CN114105817B - Method for continuously preparing adiponitrile by 1,3-butadiene hydrocyanation - Google Patents
Method for continuously preparing adiponitrile by 1,3-butadiene hydrocyanation Download PDFInfo
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- CN114105817B CN114105817B CN202111506455.7A CN202111506455A CN114105817B CN 114105817 B CN114105817 B CN 114105817B CN 202111506455 A CN202111506455 A CN 202111506455A CN 114105817 B CN114105817 B CN 114105817B
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- adiponitrile
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- valent nickel
- hydrocyanation
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- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 title claims abstract description 49
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000005669 hydrocyanation reaction Methods 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 84
- 239000003054 catalyst Substances 0.000 claims abstract description 44
- 239000003446 ligand Substances 0.000 claims abstract description 42
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 29
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims abstract description 27
- UVKXJAUUKPDDNW-NSCUHMNNSA-N (e)-pent-3-enenitrile Chemical compound C\C=C\CC#N UVKXJAUUKPDDNW-NSCUHMNNSA-N 0.000 claims abstract description 25
- CFEYBLWMNFZOPB-UHFFFAOYSA-N Allylacetonitrile Natural products C=CCCC#N CFEYBLWMNFZOPB-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000047 product Substances 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 239000006227 byproduct Substances 0.000 claims abstract description 15
- WUOIAOOSKMHJOV-UHFFFAOYSA-N ethyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(CC)C1=CC=CC=C1 WUOIAOOSKMHJOV-UHFFFAOYSA-N 0.000 claims abstract description 14
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000001502 supplementing effect Effects 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 238000004821 distillation Methods 0.000 claims abstract description 4
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 22
- -1 diphenylphosphino Chemical group 0.000 claims description 22
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 19
- 229910052698 phosphorus Inorganic materials 0.000 claims description 18
- 239000011574 phosphorus Substances 0.000 claims description 18
- 238000002360 preparation method Methods 0.000 claims description 16
- 239000002841 Lewis acid Substances 0.000 claims description 15
- 150000007517 lewis acids Chemical class 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- WBAXCOMEMKANRN-UHFFFAOYSA-N 2-methylbut-3-enenitrile Chemical compound C=CC(C)C#N WBAXCOMEMKANRN-UHFFFAOYSA-N 0.000 claims description 6
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 4
- 238000004817 gas chromatography Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- YUYQHJUMEAITFR-UHFFFAOYSA-N (2,3,4-trimethylphenyl) dihydrogen phosphite Chemical compound CC1=CC=C(OP(O)O)C(C)=C1C YUYQHJUMEAITFR-UHFFFAOYSA-N 0.000 claims description 2
- 238000003556 assay Methods 0.000 claims description 2
- 238000007664 blowing Methods 0.000 claims description 2
- 238000004587 chromatography analysis Methods 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 238000005070 sampling Methods 0.000 claims description 2
- 238000004088 simulation Methods 0.000 claims description 2
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 claims description 2
- 238000009423 ventilation Methods 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- 238000005086 pumping Methods 0.000 claims 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 abstract description 38
- 229910000073 phosphorus hydride Inorganic materials 0.000 abstract description 19
- 239000011259 mixed solution Substances 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- AJVBXLXLODZUME-UHFFFAOYSA-N ethenyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C=C)C1=CC=CC=C1 AJVBXLXLODZUME-UHFFFAOYSA-N 0.000 description 7
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 5
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical compound OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 4
- 150000008301 phosphite esters Chemical class 0.000 description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 125000003944 tolyl group Chemical group 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 2
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 150000002825 nitriles Chemical group 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- FPPLREPCQJZDAQ-UHFFFAOYSA-N 2-methylpentanedinitrile Chemical compound N#CC(C)CCC#N FPPLREPCQJZDAQ-UHFFFAOYSA-N 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000000370 acceptor Substances 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical group PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 1
- IJMWREDHKRHWQI-UHFFFAOYSA-M magnesium;ethene;chloride Chemical compound [Mg+2].[Cl-].[CH-]=C IJMWREDHKRHWQI-UHFFFAOYSA-M 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000005538 phosphinite group Chemical group 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001308 synthesis method Methods 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2495—Ligands comprising a phosphine-P atom and one or more further complexing phosphorus atoms covered by groups B01J31/1845 - B01J31/1885, e.g. phosphine/phosphinate or phospholyl/phosphonate ligands
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/322—Hydrocyanation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
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- Chemical & Material Sciences (AREA)
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- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a method for continuously preparing adiponitrile by 1,3-butadiene hydrocyanation, which mainly comprises the following steps: s1: after 1,3-butadiene passes through the catalyst system, hydrocyanation occurs to generate a product containing 3-pentenenitrile; s2: enabling the product obtained in the step S1 to pass through a catalyst system, performing hydrocyanation reaction again to produce a mixed solution containing adiponitrile, and distilling under reduced pressure to respectively evaporate and recover the product and the by-product obtained from the mixed solution; s3: supplementing the liquid subjected to reduced pressure distillation in the step S2 with a catalyst, and then repeating the hydrocyanation reaction in the step S2 to continuously prepare adiponitrile; and the catalyst system comprises a mixture consisting of 1- (diphenylphosphine) -2- (ethyldiphenylphosphine) ferrocene, zero-valent nickel and monodentate phosphine ligand. The invention can obviously prolong the service life of the catalyst system and obviously reduce the using amount of the catalyst, thereby reducing the production cost of the adiponitrile, improving the production efficiency of the adiponitrile and providing a new catalyst technology for industrial application.
