in the case of the hydrocyanation of aliphatic nitriles with ethylenic unsaturation, to improve the linearity of the dinitriies obtained, that is to say the percentage of linear dinitriles relative to the all of the dinitriles formed, and / or to increase the activity and the lifetime of the catalyst.
- Lewis acid is meant in the present text, according to the usual definition, compounds that accept electronic doublets. It is possible to use in particular the Lewis acids cited in the work edited by G.A. OLAH "Friedel-Crafts and related Reactions", volume I, pages 191 to 197 (1963).
- the Lewis acids which can be used as cocatalysts in the present process are chosen from the compounds of the elements of groups Ib, llb, llla, lllb, IVa, IVb, Va, Vb, Vlb, Vllb and VIII of the periodic table elements.
- halides such as chlorides or bromides
- Lewis acids By way of nonlimiting examples of such Lewis acids, mention may be made of zinc chloride, zinc bromide, zinc iodide, manganese chloride, manganese bromide, cadmium chloride, bromide cadmium, stannous chloride, stannous bromide, stannous sulfate, stannous tartrate, indium trifluoromethylsulfonate, chlorides or bromides of rare earth elements like lanthanum, cerium, praseodymium, neodymium, samarium, l europium, gadolinium, terbium, dysprosium, hafnium, erbium, thallium, ytterbium and lutetium, cobalt chloride, ferrous chloride, yttrium chloride.
- rare earth elements like lanthanum, cerium, praseodymium, neodymium, samarium, l europium, gadolinium,
- Organometallic compounds such as triphenylborane and titanium diisopropylate can also be used as the Lewis acid. It is of course possible to use mixtures of several Lewis acids. Among the Lewis acids, zinc chloride, zinc bromide, stannous chloride, stannous bromide, triphenylborane and zinc chloride / stannous chloride mixtures are particularly preferred.
- a Lewis acid having an anion identical or of the same nature as the anion of the ionic liquid for example zinc chloride
- the ionic liquid comprises, as an anion ZnCI 3 , aluminum chloride when the anion of the ionic liquid is the AICI 4 anion
- the lanthanum tris (bistrifluoromethylsufonylamide) when the ionic medium consists of the bistrifluoromethylsulfonylamide anion
- the tri (trifluoromethylsuifonate) of neodymium when the ion of the ionic medium is the trifluoromethylsulfonate anion.
- We can also use an ionic liquid consisting of a mixture of polynuclear anions such as Pennion Zn 2 CI 5 " and ZnCI 3 " , or AI 2 C! 7 ' and AICI 4 " .
- the Lewis acid will be provided by the anion of the ionic liquid. This ionic liquid itself brings the cocatalysis effect into the medium.
- the Lewis acid cocatalyst used generally represents from 0.01 to 50 mole per mole of transition metal compound, more particularly of nickel compound, and preferably from 1 to 10 mole per mole.
- methyl-2-butene-3-nitrile subjected to the isomerization according to the invention can be used alone or as a mixture with other compounds.
- methyl-2-butene-3-nitrile can be used in admixture with methyl-2-butene-2-nitrile, pentene-4-nitrile, pentene-3-nitriie, pentene-2-nitrile, butadiene, adiponitrile, methyl-2-glutaroronitrile, rethyl-2-succinonitriie or vaiéronitriie.
- the isomerization reaction is generally carried out at a temperature of 10 ° C to 200 ° C and preferably from 60 ° C to 120 ° C.
- the catalytic system used for isomerization can be prepared before its introduction into the reaction zone. It is also possible to prepare the catalytic system "in situ" by simple mixing of these various constituents.
- the amount of compound of the transition metal and more particularly of nickel used, as well as the amount of ligand are the same as for the hydrocyanation reaction.
- the preparation of dinitrile compounds by hydrocyanation of an olefin such as butadiene can be carried out using a reaction system in accordance with the invention for the stages of formation of the unsaturated nitriles and the stage of isomerization above, the reaction hydrocyanation of the nitriles unsaturated into dinitriles which can be used with a reaction system according to the invention or any other catalytic system already known for this reaction.
- the hydrocyanation reaction of the olefin to unsaturated nitriles and the isomerization of these can be carried out with a reaction system different from that of the invention, the step of hydrocyanation of the unsaturated nitriles into dinitriles being implemented with a reaction system according to the invention.
- 3PN 3-pentenenitrile.
- 4PN 4-pentenenitrile.
- ESN ethylsuccinonitrile TT (Y): transformation rate of the product to be hydrocyanated Y corresponding to the ratio of the number of transformed moles of Y to the number of initial moles of Y.
- RR (X) actual yield of compound X corresponding to the ratio of the number of moles formed from X to the maximum number of moles of X.
- RT (X) selectivity of compound X corresponding to the ratio of RR (X) to TT (Y).
