Title of Invention	CATALYST COMPRISIGN NICKEL, SILICA, ALUMINA AND MAGNESIUM
Abstract	The present invention relates to a catalyst nickel, silica, alumina and magnesium, wherein the nickel to magnesium atomic ratio is 5-75. In particular the present invention relates to a catalyst comprising nickel, silica, alumina and magnesium, wherein the nickel to silicium atomic ratio (Ni/Si) is 2 to 30 the nickel to aluminum atomic ratio (Ni/Al) is 9 to 40 and the nickel in magnesium atomic ratio (Ni/Mg) is 5-75. The invention further relates to a method for preparing such a catalyst. The invention futher relates in a process for hydrogenating understand organic compounds.

Title of Invention

CATALYST COMPRISIGN NICKEL, SILICA, ALUMINA AND MAGNESIUM

Abstract

The present invention relates to a catalyst nickel, silica, alumina and magnesium, wherein the nickel to magnesium atomic ratio is 5-75. In particular the present invention relates to a catalyst comprising nickel, silica, alumina and magnesium, wherein the nickel to silicium atomic ratio (Ni/Si) is 2 to 30 the nickel to aluminum atomic ratio (Ni/Al) is 9 to 40 and the nickel in magnesium atomic ratio (Ni/Mg) is 5-75. The invention further relates to a method for preparing such a catalyst. The invention futher relates in a process for hydrogenating understand organic compounds.