Description
Technical Field
The invention relates to the field of chemical industry, in particular to a method for continuously preparing adiponitrile by 1,3-butadiene hydrocyanation.
Background
Hydrocyanation is used industrially to synthesize compounds containing nitrile functions from compounds containing unsaturation. Adiponitrile is an important chemical intermediate in hydrocyanation, particularly for the production of nylon 66, and is obtained by double hydrocyanation of 1,3-butadiene. In a first hydrocyanation, 1,3-butadiene is reacted with hydrogen cyanide in the presence of zero-valent nickel (0) stabilized with phosphorus-containing ligands to give pentenenitriles, forming an isomerization mixture consisting of linear 3-pentenenitrile and branched pentenenitriles (2-methyl-3-butenenitrile). In the second process step, the branched pentenenitriles are generally isomerized to linear pentenenitriles. Finally, hydrocyanation of 3-pentenenitrile to adiponitrile in the presence of Lewis acids and secondary hydrocyanation of branched pentenenitriles (2-methyl-3-butenenitrile) to form undesired methylglutaronitrile, the selectivity of the individual sub-steps being of great economic and ecological importance for the implementation of industrial processes.
Numerous patents currently disclose processes for the preparation of adiponitrile, and processes for the preparation of corresponding catalysts, in which a large number of organophosphorus ligands, in particular phosphites, are used to catalyze such hydrocyanation reactions. Monophosphites have good activity, however the n/iso-selectivity to terminal hydrocyanated compounds (around 1:1) is to be improved. While triphenylphosphine was introduced as a ligand in the nickel-catalyzed hydrocyanation reaction, researchers have investigated the use of monophosphites as ligands for nickel catalysts. It has been found that the unique electronic effects of monophosphites (weak sigma-electron donors, strong pi-electron acceptors) accelerate the binding of their coordinated nickel catalyst active intermediates to olefin substrates, thereby accelerating the hydrocyanation reaction rate. Meanwhile, the phosphite ester is easy to prepare, and the stability to sulfide and oxide is also the advantage of the phosphite ester compared with the trivalent phosphine ligand. However, monophosphites are unstable in the reaction system and are susceptible to hydrolysis and alcoholysis, which can interfere with their use as catalyst ligands. The bisphosphite prepared by introducing a biphenol skeleton improves the stability of the phosphite, particularly the ferrocenyl diphosphine form ligand introduction, and the unique spatial structure thereof greatly improves the linear nitrile selectivity of the hydrocyanation reaction of the ligand (about 30.
Although the bisphosphine ligand can obtain high regioselectivity with a small amount of ligand, it is desired to consume an inexpensive monophosphorus ligand and to have an effect close to that of the bisphosphine ligand because of the complex synthesis and high price.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: provides a method for continuously preparing adiponitrile by 1,3-butadiene hydrocyanation, which solves the problems of complex synthesis method and low yield of the conventional method.
