# US 9,040,734 B2 · Process for making nitriles > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 9,040,734 B2 - Document ID: US9040734B2 - Status: Granted - Kind: B2 - Application number: 13/808,760 - Filed: 2011-06-16 - Published: 2013-08-15 - Granted: 2015-05-26 - Earliest claimed: 2010-07-07 - Assignees: Invista North America S.A R.L. - Applicants: Larry E. Moerbe; Tseng H. Chao - Inventors: Larry E. Moerbe; Tseng H. Chao - Web page: https://patentgrep.com/patent/US9040734B2 ## CPC - C07C 253/10: to compounds containing carbon-to-carbon double bonds - Y02P 20/584: Recycling of catalysts - C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS - Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS ## Abstract Adiponitrile is made by reacting 3-pentenenitrile with hydrogen cyanide. The 3-pentenenitrile is made by reacting 1,3-butadiene with hydrogen cyanide and by isomerizing 2-methyl-3-butenenitrile. The reaction of 1,3-butadiene with hydrogen cyanide to produce 3-pentenenitrile also produces small amounts of dinitrile compounds, including adiponitrile (ADN) and methylglutaronitrile (MGN). Methylglutaronitrile is removed to provide an adiponitrile-enriched stream, which is used in a catalyst purification step. ## Claims ### Claim 1 A process for making adiponitrile, said process comprising the steps of: (a) reacting in a first reaction zone a mixture comprising 1,3-butadiene (BD) and hydrogen cyanide (HCN) in the presence of a first catalyst comprising zero-valent Ni and a first phosphorus-containing ligand to produce a reaction product comprising 3-pentenenitrile (3PN) and 2-methyl-3-butenenitrile (2M3BN); (b) isomerizing at least a portion of the 2M3BN of step (a) in a second reaction zone in the presence of a second catalyst comprising zero-valent Ni and a second phosphorus-containing ligand to produce a reaction product comprising 3PN; and (c) reacting in a third reaction zone a mixture comprising 3PN from step (b) and hydrogen cyanide (HCN) in the presence of a third catalyst comprising zero-valent Ni and a third phosphorus-containing ligand and in the presence of Lewis acid promoter to produce a reaction product comprising adiponitrile, wherein the first catalyst flows through the first reaction zone along with reactants and products, wherein the second catalyst flows through the second reaction zone along with reactants and products, wherein the third catalyst flows through the third reaction zone along with reactants and products, wherein the reaction product of step (a) further comprises dinitriles comprising adiponitrile (ADN) and methylgiutaronitrile (MGN), wherein at least a portion of first catalyst flowing from the first reaction zone is concentrated in one or more distillation steps and recycled in at least one first catalyst recycle stream to the first reaction zone, wherein a portion of the first catalyst recycle stream is contacted with a first extraction solvent in a first liquid/liquid extraction step to produce a solvent phase and a raffinate phase, wherein a separate liquid/liquid extraction step is used to treat the product from the third reaction zone such that said third catalyst is not contacted with said extraction solvent in said first liquid/liquid extraction step, wherein the first liquid/liquid extraction step comprises introducing a portion of the first catalyst recycle stream, a first extraction solvent stream and a dinitrile recycle stream comprising adiponitrile (ADN) into a first liquid/liquid extraction zone, wherein the first liquid/liquid extraction step further comprises separating liquids in the first liquid/liquid extraction zone into a first solvent phase comprising first extraction solvent and first catalyst and a first raffinate phase comprising adiponitrile (ADN), methylglutaronitrile (MGN), compounds with a higher boiling point than adiponitrile (ADN) and compounds with a lower boiling point than methylglutaronitrile (MGN); wherein first catalyst from said solvent phase obtained in said liquid/liquid extraction step is recycled to the first reaction zone or the second reaction zone or both the first and second reaction zone, wherein said first raffinate phase is distilled in one or more distillation steps to separate adiponitrile (ADN) and methylglutaronitrile (MGN) from compounds with a higher boiling point than adiponitrile (ADN) and compounds with a lower boiling point than methylglutaronitrile (MGN) to obtain a first refined dinitrile stream, wherein said first refined dinitrile stream is further distilled to remove methylglutaronitrile (MGN) from the first refined dinitrile stream to obtain a second refined dinitrile stream enriched in adiponitrile, and wherein at least a portion of said second refined dinitrile stream is recycled to the liquid/liquid extraction step. ### Claim 2 (depends on 1) The process of claim 1, wherein said compounds having a higher boiling point than adiponitrile (ADN) comprise catalyst degradation products. ### Claim 3 (depends on 2) The process of claim 2, wherein said catalyst degradation products comprise