NL8007105A - NICKEL-BASED CATALYST APPLIED ON A CARRIER, METHOD OF PREPARING IT AND USE IN A HYDROGENATION PROCESS OF MULTIPLY UNSATURATED ORGANIC COMPOUNDS UNTIL THE PART OF THE PART AT THE SAME TIME OR AT THE SAME TIME. - Google Patents

Description

1 * * N.0. 29,758

Nickel-based supported catalyst, process for its preparation and use in a process for hydrogenation of polyunsaturated organic compounds to the corresponding partially or fully saturated compounds »

The present invention relates to a supported nickel-based catalyst, to a process for its preparation, and to the use of such a supported nickel-based catalyst in a hydrogenation process of polyunsaturated organic compounds to the corresponding partially or fully saturated compounds.

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Supported nickel catalyst with a support such as diatomaceous earth, alumina or silica gel have long been used as heterogeneous catalysts in processes of selective hydrogenation of polyunsaturated organic compounds to di- or mono-saturated compounds. One of the main processes is the hydrogenation of unsaturated fatty acids bound in vegetable oils and animal fats, or the hydrogenation of free unsaturated fatty acids, to the corresponding partially or fully saturated compounds. At present, the annual worldwide volume of oils and fats hydrogenated for further processing into food and technical products exceeds 4.10 tonnes. This fact and an attempt to maximize utilization of all food resources are forcing manufacturers to make improvements in hydrogenation technology, while achieving an optimum economic effect also requires a selective embodiment of the process.

Due to the boiling points of the processed products, the hydrogenation process is carried out in the liquid phase at an elevated temperature and pressure in the presence of a heterogeneous catalyst, thus representing a comparatively complex three-phase liquid-gas-solid system. In addition to the technological parameters of the equipment, such as a continuous or discontinuous operation, the mode of mass and heat transfer in the system, etc., it is the quality of the catalyst used that is of primary importance. In order to fully utilize the capacity of a hydrogenation unit, it is necessary to achieve a high reaction rate, for which a prerequisite is high activity of the catalyst. From the viewpoint of the possibility of obtaining a product of a required composition containing pre-selected fatty acid esters, the emphasis is also placed on a selective behavior of the hydrogenation catalyst. for example, the hydrogenation of vegetable oils »such as rapeseed oil or soybean oil containing glycerides of linolenic acid 5» requires - in order to increase the consistency of the taste and odor of the product - that the glycerides of linolenic acid are essentially or completely removed, while the content of glycerides of linoleic acid is reduced as little as possible and the content of glycerides of stearic acid is minimally increased.

Nickel catalysts which have hitherto been used in engineering practice generally do not exhibit high activity along with high selectivity for the hydrogenation of polyunsaturated organic compounds and usually only one of the properties is dominant *

According to the present invention, there is provided a nickel-based catalyst applied to an inorganic support such as diatoraene earth, alumina or silica gel containing 10 to 85% by weight of nickel, amount of which is 40 to 99% by nickel in the form of metal and 0.05 to 6.7 wt.% boron. The catalyst of the present invention may further comprise 0.01 to 10 wt.% copper, silver, chromium, zircon, thorium, tin, rhenium or any of the Group VIII metals of the periodic table or a mixture of at least two of these metals containing * 25 The aforementioned catalyst is prepared in the following manner: (1) precipitation of a suspension of an inorganic support in a nickel salt solution with an, alkali, (2) subjecting the mixture of the inorganic support and the precipitated nickel dihydroxide and / or nickel hydroxide carbonate with a composition of NiC0 ^ * x (NiiOH ^ ^ y H ^ O, where x is a number from 1 to 30 and y a random number, to the action of an alkali metal borohydride solution in an amount of. 0.005 to 1.25 moles of borohydride per mole of nickel, this treatment being carried out at a temperature between 20 and 100 ° C and at a pH of more than 10 for periods of 5 to 60 minutes, (3) washing and drying the obtained mass, (4) calcining the mass at a temperature between 300 and ¥> 500 ° 0, and 8007105 \ 3 »* 4 • (5) reducing the calcined mass at a temperature between 250 and 1 * 80 ° C to a reduction degree * ranging from 0, if0 to 0.99.

Furthermore, when a nickel-based supported catalyst is required to contain the aforementioned modifying metals, the mixture of an inorganic support and the nickel dihydroxide and / or nickel hydroxide carbonate of the aforementioned composition is treated together with an addition of a salt of copper, silver, chromium, zircon, thorium, tin, rhenium or one of the metals of group VIII of the periodic table, or a mixture of at least two of these salts in an amount corresponding to 0.1 to 10% by weight of the metal.

