Improved Nickel Boride-Polymer Catalyst Composition

Europaisches Patentamt European Patent Office © Publication number: 0 219 576 Office europeen des brevets A1

® EUROPEAN PATENT APPLICATION

© Date of publication of application: © Applicant: UNILEVER NV 29.04.87 Bulletin 87/18 Burgemeester s'Jacobplefn 1 P.O. Box 760 NL-3000 DK Rotterdam(NL) © Designated Contracting States: NL © Inventor: Boerma, Hiepke Roemer Visscherstraat 19 NL-3132 ER Vlaardingen(NL) Inventor: De Jongh, Rudolph Otto Cornelie van Zantenstraat 216 NL-2551 PR The Hague(NL) Inventor: van Dljk, Cornells Gerrft van der Veenstraat 56 NL-3333 BG Zwijndrecht(NL)

© Nickel boride hydrogenation catalysts stabilised with polyvinylpyrrolidone, having constant excellent quality, are prepared by incorporating glycerol mon- coleate before the alcohol is evaporated off.

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IMPROVED NICKEL BORIDE-POLYMER CATALYST COMPOSITION

The invention relates to hydrogenation cata- The catalyst made according to the present lysts, more particularly the invention relates to very invention is very active and very stable. The cata- finely dispersed nickelboride catalysts which are lyst is excellent for use in the hydrogenation of stabilised with an organic linear polymer containing unsaturated compounds, in particular fatty com- pyrrolidone groups, and the use of the catalyst. 5 pounds such as triglycerides. During hydrogenation Such catalysts are already known in the art. of such triglycerides the very high activity is strik- For instance, European patent specification (EP-B) ing, particularly at low temperatures, and the high 8407 (Pharmaceutische Fabrik Heyl) describes col- selectivity is also noteworthy because little loidal metal catalysts of the elements of the 8th triglyceride with only saturated fatty acid residues sub-group of the periodic table which are incor- w is formed (low percentages of solids are deter- porated in a solution of a linear polymer. Example mined by n.m.r. at 30 and 35°C), and the remain- 22 describes a nickel catalyst stabilised with poly- ing unsaturated bonds have primarily a ciscon- vinylpyrrolidone; propanol is used as the solvent. figuration. This catalyst is used in the hydrogenation of It is preferable to disperse this catalyst in oil, "Becel oil". ?5 e.g. a triglyceride. Preferably the nickel boride is US-A-4 327 235 (Nakao) describes colloidal very finely dispersed with an organic polymer in nickel boride catalysts, stabilised with polyvinylpyr- the triglyceride and the average particle size is rolidone in alcohol, and the use thereof in the between 0.5 and 10, preferably between 1 and 5 hydrogenation of unsaturated compounds having a nanometres. The amount of linear organic polymer double bond attached to a tertiary carbon atom. 20 in the oil suspension of the catalyst is usually This double bond is hydrogenated without any oth- between 0.5 and 5% by weight and the amount of er double bonds being affected. nickel boride, calculated as nickel, is between 0.1 Furthermore there is European patent and 5% by weight. In the catalyst system the application(EP-A-) 132889 (Unilever) which dis- atomic ratio of boron to nickel is between 1 and closes a finely divided nickel boride hydrogenation 25 3:1. A polar linear polymer containing vinylpyr- catalyst which is stabilised with an organic linear rolidone and optionally other monomeric groups is polymer dispersed in a fatty substance like a normally used. A copolymer of vinylpyrrolidone and triglyceride oil or a fatty amide. The catalyst is vinylacetate (PVPA/A) is preferred. The average stable upon storage and has a good selectivity. molecular weight of the polymer used is between This catalyst yields excellent results in hydrogena- 30 20,000 and 250,000, and preferably between tion processes. 30,000 and 80,000. Also there is European patent application (EP- The catalyst is prepared in a solvent, usually in A-) 159101 (Unilever), which is not a prior publica- a volatile polar solvent such as a C,-C3 alkanol. tion, describing more active nickel boride catalysts Preferably ethanol is be used. prepared by reduction with alkali borohydride of 35 The catalyst according to the invention can be solutions of nickel salts which contain less than 5 made by adding a solution or suspension of alkali moles of crystal water. borohydride (preferably NaBH«) to a solution or The present invention now provides a very suspension of the nickel salt in an atomic ratio B:Ni active, finely dispersed nickel boride catalyst com- = (1.5-3):1, at least one of the solutions containing position which has been stabilised with a linear 40 the linear organic polymer dissolved therein. The organic polymer which comprises pyrrolidone addition is made in a hydrogen or inert gas at- groups and which composition also contains a par- mosphere at a temperature of between 0 and tial fatty acid polyol ester in an amount which 80 °C, preferably between 20 and 60 °C, leading to ranges between 5 and 0.5 times the weight of the formation of very finely dispersed nickel boride. nickel. Preferably the amount of ester is between 3 45 According to the present invention a partial and 1 times the weight of nickel. ester of a polyol and fatty acid is also incorporated For the preparation of the nickel boride a nickel in the solution of the organic polar solvent. The salt, e.g. halogenide, is used, such as nickel chlo- amount of partial ester normally present is from 5- ride with 6, 4 or less molecules of crystal (lattice) 0.5 times the weight of nickel, preferably between water, particularly nickel chloride dihydrate. Other so 3 and 1 times the amount of nickel. C«rCM fatty salts, e.g. nickel acetate, can also be used if they acid esters are preferred and so are unsaturated contain non-reducible anions. Preferably the salts fatty acid esters. On completion of the reduction, contain less than 5 molecules of crystal water. oil is added to the system. After addition of the oil, Anhydrous salts can also be used. the solvent is often removed, for instance by vacu-