Full Text	WO 2004/1135204 PCT/NL 2003/000705 NICKLE CATALYST FOR HYDROGENATIONS REACTIONS The invention relates to a catalyst comprising nickel, alumina magnesium and silica, to a method for preparing such a catalyst and to a process for hydrogenating unsaturated organic compounds. Nickel/alumina catalysts with a nickel/aluminium ratio of 2-20 are 5 known to be active catalysts for the hydrogenation of unsaturated organic compounds from EP-A 0 167 201. The catalysts claimed in EP-A 0 167 201 further comprise silica in a nickel/silica ratio of 1-20. The disclosed catalysts are prepared in a process wherein first a nickel hydroxide/carbonate is precipitated and thereafter aluminium nitrale and silicate are added. The 10 resulting precipitate is thereafter activated with hydrogen. The examples show catalysts comprising at least 85 wt. % Ni that are used in the hydrogenation of fish oil. It is reported that they may retain their activity for a prolonged period and tend to show a high poison resistance. As an indication for selectivity an aspecific assay is referred to, based on a combination of melting point and 15 hydrogenation time. Besides the fact that the latter parameter has been found to be rather an indicator for activity, no quantitative data are presented on the selectivity in soy bean oil hydrogenation though. EP-A 1 101 530 describes a nickel-iron catalyst for use in the hydrogenation of resins. Magnesium (oxide) may be present. This publication 20 does not recognise the relevance of the particle size with respect to the hydrogenation of unsaturated compounds and the working examples do not mention the particle size of the used catalyst. It is not suggested to use the catalyst in the hydrogenation of fatty substances, such as vegetable or animal oils. 25 US-A 5 493 037 relates to a fixed bed process for hydrogenating fatty acids, comprising the use of a formed nickel catalyst with a relatively low nickel content. Contents of 10-50 wt. % are mentioned, without specifying how WO 2004/035204 PCT/NL2003/000705 2 the weight percentage is defined. A magnpsiuin salt may be present as a support or in the binder (clay). The publication is silent about suitable pore volumes and nickel surface areas. There is a continuing need for alternative catalysts for the 5 hydrogenation of unsaturated organic compounds. In general when searching for a suitable catalyst for the bydragenation of a particular compound, one has to compromise e.g. between activity and selectivity. For instance, certain catalyst characteristics (e.g. an open pore structure) may favour the selective hydrogenation of fatty oils while al the same tune result in longer reaction 10 times when hydrogenating more contaminated oils because of their higher susceptibility to poisoning. Therefore, often different types of catalysts are required for different types of unsaturated organic compounds. For example, a atalyst may either be suitable for clean oils, such as soy bean oil, or for more ontaminated oils, such as rape seed oil or fish oil. 15 is an object of the present invention to provide a novel catalyst hat may be used as a favourable alternative to known catalysts for ydrogenating unsaturated organic compounds, in particular fatty oils. has been found that this object can be realised by a catalyst omprising nickel, silica, alumina and also magnesium in a particular ratio. 20 ccordingly, the present invention relates to a catalyst comprising nickel, silica, alumina and magnesium, whereni the nickel to magnesium atomic ratio is 5-75, preferably 5-50. In the catalyst, magnesium is thought to act as a catalyst promotor in the hydrogenation of urtsaturated hydrocarbons, in particular fatty 25 substances, as is indicated by the Examples 1 and 2, below. In particular, the present invention relates to a catalyst comprising nickel, silica, alumina and magnesium, wherein the nickel to silicium atomic ratio (Ni/Si) is 2 to 30, the nickel to aluminium atomic ratio (Ni/AI) is 9 to 40 and the nickel to magnesium atomic ratio (Ni/Mg) is 5-75. WO 2004/-03524 PCT/NL2003/000705 3 It baa been found that a catalyst according to the present invention shows a very high activity for the hydrogenation of unsaturated compounds, in particular unsaturated fatty substances, such as fatty oils including ucsaturated fats. These oils typically mainly comprise glycerides, in particular 5 triglycerides. The invention may very suitably be employed for the hydrogenation of fatty substances of vegetable and/or animal origin for food grade applications. A catalyst according to the invention has been found to have a very high, activity as a hydrogenation catalyst. In particular, a catalyst according to 10 the invention is found to be hignly active for relatively clean oils - i.e. oils with a relatively low sulphur conteat - like soy bean, as well as for more contaminated oils, lite fish oil, having a high sulphur content. A catalyst according to the invention may very suitably be used in a slurry process. Accordingly the present invention also relates to a slurry 15 ejomprising a catalyst according to the invention. The skilled person will know how to make a suitable slurry based upon common general knowledge and the information disclosed herein. For instance, as a liquid phase the feed stock to be processed is very suitable. The total weight percentage of Ni in the reduced catalyst may be 20 chosen in a wide range, as defined by the Ni/Si, Ni/Al and Ni/Mg ranges. Preferably, the amount of nickel is at least 50 wt. % and not higher than 80 wt. %, more preferably 51-80 wt. %. Even more preferably the amount of nickel is 55-75 wt.%. Very good results have been achieved with an amount of nickel of 65-72 wt.%. 25 In a preferred embodiment, Ni/Si is at least about 2.5, more preferably at least about 3. Very good results have been achieved with a Ni/Si of at least 6.5. The Ni/Si is preferably about 22 or less, more preferably about 15 or less. Very good results have been achieved with a Ni/Si of up to about 7.5. WO 2004/035204 PCT/NL2003/000705 4 Ni/Al is preferably about 10 to about 35, more preferably about 10- 30, even more preferably about 15-25. Very good results have been achieved with a catalyst having a Ni/Al of more than 20, e.g. up to 22. Ni/Mg may preferably be chosen in the range of about 5-50, more 5 preferably 5-30, even more preferably about 6 to about 20. "Very suitable is a catalyst with a Ni/Mg of about 7.5-12.5, e.g. about. 10. In principle it is possible that small amounts of one or more other elements are present in the catalyst, but this is not required. In particular, very suitable is a catalyst of tile invention which is essentially free of iron 10 (typically having less than 0.1 % Fe). In order to prevent oxidation of the catalyst may be coated with a protective layer. The protective layer may have any form, wherein at least the cataiytically active sites of the catalyst are essentially covered with a protective material. 15 Protection of the catalyst is in principle possible by applying a layer of oxide on the catalyst, in particular on the nickel (crystallites). A method for applying a suitable film of oxide is known in generally known in the art, and may be based on DB19909175. The oxide may suitably be removed shortly before use. The skilled person will know now to remove (e.g. by reactivation) 20 the oxide, based upon a known method for reactivating known nickel catalysts on a support (e.g. on alumina, silica or a combination thereof). A highly suitable protective material for protecting a catalyst, such as a hydrogenation catalyst, in particular a catalyst according to the invention, is a material comprising a fatty substance, preferably a hardened oil or fat, 25 more preferably a hardened vegetable oil or fat. Very good results have been achieved with, a catalyst coated with hardened soy bean fat. Other highly preferred examples of fatty substances include hardened palm oil fat, hsrdsned sunflower oil and hardened rapessed oil. A mixture comprising a number of fatty substances may very suitably be used. WO 2004/035204 PCT7NL2003/000705 5 An advantage of a protective material comprising a fatty substance instead of a thin film of oxide on the catalyst, is that the catalyst does not need to be re-activated before use. At a high temperature (e.g. above about 150 °C) re-activation will generally be possible without a problem but in particular for 5 low temperature applications or for applications wherein the reaction is started at a relatively low temperature (e.g. below 150 °C), re-activation of a catalyst with a protective oxide film may take a relatively long time, resulting in a longer overall reaction time, or may not take place to a sufficient extent at all. 10 The protective material forming a protective layer may be provided around individualised particles, or at least on the catalytically active part thereof (in particular in case a layer of oxide). In particular in case of a catalyst provided with a fatty substance as a protective layer, a multiplicity of catalyst particles may be incorporated (in 15 particular dispersed) into the protective material forming the protective layer. The protective material with catalyst particles incorporated therein, may very suitably be in the form of a participate material. Such particulate material is also referred to herein as matrix particles. The size of the matrix particles is not particularly critical. Conveniently, matrix particles may for 20 instance have a size (as defined by the diameter of the enveloping circle) in the range of about 1 to about 12 mm, more in particular in the range of about 2-10 mm. The size of the catalyst particles incorporated therein is usually at least bout one or two orders of magnitude less than the matrix particles. A referred size of the catalyst particles is as the preferred particle diameters 25 efined below . has been found that in particular in an embodiment wherein the atalyst is provided with a protective layer by having the catalyst incorporated nto the protective material, the ease of handling is improved, because it ontributes to reduced dusting of the catalyst. WO 2004/035204 PCT/NL2O03/000705 6 The amount of protective material is preferably at least about 40 wt. %, more preferably at least about 55 wt. % even more preferably at least about 60 wt. %. Very good results have been achieved with an amount of at least 65 wt. %. (All wt. %'s based upon the total weight of catalyst plus 5 protective material). Preferably tbe amount of protective material is less than about 95 wt. %, more preferably less than about 90 wt.