The present invention further provides a process for hydrogenating polyunsaturated organic compounds to the corresponding partially or fully saturated compounds, wherein hydrogen is contacted at a pressure between 1.013 x 10 and g 2.7 x 10 Pa charged with a polyunsaturated organic compound at a temperature between 30 and 25 ° C in the presence of a supported nickel-based catalyst, as explained above. The contact time is chosen such that the required composition of the product is obtained.

The nickel-based catalyst of the present invention is particularly suitable for use as a catalyst for the hydrogenation of unsaturated fatty acids and their glycerides to the corresponding partially or fully saturated compounds. The process is carried out at a hydrogen pressure between 1.013 x 125 and 2.7 x 10 Pa at a temperature between 80 and 20 ° C.

The conversion time is again chosen to give the required composition of fatty acids in the product. The amount of the catalyst is suitably within the range of 0.01 to 2 wt.% Of the nickel metal based on the weight of the processed raw material, preferably within the range of 0.02 to 0.06 wt.%.

The hydrogenation process, as described here, can be carried out on a continuous or discontinuous basis.

The treatment of the resulting precipitate by mixing a nickel salt with an alkali to an alkali metal borohydride solution results in an exchange of a portion of surface hydroxyl groups of the nickel dihydroxide and / or the nickel hydroxide 8007105. K carbonate structure with the (BH ^) ”anion. The finished catalyst then exhibits several times greater activity and selectivity for the hydrogenation of polyunsaturated organic compounds to the corresponding partially or fully saturated compounds as compared to a similar product which has not been treated with the alkali metal borohydride.

The catalyst of the present invention is suitable for use in processes such as the hydrogenation of cyclooctadiene to cyclooctene. However, of paramount importance from an industrial viewpoint is the hydrogenation of unsaturated fatty acids and their glycerides to the corresponding partially or fully saturated compounds. When the process is carried out on a selective basis * to obtain partially hydrogenated vegetable oils, the hydrogenation process is usually stopped at 15-30 wt% of the original amount of linolenic acid. For example, in the processing of rapeseed oil with a minimized erusic acid content * with an initial iodine value of 115, the hydrogenation process is stopped * when an iodine value of 90-100 is reached. Under the given conditions, the content of linoleic acid esters will be reduced to 5 ° -80% by weight of the original amount. Oils treated in such a manner are then suitable for further processing of various types of salad oil * mayonnaise, margarine, etc.

The selective properties of the catalyst also make it suitable for obtaining a comparatively high yield of oleic acid upon hydrogenation of vegetable oils. For example, in the processing of rapeseed oil with a minimized erusic acid content, the maximum content of the oleic esters in the product is about 83% and the resulting product can be further processed for technical purposes.

The catalyst of the present invention is also suitable for the hydrogenation of vegetable oils to a product with a melting point of 32 - 39 ° C * which is further processed into margarine, diabetic fat, etc. *. The catalyst is also suitable for the total hydrogenation of vegetable oils or free fatty acids to products with an iodine number of 2-5, where the high activity of the catalyst plays the main role.

Example I

A suspension of diatomaceous earth in a nickel nitrate solution at 95 ° G was added with stirring to a heated solution 8007105.

of sodium carbonate. Precipitation was completed by adding sodium hydroxide solution in an amount to bring the molar ratio of alkali metal to nickel to 2: 1 *. The precipitate obtained, that after filtration, washing and drying, the composition NiCO4. 10.5 ΝΐζΟΗ) ^ 7 H 2 O, was subjected to the action of a 10% solution of sodium borohydride in water (pH = 10) at a pH of 10.5 for 60 minutes. The precipitate was then filtered, washed three times with methanol, calcined at 350 ° C and finally reduced to a reduction degree of 0.86 at 10-380 ° C for a period of 10 hours.

The resulting catalyst contained 51.1% Ni and 0.8% boron by weight, the balance being the support.

The catalyst prepared on this exhibited significantly greater activity and selectivity for the hydrogenation of cyclo-octadiene to liquid phase cyclooctene compared to a catalyst * prepared in the same manner, except that the nickel hydroxide carbonate was not treated with sodium borohydride.

The quantitative results, including the hydrogenation reaction conditions, are summarized in Table A.

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Table A

Comparison of the course of hydrogenation of cyclooctadiene to cyclooctene using a catalyst prepared as described in Example I (Catalyst A) and a similar catalyst prepared without treatment with sodium borohydride (Catalyst B).

Reaction conditions: temperature 30 ° C; hydrogen pressure 5 1 * 0374 x 10 Pa $ catalyst concentration 0 * 833 g Ni per liter reaction mixture; solvent n-heptane.

