DE3049414A1 - NICKEL-BASED HYDRATING CATALYSTS, THEIR PRODUCTION AND USE - Google Patents

Description

30494U

Ceskoslovenskä academy ved Prague, CSSR

Nickel-based hydrogenation catalysts, their manufacture and use

The invention relates to supported nickel catalysts, a process for their production and their use in the hydrogenation of, in particular, polyunsaturated organic compounds to give the corresponding partially or fully saturated compounds.

Supported nickel catalysts such as kieselguhr, aluminum oxide and silica gel have long been used as heterogeneous catalysts for selective hydrogenation of polyunsaturated organic compounds to di- and

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technically applied to monounsaturated products. One of the most important such processes is the hydrogenation of unsaturated, in vegetable oils or animal fats bound fatty acids or free unsaturated fatty acids to the corresponding partially or completely saturated compounds. Currently more than 4-10 t of oils and fats are being used for further processing worldwide hydrogenated for food or technical products. This fact »as well as efforts to maximize it Utilizing all food sources are forcing manufacturers to better manage hydrogenation technology, in which, in addition to optimal economic efficiency, a selective course of the hydrogenation process is also sought will.

With regard to the boiling point of the materials to be processed, the hydrogenation in the liquid phase is increased Temperature and elevated pressure carried out in the presence of heterogeneous catalysts, so that a relative complicated three-phase system liquid-gas-solid. In addition to the technological parameters of the device such as the discontinuous or continuous reaction, questions of mass and heat transfer The quality of the catalyst also plays an important role.

From the point of view of the maximum use of the production facilities, the economy of the process and the like is in the production of saturated fatty acids and Their glycerides strive for a high reaction rate in the hydrogenation, which results in a high activity of the Requires a catalyst. With regard to the possibility of

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by partial hydrogenation to obtain products with a desired composition, the particular selected one Containing fatty acid esters, a high selectivity of the catalyst is required at the same time. So, for example in the hydrogenation of vegetable oils from rapeseed or soy, which contain glycerides of linolenic acid, to achieve this Consistent taste and aroma properties requires these compounds completely or at least in the essential to eliminate, while at the same time only a minimal loss of glycerides of linolenic acid occurs, so the content of glycerides of stearic acid in the oil should only increase minimally.

In the case of the customary currently known nickel catalysts which are used in industrial practice for the hydrogenation of vegetable oils and animal fats and of free fatty acids, maximum activity and selectivity are generally not achieved at the same time. Only one of these two properties is dominant in Hegel. Even with homogeneous catalysts, no better activity and selectivity parameters were recorded than heterogeneous catalysts.

The invention is based on the object of a heterogeneous nickel-based hydrogenation catalyst and a process indicate its manufacture and use.

The problem is solved according to the claims.

The invention is based on the finding that the selectivity as well as the activity of a nickel catalyst increased if this is boron in addition to nickel

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contains. It has been found that the suitable composition of a catalyst based on nickel on an inorganic carrier such as diatomaceous earth, alumina or silica gel in the range between 10 and 85 wt -.% Nickel, with the proportion of metal reduced nickel 40 to 99% is , and 0.05 to 6.7 wt% boron.

The effectiveness of the catalyst according to the invention is even higher if it also contains 0.1 to 10% by weight Copper, silver, chromium, zirconium, thorium, tin, hhenium or one of the metals of group VIII of the periodic table or contains a mixture of at least two of the specified metals.

The catalysts according to the invention with the composition given above are prepared in such a way that nickel hydroxide and / or basic nickel carbonate of the composition NiG0, * x Ni (OH) ₂ ^# y HgO, where x is 1 to 30 and y is any number obtained by precipitation of a nickel salt with alkali was obtained, at temperatures between 20 and 100 ⁰ C and pH values over 10 5 to 60 minutes with a solution of an alkali borohydride in an amount of 0.005 "to 1» 25 mol per mol of nickel, after which the is incurred ground, dried and up to a reducing degree of 0.40 to 0.99 at 250 reduced after calcination at 300 to 500 ⁰ C to 480 ⁰ G.

To increase the effectiveness of the catalyst through modifying Metals, the procedure is that the nickel hydroxide and / or the basic nickel carbonate of the above

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specified composition together with added salts of copper, silver, chromium, zirconium, thorium, ziro. or rhenium or salts of a metal of group VIII of the periodic table or a mixture of at least two of the specified salts in an amount corresponding to 0.1 to 10% of the metal in the catalyst is processed.

The invention also provides a process for hydrogenating polyunsaturated organic compounds to the corresponding partially or fully saturated compounds in the liquid phase. The inventive method is based on that hydrogen is reacted at a pressure of 2.7 to 10 Pa 1,013'10 ^ up with a polyunsaturated organic compound at 30 to 240 ⁰ C in the presence of an inventive catalyst, the reaction time according to the required composition of the reaction product is chosen.

