- A synthesis section of the mixed solution directly isomerization of 2-methyl-2-crotonization method
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The invention discloses a method for synthesizing 2-methyl-2-butenenitrile through direct isomerization of alkene-nitrile mixed liquid. The method is characterized in that isomerization reaction occurs by adding calcium-containing inorganic base to the alkene-nitrile mixed liquid containing 2-methyl-3-butenenitrile and 3-pentenenitrile so as to generate a product containing the 2-methyl-2-butenenitrile. According to the method, the process of purifying the 2M3BN through reduced pressure rectification is omitted, the calcium-containing inorganic base is used as a catalyst and directly isomerizes the alkene-nitrile mixed liquid containing the 2M3BN and 3PN into the 2M2BN, and the reaction conversion rate and the selectivity are greater than 95% respectively. Compared with a conventional method, the method has the advantages that the rectification separation process of the alkene-nitrile mixed liquid is omitted, so that the whole process route is shortened, the technological process is simplified, the equipment cost and the production cost are reduced, the calcium-containing inorganic base is used as the catalyst, low in price and easy to obtain and can be recycled, and industrial wastewater, waste gases and residues are basically not generated in the whole technological process.
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Paragraph 0004
(2017/02/09)
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- PROCESS FOR MAKING NITRILES
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Adiponitrile is made by reacting 3-pentenenitrile with hydrogen cyanide. The 3- pentenenitrile is made by reacting 1,3-butadiene with hydrogen cyanide. The catalyst for the reaction of 1,3-butadiene with hydrogen cyanide to make 3-pentenenitrile is recycled. At least a portion of the recycled catalyst is purified by an extraction process, which separates catalyst degradation products and reaction byproduct from the catalyst.
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Page/Page column 86-88
(2012/02/01)
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- NICKEL METAL COMPOSITIONS AND NICKEL COMPLEXES DERIVED FROM BASIC NICKEL CARBONATES
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Nickel-metal-containing solids for use in manufacturing nickel metal complexes are disclosed. The nickel-metal-containing solids are made by reducing basic nickel carbonates. By varying the molar ratios of carbonates and bicarbonates to nickel salts, the methods provide basic nickel carbonates that produce superior nickel metal-containing solids that react more effectively with phosphorous-containing ligands. The phosphorous containing ligands can be both monodentate and bidentate phosphorous-containing ligands.
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Page/Page column 9
(2011/08/22)
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- PROCESS FOR MAKING AND REFINING 3-PENTENENITRILE, AND FOR REFINING 2-METHYL-3-BUTENENITRILE
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The invention provides an integrated, continuous process for the production of 3-pentenenitrile, the refining of 3-pentenenitrile, and the refining of 2-methyl-3-butenenitrile, the process comprising: (a) contacting, in a reaction zone, a hydrogen cyanide-containing feed, a butadiene-containing feed, and a catalyst composition, wherein the catalyst composition comprises a zero-valent nickel and at least one bidentate phosphorus-containing ligand selected from the group consisting of a phosphite, a phosphonite, a phosphinite, a phosphine, a mixed phosphorus-containing ligand, and combination thereof; (b) maintaining a residence time in the reaction zone sufficient to convert about 95% or more of the hydrogen cyanide and to produce a reaction mixture comprising 3-pentenenitrile and 2-methyl-3-butenenitrile, wherein the 2-methyl-3-butenenitrile concentration is maintained below about 15 weight percent of the total mass of the reaction mixture; (c) distilling the reaction mixture to obtain a first stream comprising 1,3-butadiene, a second stream comprising 3-pentenenitrile, 2-methyl-3-butenenitrile, (Z)-2-methyl-2-butenenitrile, and optionally 1,3-butadiene, and a third stream comprising the catalyst composition; (d) distilling the second stream to obtain a fourth stream comprising 1,3-butadiene, a fifth stream comprising 2-methyl-3-butenenitrile, (Z)-2-methyl-2-butenenitrile, and optionally 1,3-butadiene, and a sixth stream comprising 3-pentenenitrile; and (e) distilling the fifth stream to obtain a seventh stream comprising 1,3-butadiene, an eighth stream comprising (Z)-2-methyl-2-butenenitrile, and a ninth stream comprising 2-methyl-3-butenenitrile.