- L Linearity: RT A dN RTDN
- the starting materials include 2M3BN and other products.
- the molar formulation of these products is given in Table I below (the main components are indicated).
- the tube is closed with a stopper provided with a septum.
- the reaction mixture is stirred and heated at 70 ° C for 3 hours, during which time the acetone cyanohydrin is slowly added (flow rate 0.12 ml / h, 0.36 ml, 3.95 mmol, 27 equivalents).
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Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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FR0112040 | 2001-09-18 | ||
FR0112040A FR2829763B1 (fr) | 2001-09-18 | 2001-09-18 | Procede de fabrication de composes nitriles |
PCT/FR2002/003166 WO2003024919A1 (fr) | 2001-09-18 | 2002-09-17 | Procede de fabrication de composes nitriles |
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EP1427695A1 true EP1427695A1 (fr) | 2004-06-16 |
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EP02779637A Withdrawn EP1427695A1 (fr) | 2001-09-18 | 2002-09-17 | Procede de fabrication de composes nitriles |
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Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
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US7880028B2 (en) | 2006-07-14 | 2011-02-01 | Invista North America S.A R.L. | Process for making 3-pentenenitrile by hydrocyanation of butadiene |
US7897801B2 (en) | 2003-05-12 | 2011-03-01 | Invista North America S.A R.L. | Process for the preparation of dinitriles |
US7919646B2 (en) | 2006-07-14 | 2011-04-05 | Invista North America S.A R.L. | Hydrocyanation of 2-pentenenitrile |
US7973174B2 (en) | 2005-10-18 | 2011-07-05 | Invista North America S.A.R.L. | Process of making 3-aminopentanenitrile |
US7977502B2 (en) | 2008-01-15 | 2011-07-12 | Invista North America S.A R.L. | Process for making and refining 3-pentenenitrile, and for refining 2-methyl-3-butenenitrile |
US8088943B2 (en) | 2008-01-15 | 2012-01-03 | Invista North America S.A R.L. | Hydrocyanation of pentenenitriles |
US8101790B2 (en) | 2007-06-13 | 2012-01-24 | Invista North America S.A.R.L. | Process for improving adiponitrile quality |
US8178711B2 (en) | 2006-03-17 | 2012-05-15 | Invista North America S.A R.L. | Method for the purification of triorganophosphites by treatment with a basic additive |
US8247621B2 (en) | 2008-10-14 | 2012-08-21 | Invista North America S.A.R.L. | Process for making 2-secondary-alkyl-4,5-di-(normal-alkyl)phenols |
US8338636B2 (en) | 2009-08-07 | 2012-12-25 | Invista North America S.A R.L. | Hydrogenation and esterification to form diesters |
US8373001B2 (en) | 2003-02-10 | 2013-02-12 | Invista North America S.A R.L. | Method of producing dinitrile compounds |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2829763B1 (fr) | 2001-09-18 | 2004-12-03 | Rhodia Polyamide Intermediates | Procede de fabrication de composes nitriles |
PL1658268T3 (pl) * | 2003-07-17 | 2014-07-31 | Novartis Ag | Mieszaniny cieczy jonowych z kwasami Lewisa |
CN101687658B (zh) | 2007-05-14 | 2013-07-24 | 因温斯特技术公司 | 高效反应器和方法 |
FR2926549B1 (fr) * | 2008-01-18 | 2015-05-01 | Rhodia Operations | Procede de fabrication de composes nitriles |
FR2928910B1 (fr) * | 2008-03-20 | 2010-03-12 | Arkema France | Procede ameliore de production d'acide cyanhydrique |
FR2932476B1 (fr) * | 2008-06-17 | 2010-07-30 | Rhodia Operations | Procede de fabrication de composes nitriles a partir de composes a insaturation ethylenique |
CN102786449A (zh) * | 2008-12-05 | 2012-11-21 | 华中科技大学 | 一种由全氟烷基磺酰亚胺碱金属盐合成的离子液体 |
US11267707B2 (en) | 2019-04-16 | 2022-03-08 | Honeywell International Inc | Purification of bis(fluorosulfonyl) imide |
CN115433103B (zh) * | 2022-10-09 | 2023-08-18 | 山东新和成维生素有限公司 | 一种异佛尔酮腈的合成方法 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
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FR2338253A1 (fr) | 1976-01-13 | 1977-08-12 | Rhone Poulenc Ind | Procede d'hydrocyanation de composes organiques insatures comportant au moins une double liaison ethylenique |