In order to solve the problems, the invention provides a method for continuously preparing adiponitrile by 1,3-butadiene hydrocyanation, which comprises the following steps:
s1: after 1,3-butadiene passes through the first catalyst system, hydrocyanation occurs to generate a product containing 3-pentenenitrile and byproducts;
s2: enabling the 3-pentenenitrile obtained in the step S1 to pass through a second catalyst system, performing hydrocyanation again to produce a mixed solution containing adiponitrile, and distilling under reduced pressure to respectively evaporate and recycle a product and a byproduct obtained from the mixed solution;
the step S2 also comprises the operation of adding a cocatalyst of Lewis acid, and the molar ratio of the Lewis acid to the zero-valent nickel is 1-5:1.
S3: repeating the hydrocyanation reaction of step S2 to continuously produce adiponitrile;
the first catalyst system and the second catalyst system both comprise a mixture of 1- (diphenylphosphino) -2- (ethyldiphenylphosphino) ferrocene, zero-valent nickel and a monodentate phosphine ligand.
As a preferred scheme, the structural formula of the 1- (diphenylphosphine) -2- (ethyldiphenylphosphine) ferrocene is as follows:
Preferably, the 1- (diphenylphosphinyl) -2- (ethyldiphenylphosphino) ferrocene is obtained by mixing and reacting 1- (diphenylphosphino) ferrocene, vinyl diphenylphosphine, ferric trichloride and dichloromethane.
Preferably, in the catalyst system, the molar ratio of the zero-valent nickel to the monodentate phosphine ligand to the 1- (diylphenylphosphine) -2- (ethyldiphenylphosphine) ferrocene is 1 (1-5) to (2-10).
Preferably, the step S2 further includes an operation of adding a co-catalyst lewis acid, and the molar ratio of the lewis acid to the zero-valent nickel is 1 to 5:1.
Preferably, the step S1 further comprises an operation of isomerizing the by-products to produce 3-pentenenitrile again.
Preferably, the monodentate phosphine ligand is one or more of a combination of phosphine, phosphite, phosphinite and phosphonite, or a mixture thereof.
As a preferable scheme, the step S2 further includes an operation of recovering the zero-valent nickel catalyst and the phosphorus ligand by extraction, and specifically includes: and (4) recovering the zero-valent nickel catalyst and the phosphorus ligand by using an extracting agent, and then continuously adding the zero-valent nickel catalyst and the phosphorus ligand into the continuous preparation of the adiponitrile in the step S3.
Preferably, the step S3 further includes a step of supplementing zero-valent nickel, and the supplemented amount of zero-valent nickel is 0.02% of the mass of the product adiponitrile.
The invention has the following technical advantages: the first catalyst system and the second catalyst system provided by the invention can effectively catalyze 1,3-butadiene to prepare adiponitrile through continuous hydrocyanation reaction, can obviously improve the activity and selectivity of a metal complex catalyst, obviously prolong the service life of the catalyst system, and obviously reduce the usage amount of 1- (diphenylphosphine) -2- (ethyldiphenylphosphine) ferrocene, thereby reducing the production cost of adiponitrile, improving the production efficiency of adiponitrile, and providing a new catalyst technology for industrial application of adiponitrile.
Detailed Description
The technical solutions of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
this example provides a process for the continuous preparation of adiponitrile by hydrocyanation of 1,3-butadiene comprising the steps of:
s1: after 1,3-butadiene passes through the first catalyst system, hydrocyanation occurs to generate a product containing 3-pentenenitrile and byproducts; the step S1 also comprises the operation of preparing 3-pentenenitrile again by isomerizing byproducts;
s2: enabling the 3-pentenenitrile obtained in the step S1 to pass through a second catalyst system, performing hydrocyanation again to produce a mixed solution containing adiponitrile, and distilling under reduced pressure to respectively evaporate and recycle a product and a byproduct obtained from the mixed solution;
the step S2 also comprises an operation of adding a cocatalyst of Lewis acid, and the molar ratio of the Lewis acid to the zero-valent nickel is 2.5.
S3: repeating the hydrocyanation reaction of step S2 to continuously produce adiponitrile;
the first catalyst system and the second catalyst system both comprise a mixture consisting of 1- (diphenylphosphino) -2- (ethyldiphenylphosphino) ferrocene, zero-valent nickel and a monodentate phosphine ligand;
the monodentate phosphine ligand is one or more of phosphine, phosphite, hypophosphite and phosphonite or a mixture thereof; the structural formula of the 1- (diphenyl phosphine) -2- (ethyl diphenyl phosphine) ferrocene is as follows:
wherein R, R' is one of phenyl or methylphenyl, and Fe can be equivalently replaced by Co, ni, ru, os, rh, pd, pt, mn, cr or V and mixture metals thereof.