Time Catalyst A Catalyst B_ (min ·) Concentration of the individual components (mol / liter x 10 * ~ ^) _PMS_PMS_ 0 5.44 oo 5 * 38 o 0 5 3 * 38 1.96 0.0½ 4.56 0, 77 0.05 10 1.84 3.38 0.11 3 * 90 1.31 0.18 20 0.32 4 * 36 0.50 2.84 1.97 0.55 '30 0.03 4 * 36 1.02 2.10 2.23 1 * 01 40 o 3 * 88 1.54 1 * 59 2.28 1.48 50 0 3 * 40 2.02 1.18 2.21 1.98. 70 0 2.58 2.86 0.67 1 * 85 2.84 90 0 1.92 3.50 0.36 1.44 3.54 110 0 1.42 4.04 0.21 1.10 4 * 06 130 0 1.02 4.44 0.13 0.78 4.48 150 0 0.72 4.72 0.06 0.56 4.75 P: cyclooctadiene M: cyclooctene S: cyclooctane

Example II

A nickel nitrate solution, containing 10% silver nitrate, was treated by the same method as described in Example 1. The catalyst obtained by reducing the sample at 5 ° C to a reduction degree of 0.8 contained 45.8 wt% nickel , 0.53 wt.% Boron and 0.5 wt.% Silver, the balance being the support. Pe catalyst was three times more active and 2.8 times more selective for the hydrogenation of cyclododecatriene to cyclodecene compared to the same sample, which had not been treated with sodium borohydride 10.

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Example III

A precipitation reservoir was filled with a suspension of diatomaceous earth in a nickel chloride solution containing PdCl 2 in an amount corresponding to 0.1% palladium # After heating to 98 ° C, the precipitate of nickel hydroxide carbonate formed by adding sodium carbonate in an amount of 2.1 moles per mole of nickel. 0.01 mol of sodium borohydride was then added to the suspension in the mother liquor and the mixture with a pH of 13.7 was stirred at 98 ° C for 10 minutes. # After filtration, washing, drying and calcining at 1 * 00 ° C, the catalyst reduced to a reduction degree of 0.83 at 1 * 50 ° C. The resulting catalyst contained by weight 58.2% Ni, 0.85% B and 0.1% Pd with the balance being the support. The selectivity of the catalyst for the hydrogenation of cyclooctadiene to cyclooctene 15 was increased by a factor of 3 * 1 due to the treatment with sodium borohydride

Example IV

A nickel nitrate solution containing diatomaceous earth was precipitated at 30 ° C with sodium hydroxide in an amount of 1.5 moles per mole of nickel. The resulting nickel dihydroxide suspension was mixed with sodium borohydride solution (0.6 mole borohydride per mole nickel) and heated to 70 - 80 ° C for 60 minutes.

After filtration, washing, drying, calcination at 300 ° C and reduction at 350 ° C to a reduction degree of 0.63, the catalyst obtained contained 28 wt.% Nickel and 0.3 wt.% Boron. The catalyst showed 5.3 times greater selectivity for the hydrogenation of cyclooctadiene to cyclooctene compared to a similar sample that had not been treated with the alkali metal borohydride. Example V

A stainless steel autoclave equipped with a paddle wheel stirrer was charged with 80 g of refined rapeseed oil with minimized erusic acid content and with a catalyst containing 3.8 wt. Boron and 27 wt. 8% of the latter in the form of nickel metal. The amount of the catalyst was 0.01 wt% nickel based on the weight of the processed oil. The hydrogenation was carried out at 180 ° C at a hydrogen pressure of 1.52 x 105 Pa. The changes in the composition of the product during the hydrogenation are given in Table B, which clearly shows both the high selectivity and the high activity 1 * 0 of the catalyst. The quality of the products obtained 8007105 '- .0 • # * meet the requirements for further processing into ingredients of salad oil, mayonnaise, margarine, diabetic fat, etc.

Table B

Hydrogenation of rapeseed oil with minimized erusic acid content under the conditions specified in Example V.

Time Iodine Fatty acid content (wt. $) (Min.) Number stearic oleic acid linoleic acid linolenic acid 0 115 2 * 6 59.2 21.5 7.3 3 111 2.8 62.7 19.3 5.7 5 104 2.9 66.7 16.7 4.0 7 98 3.1 70.2 14.8 2.3 9 95 5.5 75.5 12.9 0.9 12 89 5.5 76.8 9. 8 0 15 85 5.7 80.7 5.7 0 17 79 5.5 83.0 3.0 0 20 76 9.7 82.0 0 0 24 70 15.2 77.1 0 0 30 63 21, 0 71.7 0 0 36 59 26.7 66.2 0 0 45 55 52.3 60.7 0 0

Example V ~ I

Using the same autoclave as described in Example V *, 80 g of sunflower oil of the following composition were hydrogenated: acid wt. # Acid wt. # Palmitin 6.73 groundnut 0.54 palmitole 0.14 eicosene 0.76 stearin 3 .96 beheen 0.81 oil 20.28 erucine 4.95 linol 61.83

The iodine value determined according to the method of Wijs turned out to be 129. The catalyst from the previous operation was filtered and recycled in an amount of 0.03 wt. $ 10 nickel based on the weight of the oil. The hydrogenation was carried out at 140 ° C and a hydrogen pressure of 1.52 x 10 ^ Pa. After 160 minutes, the melting point of the product reached 33.2 ° C and the product had the quality required for further processing into margarine.