at least one compound selected from the group consisting of Ni(CN)2 and a phosphate ligand. ### Claim 4 (depends on 1) The process of claim 1, wherein said compounds having a lower boiling point than methylglutaronitrile (MGN) comprise said extraction solvent and at least one pentenenitrile selected from the group consisting of 3PN and 2M3BN. ### Claim 5 (depends on 1) The process of claim 1, wherein the first phosphorus-containing ligand is a monodentate phosphorus-containing ligand, and wherein the third phosphorus-containing ligand is a bidentate phosphorus-containing ligand. ### Claim 6 (depends on 5) The process of claim 5, wherein the first phosphorus-containing ligand and the second phosphorus-containing ligand are the same. ### Claim 7 (depends on 1) The process of claim 1, wherein the reaction product from step (a) is distilled to remove unreacted 1,3-butadiene and produce a 1,3-butadiene-depleted reaction product stream, wherein the 1,3-butadiene-depleted reaction product stream is introduced into a distillation column comprising a feed inlet, an upper draw outlet, a bottom draw outlet and a rectifying section, wherein the rectifying section is provided between the feed inlet and the upper draw outlet, wherein the rectifying section comprises at least one stage of separation, wherein a pentenenitrile-enriched stream is withdrawn from the upper draw outlet, wherein said first catalyst recycle stream is withdrawn from the bottom draw outlet, and wherein the first catalyst recycle stream comprises at least 5% by weight of pentenenitrile. ### Claim 8 (depends on 7) The process of claim 7, wherein said distillation column further comprises a side draw outlet, wherein said rectifying section comprises at least two stages of separation, wherein said rectifying section further comprises a liquid collection apparatus, wherein liquid is collected in the liquid collection apparatus and passed through the side draw outlet to form a side draw stream, wherein said side draw stream comprises methylglutaronitrile (MGN), and wherein said side draw stream is passed as a feed to said first liquid/liquid extraction step. ### Claim 9 (depends on 1) The process of claim 1, wherein said process comprises two separate liquid/liquid extraction steps, wherein a first liquid/liquid extraction step is used to extract said first catalyst, but not said third catalyst and a separate liquid/liquid extraction step is used to extract said third catalyst, but not said first catalyst. ### Claim 10 (depends on 9) The process of claim 9, wherein said separate liquid/liquid extraction step comprises contacting reaction product from step (c) and said third catalyst from step (c) with an extraction solvent, which is different from the extraction solvent used in the first liquid/liquid extraction step, to produce a solvent phase comprising said third catalyst and a raffinate phase comprising adiponitrile product from step (c); wherein third catalyst from the solvent phase obtained in said separate liquid/liquid extraction step is recycled to the third reaction zone, but not to the first reaction zone or the second reaction zone or both the first and second reaction zone, and wherein the raffinate phase comprising adiponitrile product from step (c) is distilled in one or more distillation steps to recover a purified adiponitrile product stream. ### Claim 11 (depends on 10) The process of claim 10, wherein a portion of the purified adiponitrile product stream is recycled to the first liquid/liquid extraction step used to extract the first catalyst, but not to the separate liquid/liquid extraction step used to extract the third catalyst. ### Claim 12 (depends on 10) The process of claim 10, wherein none of the purified adiponitrile product stream is recycled to the first liquid/liquid extraction step. ### Claim 13 (depends on 10) The process of claim 10, wherein the raffinate phase from the first liquid/liquid extraction step and the raffinate phase from the separate liquid/liquid extraction step are distilled in the same or different distillation apparatus. ### Claim 14 (depends on 13) The process of claim 13, wherein the raffinate phase from the first liquid/liquid extraction step or the raffinate phase from the separate liquid/liquid extraction step or both the raffinates phases are distilled to remove extraction solvent and to obtain an extraction solvent-depleted raffinate stream, wherein the extraction solvent-depleted raffinate stream is distilled to remove pentenenitrile and obtain a pentenenitrile-depleted raffinate stream, wherein the pentenenitrile-depleted raffinate stream is distilled in a dinitrile column to remove catalyst degradation products to obtain a first dinitrile stream enriched in MGN and a second dinitrile stream enriched in adiponitrile, wherein said dinitrile column comprises a feed inlet, an upper draw outlet, a side draw outlet and a bottom draw outlet, wherein catalyst degradation products are withdrawn through said bottom draw outlet of the dinitrile column, wherein adiponitrile is withdrawn through