United States Patent 19 (11) 3,946,066 Todd (45) Mar. 23, 1976

54) DIMERISATION PROCESS AND CATALYST 3,655,724 4/1972 Linn et al...... 260/465.8 D 3,729,498 4/1973 Masada et al...... 260/465.8 D (75) Inventor: Peter Frank Todd, Stockton, England FOREIGN PATENTS OR APPLICATIONS 73 Assignee: Imperial Chemical industries 1,177,059 1/1970 United Kingdom...... 260/465.8 D. Limited, London, England 1,270,026 6/1968 Germany ...... 260/465.8 D. 22 Filed: Aug. 29, 1974 Primary Examiner-Joseph P. Brust (21) Appl. No.: 501,605 Attorney, Agent, or Firm-Cushman, Darby & Cushman (30) Foreign Application Priority Data Oct. 1, 1973 United Kingdom...... 45686/73 57 ABSTRACT (52) U.S. Cl... 260/465.8 D; 252/466 R; 260/485 R; 260/561 R A ruthenium catalyst of improved performance for the 51 Int. Cl’...... C07C 120/00 dimerisation and hydrodimerisation of olefinically un (58) Field of Search..... 260/465.8 D, 485 R, 561 R, saturated compounds, especially acrylonitrile, is ob 260/561 N tained by co-precipitating a ruthenium compound with an oxide and/or hydroxide. 56 References Cited UNITED STATES PATENTS 3 Claims, No Drawings 3,484,475 12/1969 Cornforth et al...... 260/465.8 D. 3,946,066 2 nitrile) to dimer (1,4-dicyanobutenes). Such com DIMERISATION PROCESS AND CATALYST. pounds may be co-precipitated as the oxide or hydrox ide together with the ruthenium compound and the This invention relates to catalysts suitable for the or hydroxide, for example by adding a dimerisation and hydrodimerisation of olefinically un water-soluble salt of the said element to the aqueous saturated compounds, and to methods for the prepara solution of the ruthenium salt and aluminium salt prior tion of such catalysts and for their use in such dimerisa to adding the precipitating agent. tion processes. Co-precipitation of a ruthenium compound and the it has already been proposed to dimerise and hy aluminium oxide or hydroxide may usually be achieved drodimerise olefinically unsaturated compounds using O by adding a base to an aqueous solution of the soluble ruthenium catalysts. Particulary suitable olefinically ruthenium compound and the soluble aluminium com unsaturated compounds are those which are acceptors pound giving rise to the oxide or hydroxide. In order to in Michael reactions, that is cqmpounds containing a achieve co-precipitation and to avoid precipitation of group of the general formula -C = CR the aluminium before the ruthenium we prefer to avoid in which the Group R is one which activates the double 5 the use of strong alkalis such as the alkali metal hydrox bond. Examples of such compounds may be found in ides, e.g. sodium and . Ammonium "Organic Name Reactions” by Krauch & Kunz, 1964, hydroxide may be used. We prefer to use, however, John Wiley & sons at page 315, in “Name Reactions in organic amines and, more especially, aliphatic, cycloal Organic Chemistry' by A. R. Surrey, 2nd edition, iphatic or araliphatic primary, secondary or tertiary 1961, Academic Press, at pages 173 to 174, and in 20 amines, for example ethylamine, diethylamine, triethyl "Name Index of Organic Reactions' by J. E. Gowan amine, cyclohexylamine and phenylethylamine. Urea and T. S. Wheeler, 1960, Longmans at pages 169 to may also be used as a precipitating agent. Physical 172. Particularly important examples are alpha-beta examination of the co-precipitated catalysts of our olefinically unsaturated esters, amides and nitriles, invention obtained with our preferred precipitating especially the acrylic esters and acrylonitrile. 25 agents shows that they consist essentially of ruthenium It has already been proposed to dimerise and/or hy oxy-hydroxy species intimately mixed with pseduo drodimerise acrylonitrile both in the liquid and the boohmite (i.e. AlO.OHxHO) (see X-Ray Identifica vapour phase in presence of a ruthenium catalyst which tion and Crystal Structure of Clay Mineral