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Hydrogenation Catalyst Europaisches Patentamt J European Patent Office © Publication number: 0 319 116 Office europeen des brevets A1 EUROPEAN PATENT APPLICATION © Application number: 88304443.0 © B01 J 23/89 B01J int. ci* , 23/84 , C07C 29/17 (§) Date of filing: 17.05.88 ® Priority: 27.11.87 US 125955 © Applicant: GAF CORPORATION 1361 Alps Road © Date of publication of application: Wayne, NJ 07470(US) 07.06.89 Bulletin 89/23 © Inventor: de Thomas, Waldo © Designated Contracting States: 12 Trojan Avenue AT BE CH DE FR GB IT LI LU NL SE Parsippany New Jersey 07054(US) © Representative: Ford, Michael Frederick et al MEWBURN ELLIS & CO. 2/3 Cursitor Street London EC4A1BQ(GB) © Hydrogenation catalyst. @ The invention relates to a novel supported cata- lyst comprising a combination of metals with nickel as component (a), a metal having an atomic number greater than 43 from Groups VIIB and VIII of the Periodic Table as component (b) and rhenium as component (c) in a weight ratio of (a):(b):(c) of abour 10-90:0.05-5:0.03-10 and to the use of the catalyst for high pressure hydrogenation reactions, particu- larly for the hydrogenation of butanediol product containing aldehyde, butynediol and color forming impurities. < CO o CO Q. LU Xerox Copy Centre EP0 319 116 A1 HYDROGENATION CATALYST of about 35% to 40% concentration from which In one aspect the invention relates to a novel formaldehyde has been removed by the procedure hydrogenation catalyst and to a method for its described in U.S. Patent 2,993,708, at a pH of 6.5 preparation. to about 7.5. The solution is fed to a low pressure In another aspect the invention relates to the 5 reactor containing a Raney-type nickel catalyst of use of said catalyst in hydrogenation reactions. the type described in U.S. Patent 1,638,190, which is readily prepared by treating an aluminum alloy with caustic soda to dissolve out the aluminum and BACKGROUND OF THE INVENTION leave the nickel in a highly divided form. After the 10 1 ,4-butynediol solution is charged, the reactor is maintained at a temperature of from about 50° to * Glycols such as 1 ,4-butanediol and 1,6-hex- about 1 50 C. and under a hydrogen pressure of anediol are useful as monomers in a number of 200 and 300 psig. until the desired partial hy- polymers including, thermoplastics such as the drogenation of the 1 ,4-butynediol is achieved as polyester thermoplastics and polyether thermoplas- 15 determined by the cessation of hydrogen absorp- tics. Examples of such thermoplastics include poly- tion. (1 ,4-butylene terephthalate) resin block copolymers The reaction mixture is allowed to settle and containing blocks of poly(butyl ether) and aliphatic the partially hydrogenated product is separated polyesters such as poly(hexylene adipate). from the catalyst and charged to an intermediate The glycol products also find wide application so storage zone for pumping into the subsequent high in pharmaceutical and cosmetic uses where the pressure portion of the process. From the inter- degree of purity and color is of prime consider- mediate storage zone, the partially hydrogenated ation. A common method for preparing glycols has solution is charged to a high pressure reactor involved the hydrogenation of a butynediol in the maintained at about 2,000 to about 3,000 psig at a presence of a nickel/copper/manganese catalyst at 25 temperature of about 120° to 140 C. A stream of a pressure between about 300 and about 2000. hydrogen is simultaneously charged under pres- However, this process results in a product signifi- sure to the reactor. The reactor is filled with a fixed cantly contaminated with aldehydes, alkene diols bed of catalyst comprising about 12 to 17% by and color forming impurities which are particularly weight of nickel, 4 to 8% by weight of copper and objectionable when the product is employed as an 30 0.3 to 1 .0% by weight of manganese supported on adduct in cosmetic and pharmaceutical formula- a silica gel carrier. tions. Alkene diols and acid aldehydes are particu- The hydrogenated liquid product is separated larly troublesome because of their well known skin from the residual hydrogen which is recycled to- irritating properties. Also, the presence of low boil- gether with make-up hydrogen and returned to the ing aldehydes lowers the stability of the product on 35 reactor. The separated liquid product is then cool- storage. Accordingly, improved methods for the ed to about room temperature and charged to a preparation of glycols in a more purified state has storage tank. The product so obtained can then be been the subject of current research projects. subjected to distillation to recover 1 ,4-butanediol Many catalyst combinations, such as those dis- product. It has been found, however, that the silica cussed in the following patents, have been em- 40 gel carriers employed as the catalyst supports in ployed