The 1- (diphenylphosphine) -2- (ethyldiphenylphosphine) ferrocene is obtained by mixing and reacting 1- (diphenylphosphine) ferrocene, vinyl diphenylphosphine, ferric trichloride and dichloromethane.
The molar ratio of zero-valent nickel, monodentate phosphine ligand, and 1- (diphenylphosphino) -2- (ethyldiphenylphosphino) ferrocene in the first catalyst system to the second catalyst system is 1.
The step S2 also comprises the operation of recovering the zero-valent nickel catalyst and the phosphorus ligand through extraction, and the method specifically comprises the following steps: and (3) recovering the zero-valent nickel catalyst and the phosphorus ligand by using an extracting agent, and then continuously adding the recovered catalyst into the continuous preparation of the adiponitrile in the step S3.
The step S3 also comprises a step of supplementing zero-valent nickel, and the supplementing amount of the zero-valent nickel is 0.02 percent of the mass of the product adiponitrile.
Example 1:
this example provides a process for the continuous preparation of adiponitrile by hydrocyanation of 1,3-butadiene comprising the steps of:
s1: enabling 1,3-butadiene to pass through a first catalyst system and then carrying out hydrocyanation reaction to generate a product containing 3-pentenenitrile and a byproduct; the step S1 also comprises an operation of isomerizing the byproducts to prepare the 3-pentenenitrile again;
s2: enabling the 3-pentenenitrile obtained in the step S1 to pass through a second catalyst system, performing hydrocyanation again to produce a mixed solution containing adiponitrile, and distilling under reduced pressure to respectively evaporate and recycle a product and a byproduct obtained from the mixed solution;
the step S2 also comprises the operation of adding a cocatalyst of Lewis acid, and the molar ratio of the Lewis acid to the zero-valent nickel is 1-1.
S3: repeating the hydrocyanation reaction of step S2 to continuously produce adiponitrile;
the first catalyst system and the second catalyst system both comprise a mixture consisting of 1- (diphenylphosphino) -2- (ethyldiphenylphosphino) ferrocene, zero-valent nickel, and a monodentate phosphine ligand;
the monodentate phosphine ligand is one or more of phosphine, phosphite, hypophosphite and phosphonite or a mixture thereof; the structural formula of the 1- (diphenyl phosphine) -2- (ethyl diphenyl phosphine) ferrocene is as follows:
wherein R, R' is one of phenyl or methylphenyl, and Fe can be equivalently replaced by Co, ni, ru, os, rh, pd, pt, mn, cr or V and their mixture metals.
The 1- (diylphenylphosphine) -2- (ethyldiphenylphosphine) ferrocene is obtained by mixing and reacting 1- (diphenylphosphino) ferrocene, vinyl diphenylphosphine, ferric trichloride and dichloromethane.
The molar ratio of zero-valent nickel, monodentate phosphine ligand, and 1- (diphenylphosphino) -2- (ethyldiphenylphosphino) ferrocene in the first catalyst system to the second catalyst system is 1.
The step S2 also comprises the operation of recovering the zero-valent nickel catalyst and the phosphorus ligand through extraction, and the method specifically comprises the following steps: and (3) recovering the zero-valent nickel catalyst and the phosphorus ligand by using an extracting agent, and then continuously adding the recovered catalyst into the continuous preparation of the adiponitrile in the step S3.
The step S3 also comprises a step of supplementing zero-valent nickel, and the supplementing amount of the zero-valent nickel is 0.02 percent of the mass of the product adiponitrile.
Example 2:
this example provides a process for the continuous preparation of adiponitrile by hydrocyanation of 1,3-butadiene comprising the steps of:
s1: enabling 1,3-butadiene to pass through a first catalyst system and then carrying out hydrocyanation reaction to generate a product containing 3-pentenenitrile and a byproduct; the step S1 also comprises an operation of isomerizing the byproducts to prepare the 3-pentenenitrile again;
s2: enabling the 3-pentenenitrile obtained in the step S1 to pass through a second catalyst system, performing hydrocyanation again to produce a mixed solution containing adiponitrile, and distilling under reduced pressure to respectively evaporate and recycle a product and a byproduct obtained from the mixed solution;
the step S2 also comprises the operation of adding a cocatalyst of Lewis acid, and the molar ratio of the Lewis acid to the zero-valent nickel is 5:1.
