EP1713761A1 - Verfahren zur hydrocyanierung - Google Patents
Verfahren zur hydrocyanierungInfo
- Publication number
- EP1713761A1 EP1713761A1 EP05707006A EP05707006A EP1713761A1 EP 1713761 A1 EP1713761 A1 EP 1713761A1 EP 05707006 A EP05707006 A EP 05707006A EP 05707006 A EP05707006 A EP 05707006A EP 1713761 A1 EP1713761 A1 EP 1713761A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- butadiene
- hydrocyanation
- tolyl
- hydrogen cyanide
- phenyl
- 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- Withdrawn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
- 238000005669 hydrocyanation reaction Methods 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 39
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 116
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 239000007787 solid Substances 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- UVKXJAUUKPDDNW-NSCUHMNNSA-N (e)-pent-3-enenitrile Chemical compound C\C=C\CC#N UVKXJAUUKPDDNW-NSCUHMNNSA-N 0.000 claims abstract description 12
- CFEYBLWMNFZOPB-UHFFFAOYSA-N Allylacetonitrile Natural products C=CCCC#N CFEYBLWMNFZOPB-UHFFFAOYSA-N 0.000 claims abstract description 12
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 claims description 60
- 239000002808 molecular sieve Substances 0.000 claims description 13
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000003570 air Substances 0.000 claims description 3
- 229910052756 noble gas Inorganic materials 0.000 claims description 3
- 150000002835 noble gases Chemical class 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- -1 aromatic alcohols Chemical class 0.000 description 89
- 150000001875 compounds Chemical class 0.000 description 44
- 229910052698 phosphorus Inorganic materials 0.000 description 36
- 125000003118 aryl group Chemical group 0.000 description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 19
- 229910052760 oxygen Inorganic materials 0.000 description 19
- 239000001301 oxygen Substances 0.000 description 19
- 125000004437 phosphorous atom Chemical group 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 17
- 239000000203 mixture Substances 0.000 description 17
- 239000011574 phosphorus Substances 0.000 description 17
- 239000003446 ligand Substances 0.000 description 15
- 150000003254 radicals Chemical class 0.000 description 13
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 12
- 125000004430 oxygen atom Chemical group O* 0.000 description 12
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 12
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 9
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 6
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical class [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 description 6
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical class OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 6
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 6
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 5
- 239000012267 brine Substances 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 229910052740 iodine Inorganic materials 0.000 description 5
- HCBPHBQMSDVIPZ-UHFFFAOYSA-N methylcyclohexatriene Chemical compound CC1=CC=C=C[CH]1 HCBPHBQMSDVIPZ-UHFFFAOYSA-N 0.000 description 5
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 5
- 125000005538 phosphinite group Chemical group 0.000 description 5
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 5
- IQNYBCIGGNQJDL-UHFFFAOYSA-N (4-methylphenyl) dihydrogen phosphite Chemical compound CC1=CC=C(OP(O)O)C=C1 IQNYBCIGGNQJDL-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 4
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 4
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 4
- ISBHMJZRKAFTGE-UHFFFAOYSA-N pent-2-enenitrile Chemical compound CCC=CC#N ISBHMJZRKAFTGE-UHFFFAOYSA-N 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 239000013522 chelant Substances 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 238000004141 dimensional analysis Methods 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 238000006317 isomerization reaction Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 3
- FEVFLQDDNUQKRY-UHFFFAOYSA-N tris(4-methylphenyl) phosphite Chemical compound C1=CC(C)=CC=C1OP(OC=1C=CC(C)=CC=1)OC1=CC=C(C)C=C1 FEVFLQDDNUQKRY-UHFFFAOYSA-N 0.000 description 3
- 230000007306 turnover Effects 0.000 description 3
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 2
- WBAXCOMEMKANRN-UHFFFAOYSA-N 2-methylbut-3-enenitrile Chemical compound C=CC(C)C#N WBAXCOMEMKANRN-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 2
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 2
- 150000005840 aryl radicals Chemical class 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- VHYAIWZUUQSEGU-UHFFFAOYSA-N methylcyclohexatriene Chemical compound CC1=C=CC=C[CH]1 VHYAIWZUUQSEGU-UHFFFAOYSA-N 0.000 description 2
- 150000003003 phosphines Chemical class 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-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
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- ZHZZWIQPCAMTIM-UHFFFAOYSA-N [C]1=CC=CC2=CC=CC=C12 Chemical compound [C]1=CC=CC2=CC=CC=C12 ZHZZWIQPCAMTIM-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001896 cresols Chemical class 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 150000002909 rare earth metal compounds Chemical class 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
- 239000008096 xylene Substances 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
- C07C255/00—Carboxylic acid nitriles
- C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
- C07C255/06—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms of an acyclic and unsaturated carbon skeleton
- C07C255/07—Mononitriles
Definitions
- the present invention relates to a process for the preparation of 3-pentenenitrile by hydrocyanation of 1,3-butadiene with hydrogen cyanide over at least one catalyst.