%, even more preferably less than about 85 wt. %. Very good results have been achieved with a weight percentage of up to about 82 wt % (All wt. %'s based upon the total weight of 10 catalyst plus protective material). The melting temperature of the protective material with which the catalyst is coated is preferably leas than, the temperature at which the hydrogenation is carried out, in order to facilitate dissolution of the protective material at the beginning of a hydrogenation process in accordance with the 15 invention. Good results have inter alia been achieved with a protective material have a melting temperature of less than about 90oC, more in particular of less than about 35oC. Very good results have been achieved with a melting temperature of less than 80°C. For practical reasons, the minimum melting temperature of the 20 protective material is in general higher than the temperature at which the catalyst is stored before use. Preferably the melting temperature is at least about 40°C, more preferably at least about 50oC. In particular, when the catalyst is used in a slurry process, the protective coating will preferably dissolve in the feedstock. Else, the coating 25 may be removed from the process, shortly before using the catalyst in a hydrogenation process. The coating may very suitably be removed by contacting the catalyst with a solvent, such as a feedstock, preferably at a temperature higher than the melting point of the coating fat. For a good activity, the pore volume (as measured by N2 desorption, 30 20-600 A, on a Quantachrome Autosorb 6) is preferably at least 0.4 ml/g, more WO 2004/035204 PCT/NL2003/000705 7 preferably at least 0.5 ml/g, even more preferably at least 0.55 ml/g. The upper limit is not particularly critical. Very good results have been achieved in the range of 0.4 to 1 ml/g. More preferably, the pore volume is up to about 0.75 ml/g, e.g. 0.6-0.7 ml/g. 5 The volume average particle size (D(v.0,5)) of a catalyst according to the invention may be chosen in a wide range, inter alia depending upon the intended use, in particular if the catalyst is provided with a protective coating. In practice, in particular for improving the hydrogenation reaction rate of unsaturated fatty substances, one may favourably choose to use a 10 catalyst with a D(v_0,5) of less than about 20 µm. Very suitable is a D(v.0,5) of less than about 15 µm, in particular of less than about 10 µm, more in particular of less than about 8.5 µm. The volume average particle size is preferably at least about 1 µm. more preferably at least about 2 µm, even more preferably at least about 3. 15 A volume average particle size in the range of about 3 to about 8 µm has been found to be highly advantageous. In particular when compared to a catalyst with a higher average particle size (e.g. 8.6 µm) such a catalyst has been found to have a higher activity with respect to hydrogenation of a unsaturated organic compound, especially a fatty substance. 20 Very good results have been achieved with a catalyst having a volume average particle size of about 4 to about 7µm. D(v.0,5), as used herein, is the value as measured by LASER diffraction with a Malvern MS 1002, lens 45 mm - which corresponds to a measuring range of 0.1-100 µm - using "Independent" as the model for 25 calculating the particle size. The (D(v.0,5)) as used herein is the diameter of the catalyst per se, i.e. without a protective coating. The catalyst preferably comprises nickel crystallites. The majority of the nickel crystallites preferably has a diameter of less tlian 60 Aµ, more preferably of about 20-50 Aµ, even more preferably of about 20-40 Aµ. The size as 30 used herein is the value as determinable by XRD on the reduced catalyst WO 2004/035204 PCT/NL2003/OO0705 8 protected by a coating of a fatty substance (such as hardened soybean fat) (See also Examples). The nickel surface area is preferably 75 to 200 m2/g of nickel, more preferably approximately 100-175 m2/g of nickel, ever more preferably 5 approximately 100-150 m2/g of nickel. Very good results have been achieved with, a catalyst having a nickel surface area of 110-145 m2/g of nickel. The nickel surface area as used herein is the value can be determined by hydrogen chemisorption at 50 °C, after in situ reduction with hydrogen (60 ml/rain) for 2 hours at 400 °C and subsequently degassing for 14 hours at 350 10 °C in a Carlo Erba Sorptomatic 1900. The amount of adsorbed hydrogen is determined by extrapolation of the reduction isotherm to zero pressure and the nickel surface area is calculated assuming a site density of 6.77 Å2/atom. The BET surface area preferably is about 300 to about 450 m2/g catalyst, more preferably about 350 to about 400 m2/g catalyst. The BET 15 surface avea as used herein is toe value that can be measured by determining the amount of nitrogen adsorbed at 77 K and P/Po of approximately 0.3 and assuming a nitrogen cross sectional area of 16.2 Â 2, after degassing the catalyst sample at 180°C. The average pore diameter (APD), as calculated from the measured 20 pore volume (PV) and BET surface area by the formula APD= 4000G*PV/BET, rnay for example very suitably be chosen in the range of about 10-500 Å, preferably in the range of about 40- 200 Å, more preferably about 60 - 100 Å. It is possible to make a catalyst in a process wherein first a nickel precipitate is made, which is subsequently aged with an alumina source and 25 with a silica source (which may be added together with the alumina or thereafter). In a preferred embodiment, the catalyst is made from a catalyst precursor that is prepared by co-precipitation., of which it will be clear to the skilled professional how to choose suitable method conditions, In a co- 30 precipitation method according to the invention nickel, alumina, silica and WO 2004/035204 PCT/NL2003/000705 9 magnesium are precipitated together (i.e. without forming intermediate precipitates of only one or some of the camponents). In such a method, a nickel source, a silica source, an alumina source and a magnesium source may be mixed, in a liquid, (e.g. water or an aqueous solution) to form a precipitate (a 5 catalyst precursor), comprising all four said coinponents- Prefexably the co-precipitation ia carried out with the aid of a precipitant, e.g. an alkali metal carbonate (such as Na2CO3) or an alkali, metal hydroxide (such as NaOH). It is an advantage of the above co-precipitation methodology that it 10 can be performed in a single co-precipitation step. Very good results have been achieved with a method wherein the co- precipitation is performed at alkaline pH, e.g. at a pH of approximately 7.5-8.5 (as measured at 25 °C). It has been found that under alkaline conditions a very efficient, generally a substantially complete precipitation of nickel and 15 magnesium, can be realised, in particular at elevated temperatures e.g. in the range of 50-100 °C. In a preferred embodiment, the precipitation is carried out at a temperature in the range of 20-100 °C . Very good results have been achieved at a temperature in the range of 50-100 °C, in particular at a temperature in 20 the range of 75-98oC. The catalyst precursor may thereafter be isolated, e.g. by filtration, from the liquid and calcined, e.g. at a temperature of 200-750 °C for 1-5 hours. The catalyst may very suitably be activated by reduction with hydrogen, e.g. at a temperature of 250-600 °C, e.g. for 1-5 hours. The nickel, silica, alurnina and magnesium sources may be chosen 25 from sources commonly used to prepare catalysts. Suitable nickel sources include inorganic nickel salts, preferably Ni(NO3)2, NiCl2, NiSO4, and organic nickel salts, preferably nickel acetate. Preferably the nickel source is a solution or suspension of any of these salts. WO 2004/0353204 PCT/NL2003/000705 10 Suitable silica sources include water glass, sodium silicate (Na2SiO3) and colloidal silica. Preferably the silica source is a solution or suspension of any of these components. Suitable alumina sources include aluminium salts, preferably 5 inorganic salts suck as AlCl3, Al(NO3)3 and sadium aluminate (NaAlO2). Preferably the alumina source is a solution or suspension of any of these salts. Suitable magnesium sources include magnesium salts, preferably inorganic salts such as Mg(NO3)2, MgCl2, and MgSO4. Preferably the magnesium source is a solution or suspension of any of these salts. 