S3: repeating the hydrocyanation reaction of step S2 to continuously produce adiponitrile;
the first catalyst system and the second catalyst system both comprise a mixture consisting of 1- (diphenylphosphino) -2- (ethyldiphenylphosphino) ferrocene, zero-valent nickel, and a monodentate phosphine ligand;
the monodentate phosphine ligand is one or more of phosphine, phosphite ester, hypophosphite and phosphonite or the mixture of the phosphine, the phosphite ester, the hypophosphite and the phosphonite; the structural formula of the 1- (diphenyl phosphine) -2- (ethyl diphenyl phosphine) ferrocene is as follows:
wherein R, R' is one of phenyl or methylphenyl, and Fe can be equivalently replaced by Co, ni, ru, os, rh, pd, pt, mn, cr or V and mixture metals thereof.
The 1- (diylphenylphosphine) -2- (ethyldiphenylphosphine) ferrocene is obtained by mixing and reacting 1- (diphenylphosphino) ferrocene, vinyl diphenylphosphine, ferric trichloride and dichloromethane.
The molar ratio of zero-valent nickel, monodentate phosphine ligand, and 1- (diphenylphosphino) -2- (ethyldiphenylphosphino) ferrocene in the first catalyst system to that in the second catalyst system is 1.
The step S2 also comprises the operation of recovering the zero-valent nickel catalyst and the phosphorus ligand through extraction, and specifically comprises the following steps: and (3) recovering the zero-valent nickel catalyst and the phosphorus ligand by using an extracting agent, and then continuously adding the recovered catalyst into the continuous preparation of the adiponitrile in the step S3.
The step S3 also comprises a step of supplementing zero-valent nickel, and the supplementing amount of the zero-valent nickel is 0.02 percent of the mass of the product adiponitrile.
Example 4:
example 4 provides the raw materials, raw material quality, reaction conditions and yields for a particular run as follows:
preparation of catalyst 1- (diphenylphosphino) -2- (ethyldiphenylphosphino) ferrocene:
(1) Synthesis of 1- (diphenylphosphinyl) ferrocene and synthesis of vinyl diphenylphosphine
Ferrocene (1mol, 186g) was added sequentially to a dry reactor at-20 ℃ under argon protection, and n-butyllithium n-BuLi (7 00mL,1.1mol,1.6M n-hexane solution) was injected using a disposable syringe. Injecting N, N, N ', N' -Tetramethylethylenediamine (TMEDA) (1mL, 6.7mmol) into a 20-ml disposable syringe under inert gas atmosphere and stirring for 2 hours, then dropwise adding diphenyl phosphine chloride (1mol, 180g) into the system at-20 ℃, then reacting for 3 hours at-20 ℃, adding water into the system for quenching, then separating liquid, drying an organic layer with anhydrous magnesium sulfate, filtering, distilling under reduced pressure to remove a solvent to obtain yellow solid, and recrystallizing methanol under the protection of argon to obtain 317g of 1- (diphenylphosphino) ferrocene, wherein the yield is 96%;
under the protection of argon, diphenyl phosphine chloride (1mol, 220g) and 0.5L tetrahydrofuran are added into a drying reactor, then a 2M tetrahydrofuran solution of vinyl magnesium chloride (1.1mol, 0.55L) is dropwise added into the system at 0 ℃, the reaction is carried out for 10 hours at room temperature after the dropwise addition, water is added into the system for quenching, then liquid separation is carried out, an organic layer is dried by anhydrous magnesium sulfate and filtered, the solvent is removed by reduced pressure distillation to obtain a white solid, and dichloromethane and methanol are recrystallized to obtain 201g of vinyl diphenylphosphine, wherein the yield is 95%.