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Example VII

80 g of fatty acids with an iodine number of 56 distilled from and animal fats were hydrogenated in the same autoclave as described in example V * The hydrogenation was carried out at 5 200 ° C and a hydrogen pressure of 2 554 x 10 ^ Pa in the presence of a catalyst, containing 0.25 wt.% boron and 45 wt.% nickel, 87% of the latter being in the form of nickel metal · The amount of catalyst was 0.43 nickel based on the weight of the processed fatty acids · After 90 minutes an iodine number 10 of 2.5.

8007105

Claims (9)

1. Nickel based catalyst supported on an inorganic support such as diatomaceous earth, alumina or silica gel containing 10 to 85% nickel by weight. , of which 40 to 99% is formed, 0 6V3, u · 5 by nickel in the form of the metal »and 0.05 to 6.7 wt.% boron * / Catalyst according to claim 1, characterized in that the catalyst is 0.1 to 10% by weight of copper, silver, chromium, zircon, thorium, tin, rhenium or one of the metals of group VIII of the periodic system or a mixture of at least two of 10 containing these metals. A process for preparing a nickel-based catalyst according to claim 1, characterized in that (1) a suspension of an inorganic support in a nickel salt solution is precipitated with an alkali, (2) the mixture of the inorganic support and the precipitated nickel dihydroxide and / or nickel hydroxide carbonate with a composition of NiCO * x Ni (0H) 2 * y H 2 O, where x is a number from 1 to 30 and y is a random number, subject to the action of an alkaline borohydride solution in an amount of 0.005 to 1.25 moles of borohydride per mole of nickel, at a temperature between 20 and 100 ° C and at a pH of more than 10 for a period of 5 to 60 minutes, (3) the obtained mass washes and dries, (4) calcines at a temperature between 300 and 500 ° C, and (5) reduces at a temperature between 250 and 480 ° C to a degree of reduction ranging from 0.40 to 0.99 · 4. Process for preparing a nickel-based catalyst according to claim 2, characterized in that (1) a suspension of an inorganic support in a nickel salt suspension is precipitated with an alkali, (2) a mixture of the inorganic support, the precipitated nickel dihydroxide and / or nickel hydroxide carbonate with a composition of NiCO 2 x Ni (0H) 2 * y H 2 O, where x is a number from 1 to 30 and y is a random number, and a salt of 35 copper, silver, chromium, zircon, thorium, tin, rhenium and one of the Group VIII metals of the periodic table or a mixture of at least two of the salts in an amount corresponding to 0.1 to 10% by weight of the metal, subject to the action of an alkaline borohydride solution 40 in an amount of 0.005 to 1.25 moles of borohydride 8007105 • per mole of nickel at a temperature between 20 and 100 ° C and at a pH of more than 10 for a period of 5 to 60 minutes (3) was the mass obtained t and dries »5 (if) calcines at a temperature between 300 and 500 ° C, and (5) reduces at a temperature between 230 and if80 ° C to a reduction degree ranging from 0, ifQ to 0.99 Process for the hydrogenation of polyunsaturated organic compounds to the corresponding partially or fully saturated compounds in the liquid phase, characterized in that hydrogen is contacted at a pressure of 1.013 x 10 to 2.7 x 10 Pa with a polyunsaturated organic compound at a temperature between 30 and 205 ° C in the presence of a nickel-based catalyst according to claim 1 13 or 2 »for such a period of time that a required composition of the product is obtained · 6 * Process for the hydrogenation of unsaturated fatty acids and / or their glycerides to the corresponding partially or fully saturated compounds in the liquid phase, characterized in that hydrogen is pressured at a pressure of 1.013 x 10 to g 2.7 x 10 Contacting Pa with an unsaturated fatty acid or a mixture of unsaturated fatty acids and / or their glycerides at a temperature between 80 and 20 ° C in the presence of a nickel-based catalyst according to claim 1 or 2, for such a time that the required composition of the product is obtained * Process according to claim 6, characterized in that an amount of catalyst is used between 0.01 and 2% by weight of nickel metal based on the weight of the processed raw material. 8. Process according to claim 7, characterized in that an amount of catalyst is used between 0.02 and 0.06% by weight of nickel metal based on the weight of the processed raw material. Partially or fully saturated organic compounds prepared essentially as described herein using a nickel based catalyst according to claim 1 or 2. ******* 8007105