10 The catalyst may be coated with a protective layer, e.g. a fatty substance such as hardened soy bean fat, nardened palm oil fat, hardened sun flower oil fat or a combination thereof, which may serve to avoid oxidation of (parts 01) the catalyst (see also above). The skilled person will know haw to provide a protective coating, 15 based upon common general knowledge and the information disclosed herein. This may for example be done by blending a (reduced) catalyst powder into the molten coating material (such as the molten fat) and subsequently solidifying the resulting suspension to form flakes or droplets of coated catalyst particles. For instance, one may let droplets of the suspension fall on a surface having a 20 temperature below the melting temperature of the fatty substance (such as a cooled plate) thereby solidifying the droplets to form matrix particles. Such method is very suitable for preparing particles generally having an essentially hemispherical shape. Another way to produce matrix particles is to let the droplets fell in a fluid (generally cooled fluid) wherein the particles solidify. 25 Thus more or less spherical matrix particles may be formed. It is also an option to flake the suspension to flakes of a suitable thickness. A catalyst according to the present invention may be used for a variety of applications, and in particular for catalytic hydrogenation. The catalyst may be employed in a process for hydrogenating organic compounds 30 wherein said compound is contacted with hydrogen in the presence of the WO 2004/035204 PCT/NL2003/000705 11 catalyst. The process conditions may be chosen from the processes typically used for the hydrogenation of a particular compound. The process may be a batch or a continuous process. Preferably, the process is a slurry-process. An important advantage of a hydrogenation process according to the 5 invention is the possibility to decrease the dosage of catalyst in order to achieve a particular conversion within the same hydrogenation time (contact time of feed (substrate) and catalyst) or to reduce the hydrogenation time at a particular catalyst dosage. A process according to the invention has been found to be 10 particularly suitable for the hydrogenation of a relatively clean oil (e.g. soy bean oil) and/or a more contaminated oil (e.g. fish oil or rape seed oil). A fatty substance hydrogenated in accordance with the present invention preferably mainly comprises triglycerides, such that the content of free fatty acids is quite low. For instance in a preferred feed stock 15 hydrogenated in accordance with the invention, such as a fully refined vegetable or animal oils, usually less than about 0.1 wt.% free fatty acids and preferably less than 0.05 wt.% is present. Since high concentrations of free fatty acids may deactivate the catalyst by nickel soap formation, their presence is preferably below said levels. 20 On the one hand it has been found, possible to maintain a high activity in the presence of contaminations such as sulphur in the contaminated oil. On the other hand the selectivity has been found to remain high enough to achieve a favourable conversion of the unsaturated compounds. As a result the present invention also offers a considerable advantage since it offers the 25 advantage that a single type of catalyst can very favourably be used in the hydrogenation of contaminated oil and also in the hydrogenation of clean oil. Thus a single stock of catalyst may be kept for the conversion of either of these products. The invention will now be illustrated by the following examples. 30 WO 2004/035204 PCT/NL2003/000705 12 Example 1 A metal solution (1000 ml) containing 95 g Ni/1 and 5g Mg/l was prepared from a NiCl2 solution (198 g Ni/1) and MgCl2.6H2O. The base solution 5 was prepared by dissolving 183 g Na2CO3 and 44.4 g Na2SiO3.5H2O in 1000 ml of demineralised water. The metal and base solution were injected at equal flaw sates (1000 ml/hr) into a. well stirred precipitation vessel containing 1725 ml of demineralised water and 3.8 g of Al2O2 as sodium aluminate. The temperature during precipitation wae maintained at 90 oC while the pH was 10 between 7.5 and 8.5. After precipitation the precipitate was washed with demineralised water and dried overnight at 110 °C. The dried catalyst was calcined for 1.5 hours at 375 oC and subsequently activated by reduction in hydrogen for 2 hours at 400 °C. The reduced catalyst powder was protected from air oxidation by 15 dispersing it in an inert atmosphere in molten, hardened soybean, fat at 80- 100 °C. Catalyst flakes were formed by solidifying the blend of reduced catalyst powder and coating fat on a cooling plate. The catalyst properties of the calcined sample are as summarised in Table 1. 20 Example 2 The catalyst of Example 2 was prepared according the procedure as described in Example 1, except that no magnesium, was added. 25 Example 3 The catalyst of Example 3 was prepared according the procedure as described in Example 1, except that no alumina was added. WO 2004/035204 PCT/NL2003/000705 13 Examples 4 and 5 The catalysts of Examples 4 and 5 were prepared according to the procedure as described in Example 1, except that variations were made in the 5 amount of starting materials resulting in catalyst properties as indicated in Table 1. Examples 6 and 7 10 The catalyst of Examples 6 and 7 were prepared according to the procedure as described with example 1, except that magnesium was replaced by copper and cobalt respectively. Example 8 15 The catalyst of Example 8 was prepared according to the procedure as describedin Example 1 except that a different agitation speed was used during the precipitation, (an agitation speed of 400 instead of 475 rpm was used). 20 Example 9: Characterisation and performance of the catalysts The pore volume and BET surface area of the catalysts were measured by nitrogen adsorption/desorption using a Quantachrome Autosorb-6. Particle size was determined by laser diffraction using a Malvern Mastersizer 1002. 25 The nickel surface area was measured by hydrogen chemisorption with a Carlo Erba Sorptometic 1900. The nickel crystallite size was measured with a Phillips DW1820 roöntgeii diffractometer using the Ni(111) peak (d-value 2.06 Ä). The soy bean oil (SBO) hydrogenating activity of the catalysts was 30 determined by the hydrogenation of 500 g of soybean oil (iodine value 130) and WO 2004/035204 PCT/NL2003/000705 14 measuring the time needed to reach an iodine value of 70. The catalyst loading was 0.0075% as nickel, the hydrogen pressure was 0.7 bar and the temperature was 204 °C. Tbe iodine value was measured by the Wijs melhod as described in A.O.C.S. Official Method Cd 1-25 (1990). 5 The fish, oil (FO) bydrogenation activity of the catalysts was determined by the hydrogenation of 500 g of fish oil (iodine vylue 160) at 180 °C, 2 bar hydrogen pressure and a nickel loading of 0.031%. The activity is exprsssad as the time in minutes required to reach an iodine value (IV) of 115. The iodine value was measured by the Wijs method. 10 Table 1: Properties of the catalysts. WO 2004/035204 PCT/NL2003/000705 15 Table 1 - continued. WO 2004/035204 PCT/NL2003/000705 16 Table 1 - continued. 17 Claims 1 Catalyst comprising nickel, silica, alumina and magnesium, wherein the nickel to silicium stomic ratio is 2 to 30, the nickel to aluinium atomic ratio is 9 to 40, and the nickel to magnesium atomic ratio is 5-75, said catalyst having an average particle size of about 1 to about 20 µm. 5 2 Catalyst comprising nickel, silica, alumina and magnesium, wherein the nickel to silicium atomic ratio is 2 to 30, the nickel to aluminium atomic ratio is S to 40, and the nickel to magnesium atomic ratio is 5-75, and the nickel surface area is at least 75 m2/g of nickel, and wherein the catalyst is coated with a protective layer, effective in proventing oxidation of the catalyst. 10 3 Catalyst according to claims 1 or 2, having an avevage particle size of 3 to 8 µm. 4 Cataiyst according to any of the preceding claims, wherein the nickel to silicium automic ratio is at least 6.5, preferably, 6.5 to about 22, more preferably 6.5 to about 15. 15 5 Catalyst according to any of the preceding claims , wherein the nickel to aluminium stomic ratio is about 10-35, preferably about 15 to about 22. 6 Catalyst according to any of the preceding claims, wherein the nickel to magnesium atomic ratio is about 5-50, preferably about 6 to about 20. 20 7 Method for preparing a catalyst according to any of the claims 1-6, wherein - a nickel source, a silica source, an alumina source and a magnesium source are mixed in a liquid and co-precipitated there from to form a catalyst precursor, 25 - the catalyst precursor is isolated from the solution, and - the catalyst precursor is activated to form the catalyst, said activation step preferably comprising a reduction of at least part of the nickel content of the 217 catalyst precursor, and optionally calcining the catalyst precursor before being reduced. 8 Process for hydrogenating an unsaturated organic compound, wherein the unsaturated organic compound is contacted with hydrogen in the 5 presence of a catalyst as defined in any of the claims 1-6. 9 Process for hydrogenating an unsaturated fatty substance comprising the contacting of the unsaturated fatty substance with hydrogen in the presence of a catalyst comprising nickel, silica, alumina and magnesium. wherein the nickel to silicium atomic ratio is 2 to 30, the nickel to aluminium 10 atomic ratio is 9 to 40, and the nickel to magnesium atomic ratio is 5-75 10 Process according to claim 9, wherein the unsaturated fatty substance is a containated oil, a clean oil or a combination thereof. The present invention relates to a catalyst nickel, silica, alumina and magnesium, wherein the nickel to magnesium atomic ratio is 5-75. In particular the present invention relates to a catalyst comprising nickel, silica, alumina and magnesium, wherein the nickel to silicium atomic ratio (Ni/Si) is 2 to 30 the nickel to aluminum atomic ratio (Ni/Al) is 9 to 40 and the nickel in magnesium atomic ratio (Ni/Mg) is 5-75. The invention further relates to a method for preparing such a catalyst. The invention futher relates in a process for hydrogenating understand organic compounds.