- Adiponitrile is an important starting product in nylon production, which is obtained by double hydrocyanation of 1,3-butadiene.
- 1,3-butadiene is hydrocyanated to 3-pentenenitrile.
- 3-pentenenitrile is reacted with hydrogen cyanide to give adiponitrile. Both hydrocyanations are catalyzed by nickel (0) -phosphorus complexes.
- the nickel (0) -phosphorus complexes used in the hydrocyanation of 1,3-butadiene are sensitive to protic compounds such as water, aliphatic or aromatic alcohols. Since 1,3-butadiene or hydrogen cyanide generally contain water and tert-butyl catechol (stabilizer of 1,3-butadiene), the nickel (0) -phosphorus complexes have a limited service life.
- No. 3,852,329 describes a process for the isomerization of 2-methyl-3-butenenitrile over a nickel (0) -phosphorus complex as a catalyst to 3-pentenenitrile. 2-Methyl-3-butenenitrile or the catalyst is brought into contact with a molecular sieve before the actual isomerization. According to US 3,852,329, it is also possible to carry out the isomerization directly in the presence of a molecular sieve.
- No. 3,846,474 describes a process for the hydrocyanation of 3-pentenenitrile over a nickel (0) -phosphorus catalyst.
- 3-pentenenitrile is brought into contact with a molecular sieve before the hydrocyanation.
- the molecular sieve is used during the hydrocyanation or that the catalyst solution is treated with a molecular sieve before it is used in the hydrocyanation.
- the object of the present invention is therefore to provide a process for the preparation of 3-pentenenitrile by hydrocyanation of 1,3-butadiene with hydrogen cyanide over at least one catalyst, the catalyst used in the process having a long service life.
- the solution to this problem according to the invention is based on a process for the preparation of 3-pentenenitrile by hydrocyanation of 1,3-butadiene with cyanide. hydrogen on at least one catalyst.
- the process according to the invention is then characterized in a first embodiment in that 1,3-butadiene and / or hydrogen cyanide are brought into contact with at least one microporous solid before the reaction.
- the 1,3-butadiene used in the hydrocyanation may contain water due to the manufacturing process.
- 1,3-butadiene is usually stored and transported with stabilizers.
- stabilizers For example, tert-butyl catechol (TBC) is used as a stabilizer.
- the contact time of 1,3-butadiene with the at least one microporous solid increases the service life of the nickel (O) phosphorus catalyst.
- the effect of the increased service life of the catalyst on the removal of water and the stabilizer tert-butyl catechol is attributed.
- the 1,3-butadiene and the hydrogen cyanide can be brought into contact with the at least one microporous solid together or separately. It is preferred that the 1,3-butadiene and / or the hydrogen cyanide are freed from the at least one microporous solid before the actual hydrocyanation with the at least one catalyst.
- the 1, 3-butadiene and / or the cyanohydrogen are brought into contact in pipes with beds, the flow conditions of 1,3-butadiene and / or hydrogen cyanide being selected such that a plug-flow characteristic, ie. H. a flow is generated across the cross-section without large radial speed differences, so that backmixing of the system is almost impossible.
- a plug-flow characteristic ie. H. a flow is generated across the cross-section without large radial speed differences
- the present invention relates to a process for the preparation of 3-pentenenitrile by hydrocyanating 1,3-butadiene with hydrogen cyanide with at least one catalyst, the process according to the invention being characterized in that the hydrocyanation takes place in the presence of the at least one microporous solid ,
- the phosphorus-containing ligands of the nickel (0) complexes and the free phosphorus-containing ligands are preferably selected from mono- or bidentate phosphines, phosphites, phosphinites and phosphonites.
- These phosphorus-containing ligands preferably have the formula I: P (X 1 R 1 ) (X 2 R 2 ) (X 3 R 3 ) (I)
- compound I is understood to mean a single compound or a mixture of different compounds of the aforementioned formula.