The catalyst according to the invention is particularly suitable for the hydrogenation of unsaturated fatty acids and their glycerides to give the corresponding, partially or fully saturated compounds. * The process is carried out at a hydrogen pressure of from 1.013 * 10 to 2.7 to 10 Pa and a temperature of 80 to 240 ⁰ C. The duration of the reaction is selected according to the required composition of the fatty acids in the reaction product. The amount of catalyst used is between 0.01 and 2 wt .-% metallic nickel, based on the weight of the processed raw material, and preferably between 0.02 and 0.06 wt .-%.

Due to the action of the alkali borohydride solution

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on the precipitation product that results from the implementation of the solution of a soluble Niekelsalζes with the corresponding Alkali results, there is an exchange of certain hydroxyl groups in the surface layers of the Structure of the nickel hydroxide and / or the basic nickel carbonate by the anion (BH ^) "*.

The resulting catalyst has a much higher activity and selectivity in the hydrogenation several times unsaturated organic substances, for example in the hydrogenation of cyclododecatriene to cyclodecene or of Cyclooctadiene to cyclooctene.

From an industrial point of view, the most important application of the catalyst according to the invention is the aforementioned hydrogenation of unsaturated fatty acids and their glycerides to give the corresponding partially or fully saturated compounds. This process is carried out in the temperature range 80-240 ⁰ C and at pressures between 1,013'10 ^ 2.7 * 10 ⁶ Pa. The amount of the catalyst used here is between 0.01 and 2% by weight of metallic nickel, based on the raw material to be processed; Quantities from 0.02 to 0.06% by weight are particularly advantageous .

The duration of the reaction is selected according to the required composition of the fatty acids in the product. The hydrogenation can be carried out both batchwise and continuously.

If the hydrogenation of vegetable oils is carried out selectively to produce only partially hydrogenated products, the

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Hydrogenation usually at a content of 0 to 30 % By weight of the original amount of linolenic acid terminated; at Processing of rapeseed oil with a minimal erucic acid content corresponds to this with an initial soda number of 115 almost reaching an iodine number of 90 to 100. The content of linoleic acid esters falls below the specified Conditions to about 50 to 80% by weight of the original existing amount. Fats processed in this way are suitable for the production of salad oils, hayonnaise, Edible fats, etc.

Due to the selectivity of that used according to the invention Catalyst, a relatively high yield of oleic acid can be achieved in the hydrogenation of vegetable oils at the same time. For example, when processing rapeseed oil with a minimal erucic acid content, the maximum content is of oleic acid esters in the product at about 83%; such a Raw material can be further processed into technical products.

The catalyst according to the invention can also be used advantageously in the hydrogenation of vegetable oils to products with a melting point of 32 to 39 ⁰ O, which are well suited for subsequent processing into edible fats, diet fats, etc., and also for the total hydrogenation of vegetable oils or fatty acids for technical purposes up to an iodine number of 2 to 5 », whereby use is made primarily of the high activity of the catalyst.

The invention is illustrated below with reference to examples for the preparation of the catalyst and its application in

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Hydrogenation processes explained.

example 1

A suspension of kieselguhr in a nickel sulfate solution was ^{poured into a heated soda solution with stirring at 95 °} C. The precipitation was terminated by adding sodium hydroxide solution in such an amount that a molar ratio of alkali to nickel of 2: 1 was achieved Precipitate, which after filtration, washing and drying had the composition NiCO ₅ -IO.5.5 1 (0Η) ₂ · _{7H 2} O, was exposed to a 10% aqueous sodium borohydride solution (pH The precipitate was then filtered, washed three times with methanol, ^{calcined at 350 °} C. and finally reduced for 10 hours at 360 to 380 ^° C. until a degree of reduction of 0.86 was achieved Wt% nickel and 0.8 wt% boron.

The catalyst prepared in this way had a much higher activity and selectivity in the hydrogenation of Cyclooctadiene in the liquid phase as a catalyst prepared in a similar manner, but in which the Precipitation of the alkaline nickel carbonate had not been reacted with sodium borohydride. The quantitative In addition to the hydrogenation conditions, the results are compiled in Table I below.

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! Table I.

Course of the hydrogenation of cyclooctadiene with a catalyst prepared according to Example 1 (Catalyst A) and one in a similar manner, but without reaction with sodium borohydride produced catalyst (catalyst B).

Reaction conditions: temperature 30 C; Hydrogen printing 1.0374- "1CV Pa; catalyst concentration 0.833 g nickel / l reaction mixture; Solvent n-heptane.