Full Text

WO 2004/1135204 PCT/NL 2003/000705
NICKLE CATALYST FOR HYDROGENATIONS REACTIONS
The invention relates to a catalyst comprising nickel, alumina
magnesium and silica, to a method for preparing such a catalyst and to a
process for hydrogenating unsaturated organic compounds.
Nickel/alumina catalysts with a nickel/aluminium ratio of 2-20 are
5 known to be active catalysts for the hydrogenation of unsaturated organic
compounds from EP-A 0 167 201. The catalysts claimed in EP-A 0 167 201
further comprise silica in a nickel/silica ratio of 1-20. The disclosed catalysts
are prepared in a process wherein first a nickel hydroxide/carbonate is
precipitated and thereafter aluminium nitrale and silicate are added. The
10 resulting precipitate is thereafter activated with hydrogen. The examples show
catalysts comprising at least 85 wt. % Ni that are used in the hydrogenation of
fish oil. It is reported that they may retain their activity for a prolonged period
and tend to show a high poison resistance. As an indication for selectivity an
aspecific assay is referred to, based on a combination of melting point and
15 hydrogenation time. Besides the fact that the latter parameter has been found
to be rather an indicator for activity, no quantitative data are presented on the
selectivity in soy bean oil hydrogenation though.
EP-A 1 101 530 describes a nickel-iron catalyst for use in the
hydrogenation of resins. Magnesium (oxide) may be present. This publication
20 does not recognise the relevance of the particle size with respect to the
hydrogenation of unsaturated compounds and the working examples do not
mention the particle size of the used catalyst. It is not suggested to use the
catalyst in the hydrogenation of fatty substances, such as vegetable or animal
oils.
25 US-A 5 493 037 relates to a fixed bed process for hydrogenating fatty
acids, comprising the use of a formed nickel catalyst with a relatively low
nickel content. Contents of 10-50 wt. % are mentioned, without specifying how

WO 2004/035204 PCT/NL2003/000705
2
the weight percentage is defined. A magnpsiuin salt may be present as a
support or in the binder (clay). The publication is silent about suitable pore
volumes and nickel surface areas.
There is a continuing need for alternative catalysts for the
5 hydrogenation of unsaturated organic compounds. In general when searching
for a suitable catalyst for the bydragenation of a particular compound, one has
to compromise e.g. between activity and selectivity. For instance, certain
catalyst characteristics (e.g. an open pore structure) may favour the selective
hydrogenation of fatty oils while al the same tune result in longer reaction
10 times when hydrogenating more contaminated oils because of their higher
susceptibility to poisoning. Therefore, often different types of catalysts are
required for different types of unsaturated organic compounds. For example, a
atalyst may either be suitable for clean oils, such as soy bean oil, or for more
ontaminated oils, such as rape seed oil or fish oil.
15 is an object of the present invention to provide a novel catalyst
hat may be used as a favourable alternative to known catalysts for
ydrogenating unsaturated organic compounds, in particular fatty oils.
has been found that this object can be realised by a catalyst
omprising nickel, silica, alumina and also magnesium in a particular ratio.
20 ccordingly, the present invention relates to a catalyst comprising
nickel, silica, alumina and magnesium, whereni the nickel to magnesium
atomic ratio is 5-75, preferably 5-50.
In the catalyst, magnesium is thought to act as a catalyst promotor
in the hydrogenation of urtsaturated hydrocarbons, in particular fatty
25 substances, as is indicated by the Examples 1 and 2, below.
In particular, the present invention relates to a catalyst comprising
nickel, silica, alumina and magnesium, wherein the nickel to silicium atomic
ratio (Ni/Si) is 2 to 30, the nickel to aluminium atomic ratio (Ni/AI) is 9 to 40
and the nickel to magnesium atomic ratio (Ni/Mg) is 5-75.

WO 2004/-03524 PCT/NL2003/000705
3
It baa been found that a catalyst according to the present invention
shows a very high activity for the hydrogenation of unsaturated compounds, in
particular unsaturated fatty substances, such as fatty oils including
ucsaturated fats. These oils typically mainly comprise glycerides, in particular
5 triglycerides. The invention may very suitably be employed for the
hydrogenation of fatty substances of vegetable and/or animal origin for food
grade applications.
A catalyst according to the invention has been found to have a very
high, activity as a hydrogenation catalyst. In particular, a catalyst according to
10 the invention is found to be hignly active for relatively clean oils - i.e. oils with
a relatively low sulphur conteat - like soy bean, as well as for more
contaminated oils, lite fish oil, having a high sulphur content.
A catalyst according to the invention may very suitably be used in a
slurry process. Accordingly the present invention also relates to a slurry
15 ejomprising a catalyst according to the invention. The skilled person will know
how to make a suitable slurry based upon common general knowledge and the
information disclosed herein. For instance, as a liquid phase the feed stock to
be processed is very suitable.
The total weight percentage of Ni in the reduced catalyst may be
20 chosen in a wide range, as defined by the Ni/Si, Ni/Al and Ni/Mg ranges.
Preferably, the amount of nickel is at least 50 wt. % and not higher than
80 wt. %, more preferably 51-80 wt. %. Even more preferably the amount of
nickel is 55-75 wt.%. Very good results have been achieved with an amount of
nickel of 65-72 wt.%.
25 In a preferred embodiment, Ni/Si is at least about 2.5, more
preferably at least about 3. Very good results have been achieved with a Ni/Si
of at least 6.5.
The Ni/Si is preferably about 22 or less, more preferably about 15 or
less. Very good results have been achieved with a Ni/Si of up to about 7.5.

WO 2004/035204 PCT/NL2003/000705
4
Ni/Al is preferably about 10 to about 35, more preferably about 10-
30, even more preferably about 15-25. Very good results have been achieved
with a catalyst having a Ni/Al of more than 20, e.g. up to 22.
Ni/Mg may preferably be chosen in the range of about 5-50, more
5 preferably 5-30, even more preferably about 6 to about 20. "Very suitable is a
catalyst with a Ni/Mg of about 7.5-12.5, e.g. about. 10.
In principle it is possible that small amounts of one or more other
elements are present in the catalyst, but this is not required. In particular,
very suitable is a catalyst of tile invention which is essentially free of iron
10 (typically having less than 0.1 % Fe).
In order to prevent oxidation of the catalyst may be coated with a
protective layer. The protective layer may have any form, wherein at least the
cataiytically active sites of the catalyst are essentially covered with a
protective material.
15 Protection of the catalyst is in principle possible by applying a layer
of oxide on the catalyst, in particular on the nickel (crystallites). A method for
applying a suitable film of oxide is known in generally known in the art, and
may be based on DB19909175. The oxide may suitably be removed shortly
before use. The skilled person will know now to remove (e.g. by reactivation)
20 the oxide, based upon a known method for reactivating known nickel catalysts
on a support (e.g. on alumina, silica or a combination thereof).
A highly suitable protective material for protecting a catalyst, such
as a hydrogenation catalyst, in particular a catalyst according to the invention,
is a material comprising a fatty substance, preferably a hardened oil or fat,
25 more preferably a hardened vegetable oil or fat. Very good results have been
achieved with, a catalyst coated with hardened soy bean fat. Other highly
preferred examples of fatty substances include hardened palm oil fat,
hsrdsned sunflower oil and hardened rapessed oil. A mixture comprising a
number of fatty substances may very suitably be used.