- X 1 , X 2 , X 3 are independently oxygen or a single bond. If all of the groups X 1 , X 2 and X 3 are individual bonds, compound I is a phosphine of the formula P (R 1 R 2 R 3 ) with the meanings given for R 1 , R 2 and R 3 in this description ,
- compound I is a phosphinite of the formula P (OR 1 ) (R 2 ) (R 3 ) or P (R 1 ) (OR 2 ) (R 3 ) or P (R 1 ) (R 2 ) (OR 3 ) with the meanings given below for R 2 and R 3 .
- compound I represents a phosphonite of the formula P (OR 1 ) (OR 2 ) (R 3 ) or P (R 1 ) (OR 2 ) (OR 3 ) or P (OR 1 ) (R 2 ) (OR 3 ) with the meanings given for R 2 and R 3 in this description.
- all of the groups X 1 , X 2 and X 3 should stand for oxygen, so that compound I is advantageously a phosphite of the formula P (OR 1 ) (OR 2 ) (OR 3 ) with those for R 1 , R 2 and R 3 represents meanings mentioned below.
- R 1 , R 2 , R 3 independently of one another represent identical or different organic radicals.
- R 1 , R 2 and R 3 are, independently of one another, alkyl radicals, preferably having 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, Aryl groups, such as phenyl, o-tolyl, m-tolyl, p-tolyl, 1-naphthyl, 2-naphthyl, or hydrocarbyl, preferably with 1 to 20 carbon atoms, such as 1,1-biphenol, 1,1 ' -Binaphthol into consideration.
- the groups R 1 , R 2 and R 3 can be directly connected to one another, i.e. not only via the central phosphorus atom.
- the groups R 1 , R 2 and R 3 are
- groups R 1 , R 2 and R 3 are selected from the group consisting of phenyl, o-tolyl, m-tolyl and p-tolyl. In a particularly preferred embodiment, a maximum of two of the groups R 1 , R 2 and R 3 should be phenyl groups.
- a maximum of two of the groups R 1 , R 2 and R 3 should be o-tolyl groups.
- Particularly preferred compounds I are those of the formula I a (o-tolyl-O-) w (m-tolyl-O-) x (p-tolyl-O-) y (phenyl-O-) z P (I a)
- Such compounds I a are, for example, (p-tolyl-O -) (phenyl-O-) 2 P, (m-tolyl-O -) (phenyl-O-) 2 P, (o-tolyl-O-) (phenyl -O-) 2 P, (p-tolyl-O-) 2 (phenyl-O-) P, (m-tolyl-O-) 2 (phenyl-O-) P, (o-tolyl-O-) 2 (Phenyl-O-) P, (m-tolyl-O -) (p-tolyl-O) (phenyl-O-) P, (o-tolyl-O -) (p-tolyl-O -) (phenyl- O-) P, (o-tolyl-O -) (m-tolyl-O -) (phenyl-O-) P, (p-tolyl-O-) 3 P, (m-tolyl-
- Mixtures containing (m-tolyl-O-) 3 P, (m-tolyl-O-) 2 (p-tolyl-O-) P, (m-tolyl-O -) (p-tolyl-O-) 2 P and (p-tolyl-O-) 3 P can be obtained, for example, by reacting a mixture containing m-cresol and p-cresol, in particular in a molar ratio of 2: 1, as is obtained in the working up of petroleum by distillation, with a phosphorus trihalide, such as phosphorus trichloride , receive.
- a phosphorus trihalide such as phosphorus trichloride
- phosphites of the formula Ib described in more detail in DE-A 19953058 are suitable as phosphorus-containing ligands:
- R 1 aromatic radical with a C 8 -C 8 alkyl substituent in the o-position to the oxygen atom that connects the phosphorus atom to the aromatic system, or with an aromatic substituent in the o-position to the oxygen atom that connects the phosphorus atom to the aromatic system , or with an aromatic system fused in the o-position to the oxygen atom, which connects the phosphorus atom with the aromatic system,
- R 2 aromatic radical with a CC 18 alkyl substituent in the m-position to the oxygen atom which connects the phosphorus atom to the aromatic system, or with an aromatic substituent in the m-position to the oxygen atom which connects the phosphorus atom to the aromatic system, or with an aromatic system fused in the m-position to the oxygen atom which connects the phosphorus atom to the aromatic system, the aromatic radical in the o-position to the oxygen atom which connects the phosphorus atom to the aromatic system carries a hydrogen atom .