Time
(min) catalyst A. catalyst B. Concentration of the individual _Q components
(mol / 1-10 "^ M. S. D. M. S. 0 D. 0 0 5.38 0 0 5 5.44 1.96 0.04 4.56 0.77 0.05 10 3.38 3.38 0.11 3.90 1.31 0.18 20th 1.84 4.56 0.50 2.84 1.97 o, 55 30th 0.32 4.36 1.02 2.10 2.23 1.01 40 0.03 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 0

D: cyclooctadiene

M: Cyeloocten

S: cyclooctane

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Example 2

The procedure was as in Example 1, with the only difference that a nickel nitrate solution containing 10 % silver nitrate was used for the precipitation. The catalyst obtained by reducing a sample at 350 ^° C. to a degree of reduction of 0.8 contained 4S, 8% by weight Ni, 0.53% by weight B and 0.5% by weight Ag. The catalyst was three times more active and 2.8 times more selective in the hydrogenation of cyclododecatriene to cyclodecene than a similarly prepared catalyst which had not been reacted with sodium borohydride solution during preparation.

Example 3

A suspension of kieselguhr in a nickel chloride solution containing PdCl ^ was placed in the precipitation vessel. After heating to 98 ^° C., the basic nickel carbonate was precipitated with soda in an amount of 2.1 mol per mol of nickel. 0.01% mol of sodium borohydride was added to the suspension of the precipitate in its mother liquor, whereupon the mixture with a pH of 13.7 was stirred ^{at 98 ° C. for a further 10 minutes.} After filtration, washing, drying and calcination at 400 ⁰ G, the catalyst at 4-50 ⁰ C was reduced to achieve a degree of reduction of 0.85. The resulting catalyst contained 5812% by weight Ni, 0.85% by weight B and 0.1% by weight Pd. The selectivity of the catalyst obtained in the hydrogenation of cyclooctadiene to cyclooctene increased as a result of the reaction with

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Sodium borohydride by a factor of 3 * 1

Example 4 -

Eiie diatomaceous nickel nitrate solution containing precipitated "mol at 30 ⁰ C with sodium hydroxide in an amount of 1.5 per. Mol of nickel. The resulting suspension of nickel hydroxide was mixed with a solution of sodium borohydride in an amount of 0.6 mol per mole of nickel, and Heated to 70 "to 80 ⁰ C for 60 min. After filtration, washing, calcination at 300 ⁰ C and reducing at 350 ° 0 to a degree of reduction of the catalyst is 0.63% Ni and 0.3 part by weight 96 contained 28 wt .- B. The catalyst had in the hydrogenation of Cyclooctadiene to cyclooctene has a 5> 3-fold higher selectivity than a similarly prepared catalyst, which was not reacted with the alkali borohydride during its preparation.

Example 5

80 g of refined rapeseed oil with a minimal erucic acid content and a catalyst containing 3.8% by weight of boron and 2? Contained by weight nickel, 48 % of which was in the form of metallic nickel. The amount of catalyst was 0.04% by weight of nickel, based on the initially charged oil.

The hydrogenation was at 180 ⁰ C under one

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Hydrogen pressure of 1.52 x 1CK Pa. The composition of the product during the hydrogenation is given in Table II, from which the high selectivity as the high activity of the catalyst can also be seen. The resulting products corresponded in their Quality meets the requirements for further processing into components of salad oils, mayonnaise, edible fats, Diet fats and similar products.

! Table II

Hydrogenation of rapeseed oil with minimal erucic acid content under the conditions of Example 5

Time
(min) Iodine number Content of Fatty acids (Wt%) Linoles
acid 0 115 stearin
acid oleic acid Linoleum
acid 7.3 3 111 2.6 59.2 21.3 5.7 5 104 2.8 62.7 19.3 4.0 7th 98 2.9 66.7 16.7 2.3 9 95 3.1 70.2 14.8 0.9 12th 89 3.3 73.5 12.9 0 15th 85 3.5 76.8 9.8 0 17th 79 3.7 80.7 5.7 0 20th 76 5.5 83.0 3.0 0 24 70 9.7 82.0 0 0 30th 63 15.2 77.1 0 0 36 59 21.0 71.7 0 0 45 26.7 66.2 0 0 32.2 60.7 0

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Example 6

In the same device as in Example 5, 80 g of sunflower oil of the following composition were hydrogenated:

acid Jew - ^ acid Weight % Palmitic acid 6.73 Arachidic acid 0.54 Palmitoleic acid 0.14 Eicosenoic acid 0.76 Stearic acid 3.96 Behenic acid 0.81 oleic acid 20.28 Erucic acid 4.95 Lino! Acid 61.83

The iodine number determined according to Wijs was 129 · The catalyst was reused after a previous hydrogenation after filtering off in an amount of 0.03% by weight Uiekel, based on the amount of oil. The temperature was 140 ⁰ C, the hydrogen pressure 1,52'10 ^ Pa. After 160 min, a melting point of the product of 33.2 ⁰ O was achieved, the consistency properties that are required for subsequent processing in the production of edible fats were obtained.