WO 2004/035204 PCT7NL2003/000705
5
An advantage of a protective material comprising a fatty substance
instead of a thin film of oxide on the catalyst, is that the catalyst does not need
to be re-activated before use. At a high temperature (e.g. above about 150 °C)
re-activation will generally be possible without a problem but in particular for
5 low temperature applications or for applications wherein the reaction is
started at a relatively low temperature (e.g. below 150 °C), re-activation of a
catalyst with a protective oxide film may take a relatively long time, resulting
in a longer overall reaction time, or may not take place to a sufficient extent at
all.
10 The protective material forming a protective layer may be provided
around individualised particles, or at least on the catalytically active part
thereof (in particular in case a layer of oxide).
In particular in case of a catalyst provided with a fatty substance as
a protective layer, a multiplicity of catalyst particles may be incorporated (in
15 particular dispersed) into the protective material forming the protective layer.
The protective material with catalyst particles incorporated therein,
may very suitably be in the form of a participate material. Such particulate
material is also referred to herein as matrix particles. The size of the matrix
particles is not particularly critical. Conveniently, matrix particles may for
20 instance have a size (as defined by the diameter of the enveloping circle) in the
range of about 1 to about 12 mm, more in particular in the range of about 2-10
mm. The size of the catalyst particles incorporated therein is usually at least
bout one or two orders of magnitude less than the matrix particles. A
referred size of the catalyst particles is as the preferred particle diameters
25 efined below .
has been found that in particular in an embodiment wherein the
atalyst is provided with a protective layer by having the catalyst incorporated
nto the protective material, the ease of handling is improved, because it
ontributes to reduced dusting of the catalyst.

WO 2004/035204 PCT/NL2O03/000705
6
The amount of protective material is preferably at least about 40
wt. %, more preferably at least about 55 wt. % even more preferably at least
about 60 wt. %. Very good results have been achieved with an amount of at
least 65 wt. %. (All wt. %'s based upon the total weight of catalyst plus
5 protective material).
Preferably tbe amount of protective material is less than about
95 wt. %, more preferably less than about 90 wt.%, even more preferably less
than about 85 wt. %. Very good results have been achieved with a weight
percentage of up to about 82 wt % (All wt. %'s based upon the total weight of
10 catalyst plus protective material).
The melting temperature of the protective material with which the
catalyst is coated is preferably leas than, the temperature at which the
hydrogenation is carried out, in order to facilitate dissolution of the protective
material at the beginning of a hydrogenation process in accordance with the
15 invention. Good results have inter alia been achieved with a protective
material have a melting temperature of less than about 90oC, more in
particular of less than about 35oC. Very good results have been achieved with
a melting temperature of less than 80°C.
For practical reasons, the minimum melting temperature of the
20 protective material is in general higher than the temperature at which the
catalyst is stored before use. Preferably the melting temperature is at least
about 40°C, more preferably at least about 50oC.
In particular, when the catalyst is used in a slurry process, the
protective coating will preferably dissolve in the feedstock. Else, the coating
25 may be removed from the process, shortly before using the catalyst in a
hydrogenation process. The coating may very suitably be removed by
contacting the catalyst with a solvent, such as a feedstock, preferably at a
temperature higher than the melting point of the coating fat.
For a good activity, the pore volume (as measured by N2 desorption,
30 20-600 A, on a Quantachrome Autosorb 6) is preferably at least 0.4 ml/g, more

WO 2004/035204 PCT/NL2003/000705
7
preferably at least 0.5 ml/g, even more preferably at least 0.55 ml/g. The upper
limit is not particularly critical. Very good results have been achieved in the
range of 0.4 to 1 ml/g. More preferably, the pore volume is up to about 0.75
ml/g, e.g. 0.6-0.7 ml/g.
5 The volume average particle size (D(v.0,5)) of a catalyst according to
the invention may be chosen in a wide range, inter alia depending upon the
intended use, in particular if the catalyst is provided with a protective coating.
In practice, in particular for improving the hydrogenation reaction
rate of unsaturated fatty substances, one may favourably choose to use a
10 catalyst with a D(v_0,5) of less than about 20 µm. Very suitable is a D(v.0,5) of
less than about 15 µm, in particular of less than about 10 µm, more in
particular of less than about 8.5 µm.
The volume average particle size is preferably at least about 1 µm.
more preferably at least about 2 µm, even more preferably at least about 3.
15 A volume average particle size in the range of about 3 to about 8 µm
has been found to be highly advantageous. In particular when compared to a
catalyst with a higher average particle size (e.g. 8.6 µm) such a catalyst has
been found to have a higher activity with respect to hydrogenation of a
unsaturated organic compound, especially a fatty substance.
20 Very good results have been achieved with a catalyst having a
volume average particle size of about 4 to about 7µm.
D(v.0,5), as used herein, is the value as measured by LASER
diffraction with a Malvern MS 1002, lens 45 mm - which corresponds to a
measuring range of 0.1-100 µm - using "Independent" as the model for
25 calculating the particle size. The (D(v.0,5)) as used herein is the diameter of
the catalyst per se, i.e. without a protective coating.
The catalyst preferably comprises nickel crystallites. The majority of
the nickel crystallites preferably has a diameter of less tlian 60 Aµ, more
preferably of about 20-50 Aµ, even more preferably of about 20-40 Aµ. The size as
30 used herein is the value as determinable by XRD on the reduced catalyst

WO 2004/035204 PCT/NL2003/OO0705
8
protected by a coating of a fatty substance (such as hardened soybean fat) (See
also Examples).
The nickel surface area is preferably 75 to 200 m2/g of nickel, more
preferably approximately 100-175 m2/g of nickel, ever more preferably
5 approximately 100-150 m2/g of nickel. Very good results have been achieved
with, a catalyst having a nickel surface area of 110-145 m2/g of nickel. The
nickel surface area as used herein is the value can be determined by
hydrogen chemisorption at 50 °C, after in situ reduction with hydrogen (60
ml/rain) for 2 hours at 400 °C and subsequently degassing for 14 hours at 350
10 °C in a Carlo Erba Sorptomatic 1900. The amount of adsorbed hydrogen is
determined by extrapolation of the reduction isotherm to zero pressure and the
nickel surface area is calculated assuming a site density of 6.77 Å2/atom.
The BET surface area preferably is about 300 to about 450 m2/g
catalyst, more preferably about 350 to about 400 m2/g catalyst. The BET
15 surface avea as used herein is toe value that can be measured by determining
the amount of nitrogen adsorbed at 77 K and P/Po of approximately 0.3 and
assuming a nitrogen cross sectional area of 16.2 Â 2, after degassing the
catalyst sample at 180°C.
The average pore diameter (APD), as calculated from the measured
20 pore volume (PV) and BET surface area by the formula APD= 4000G*PV/BET,
rnay for example very suitably be chosen in the range of about 10-500 Å,
preferably in the range of about 40- 200 Å, more preferably about 60 - 100 Å.
It is possible to make a catalyst in a process wherein first a nickel
precipitate is made, which is subsequently aged with an alumina source and
25 with a silica source (which may be added together with the alumina or
thereafter).
In a preferred embodiment, the catalyst is made from a catalyst
precursor that is prepared by co-precipitation., of which it will be clear to the
skilled professional how to choose suitable method conditions, In a co-
30 precipitation method according to the invention nickel, alumina, silica and