said side draw outlet of the dinitrile column, and wherein MGN is withdrawn through said upper draw outlet of the dinitrile column. ### Claim 15 (depends on 13) The process of claim 13, wherein the raffinate phase from the first liquid/liquid extraction step is distilled to remove extraction solvent and to obtain an extraction solvent-depleted raffinate stream, wherein the extraction solvent-depleted raffinate stream is distilled to remove pentenenitrile and obtain a pentenenitrile-depleted raffinate stream, wherein the pentenenitrile-depleted raffinate stream is distilled in a dinitrile column to remove catalyst degradation products to obtain a first dinitrile stream enriched in MGN and a second dinitrile stream enriched in adiponitrile, wherein said dinitrile column comprises a feed inlet, an upper draw outlet, a side draw outlet and a bottom draw outlet, wherein catalyst degradation products are withdrawn through said bottom draw outlet of the dinitrile column, wherein adiponitrile is withdrawn through said side draw outlet of the dinitrile column, wherein MGN and compounds with lower boiling point than MGN are withdrawn through said upper draw outlet of the dinitrile column, and wherein adiponitrile from said side draw outlet of the dinitrile column is recycled to the first liquid/liquid extraction step extractor. ### Claim 16 (depends on 14) The process of claim 14, wherein the raffinate from the first liquid/liquid extraction step and the raffinate from the separate liquid/liquid extraction step are distilled in different distillation apparatus. ### Claim 17 (depends on 16) The process of claim 16, wherein the catalyst degradation products withdrawn through said bottom draw outlet of the dinitrile column comprise adiponitrile, and wherein said catalyst degradation products withdrawn through said bottom draw outlet of the dinitrile column are passed to a wiped film evaporator (WFE) to separate and recover adiponitrile from said catalyst degradation products withdrawn through said bottom draw outlet of the dinitrile column. ### Claim 18 (depends on 17) The process of claim 17, wherein the same wiped film evaporator (WFE) is used to recover adiponitrile from catalyst degradation products separated from both the raffinate phase from the first liquid/liquid extraction step and the raffinate phase from the separate liquid/liquid extraction step. ### Claim 19 (depends on 1) The process of claim 1, wherein said first phosphorus-containing ligand, said second phosphorus-containing ligand and said third phosphorus-containing ligand are selected from the group consisting of a monodentate or bidentate phosphite ligand, a monodentate or bidentate phosphine ligand, a monodentate or bidentate phosphorite ligand, a monodentate or bidentate phosphinite ligand, and a mixture of these ligands. ### Claim 20 (depends on 1) The process of claim 1, wherein the first phosphorus-containing ligand of the catalyst which flows through the first reaction zone is a monodentate phosphorus-containing ligand, and wherein the second phosphorus-containing ligand is the same as the first phosphorus-containing ligand. ### Claim 21 (depends on 19) The process of claim 19, wherein said first phosphorus-containing ligand and said second phosphorus-containing ligand is at least one ligand of Formula I, where Formula I is P(OR2)(OR3)(OR4) (I) where R2, R3 and R4 are the same or different and are aryl groups, where the aryl groups are each optionally substituted with up to four alkyl groups, each alkyl group having from 1-4 carbon atoms. ### Claim 22 (depends on 21) The process of claim 21, wherein R2, R3 and R4 are the same or different phenyl or tolyl groups. ### Claim 23 (depends on 22) The process of claim 22, wherein the phosphorus-containing ligand of Formula I is one or more ligands selected from the group consisting of (o-tolyl-O—)3P, (p-tolyl-O—)(phenyl-O—)2P, (m-tolyl-O—) (phenyl-O—)2P, (o-tolyl-O—)(phenyl-O—)2P, (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—)3P, (m-tolyl-O—)(p-tolyl-O—)2P, (o-tolyl-O—)(p-tolyl-O—)2P, (m-tolyl-O—)2(p-tolyl-O—)P, (o-tolyl-O—)2(p-tolyl-O—)P, (o-tolyl-O—)(m-tolyl-O—)(p-tolyl-O—)P, (m-tolyl-O—)3P, (o-tolyl-O—)(m-tolyl-O—)2P, and (o-tolyl-O—)2(m-tolyl-O—)P. ### Claim 24 (depends on 19) The process of claim 19, wherein said Lewis acid promoter is an inorganic compound or an organometallic compound comprising a cation of a metal selected from the group consisting of scandium, titanium, vanadium, chromium, manganese, iron, cobalt, copper, zinc, boron, aluminum, yttrium, zirconium, niobium, molybdenum, cadmium, rhenium, lanthanum, erbium, ytterbium, samarium, tantalum, and tin. ### Claim 25 (depends on 19) The process of claim 19, wherein said Lewis acid promoter is selected from the group consisting of salts of metals having atomic numbers 13, 21-32, 39-50, and 57-80 and compounds of the formula BR′3 wherein R′ is an alkyl or an aryl radical of up to 18 carbon atoms ### Claim 26 (depends on 25) The process of claim 25, wherein said Lewis acid promoter comprises ZnCl2 or triphenylboron.