to achieve this end. the high pressure reactors of the above-described Of interest particular in the background of the processes physically degrade under the process present invention is the catalytic conversion 1,4- conditions resulting in the production of fines which 1 butynediol to ,4-butanediol as described in U.S. cause pressure fluctuations in the high pressure patent 3,759,845 entitled CATALYST FOR PRE- 45 reactor. These pressure fluctuations result in inter- PARING 1 ,4-BUTANEDIOL This patent discloses a mittent shut-downs, high catalyst replacement nickel/copper/manganese on alumina hydrogena- costs and consequent loss of production. tion catalyst which has improved stability and long- Accordingly, it is an object of the present in- er life than catalysts previously employed in similar vention to provide an improved hydrogenation cata- reactions. 50 lyst system which overcomes the deficiencies of Another process for the conversion of 1,4- the above hydrogenation processes while exhibiting butynediol to 1 ,4-butanediol is described in U.S. longer life and higher activity resulting, in longer Patent 3,499,445 to Wetherill. The process de- productivity and improved process economics. scribed therein comprises a partial hydrogenation Another obiect of this invention is to provide an of a pretreated aqueous solution of 1 ,4-butynediol improved catalyst for the hydrogenation of corn- EP0 319 116 A1 pounds containing carbon to carbon unsaturation or perature, e.g. 100°C.-150 C, and then calcining * " a carbonyl group. the dried product at 350 C.-475 C. for about 10 to It is another object of the present invention to about 20 hours, preferably 12 to 15 hours, to provide an improved hydrogenation process for the convert the nickel salts to oxides. The absorption conversion of 1 ,4-butynediol to 1 ,4-butanediol in 5 step can be accomplished in one or more stages to high yields and selectivity. arrive at a nickel concentration within the above It is another object of the present invention to range. For example, when a plurality of absorption provide a highly active hydrogenation catalyst steps are employed, the support may be immersed which be can prepared by an economical and in the aqueous solution for a short period, e.g. 0.5 commercially feasible process. 10 to 10 minutes with agitation, after which the unab- These and other objects of the invention will sorbed solution is decanted and the impregnated become apparent from the following description support dried by moderate heating to drive off and disclosure. water. The decanted solution is then employed to rewet the initially impregnated support for addi- 75 tional absorption of nickel salt and again dried. THE INVENTION These immersion, decanting and drying steps can be repeated as many times as required to provide the desired content of nickel before calcining the In accordance with this invention there is pro- nickel impregnated support. vided a highly active hydrogenation catalyst of (a) 20 The calcined, supported nickel oxide is then nickel, (b) a metal having an atomic number great- contacted with an aqueous solution of metal com- er than 43 selected from Groups VIIB and VIII of ponent (b) nitrate, acetate or carbonate and per- the Periodic Table and (c) rhenium combined in a rhenic acid, rhenium oxide or rhenium acetate con- weight ratio of between about 10 and about 90 wt. taining proportions of component (b) and rhenium % of metallic nickel, between about 0.05 and about 25 suitable to provide concentrations of these metals 5 % wt. of (b) and between about 0.03 and about within the above catalyst ranges. The absorption of 10 wt. % of metallic rhenium; the most preferred the component (b) and rhenium can be effected weight ratio being between about 12 and about 25 separately or in admixture in one or more stages wt. % nickel to between about 0.09 and about 0.6 as by the procedure described above. wt. % (b) to between about 0.09 and about 0.6 wt. 30 After the amount of metals desired in the final % rhenium. The remaining amount of the catalyst, product have been absorbed and dried on the composition, e.g. about 5% to about 90% of the support, the composition is calcined as described composition, represents the support on which the above, whereby oxides of the respective metals are metals are deposited. Suitable supports include obtained. carbon, magnesium silicate, bentonite, zeolite, met- 35 The product is recovered in discrete particles al alloys, silica- alumina and magnesium oxide- such as granules, dust or powder which can be silicon oxide mixtures. The most preferred support formed into tablets or hollow or solid core extruded for the present catalyst system is 7-alumina in fluted shapes or any other convenient form, de- fluted form although any crystalline high surface pending on the support selected, by conventional form can be employed.
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