WO 2004/035204 PCT/NL2003/000705
9
magnesium are precipitated together (i.e. without forming intermediate
precipitates of only one or some of the camponents). In such a method, a nickel
source, a silica source, an alumina source and a magnesium source may be
mixed, in a liquid, (e.g. water or an aqueous solution) to form a precipitate (a
5 catalyst precursor), comprising all four said coinponents-
Prefexably the co-precipitation ia carried out with the aid of a
precipitant, e.g. an alkali metal carbonate (such as Na2CO3) or an alkali, metal
hydroxide (such as NaOH).
It is an advantage of the above co-precipitation methodology that it
10 can be performed in a single co-precipitation step.
Very good results have been achieved with a method wherein the co-
precipitation is performed at alkaline pH, e.g. at a pH of approximately 7.5-8.5
(as measured at 25 °C). It has been found that under alkaline conditions a very
efficient, generally a substantially complete precipitation of nickel and
15 magnesium, can be realised, in particular at elevated temperatures e.g. in the
range of 50-100 °C.
In a preferred embodiment, the precipitation is carried out at a
temperature in the range of 20-100 °C . Very good results have been achieved
at a temperature in the range of 50-100 °C, in particular at a temperature in
20 the range of 75-98oC. The catalyst precursor may thereafter be isolated, e.g.
by filtration, from the liquid and calcined, e.g. at a temperature of 200-750 °C
for 1-5 hours. The catalyst may very suitably be activated by reduction with
hydrogen, e.g. at a temperature of 250-600 °C, e.g. for 1-5 hours.
The nickel, silica, alurnina and magnesium sources may be chosen
25 from sources commonly used to prepare catalysts.
Suitable nickel sources include inorganic nickel salts, preferably
Ni(NO3)2, NiCl2, NiSO4, and organic nickel salts, preferably nickel acetate.
Preferably the nickel source is a solution or suspension of any of these salts.

WO 2004/0353204 PCT/NL2003/000705
10
Suitable silica sources include water glass, sodium silicate (Na2SiO3)
and colloidal silica. Preferably the silica source is a solution or suspension of
any of these components.
Suitable alumina sources include aluminium salts, preferably
5 inorganic salts suck as AlCl3, Al(NO3)3 and sadium aluminate (NaAlO2).
Preferably the alumina source is a solution or suspension of any of these salts.
Suitable magnesium sources include magnesium salts, preferably
inorganic salts such as Mg(NO3)2, MgCl2, and MgSO4. Preferably the
magnesium source is a solution or suspension of any of these salts.
10 The catalyst may be coated with a protective layer, e.g. a fatty
substance such as hardened soy bean fat, nardened palm oil fat, hardened sun
flower oil fat or a combination thereof, which may serve to avoid oxidation of
(parts 01) the catalyst (see also above).
The skilled person will know haw to provide a protective coating,
15 based upon common general knowledge and the information disclosed herein.
This may for example be done by blending a (reduced) catalyst powder into the
molten coating material (such as the molten fat) and subsequently solidifying
the resulting suspension to form flakes or droplets of coated catalyst particles.
For instance, one may let droplets of the suspension fall on a surface having a
20 temperature below the melting temperature of the fatty substance (such as a
cooled plate) thereby solidifying the droplets to form matrix particles. Such
method is very suitable for preparing particles generally having an essentially
hemispherical shape. Another way to produce matrix particles is to let the
droplets fell in a fluid (generally cooled fluid) wherein the particles solidify.
25 Thus more or less spherical matrix particles may be formed. It is also an
option to flake the suspension to flakes of a suitable thickness.
A catalyst according to the present invention may be used for a
variety of applications, and in particular for catalytic hydrogenation. The
catalyst may be employed in a process for hydrogenating organic compounds
30 wherein said compound is contacted with hydrogen in the presence of the

WO 2004/035204 PCT/NL2003/000705
11
catalyst. The process conditions may be chosen from the processes typically
used for the hydrogenation of a particular compound. The process may be a
batch or a continuous process. Preferably, the process is a slurry-process.
An important advantage of a hydrogenation process according to the
5 invention is the possibility to decrease the dosage of catalyst in order to
achieve a particular conversion within the same hydrogenation time (contact
time of feed (substrate) and catalyst) or to reduce the hydrogenation time at a
particular catalyst dosage.
A process according to the invention has been found to be
10 particularly suitable for the hydrogenation of a relatively clean oil (e.g. soy
bean oil) and/or a more contaminated oil (e.g. fish oil or rape seed oil).
A fatty substance hydrogenated in accordance with the present
invention preferably mainly comprises triglycerides, such that the content of
free fatty acids is quite low. For instance in a preferred feed stock
15 hydrogenated in accordance with the invention, such as a fully refined
vegetable or animal oils, usually less than about 0.1 wt.% free fatty acids and
preferably less than 0.05 wt.% is present. Since high concentrations of free
fatty acids may deactivate the catalyst by nickel soap formation, their presence
is preferably below said levels.
20 On the one hand it has been found, possible to maintain a high
activity in the presence of contaminations such as sulphur in the contaminated
oil. On the other hand the selectivity has been found to remain high enough to
achieve a favourable conversion of the unsaturated compounds. As a result the
present invention also offers a considerable advantage since it offers the
25 advantage that a single type of catalyst can very favourably be used in the
hydrogenation of contaminated oil and also in the hydrogenation of clean oil.
Thus a single stock of catalyst may be kept for the conversion of either of these
products.
The invention will now be illustrated by the following examples.
30

WO 2004/035204 PCT/NL2003/000705
12
Example 1
A metal solution (1000 ml) containing 95 g Ni/1 and 5g Mg/l was
prepared from a NiCl2 solution (198 g Ni/1) and MgCl2.6H2O. The base solution
5 was prepared by dissolving 183 g Na2CO3 and 44.4 g Na2SiO3.5H2O in 1000 ml
of demineralised water. The metal and base solution were injected at equal
flaw sates (1000 ml/hr) into a. well stirred precipitation vessel containing
1725 ml of demineralised water and 3.8 g of Al2O2 as sodium aluminate. The
temperature during precipitation wae maintained at 90 oC while the pH was
10 between 7.5 and 8.5.
After precipitation the precipitate was washed with demineralised water
and dried overnight at 110 °C. The dried catalyst was calcined for 1.5 hours at
375 oC and subsequently activated by reduction in hydrogen for 2 hours at
400 °C. The reduced catalyst powder was protected from air oxidation by
15 dispersing it in an inert atmosphere in molten, hardened soybean, fat at 80-
100 °C. Catalyst flakes were formed by solidifying the blend of reduced
catalyst powder and coating fat on a cooling plate. The catalyst properties of
the calcined sample are as summarised in Table 1.
20 Example 2
The catalyst of Example 2 was prepared according the procedure as
described in Example 1, except that no magnesium, was added.
25 Example 3
The catalyst of Example 3 was prepared according the procedure as
described in Example 1, except that no alumina was added.