- R 3 aromatic radical with a CrCi ⁇ alkyl substituent in the p-position to the oxygen atom that connects the phosphorus atom to the aromatic system, or with an aromatic substituent in the p-position to the oxygen atom that connects the phosphorus atom to the aromatic system, wherein the aromatic radical in the o-position to the oxygen atom which connects the phosphorus atom to the aromatic system carries a hydrogen atom,
- R aromatic radical which, in the o-, m- and p-positions to the oxygen atom which connects the phosphorus atom to the aromatic system, bears other substituents than those defined for R 1 , R 2 and R 3 , the aromatic radical in o-position to the oxygen atom that connects the phosphorus atom to the aromatic system carries a hydrogen atom,
- the radical R 1 advantageously includes o-tolyl, o-ethyl-phenyl, on-propyl-phenyl, o-isopropyl-phenyl, on-butyl-phenyl, o-sec-butyl-phenyl, o- tert-Butyl-phenyl, (o-phenyl) -phenyl or 1-naphthyl groups into consideration.
- the radical R 2 is m-tolyl, m-ethyl-phenyl, mn-propyl-phenyl, m-isopropyl-phenyl, mn-butyl-phenyl, m-sec-butyl-phenyl, m-tert -Butyl-phe ⁇ yl-, (m-Pheny ⁇ ) -phenyl or 2-naphthyl groups preferred.
- the radical R 3 is advantageously p-tolyl, p-ethyl-phenyl, pn-propyl-phenyl, p-isopropyl-phenyl, pn-butyl-phenyl, p-sec-butyl-phenyl, p- tert-Butyl-phenyl or (p-phenyl) phenyl groups into consideration.
- R 4 is preferably phenyl.
- P is preferably zero.
- Preferred phosphites of the formula Ib are those in which p is zero and R 1 , R 2 and R 3 are selected independently of one another from o-isopropylphenyl, m-tolyl and p-tolyl, and R 4 is phenyl.
- Particularly preferred phosphites of the formula Ib are those in which R 1 is the o-isopropylphenyl radical, R 2 is the m-tolyl radical and R 3 is the p-tolyl radical with the indices mentioned in the table above; also those in which R 1 is the o-tolyl radical, R 2 is the m-tolyl radical and R 3 is the p-tolyl radical with the indices specified in the table; furthermore those in which R 1 is the 1-naphthyl radical, R 2 is the m-tolyl radical and R 3 is the p-tolyl radical with the indices specified in the table; also those in which R is the o-tolyl radical, R 2 is the 2-naphthyl radical and R 3 is the p-tolyl radical with the indices specified in the table; and finally those in which R 1 is the o-isopropylphenyl radical, R 2 is the 2-naphthyl radical
- Phosphites of formula I b can be obtained by a) reacting a phosphorus trihalide with an alcohol selected from the group consisting of R 1 OH, R 2 OH, R 3 OH and R 4 OH or mixtures thereof to give a dihalophosphoric acid monoester,
- the said dihalophosphoric acid monoester is reacted with an alcohol selected from the group consisting of R 1 OH, R 2 OH, R 3 OH and R 4 OH or mixtures thereof to give a monohalophosphoric acid diester and
- the implementation can be carried out in three separate steps. Two of the three steps can also be combined, i.e. a) with b) or b) with c). Alternatively, all of steps a), b) and c) can be combined with one another.
- Suitable parameters and amounts of the alcohols selected from the group consisting of R 1 OH, R 2 OH, R 3 OH and R 4 OH or their mixtures can easily be determined by a few simple preliminary tests.
- Suitable phosphorus trihalides are in principle all phosphorus trihalides, preferably those in which Cl, Br, I, in particular Cl, is used as the halide, and mixtures thereof. Mixtures of different identical or different halogen-substituted phosphines can also be used as the phosphorus trihalide. PCI 3 is particularly preferred. Further details on the reaction conditions in the preparation of the phosphites Ib and on the workup can be found in DE-A 199 53 058.
- the phosphites Ib can also be used as a ligand in the form of a mixture of different phosphites Ib. Such a mixture can occur, for example, in the production of the phosphites Ib.
- the phosphorus-containing ligand is multidentate, in particular bidentate.
- the ligand used therefore preferably has the formula II
- R 21 , R 22 independently of one another are identical or different, individual or bridged organic radicals,
- compound II is understood to mean a single compound or a mixture of different compounds of the abovementioned formula.
- X 11 , X 12 , X 13 , X 21 , X 22 , X 23 can represent oxygen.