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Page/Page column 24-25
(2009/07/25)
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- PROCESS FOR MAKING 3-PENTENENITRILE BY HYDROCYANATION OF BUTADIENE
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The invention provides a continuous process for the production of 3-pentenenitrile, comprising: (a) contacting, in a reaction zone, a hydrogen cyanide-containing feed, a 1,3-butadiene-containing feed, and a catalyst precursor composition, wherein the cata
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Page/Page column 9; 9-10; 10
(2008/06/13)
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- PROCESS FOR MAKING 3-PENTENENITRILE BY HYDROCYANATION OF BUTADIENE
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The invention provides a continuous process for the production of 3-pentenenitrile comprising: (a) contacting, in a reaction zone, a hydrogen cyanide-containing feed, a butadiene-containing feed, and a catalyst precursor composition, wherein the catalyst
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Page/Page column 6; 6-7; 7
(2008/06/13)
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- Highly selective hydrocyanation of butadiene toward 3-pentenenitrile
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A triptycene-based diphosphine ligand was synthesized in good yield following a new route. The corresponding Pt(II)- and Ni(0)-complexes were characterized. In butadiene hydrocyanation the tript-PPh2Ni(cod) catalyst leads to exceptionally high selectivities for the linear product 3-pentenenitrile, combining high activity for both hydrocyanation and isomerization. This one-step procedure could be the key toward process intensification. Copyright
- Bini, Laura,Mueller, Christian,Wilting, Jos,Von Chrzanowski, Lars,Spek, Anthony L.,Vogt, Dieter
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p. 12622 - 12623
(2008/03/14)
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- Binaphthol-based diphosphite ligands in asymmetric nickel-catalyzed hydrocyanation of styrene and 1,3-cyclohexadiene: Influence of steric properties
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A series of chiral (R)-binaphthol-based diphosphite ligands with different substituents was prepared and applied in the asymmetric nickel-catalyzed hydrocyanation of styrene and 1,3-cyclohexadiene to investigate the influence of their steric properties. The optimum steric properties for the hydrocyanation reaction lie within a narrow window. With the optimized ligand, hydrocyanation of styrene gave full conversion (Subs/Ni = 100) with 49% ee, the TON was determined to be 600. Hydrocyanation of 1,3-cyclohexadiene gave 50% conversion (Subs/Ni = 500) with an excellent ee of 86 %. This demonstrates that high ees are not only accessible for vinylarenes but also for conjugated dienes in the asymmetric nickelcatalyzed hydrocyanation.
- Wilting, Jos,Janssen, Michele,Mueller, Christian,Lutz, Martin,Spek, Anthony L.,Vogt, Dieter
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p. 350 - 356
(2008/02/07)
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- Catayzed vapor-phase hydrocyanation of diolefinic compounds
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A catalysed vapor-phase process for the hydrocyanation of acyclic diolefinic compounds to olefinic nitriles in which the olefinic double bond is not conjugated to the triple bond of the cyano group, wherein a supported catalyst composition comprising at least one multidentate phosphite ligand and zero-valent nickel is preferably used with specially selected or treated supports.
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Page/Page column 7-8
(2008/06/13)
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- METHOD FOR THE PRODUCTION OF ADIPODINITRILE BY HYDROCYANATION OF 1,3-BUTADIENE
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Disclosed is a method for the production of adipodinitrile by hydrocyanation of 1,3-butadiene on a catalyst, wherein in a first step 1,3-Butadiene is hydrocyanated to form 3-Pentene nitrile on at least one nickel(0) catalyst and, in a second step, 3-Pentene nitrile is hydrocyanated to form adipodinitrile on at least one nickel(0)-catalyst by adding at least one Lewis acid. At least one of the at least one nickel(0) catalysts used in the respective steps of the inventive method is converted in the other step.