WO 2004/035204 PCT/NL2003/000705
13
Examples 4 and 5
The catalysts of Examples 4 and 5 were prepared according to the
procedure as described in Example 1, except that variations were made in the
5 amount of starting materials resulting in catalyst properties as indicated in
Table 1.
Examples 6 and 7
10 The catalyst of Examples 6 and 7 were prepared according to the
procedure as described with example 1, except that magnesium was replaced
by copper and cobalt respectively.
Example 8
15
The catalyst of Example 8 was prepared according to the procedure as
describedin Example 1 except that a different agitation speed was used during
the precipitation, (an agitation speed of 400 instead of 475 rpm was used).
20 Example 9: Characterisation and performance of the catalysts
The pore volume and BET surface area of the catalysts were measured
by nitrogen adsorption/desorption using a Quantachrome Autosorb-6. Particle
size was determined by laser diffraction using a Malvern Mastersizer 1002.
25 The nickel surface area was measured by hydrogen chemisorption with a Carlo
Erba Sorptometic 1900.
The nickel crystallite size was measured with a Phillips DW1820
roöntgeii diffractometer using the Ni(111) peak (d-value 2.06 Ä).
The soy bean oil (SBO) hydrogenating activity of the catalysts was
30 determined by the hydrogenation of 500 g of soybean oil (iodine value 130) and

WO 2004/035204 PCT/NL2003/000705
14
measuring the time needed to reach an iodine value of 70. The catalyst loading
was 0.0075% as nickel, the hydrogen pressure was 0.7 bar and the
temperature was 204 °C. Tbe iodine value was measured by the Wijs melhod
as described in A.O.C.S. Official Method Cd 1-25 (1990).
5 The fish, oil (FO) bydrogenation activity of the catalysts was determined
by the hydrogenation of 500 g of fish oil (iodine vylue 160) at 180 °C, 2 bar
hydrogen pressure and a nickel loading of 0.031%. The activity is exprsssad as
the time in minutes required to reach an iodine value (IV) of 115. The iodine
value was measured by the Wijs method.
10
Table 1: Properties of the catalysts.

WO 2004/035204 PCT/NL2003/000705
15
Table 1 - continued.

WO 2004/035204 PCT/NL2003/000705
16
Table 1 - continued.

17
Claims
1 Catalyst comprising nickel, silica, alumina and magnesium, wherein
the nickel to silicium stomic ratio is 2 to 30, the nickel to aluinium atomic
ratio is 9 to 40, and the nickel to magnesium atomic ratio is 5-75, said catalyst
having an average particle size of about 1 to about 20 µm.
5 2 Catalyst comprising nickel, silica, alumina and magnesium, wherein
the nickel to silicium atomic ratio is 2 to 30, the nickel to aluminium atomic
ratio is S to 40, and the nickel to magnesium atomic ratio is 5-75, and the
nickel surface area is at least 75 m2/g of nickel, and wherein the catalyst is
coated with a protective layer, effective in proventing oxidation of the catalyst.
10 3 Catalyst according to claims 1 or 2, having an avevage particle size
of 3 to 8 µm.
4 Cataiyst according to any of the preceding claims, wherein the nickel
to silicium automic ratio is at least 6.5, preferably, 6.5 to about 22, more
preferably 6.5 to about 15.
15 5 Catalyst according to any of the preceding claims , wherein the
nickel to aluminium stomic ratio is about 10-35, preferably about 15 to about
22.
6 Catalyst according to any of the preceding claims, wherein the nickel
to magnesium atomic ratio is about 5-50, preferably about 6 to about 20.
20 7 Method for preparing a catalyst according to any of the claims 1-6,
wherein
- a nickel source, a silica source, an alumina source and a magnesium source
are mixed in a liquid and co-precipitated there from to form a catalyst
precursor,
25 - the catalyst precursor is isolated from the solution, and
- the catalyst precursor is activated to form the catalyst, said activation step
preferably comprising a reduction of at least part of the nickel content of the

217
catalyst precursor, and optionally calcining the catalyst precursor before being
reduced.
8 Process for hydrogenating an unsaturated organic compound,
wherein the unsaturated organic compound is contacted with hydrogen in the
5 presence of a catalyst as defined in any of the claims 1-6.
9 Process for hydrogenating an unsaturated fatty substance
comprising the contacting of the unsaturated fatty substance with hydrogen in
the presence of a catalyst comprising nickel, silica, alumina and magnesium.
wherein the nickel to silicium atomic ratio is 2 to 30, the nickel to aluminium
10 atomic ratio is 9 to 40, and the nickel to magnesium atomic ratio is 5-75
10 Process according to claim 9, wherein the unsaturated fatty
substance is a containated oil, a clean oil or a combination thereof.

The present invention relates to a catalyst nickel, silica, alumina and magnesium, wherein the nickel to magnesium
atomic ratio is 5-75. In particular the present invention relates to a catalyst comprising nickel, silica, alumina and magnesium,
wherein the nickel to silicium atomic ratio (Ni/Si) is 2 to 30 the nickel to aluminum atomic ratio (Ni/Al) is 9 to 40 and the nickel
in magnesium atomic ratio (Ni/Mg) is 5-75. The invention further relates to a method for preparing such a catalyst. The invention
futher relates in a process for hydrogenating understand organic compounds.

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Patent Number

221538

Indian Patent Application Number

00925/KOLNP/2005

PG Journal Number

26/2008

Publication Date

27-Jun-2008

Grant Date

25-Jun-2008

Date of Filing

18-May-2005

Name of Patentee

ENGELHARD CORPORATION

Applicant Address

101 WOOD AVENUE, ISELIN, NJ 08830-0770

Inventors:

#	Inventor's Name	Inventor's Address
1	BERBEN, PIETER HILDEGARDUS	VINKENBUURT 12 3951 CZ MAARN
2	REKKER, TJALLING	MARGA KIOMPESTRAAT 4 4105 JD CULEMBORG

PCT International Classification Number

B01J 23/78, 33/00

PCT International Application Number

PCT/NL2003/000705

PCT International Filing date

2003-10-17

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	02079362.6	2002-10-18	U.S.A.