- the bridge group Y is linked to phosphite groups.
- X 11 and X 12 oxygen and X 13 can be a single bond or X 11 and X 13 oxygen and X 12 can be a single bond, so that the phosphorus atom surrounded by X 11 , X 12 and X 13 is the central atom of a phosphonite.
- X 21 , X 22 and X 23 oxygen or X 21 and X 22 oxygen and X 23 a single bond or X 21 and X 23 oxygen and X 22 a single bond or X 23 oxygen and X 21 and X 22 a single bond or X 21 oxygen and X 22 and X 23 represent a single bond or X 21 , X 22 and X 23 represent a single bond, so that the phosphorus atom surrounded by X 21 , X 22 and X 23 preferably represents a phosphite, phosphonite, phosphinite or phosphine a phosphonite.
- X 13 oxygen and X 11 and X 12 can be a single bond or X 11 oxygen and X 12 and X 13 can be a single bond, so that the phosphorus atom surrounded by X 11 , X 12 and X 13 is a central atom
- Is phosphonite Is phosphonite.
- X 21 , X 22 and X 23 oxygen or X 23 oxygen and X 21 and X ⁇ a single bond or X 21 oxygen and X 22 and X 23 a single bond or X 21 , X 22 and X 23 a single bond , so that the phosphorus atom surrounded by X 21 , X 22 and X 23 can be the central atom of a phosphite, phosphinite or phosphine, preferably a phosphinite.
- X 11 , X 12 and X 13 can represent a single bond, so that the phosphorus atom surrounded by X 11 , X 12 and X 13 is the central atom of a phosphine.
- X 21 , X 22 and X 23 oxygen or X 21 , X 22 and X 23 represent a single bond, so that the phosphorus atom surrounded by X 21 , X 22 and X 23 is the central atom of a phosphite or phosphine, preferably a phosphine , can be.
- Suitable bridging groups Y are preferably substituted, for example with CC 4 -alkyl, halogen, such as fluorine, chlorine, bromine, halogenated alkyl, such as trifluoromethyl, aryl, such as phenyl, or unsubstituted aryl groups, preferably those having 6 to 20 carbon atoms in the aromatic system , in particular pyrocatechol, bis (phenol) or bis (naphthol).
- halogen such as fluorine, chlorine, bromine
- halogenated alkyl such as trifluoromethyl
- aryl such as phenyl
- unsubstituted aryl groups preferably those having 6 to 20 carbon atoms in the aromatic system , in particular pyrocatechol, bis (phenol) or bis (naphthol).
- R 11 and R 12 can independently represent the same or different organic radicals.
- R 11 and R 12 are advantageously aryl radicals, preferably those having 6 to 10 carbon atoms, which may be unsubstituted or mono- or polysubstituted, in particular by C 1 -C 4 -alkyl, halogen, such as fluorine, chlorine, bromine, halogenated alkyl such as trifluoromethyl, aryl such as phenyl or unsubstituted aryl groups.
- R 21 and R 22 can independently represent the same or different organic radicals.
- R 21 and R 22 are advantageously aryl radicals, preferably those having 6 to 10 carbon atoms, which may be unsubstituted or mono- or polysubstituted, in particular by CrC 4 -alkyl, halogen, such as fluorine, chlorine, bromine or halogenated alkyl , such as trifluoromethyl, aryl, such as phenyl, or unsubstituted aryl groups.
- the radicals R 11 and R 12 can be individually or bridged.
- the radicals R 21 and R 22 can also be individual or bridged.
- the radicals R 11 , R 12 , R 21 and R 22 can all be individually, two bridged and two individually or all four bridged in the manner described.
- the compounds of the formula I, II, III, IV and V mentioned in US Pat. No. 5,723,641 are suitable.
- the compounds of the formula I, II, III, IV, V, VI and VII mentioned in US Pat. No. 5,512,696, in particular the compounds used there in Examples 1 to 31, come into consideration.
- the compounds mentioned in US Pat. No. 6,127,567 and the compounds used there in Examples 1 to 29 are suitable.
- the compounds of the formula I, II, III, IV, V, VI, VII, VIII, IX and X mentioned in US Pat. No. 6,020,516, in particular the compounds used there in Examples 1 to 33 come into consideration.
- the compounds mentioned in US Pat. No. 5,959,135 and the compounds used there in Examples 1 to 13 are suitable.
- the compounds of the formula I, II and III mentioned in US Pat. No. 5,847,191 are suitable.
- the compounds mentioned in WO 98/27054 are suitable.