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Page/Page column 30-32
(2008/06/13)
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- METHOD FOR PRODUCING 3-PENTENENITRILE
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The invention relates to a method for producing 3-pentenenitrile, said method being characterised by the following steps: (a) 1,3-butadiene is reacted with hydrogen cyanide on at least one catalyst to obtain a flow (1) containing 3-pentenenitrile, 2-methyl-3-butenenitrile, the at least one catalyst, and 1,3-butadiene; (b) the flow (1) is distilled in a column to obtain a top product flow (2) rich in 1,3-butadiene, and a bottom product flow (3) that is poor in 1,3-butadiene and contains 3-pentenenitrile, the at least one catalyst, and 2-methyl-3-butenenitrile; (c) the flow (3) is distilled in a column to obtain a top product flow (4) containing 1,3-butadiene, a flow (5) in a side-tap of the column, containing 3-pentenenitrile and 2-methyl-3-butenenitrile, and a bottom product flow (6) containing the at least one catalyst; and (d) the flow (5) is distilled to obtain a top product flow (7) containing 2-methyl-3-butenenitrile, and a bottom product flow (8) containing 3-pentenenitrile.
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Page/Page column 35-38; sheet 5
(2008/06/13)
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- PRODUCTION OF 3-PENTENENITRILE FROM 1,3-BUTADIENE
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The invention relates to a method for producing 3-pentenenitrile by means of the hydrocyanation of 1,3-butadiene, whereby 1,3-butadiene is reacted with hydrogen cyanide in the presence of at least one catalyst, and the resulting flow is purified by distillation, the bottom temperature not exceeding 140 °C during the distillation.
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Page/Page column 25-29; sheet 2
(2008/06/13)
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- METHOD FOR PRODUCING LINEAR PENTENENITRILE
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The invention relates to a method for producing 3-pentenenitrile, characterised by the following steps: (a) isomerisation of an educt stream containing 2-methyl-3-butenenitrile on at least one dissolved or dispersed isomerisation catalyst to form a stream (1), which contains the isomerisation catalyst(s), 2-methyl-3-butenenitrile, 3-pentenenitrile and (Z)-2-methyl-2-butenenitrile; (b) distillation of the stream (1) to obtain a stream (2) as the overhead product, which contains 2-methyl-3-butenenitrile, 3-pentenenitrile and (Z)-2-methyl-2-butenenitrile and a stream (3) as the bottom product, which contains the isomerisation catalyst(s); (c) distillation of the stream (2) to obtain a stream (4) as the overhead product, which is enriched with (Z)-2-methyl-2-butenenitrile in comparison to stream (2), (in relation to the sum of all pentenenitriles in stream (2)) and a stream (5) as the bottom product, which is enriched with 3-pentenenitrile and 2-methyl-3-butenenitrile in comparison to stream (2), (in relation to the sum of all pentenenitriles in stream (2); (d) distillation of stream (5) to obtain a stream (6) as the bottom product, which contains 3-pentenenitrile and a stream (7) as the head product, which contains 2-methyl-3-butenenitrile.
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Page/Page column 72-76; sheet 2
(2008/06/13)
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- CONTINUOUS METHOD FOR THE PRODUCTION OF LINEAR PENTENE NITRILES
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The invention relates to a method for continuous hydrocyanation of 1,3-butadiene in the presence of at least one nickel(0)-catalyst with chelate ligands, wherein 1,3-butadiene and cyanohydrogen are used in a molar ratio of 1,6 - 1,1 to 1.
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Page/Page column 18-19
(2008/06/13)
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- METHOD FOR THE PRODUCTION OF PENTENE NITRILES FROM N-BUTANE
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The invention relates to a method for hydrocyanation of 1,3-butadiene on at least one nickel(o) complex with phosphor-containing ligands as a catalyst, wherein 1,3-butadiene is used in a mixture with n-butane and the mixture contains 60 - 90 vol. % 1,3-butadiene and 40 -10 vol. % n-butane.
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Page/Page column 27
(2008/06/13)
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- HYDROCYANATION METHOD
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The invention relates to a method for the production of 3-pentene nitrile by hydrocyanation of 1,3-Butadiene with cyanohydrogen on at least one catalyst, wherein the 1,3-Butadiene and/or cyanohydrogen is brought into contact with at least one microporous solid prior to reaction.