(2) Synthesis of 1- (diphenylphosphine) -2- (ethyldiphenylphosphine) ferrocene
Under the protection of argon, 1- (diphenylphosphino) ferrocene (0.5 mol, 165g), vinyl diphenylphosphine (0.5 mol, 106g), ferric trichloride (0.05mol, 8.1g) and 1L dichloromethane were sequentially added to a drying reactor, and then reacted at 25 ℃ for 12 hours, water was added to the system to quench, followed by liquid separation, the organic layer was dried over anhydrous magnesium sulfate, filtered, and distilled under reduced pressure to remove the solvent to obtain a yellow solid, and recrystallization was performed with a mixed solution of dichloromethane and methanol to obtain 249g of (I), the yield of which was 92%.
S1:1,3-hydrocyanation of butadiene:
under the protection of nitrogen in a ventilation kitchen, 5g of nano-nickel (0) powder, 80g of 1- (diphenylphosphino) -2- (ethyldiphenylphosphino) ferrocene and 250g of trimethylphenyl phosphite are sequentially added into a 2000mL autoclave, and 400g of dehydrated butadiene is added after the reaction and mixing for about 1 hour, the mixture is heated to 70-90 ℃, and the reaction pressure is set to be 15bar. 200g of freshly distilled hydrocyanic acid at 0 ℃ were metered in continuously over 60 minutes, and the reaction was then completed by holding 100 ℃ for 60 minutes. Then cooled and the pressure dropped to 1bar. After this sampling, no cyanide was found in the Volhard cyanide assay and hydrogen cyanide had been completely converted.
By gas chromatographic analysis with an internal standard (benzonitrile), calculated on the basis of hydrogen cyanide, yields of 85% for 3-pentenenitrile and 2-methyl-3-butenenitrile, 3-pentenenitrile: 2-methyl-3-butenenitrile ratio =30:1.
s2: preparation of adiponitrile:
taking 0.003mol of zero-valent nickel catalyst, and enabling the concentration of zero-valent nickel Ni (0) to be 300mg/L by a catalyst mixing system, wherein the molar ratio of the zero-valent nickel Ni (0)/monodentate phosphorus ligand/1- (diphenylphosphine) -2- (ethyldiphenylphosphine) ferrocene is 1:2:4. under the protection of nitrogen, dissolving Lewis acid in a certain amount of 3-pentenenitrile (the molar ratio of the 3-pentenenitrile to the zero-valent nickel catalyst is 160: 1), and adding the solution into a reaction bottle with a mechanical stirring and condensing reflux pipe; wherein the molar ratio of the Lewis acid to the zero-valent nickel catalyst is 2:1, using monodentate phosphorus ligand as trimethyl phosphite, starting stirring, heating to 70-90 ℃, and then blowing liquid hydrocyanic acid into a reaction bottle at a certain flow rate by using nitrogen; after the hydrocyanic acid feeding is finished, the reaction solution is kept at the normal pressure for 4.5 hours. After the heat preservation is finished, evaporating and recycling unreacted hydrocyanic acid, 3-pentenenitrile, a product adiponitrile and other byproducts by reduced pressure distillation, and extracting and recycling the zero-valent nickel catalyst and the phosphorus ligand by an extracting agent.
The product adiponitrile is analyzed by gas chromatography, and calculated by taking hydrocyanic acid as a reference, so that the reaction achieves the conversion rate of 96 percent and the selectivity of 92 percent.
S3: continuous preparation of adiponitrile
The double hydrocyanation reaction was continuously repeated according to the above S2 operation. After the operation is continuously carried out for 120 hours, the zero-valent nickel catalyst and the phosphorus ligand are extracted and recovered by an extracting agent, 0.001mol of zero-valent nickel is supplemented, and the same reaction is carried out in the single kettle simulation cycle test mode to obtain a product.
The product adiponitrile is analyzed by gas chromatography, and calculated by taking hydrocyanic acid as a reference, the reaction achieves the conversion rate of 98.5 percent and the selectivity of 92 percent.
The above examples further demonstrate that adiponitrile prepared by the present invention has high production efficiency and a simple preparation method, and the adiponitrile prepared by the continuous preparation method has a greatly improved yield compared with adiponitrile obtained by the initial reaction.
While the foregoing specification illustrates and describes several preferred embodiments of the invention, it is to be understood that the invention is not limited to the precise forms disclosed herein and is not to be considered as exclusive of other embodiments, as may be used in various other combinations, modifications, and environments and is capable of changes within the scope of the inventive concept as expressed herein, either as expressed above or as known in the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Although the present disclosure has been described above, the scope of the present disclosure is not limited thereto. Those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present disclosure, and such changes and modifications will fall within the scope of the present invention.