- the compounds mentioned in WO 99/13983 are suitable.
- the compounds mentioned in WO 99/64155 come into consideration.
- the compounds mentioned in German patent application DE 100 380 37 come into consideration.
- the compounds mentioned in German patent application DE 100460 25 come into consideration.
- the compounds mentioned in German patent application DE 101 50285 come into consideration.
- the compounds mentioned in German patent application DE 101 502 86 come into consideration.
- the compounds mentioned in German patent application DE 102 071 65 come into consideration.
- the phosphorus-containing chelate ligands mentioned in US 2003/0100442 A1 come into consideration.
- the phosphorus-containing chelate ligands mentioned in the unpublished German patent application file number DE 10350999.2 dated October 30, 2003 come into consideration.
- the compounds I, I a, I b and II described and their preparation are known per se. Mixtures containing at least two of the compounds I, I a, I b and II can also be used as the phosphorus-containing ligand.
- the phosphorus-containing ligand of the nickel (0) complex and / or the free phosphorus-containing ligand is selected from tritolylphosphite, bidentate phosphorus-containing chelate ligands, and the phosphites of the formula Ib
- the hydrocyanation according to the first and second embodiment can be carried out in any suitable device known to the person skilled in the art.
- Conventional apparatus such as that described, for example, in: Kirk-Othmer, Encyclopedia of Chemical Technology, 4th Ed. Vol. 20, John Wiley & Sons, New York 1996, pages 1040 to 1055, such as stirred tank reactors, loop reactors, gas circulation reactors, bubble column reactors or tubular reactors, each optionally with devices for dissipating heat of reaction.
- the reaction can be carried out in several, such as 2 or 3, apparatus.
- Reactors with backmixing characteristics or cascades of reactors with backmixing characteristics have proven to be advantageous.
- Cascades from reactors with backmixing characteristics have been found to operate in cross-flow mode in relation to the metering of hydrogen cyanide.
- the hydrocyanation can be carried out in batch mode, continuously or in semi-batch mode.
- the hydrocyanation is preferably carried out continuously in one or more stirred process steps. If a plurality of method steps are used, it is preferred that the method steps are connected in series.
- the product is transferred directly from one process step to the next process step.
- the hydrogen cyanide can be fed directly into the first process step or between the individual process steps.
- the catalyst components and 1,3-butadiene are introduced into the reactor while hydrogen cyanide is metered into the reaction mixture over the reaction time.
- the hydrocyanation can be carried out in the presence or absence of a solvent. If a solvent is used, the solvent should be liquid at the given reaction temperature and the given reaction pressure and inert to the unsaturated compounds and the at least one catalyst.
- a solvent for example benzene or xylene, or nitriles, for example acetonitrile or benzonitrile, are used as solvents.
- a ligand is preferably used as the solvent.
- the hydrocyanation reaction can be carried out by loading all reactants into the device. However, it is preferred if the device is filled with the at least one catalyst, 1, 3-butadiene and optionally the solvent.
- the gaseous hydrogen cyanide preferably hovers over the surface of the reaction mixture or is preferably passed through the reaction mixture. Another procedure for loading the device is to fill the device with the at least one catalyst, hydrogen cyanide and, if appropriate, the solvent and slowly add the 1,3-butadiene to the reaction mixture.
- the reactants to be introduced into the reactor and for the reaction mixture to be brought to the reaction temperature at which the hydrogen cyanide is added to the mixture in liquid form.
- the hydrogen cyanide can also be added before heating to the reaction temperature become.
- the reaction is carried out under conventional hydrocyanation conditions for temperature, atmosphere, reaction time, etc.
- the hydrocyanation is preferably carried out at pressures of 0.1 to 500 MPa, particularly preferably 0.5 to 50 MPa, in particular 1 to 5 MPa.
- the reaction is preferably carried out at temperatures from 273 to 473 K, particularly preferably 313 to 423 K, in particular at 333 to 393 K.
- the hydrocyanation can be carried out in the liquid phase in the presence of a gas phase and, if appropriate, a solid suspended phase.
- the starting materials hydrogen cyanide and 1,3-butadiene can each be metered in in liquid or gaseous form.
- the hydrocyanation can be carried out in the liquid phase, the pressure in the reactor being such that all starting materials such as 1,3-butadiene, hydrogen cyanide and the at least one catalyst are metered in liquid and in the reaction mixture in the liquid phase available.