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Page/Page column 16-17
(2008/06/13)
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- STERICALLY HINDERED CHELATE PHOSPHINITE-PHOSPHITE LIGAND, CATALYST, COMPRISING AT LEAST ONE NICKEL(0) COMPLEX STABILIZED BY SAID LIGAND AND METHOD FOR PRODUCTION OF NITRILES
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The invention relates to phosphinite phosphites I of formula 1, 2, 3, 4, 5 or 6 and mixtures thereof, wherein R1, R2, R4 independently represent an alkyl or alkylene group with 1 to 8 carbon atoms, provided that at least one of the groups R1, R2, R4 is different from H; R5 to R22 independently represent H, an alkyl or alkylene group with 1 to 8 carbon atoms; R3 is H, methyl or ethyl; X is F, Cl or CF3, if n = 1 or 2 and X is H, if n = 0.
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Page/Page column 18
(2008/06/13)
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- PHOSPHONITE LIGANDS AND THEIR USE IN HYDROCYANATION
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Disclosed herein are processes for hydrocyanation and isomerization of olefins by using at least one multidentate phosphonite ligands, including organometallic phosphonite ligands with a Group VIII metal or Group VIII metal compound, and optionally, a Lewis acid promoter.
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Page/Page column 9-10
(2008/06/13)
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- Process for the isomerization of nonconjugated 2-alkyl-3-monoalkenenitriles
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A process for isomerizing 2-alkyl-3-monoalkenenitrile to form linear nitriles employing a catalyst comprising the combination of a zero valent nickel compound and certain bidentate phosphorus compounds.
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- Catalyst comprising at least one phosphonite ligand based nickel (O) complex and method for the production of nitriles
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A catalyst comprising at least one nickel(0) complex which comprises at least one mono-, bi- or multidentate phosphonite ligand of the formula I or salts and mixtures thereof, is prepared as described, and the catalysts are used to prepare mixtures of monoolefinic C5mononitriles with nonconjugated C═C and C≡N bonds by catalytic hydrocyanation of butadiene or of a 1,3-butadiene-containing hydrocarbon mixture in the presence of a catalyst of this type.
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- Hydrocyanation of diolefins and isomerization of nonconjugated 2-alkyl-3-monoalkenenitriles
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Improved liquid phase process useful in the hydrocyanation of diolefinic compounds to produce nonconjugated acyclic nitrites and to the liquid phase process of isomerization of the nitrites to 3- and/or 4-monoalkene linear nitriles. The improvement involves conducting the process in the presence of zero-valent nickel and a multidentate phosphite ligand. The invention also provides a novel method of making phosphorochloridite.
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- Chelating Diphosphite Complexes of Nickel(0) and Platinum(0): Their Remarkable Stability and Hydrocyanation Activity
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The synthesis, stability and hydrocyanation catalytic activity of nickel(0) complexes af the diphosphite 1 derived from 2,2'-biphenol are described; the X-ray crystal structures of the legand 1 and its platinum(0) complexes 2b are reported.
- Baker, Michael J.,Harrison, Karl N.,Orpen, A. Guy,Pringle, Paul G.,Shaw, Gordon
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p. 803 - 804
(2007/10/02)
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- The Stereochemistry of Organometallic Compounds. XXVIII The Nickel-Catalysed Addition of Hydrogen Cyanide to Aliphatic Dienes
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Reaction of hydrogen cyanide with a wide range of aliphatic dienes in the presence of nickel(0) catalysts leads to rearrangement of the diene and formation of β,γ-unsaturated nitriles in moderate to very high yields.The mechanism of reaction is discussed in terms of ?-allyl-nickel intermediates.
- Campi, Eva M.,Elmes, Patricia S.,Jackson, W. Roy,Lovel, Craig G.,Probert, Michael K. S.
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p. 1053 - 1061
(2007/10/02)
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- Manufacture of organic nitriles
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A process for the manufacture of adiponitrile is described by reacting butadiene with hydrogen cyanide and a catalyst which is a complex of a copper salt and an organic nitrile to form 3-pentenenitrile, which is then hydrocyanated to adiponitrile in which the solvent and sole nitrile complexing agent for the copper is 3-methylglutaronitrile or a mixture of 3-methylglutaronitrile with 2-ethylsuccindinitrile or with 2-ethylsuccindinitrile and adiponitrile.
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- Manufacture of organic nitriles
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Olefins are converted to nitriles by reacting with hydrogen cyanide in the presence of an organic thiol or sulphide and a catalytic amount of a cuprous salt which is soluble therein; especially for making 3-pentene nitrile from butadiene.
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