> 3 0 219 576 4 um evaporation at a temperature between 15 and The rate of hydrogenation (iodine value de- 60 °C, with stirring. crease) per minute can be monitored conveniently The oil or fat in which the catalyst is sus- by observing the refractive index of the oil and/or pended preferably has a melting point below 40°C. by following the consumption of hydrogen so as to It was found that the transfer of the nickel 5 determine the proper end point. boride to the oil is improved by addition of a fatty The invention will now be illustrated by the acid partial ester such as glycerol mono-oleate - following Examples. (G.M.O.) or monostearate. Evaporation of alcohol at 50°C can proceed faster and without foaming oc- curring, giving better and reproducible catalysts of w Example I high activity and high selectivity. The polyol partial ester can be added to the organic polar solution The catalyst was prepared in a three-necked before or after the reduction with alkali flask connected to a gasmeter. 9.6 gram NiCI,.6H20 borohydride. Preferably, especially in the case of was heated at 55 °C for 30 minutes under vacuum unsaturated fatty acid partial esters, it is added 75 by an oil pump to be converted to the dihydrate. 3 after the reduction. Partial esters containing glyc- gram PVP/VA (50% alcoholic solution E 735, ex erol mon-oleate are preferred. GAF-Europe, Schiedam, Netherlands) in 40 ml ab- The invention also comprises a process for solute ethanol was then added to the reactor. 3.8 hydrogenating unsaturated fatty compounds de- gram NaBH. suspended in 160 ml absolute ethanol rived from C,0-C2» carboxylic acids, particularly 20 was added at room temperature and in a hydrogen triglycerides, fatty acid methylesters and nitriles, atmosphere. 200 mi nickel boride solution was thus using a finely dispersed nickel boride catalyst pre- formed containing 1.2% nickel (calculated as met- pared from a suitable nickel salt, stabilised with a al). linear organic polymer and a partial polyol fatty To this solution 120 gram soyabean oil (IV acid ester. 25 133) and 6 gram G.M.O. (glycerol mono-oleate Between 5 and 500 ppm, preferably between 5 60%, ex PPF, Zwijndrecht) were added. Evapora- and 200 ppm nickel is usually added in the form of tion of alcohol was carried out in vacuo under nickelboride (ppm equals here mg Ni per kg un- stirring at 50 °C in 40 minutes. No foaming was saturated compound). The hydrogen pressure is observed and the catalyst was found to be very between 100 and 5000 kPa and the reaction mix- • 30 active. ture is stirred. The hydrogenation temperature is For the purpose of comparison, the above was between 20 and 180°C. On completion of the hy- repeated in the absence of G.M.O. and the alcohol drogenation, the catalyst and polymer are removed, was evaporated irj vacuo under stirring at approxi- partly by filtration and/or by washing with a dilute mately 35°C in 120 minutes. At the end of the acid solution, e.g. citric acid, and, if necessary, by 35 transfer, foaming occurs, hampering the evapora- treating the oil with bleaching earth. tion. A 2% nickel boride (calculated as metal) dis- The present invention accordingly provides persion is formed. novel and very active hydrogenation catalyst compositions comprising finely divided nickel boride stabilised with a linear polymer containing pyr- ao Example II rolidone and also containing a partial fatty acid polyol ester group, which catalyst compositions are Example I was repeated, but the nickel boride so active that with said catalyst neutralised, solution contained 4 gram polyvinylpyrrolidone - bleached and deodorised soybean oil with an io- [average molecular weight 40,000) K 30 (ex Fluka, dine value of between 130 and 135 can be hy- 45 3uchs, Germany) instead of the copolymer PVP/VA jrogenated in a 1 litre Parr autoclave (ex Parr Df Example I. Evaporation of the alcohol |n vacuo Instrument Comp. Inc., Illinois, U.S.A.) at 110°C was carried out at 50°C in 25 minutes. Hardly any and 600 kPa hydrogen pressure with a head space oaming occurred. The catalyst was active and Df 50% of the capacity and a stirring rate of 700 selective. -.p.m. with 50 ppm of nickel (calculated as metal) 50 For the purpose of comparison, the above Ex- :o a decrease in iodine value of the soyabean oil of ample was repeated, with the difference that no 35 units in less than 35 minutes. 3.M.O. was present. Evaporation, in the absence of More in particular, the present invention pro- 3.M.O., was carried out at 10°C in 150 minutes /ides a catalyst, having by the feature that the rate with strong foaming. This catalyst was less active yi iodine value decrease is at least 1 unit in iodine 55 han the reference. /alue per minute if the hydrogenation is carried out as described in the previous paragraph.