- a solid suspended phase can be present in the reaction mixture, which can also be metered in together with the at least one catalyst, for example consisting of degradation products of the catalyst system containing, inter alia, nickel (M) compounds.
- microporous solid obtained after the treatment of the 1,3-butadiene and / or hydrogen cyanide, or the microporous solid used in the hydrocyanation can, after use, be heated by reduced pressure in an atmosphere which is formed by gases selected from the group consisting of consisting of noble gases, air and nitrogen. This means that the microporous solid can be used again.
- the 1,3-butadiene has an acetylene content which is less than 1000 ppm, particularly preferably less than 100 ppm, in particular less than 50 ppm.
- the at least one microporous solid used in the process according to the invention is preferably selected from the group consisting of aluminum oxides and molecular sieves, and preferably has a particle size of 0.01 to 20 mm, particularly preferably 0.1 to 10 mm, in particular 1 to 5 mm , on.
- the porosity of the Shaped body is between 0 and 80% in terms of particle volume. Both strand-shaped and round particles or particles shaped indefinitely by breaking can be used.
- the aluminum oxide can be contaminated with rare earth metal compounds, alkali metal compounds or alkaline earth metal compounds in the range from 0 to 20% by weight, particularly preferably 0 to 10% by weight, based in each case on the solid mass used his.
- molecular sieve is used as the microporous solid in the process according to the invention, reference is made to molecular sieves with an average pore radius of 0.1 to 20 A, preferably 1 to 10 A.
- the storage and transport is subsequently carried out before the actual hydrocyanation of the 1,3 -Butadiene at temperatures of less than 50 ° C., particularly preferably less than 20 ° C., in particular less than 0 ° C. is advantageous in order to avoid polymerizations.
- a stainless steel column with an inner diameter of 300 mm was filled with aluminum oxide F200 from Almatis (spheres with an average diameter of approx. 3 mm) so that a 3000 mm high bed was formed.
- the stainless steel column had a double jacket, which could be flowed through with throttled 35 bar steam or brine from a brine cooling circuit.
- Thermocouples were inserted into the bed with which the temperature in the fixed bed could be tracked. Both at the entry of the column and after leaving the Column was measured with a suitable measuring device for determining water in butadiene (General Eastern, type AMY 170), the moisture of the butadiene stream.
- 1,3-butadiene was continuously passed over the bed at an internal temperature of 0 ° C. (brine cooling in the jacket space). Before entering the column, this butadiene contained 367 ppm by weight of water. After leaving the column, the water content after flowing through the bed was at a value of 0 ppm by weight for about 3 days.
- This example illustrates the need to dry butadiene before using a hydrocyanation catalyst system of Ni (0) complex with e.g. Tritolyl phosphite is brought into contact as a ligand.
- Example 1 The apparatus described in Example 1 with the bed listed there was charged with butadiene until the water content in the outlet stream had risen to a measured value of 50 ppm by weight of water. Then the butadiene feed was stopped. The double jacket was then transferred from brine cooling to heating with throttled 35 bar steam. The bed was then flowed through with 1 m 3 / h of nitrogen and successively raised to 210 ° C. over three days. heated. When the final temperature was reached, the steam heating was switched off and nitrogen was passed through the bed until 60 ° C. had been reached inside the bed. By reclosing the double jacket on brine cooling, the bed was brought back to 0 ° C. and then butadiene was added again. After wetting had ended, the water measurement at the outlet was restarted. The measured values were again 1 ppm by weight of water with respect to butadiene.
- a container made of boiler plate (diameter 50 mm) was filled with a 200 mm high bed of molecular sieve from Karl Roth GmbH (product number 4062020) and cooled to 0 ° C. via a double jacket. Then butadiene was added at 100 g / h mass flow. At the outlet of the fill, no detectable amounts of water were found over a period of 2 weeks using a measuring device for determining water in butadiene (General Eastern, type AMY 170). Accordingly, the butadiene was dry after flowing through the bed.
- Nickel (0) - (m- / p-tolyl phosphite) corresponds to a solution of 0.9% by weight nickel (O) with 19% by weight 3PN and 79.1% by weight m- / p-tolyphosphite
- 2M3BN / 3PN was 1.89 / 1.
- the loss of Ni (0) based on the value product formed was 0.48 kg Ni (0) / t value product (3PN / 2M3BN).