FR2711987B1 (fr) * | 1993-11-03 | 1995-12-15 | Rhone Poulenc Chimie | Procédé d'hydrocyanation de nitriles insaturés en dinitriles. |
FR2739378B1 (fr) * | 1995-09-29 | 1997-10-31 | Rhone Poulenc Fibres | Procede d'hydrocyanation de composes organiques a insaturation ethylenique |
DE19652273A1 (de) * | 1996-12-16 | 1998-06-18 | Basf Ag | Monoolefinische C¶5¶-Mononitrile, Verfahren zu ihrer Herstellung und ihre Verwendung |
AU2165000A (en) * | 1998-12-04 | 2000-06-19 | Symyx Technologies, Inc. | Combinatorial discovery and testing of ionic liquids |
FR2787446B1 (fr) * | 1998-12-22 | 2001-02-02 | Rhone Poulenc Fibres | Procede d'hydrocyanation de composes organiques a insaturations ethyleniques |
DE10206697A1 (de) * | 2001-02-19 | 2002-08-29 | Basf Ag | Hydroformylierungsverfahren |
FR2829763B1 (fr) | 2001-09-18 | 2004-12-03 | Rhodia Polyamide Intermediates | Procede de fabrication de composes nitriles |
-
2001
- 2001-09-18 FR FR0112040A patent/FR2829763B1/fr not_active Expired - Fee Related
-
2002
- 2002-09-17 WO PCT/FR2002/003166 patent/WO2003024919A1/fr active Application Filing
- 2002-09-17 KR KR10-2004-7003992A patent/KR20040068537A/ko not_active Ceased
- 2002-09-17 EP EP02779637A patent/EP1427695A1/fr not_active Withdrawn
- 2002-09-17 RU RU2004111655/04A patent/RU2265591C2/ru not_active IP Right Cessation
- 2002-09-17 JP JP2003528767A patent/JP4166155B2/ja not_active Expired - Fee Related
- 2002-09-17 CN CNB028198514A patent/CN100455562C/zh not_active Expired - Fee Related
- 2002-09-17 US US10/489,838 patent/US20040260112A1/en not_active Abandoned
-
2008
- 2008-10-02 US US12/244,233 patent/US8039660B2/en not_active Expired - Fee Related
Non-Patent Citations (1)
Title |
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See references of WO03024919A1 * |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8373001B2 (en) | 2003-02-10 | 2013-02-12 | Invista North America S.A R.L. | Method of producing dinitrile compounds |
US7897801B2 (en) | 2003-05-12 | 2011-03-01 | Invista North America S.A R.L. | Process for the preparation of dinitriles |
US7973174B2 (en) | 2005-10-18 | 2011-07-05 | Invista North America S.A.R.L. | Process of making 3-aminopentanenitrile |
US8178711B2 (en) | 2006-03-17 | 2012-05-15 | Invista North America S.A R.L. | Method for the purification of triorganophosphites by treatment with a basic additive |
US7880028B2 (en) | 2006-07-14 | 2011-02-01 | Invista North America S.A R.L. | Process for making 3-pentenenitrile by hydrocyanation of butadiene |
US7919646B2 (en) | 2006-07-14 | 2011-04-05 | Invista North America S.A R.L. | Hydrocyanation of 2-pentenenitrile |
US8394981B2 (en) | 2006-07-14 | 2013-03-12 | Invista North America S.A R.L. | Hydrocyanation of 2-pentenenitrile |
US8101790B2 (en) | 2007-06-13 | 2012-01-24 | Invista North America S.A.R.L. | Process for improving adiponitrile quality |
US7977502B2 (en) | 2008-01-15 | 2011-07-12 | Invista North America S.A R.L. | Process for making and refining 3-pentenenitrile, and for refining 2-methyl-3-butenenitrile |
US8088943B2 (en) | 2008-01-15 | 2012-01-03 | Invista North America S.A R.L. | Hydrocyanation of pentenenitriles |
US8247621B2 (en) | 2008-10-14 | 2012-08-21 | Invista North America S.A.R.L. | Process for making 2-secondary-alkyl-4,5-di-(normal-alkyl)phenols |
US8338636B2 (en) | 2009-08-07 | 2012-12-25 | Invista North America S.A R.L. | Hydrogenation and esterification to form diesters |
Also Published As
Publication number | Publication date |
---|---|
JP4166155B2 (ja) | 2008-10-15 |
US20090247780A1 (en) | 2009-10-01 |
FR2829763B1 (fr) | 2004-12-03 |
RU2004111655A (ru) | 2005-04-10 |
KR20040068537A (ko) | 2004-07-31 |
CN100455562C (zh) | 2009-01-28 |
FR2829763A1 (fr) | 2003-03-21 |
JP2005503410A (ja) | 2005-02-03 |
US20040260112A1 (en) | 2004-12-23 |
RU2265591C2 (ru) | 2005-12-10 |
US8039660B2 (en) | 2011-10-18 |
CN1564807A (zh) | 2005-01-12 |
WO2003024919A1 (fr) | 2003-03-27 |
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