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example in that the composition also contains a partial fatty acid polyol ester in an amount which ranges be- Example I was repeated, with the difference tween 5 and 0.5 times the weight of nickel. that 6 gram G.M.O. was added to the reaction 2. Catalyst according to claim 1, characterised mixture before addition of NaBH4. Evaporation of 5 in that the partial fatty acid polyol ester is a glyc- alcohol was carried out at 50°C in 30 minutes. No erol ester. foaming was observed and the catalyst was found 3. Catalyst according to claim 1 or 2, charac- to be very active and selective. terised in that the fatty acid polyol ester is a Co-Cx fatty acid ester. 10 4. Catalyst according to any of the claims 1-3, Examples iv-vi characterised in that the fatty acid group of the ester contains at least one ethenic double bond. The catalysts suspended in soyabean oil as 5. Catalyst according to any of the claims 1-4, described in Examples I, II and III were compared characterised in that the catalyst composition is as to their activities. 450 gram soyabean oil (IV 75 dispersed in an alcohol, fatty ester or fatty amide 133) was hydrogenated to IV 97-98 at 110°C and material. 600 kPa hydrogen pressure in an autoclave having 6. Process for the preparation of a catalyst a capacity of 1 litre (ex Parr,' Illinois, U.S.A.). stirred composition according to claim 1, whereby an at at 700 r.p.m. least partly dissolved nickel salt is reduced with With an input of 25 ppm Ni of the nickel boride 20 alkali borohydride in the presence of a linear poly- suspension, a hydrogenation time is found of: mer which is also at least partly dissolved in a Example I 35 minutes Comparison 60 min- polar organic solvent, characterised in that a partial utes fatty acid polyol ester is incorporated in the polar Example II 60 minutes Comparison 90 min- organic solution. utes 25 7. Process according to claim 6, characterised Example III 25 minutes Comparison 60 min- in that the polar solvent is a C,-C3 alkanol. utes (according to Example I) 8. Process according to claim 6 or 7, charac- The activities of the catalyst compositions ac- terised in that, after the nickel boride has been cording to the invention in Examples I, II and III prepared, a triglyceride oil is added and the polar were found to be reproducible within a narrow 30 solvent is removed by evaporation. range, whereas those of the comparisons were not 9. Process for the hydrogenation of unsaturated quite reproducible. fatty compounds, characterised in that finely dispersed nickel boride composition according to any of the claims 1-5 is used. Claims 35 10. Process according to claim 9, characterised in that the amount of nickel boride catalyst used, 1. Catalyst composition comprising finely dis- calculated as nickel, is between 5 and 500, prefer- Dersed nickel boride stabilised with a linear poly- ably less than 200 ppm. ner containing pyrrolidone groups, characterised in 40

>5 J European raieni Application number Office EUROPEAN SEARCH REPORT EP 85 20 1708

uvjuuimcw l a WNSIPEHEP TO Be RELEVANT wimiwn ui uwuiuviii wun uiuibaiion. wnere appropriate, Heievant CLASSIFICATION OF THE of relevant passages to claim APPLICATION (Int. CM)

B 01 J 31/28 jir-A-u xja atsy ( ujNiLiiVjSK) 1-10 C11C 3/12 * Claims 1-10 *

1-10 (METALLGESELLSCHAFT) * Claims 1-9 *

1-10 * Claims 1-5 *

TECHNICAL FIELDS SEARCHED (Int. CI.*)

B 01 J C11C

@~ a^it.11 i«>juii iw uiBii urawn up tot si i claims ww ui completion or ine searcn Examiner CHE HAGUE 18-06-1986 1EERTENS J.

: tneory or principle underlying the invention I : earlier patent document, but published on, or I : particularly relevant if taken alone after the filing date : particularly relevant if combined with another ) : document cited in the application document of the same category : document cited for other reasons i : technological background . ) : non-written disclosure i . member of the same patent family, corresponding ' : intermediate document document