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DE102004004684A DE102004004684A1 (de) | 2004-01-29 | 2004-01-29 | Verfahren zur Hydrocyanierung |
PCT/EP2005/000723 WO2005073168A1 (de) | 2004-01-29 | 2005-01-26 | Verfahren zur hydrocyanierung |
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EP (1) | EP1713761A1 (zh) |
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AR (1) | AR047423A1 (zh) |
BR (1) | BRPI0507199A (zh) |
CA (1) | CA2560096A1 (zh) |
DE (1) | DE102004004684A1 (zh) |
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Cited By (11)
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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)
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DE10136488A1 (de) * | 2001-07-27 | 2003-02-06 | Basf Ag | Ni(O) enthaltendes Katalysatorsystem |
DE102004004720A1 (de) * | 2004-01-29 | 2005-08-18 | Basf Ag | Verfahren zur Herstellung von 3-Pentennitril |
DE102004004724A1 (de) * | 2004-01-29 | 2005-08-18 | Basf Ag | Herstellung von 3-Pentennitril aus 1,3-Butadien |
DE102004004718A1 (de) | 2004-01-29 | 2005-08-18 | Basf Ag | Verfahren zur Hydrocyanierung |
JP2010500317A (ja) | 2006-08-08 | 2010-01-07 | ビーエーエスエフ ソシエタス・ヨーロピア | 1,3−ブタジエンのヒドロシアン化による3−ペンテンニトリルの製造方法 |
CN101687658B (zh) | 2007-05-14 | 2013-07-24 | 因温斯特技术公司 | 高效反应器和方法 |
EP2407444A3 (en) * | 2008-03-19 | 2012-12-05 | Invista Technologies S.à.r.l. | Process for the preparation of dodecanedioic acid |
KR101692089B1 (ko) * | 2009-01-23 | 2017-01-02 | 가부시키가이샤 브리지스톤 | 폴리시아노 화합물로 관능화된 중합체 |
CN103209956B (zh) | 2010-07-07 | 2015-08-12 | 因温斯特技术公司 | 用于制备腈的方法 |
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US2571099A (en) | 1950-01-07 | 1951-10-16 | Du Pont | Process for hydrocyanation of conjugated diolefinic compounds |
US3778462A (en) * | 1971-06-07 | 1973-12-11 | Gulf Research Development Co | Olefin hydrocyanation reaction |
US3852329A (en) | 1973-10-02 | 1974-12-03 | Du Pont | Process for isomerization of 2-methyl-3-butene-nitrile to a linear pentenenitrile |
US3846474A (en) | 1973-10-02 | 1974-11-05 | Du Pont | Process for hydrocyanation of olefinic compounds |
US4382038A (en) * | 1981-10-01 | 1983-05-03 | E. I. Du Pont De Nemours And Company | Hydrocyanation of olefins |
US4714773A (en) * | 1987-01-09 | 1987-12-22 | E. I. Du Pont De Nemours And Company | Hydrocyanation of butadiene |
US6093285A (en) * | 1998-08-31 | 2000-07-25 | Phillips Petroleum Company | Purification of 1,3-butadiene |
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- 2004-01-29 DE DE102004004684A patent/DE102004004684A1/de not_active Withdrawn
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2005
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- 2005-01-26 CA CA002560096A patent/CA2560096A1/en not_active Abandoned
- 2005-01-26 TW TW094102235A patent/TW200530159A/zh unknown
- 2005-01-26 EP EP05707006A patent/EP1713761A1/de not_active Withdrawn
- 2005-01-26 CN CNA200580003677XA patent/CN1914158A/zh active Pending
- 2005-01-26 BR BRPI0507199-2A patent/BRPI0507199A/pt not_active IP Right Cessation
- 2005-01-26 WO PCT/EP2005/000723 patent/WO2005073168A1/de active Application Filing
- 2005-01-26 JP JP2006550080A patent/JP2007519664A/ja active Pending
- 2005-01-27 MY MYPI20050306A patent/MY139378A/en unknown
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Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
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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 |
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US7439381B2 (en) | 2008-10-21 |
KR20070000454A (ko) | 2007-01-02 |
JP2007519664A (ja) | 2007-07-19 |
BRPI0507199A (pt) | 2007-06-26 |
MY139378A (en) | 2009-09-30 |
CA2560096A1 (en) | 2005-08-11 |
TW200530159A (en) | 2005-09-16 |
DE102004004684A1 (de) | 2005-08-18 |
WO2005073168A1 (de) | 2005-08-11 |
AR047423A1 (es) | 2006-01-18 |
CN1914158A (zh) | 2007-02-14 |
US20070155977A1 (en) | 2007-07-05 |
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