Patent GB-1181612-A (GB)
Title: Production of Adiponitrile
Filed: 1968-03-08
Abstract: 1,181,612. Production of adiponitrile. TOYO KOATSU INDUSTRIES Inc. E March, 1968 [15 March, 1967; 5 April, 1967; 13 April, 1967; 28 April, 1967(3); 10 May, 1967; 12 May, 1967; 15 May, 1967; 17 May, 1967; 22 May, 1967; 7 June, 1967; 13 June, 1967; 28 July, 1967; 31 July, 1967; 12 Oct., 1967]. No. 11508/68. Heading C2C. A process for producing adiponitrile by hydrodimerization of acrylonitrile which comprises reacting as aqueous solution of acrylonitrile and an acid chosen from inorganic acids, organic acids and acidic substances capable of providing acidity in aqueous solution, in the presence of an alkali metal amalgam and of at least one catalyst chosen from chelating agents, which may be amino polycarboxylic acids and sulpho compounds; amino acids, which may be neutral, acid or basic amino acids and may be of a DL, racemic, D or L type, compounds of transition metals chosen from Zr, Nb, Mo, Tc, Ru, Rh, Pd, Hf, Ta, W, Re, Os, Ir, Pt, which may be the chlorides, bromides, iodides, nitrates and cyanides of zirconium, molybdenum, ruthenium, rhodium and palladium, and chlorides and oxychlorides of hafnium, tantalum, tungsten, rhenium, osmium and platinum; trialkanolamine borates which may be of formula wherein R 11 , R 12 , R<SP>1</SP> 11 , R<SP>1</SP> 12 , R<SP>11</SP> 11  and R<SP>11</SP> 12  are hydrogen or C 1-20  alkyl radicals which may have straight or branch chains, and n is 1 to 4; trialkylboron-trialkylamine adducts which may be of formula wherein R 21 , R 22 , R 23 , R<SP>1</SP> 21 , R<SP>1</SP> 22  and R<SP>1</SP> 23  are C 1-20  alkyl radicals which are homogenous, heterogenous or mixed straight or branch chain types; trialkylamine oxides which may be of formula wherein R 31 , R 32  and R 33  are C 1-20  alkyl radicals which are homogenous, heterogenous, or mixed straight or branch chain types; dialkyl nitrosoamines which may be of formula in which R 41  and R 42  are as defined above for R 31  and R 32 ; nitrilotriacetic acid derivatives which may be of formula wherein R 14 , R 24  and R 34  are nitrile groups, carboxylic acid groups or alkyl ester groups of 1 to 8 carbon atoms inclusive and may be different or the same, further the carboxylic acid groups may be in the form of sodium or potassium salts; nitrobenzene derivatives which may be of the formula: wherein R 5  is a hydroxyl radical or carboxyl radical, carboxy sodium salt radical, carboxy potassium salt radical, carboxyl ammonium salt radical, carboxyl ester radical or carboxyl amide radical, Y is C 1-4  alkyl radical, nitro radical, hydroxyl radical, sulphonic acid radical or halogen and m is 0 to 2; imidazole and its derivatives which may be chosen from compounds having at least one C 1-4  alkyl radical, phenyl or benzyl radicals in the 1, 2, 4 and 5 positions; acid amides such as succinimide or saccharin; pyrazole and its derivatives which may be chosen from compounds having at least one alkyl radical of 1 to 4 carbon atoms inclusive, phenyl or benzyl radicals in the 1, 3, 4 and 5 positions; triazole and its derivatives which may be chosen from compounds having a C 1-4  alkyl radical or phenyl or benzyl radicals; thiazole or isothiazole, oxazole and isoxazole; nitrogenous cyclic compounds which may be of the formula wherein R 1  and R 2  are hydrogen or C 1-20  alkyl radicals, R 3  is an oxygen or sulphur atom, R 4  is a chain structure of 2 or 3 atoms containing a nitrogen atom or ketone radical; metallic acetylacetone complex salts which may be of cobalt, nickel, manganese, magnesium, zinc, copper, chromium, palladium, indium, aluminium, vanadium (11) oxide, rhodium and molybdenum (IV) oxide; phosphine compounds which may be of the formula wherein R 15 , R 25  and R 35  are C 1-20  alkyl radicals, aryl radicals, aralkyl radicals or aliphatic cyclic radicals and may be different or the same and diphosphine compounds of formula wherein R<SP>1</SP> 15  is a C 1-20  alkylene radical, R 15 , R 25  and R 35  are as defined above and R 45  has the same significance as R 15 ; inorganic phosphites or borates which may be of the formula wherein M is phosphorus or boron, R 16 , R 26  and R 36  are C 1-4  alkyl radicals or aryl or alkylaryl radicals and may be the same or different; benzoic acid and its derivatives; and phosphinemetallic double salts which may be of the formula wherein R 18 , R 28  and R 38  are C 1-20  alkyl radicals, aryl radicals, aralkyl radicals or aliphatic cyclic radicals and may be the same or different, M is a transition metal and X is chlorine, bromine, iodine, nitrate or thiocyano radicals and m and n are 1 to 3 inclusive; while keeping the pH of the resulting reaction solution in the range of 2 to 12.