Claims (1)
1. A method for continuously preparing adiponitrile by 1,3-butadiene hydrocyanation, comprising the steps of:
s1:1,3-hydrocyanation of butadiene:
under the protection of nitrogen in a ventilation kitchen, sequentially adding 5g of nanoscale zero-valent nickel powder, 80g of 1- (diphenylphosphino) -2- (ethyldiphenylphosphino) ferrocene and 250g of trimethylphenyl phosphite into a 2000mL high-pressure autoclave, reacting and mixing for 1 hour, adding 400g of dehydrated butadiene, heating the mixture to 70-90 ℃, and setting the reaction pressure to be 15bar; continuously pumping 200g of hydrocyanic acid with the temperature of 0 ℃ which is newly distilled in a metering way for 60 minutes, keeping the temperature of 100 ℃ for 60 minutes to ensure that the reaction is complete, and then cooling the mixture, and reducing the pressure to 1bar; after this sampling, no cyanide was found in the Volhard cyanide assay and hydrogen cyanide had been completely converted;
by gas chromatographic analysis with an internal benzonitrile standard, calculated on the basis of hydrogen cyanide, yields of 85% for 3-pentenenitrile and 2-methyl-3-butenenitrile, 3-pentenenitrile: 2-methyl-3-butenenitrile ratio =30:1;
s2: preparation of adiponitrile:
taking 0.003mol of zero-valent nickel catalyst, and enabling the concentration of zero-valent nickel in a catalyst mixing system to be 300mg/L, wherein the molar ratio of zero-valent nickel/monodentate phosphorus ligand/1- (diphenylphosphine) -2- (ethyldiphenylphosphine) ferrocene is 1:2:4; under the protection of nitrogen, dissolving Lewis acid in a certain amount of 3-pentenenitrile, and adding the solution into a reaction bottle with a mechanical stirring and condensing reflux pipe; wherein the molar ratio of the 3-pentenenitrile to the zero-valent nickel catalyst is 160:1, the molar ratio of the Lewis acid to the zero-valent nickel catalyst is 2:1, starting stirring a monodentate phosphorus ligand trimethyl phosphite, heating to 70-90 ℃, and then blowing liquid hydrocyanic acid into a reaction bottle at a certain flow rate by using nitrogen; after the hydrocyanic acid feeding is finished, preserving the temperature of the reaction liquid for 4.5 hours at normal pressure; after the heat preservation is finished, evaporating and recovering unreacted hydrocyanic acid, 3-pentenenitrile, a product adiponitrile and other byproducts by reduced pressure distillation, and extracting and recovering a zero-valent nickel catalyst and a phosphorus ligand by using an extracting agent;
the product adiponitrile is analyzed by gas chromatography, and calculated by taking hydrocyanic acid as a reference, the reaction reaches the conversion rate of 96 percent and the selectivity of 92 percent;
s3: continuous preparation of adiponitrile
Continuously and repeatedly carrying out secondary hydrocyanation reaction according to the operation step S2, after continuously operating for 120 hours, extracting and recovering the zero-valent nickel catalyst and the phosphorus ligand by using an extracting agent, supplementing 0.001mol of zero-valent nickel, and carrying out the same reaction in the single kettle simulation cycle test mode to obtain a product;
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WO1999007671A1 (en) * | 1997-08-04 | 1999-02-18 | Basf Aktiengesellschaft | Method for producing mixtures of monoolefinic c5-mononitriles by catalytic hydrocyanation in the presence of a catalyst containing at least one metallocene phosphor (iii)-nickel-(0) complex |
CN103080074A (en) * | 2010-07-07 | 2013-05-01 | 因温斯特技术公司 | Process for making nitriles |
CN103694136A (en) * | 2014-01-06 | 2014-04-02 | 重庆中平紫光科技发展有限公司 | One-step method for synthesizing adiponitrile by using butadiene |
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WO1999007671A1 (en) * | 1997-08-04 | 1999-02-18 | Basf Aktiengesellschaft | Method for producing mixtures of monoolefinic c5-mononitriles by catalytic hydrocyanation in the presence of a catalyst containing at least one metallocene phosphor (iii)-nickel-(0) complex |
CN103080074A (en) * | 2010-07-07 | 2013-05-01 | 因温斯特技术公司 | Process for making nitriles |
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