United States Patent 19 (11) 3,946,066 Todd (45) Mar
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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 aluminium 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 aluminium oxide 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 potassium hydroxide. 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 Minerals, edited G. may, if desired, be supported on a conventional catalyst Brown, The Mineralogical Society, London, 1961, support, for example alumina. 30 page 362). The morphology of these catalysts remains According to our invention a particularly suitable unchanged during use, although heating attempera catalyst for the dimerisation and hydrodimerisation of tures in excess of about 200'C should be avoided since olefinically unsaturated compounds comprises ruthe the catalyst then undergoes dehydration and phase nium co-precipitated with an aluminium oxide and/or transistion to a less active form. hydroxide. 35 The proportion of ruthenium to aluminium in the The catalysts of our invention may be manufactured, co-precipitated catalyst is not critical. Normally it will for example, by co-precipitating a ruthenium com fall with the ratio of 1 : 40 to 10: 1 by weight. It may pound and an aluminium oxide or hydroxide from a be desirable for the catalyst to be supported on a suit solvent containing a soluble ruthenium compound and able support, for example pumice, kieselguhr, carbon, a soluble aluminium compound giving rise to the oxide 40 alumina or silica, and this may be effected, for exam or hydroxide. ple, by co-precipitating the catalyst on the support. A particularly suitable solvent is water. However, After co-precipitation of the catalyst it may be sepa mixtures of water with water-miscible organic solvents, rated from the solvent, for example by filtration or by for example alkanols, especially methanol, ethanol and centrifuging, and, if desired, it may be washed free the propanols, may be used in suitable cases. As water 45 from soluble matter, for example of water soluble salts, soluble ruthenium compounds there may be used the and, if desired, dried. Drying is preferably effected at salts of ruthenium, for example the halides (e.g. chlo temperatures not in excess of 110°C. ride and bromide), and the sulphate and nitrate as well The catalyst of our invention may be used for the as salts of organic acids, especially of the aliphatic dimerisation or hydrodimerisation of olefinically unsat acids, for example the acetate or lactate. Ruthenates, 50 urated compounds and especially of acrylonitrile in for example ammonium pentachlororuthenate, may either the liquid or the vapour phase. When used in the also be used. liquid phase, it is an advantage of the catalyst of our Water-soluble compounds of aluminium from the invention that it has very low solubility in the reaction aqueous solutions of which the oxide or hydroxide may medium and may readily be separated from it, for ex be precipitated are well-known and generally include 55 ample by filtration or centrifuging, without significant the salts, for example the halides (e.g. chloride and loss of the costly ruthenium. Moreover, the catalyst bromide), and sulphate, and the salts of organic acids, remains effective and may be re-used. especially of the aliphatic acids, for example, the ace It is desirable for dimerisation to be effected in pres tate or lactate. Mixtures of aluminium oxide and hy ence of hydrogen since this not only increases the total droxide may be used, and also mixtures with other 60 proportion of dimer plus hydrodimer formed, but also compounds. Such mixtures may be used to modify the increases the relative proportion of hydrodimer to di effect of the catalyst. For example the oxide or hydrox mer. Instead of gaseous hydrogen itself a hydrogen ide of aluminum may be mixed with other compounds, donor, that is a compound which under the conditions for example those of tin, copper, bismuth, nickel, palla of the reaction is capable of supplying hydrogen, may dium or cadmium. Thus, in dimerisation of acrylonitrile 65 be used, for example a metal hydride such as calcium the inclusion of a proportion of bismuth when prepar hydride, sodium borohydride or lithium aluminium ing a catalyst by co-precipitating ruthenium with alu hydride, a metal alkyl such as aluminium triethyl and mina, gives a highehr proportion of hydrodimer (adipo zinc dibutyl, and hydrogen transfer agents such as iso 3,946,066 3 4 propanol and cyclohexene. Analysis of the catalyst gave the following result, 7.9% Although the temperature of the dimerisation or w/w Ru, 23% w/w Al. hydrodimerisation reaction may vary widely, when using our catalysts we prefer to operate in the range EXAMPLE 2 from 50° to 200°C, more preferably 100° to 150°C in 5 In a similar way, 10 parts of aluminium chloride hex order to preserve the catalyst activity and to reduce ahydrate and 1 part of commercial ruthenium chloride production of undesired organic by-products. The re hydrate were dissolved in 100 parts of deionised water, action may be carried out under pressure, and when a solution of 0.5 parts of bismuth nitrate pentahydrate conducting the reaction in presence of gaseous hydro in 5 parts of 6N nitric acid was added and with rapid gen, or when using volatile reactants in the liquid O stirring at 20°C the mixture was made alkaline (to pH phase, pressure will normally be employed, for example 9) with about 40 parts of triethylamine. A thick gelati pressures up to 250 atmospheres. If desired, a solvent nous brown precipitate was then thrown down. After may be used, for example acetonitrile, propionitrile or stirring a further 15 mins. the precipitate was removed other solvents which are inert under the reaction condi by filtration and washed with water. The catalyst was tions, for example hydrocarbon solvents such as ben 5 dried by heating in an oven at 110°C for 12 hours and zene, toluene and cyclohexane, chlorinated hydrocar finely ground. bons such as chlorobenzene, and oxygen-containing organic compounds such as alcohols (e.g. methanol, EXAMPLE 3 ethanol and the propanols), ethylene glycol mono 1 part of catalyst as prepared in Example 1 was methyl or monoethyl ether and dioxan.