Example 7

In the same autoclave, 80 g of distilled fatty acids derived from animal fats, with an initial iodine value of 56 at 200 ⁰ C and a pressure of 2,354 Pa * 10 were mixed with

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hydrogenated a catalyst, the 0.25 wt .-% boron and 45 Contained by weight nickel, of which 87% was in the form of metallic Nickel templates. The amount of catalyst was 0.43% by weight of nickel, based on the fatty acids. After 90 min an iodine number of 2.5 was reached.

The hydrogenation catalysts according to the invention Ni-base with an inorganic carrier containing 10 to 85 wt .-% of nickel, of which there are 40 to 99% in the form of reduced metallic nickel, 0.05 his 6.7 wt -.% Boron, and optionally 0.1 up to 10% by weight of Cu, Ag, Cr, Zr, Th, Sn, Re and / or a metal of YIII. Group of the periodic table.

The hydrogenation catalysts are made by reacting nickel hydroxide and / or basic Niekelarbonat, which were obtained by precipitation of a nickel salt with alkali, at 20 to 100 ⁰ C and pH-Verten over 10 with a solution of an alkali borohydride in an amount of 0.005 to 1.25 mol , washing of the accumulated mass, drying and calcination produced per mole of nickel at 300 to 500 ⁰ C and reduction to a degree of reduction from 0.40 to 0.99 at 25? C to 480 ^0.

The hydrogenation catalysts according to the invention are suitable especially for the hydrogenation of polyunsaturated organic compounds to partially or fully saturated ones Compounds and especially for the hydrogenation of unsaturated fatty acids and their glycerides to the corresponding, partially or fully saturated

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Links.

The hydrogenation catalysts according to the invention are notable for their unexpectedly high activity and selectivity the end.

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Claims (8)

Claims 1. Hydrogenation catalysts based on nickel with an inorganic one Carrier (kieselguhr, aluminum oxide or silica gel), marked by 10 to 85% by weight of nickel, of which 40 to 99 % is in the form of reduced nickel in metallic form, and 0.05 to 6.7 wt% boron. 2. Hydrogenation catalysts according to claim 1, characterized by 0.1 to 10 wt .-% Copper, silver, chromium, zirconium, thorium, tin, rhenium or one of the metals of group VIII des Periodic table or a mixture of at least two of these metals. 3. Process for the preparation of the hydrogenation catalysts according to claim 1 or 2, marked by 233- (S9834-) - SF / Nu 130038/0974 OR.'G? M.i; 30A94U Implementation τοπ nickel hydroxide and / or basic nickel carbonate obtained by precipitation of a nickel salt with alkali having a composition ΝίΟΟ, · χ Ni (OH) p «• y HO, where χ is a number τοη 1 to 30 and y is any number, from 20 to 100 ⁰ C and pH values above 10 for 5 to 60 min with a solution of an alkali borohydride in an amount of 0.005 to 1.25 mol per mol of nickel, Vaschen the accumulated mass,
Dry, Calcination at 3OO to 500 ⁰ C to a degree of reduction from 0.40 to 0.99 and Reduce at 250 to 480 ⁰ C. 4. The method according to claim 3 »characterized in that the nickel hydroxide and / or the basic nickel carbonate together with an added salt of copper, silver, chromium, zirconium, thorium, tin or rhenium or a salt of a metal of group VIII of the periodic table or a mixture of at least two of the salts mentioned is processed in an amount of 0.1 to 10 % of the metal in the catalyst. 5 «Use of the hydrogenation catalysts according to claim 1 or 2 for the hydrogenation of unsaturated organic compounds. 130038/0974 30494U 6. Process for the hydrogenation of polyunsaturated organic compounds to the corresponding partially or fully saturated compounds in the liquid phase, characterized, that the multiply saturated organic compound is ^{hydrogenated at 550 to 240 0} C in the presence of a hydrogenation catalyst according to claim 1 or 2 with hydrogen at a pressure of 1.013 * 10 ^ to 2.7 «10 ⁶ , the reaction time depending on the required composition of the reaction products is chosen. 7 · Process for the hydrogenation of unsaturated fatty acids and / or their glycerides to the corresponding, partially or fully saturated compounds in liquid phase, characterized, that the unsaturated fatty acids or mixtures of unsaturated fatty acids and / or their glycerides are ^{hydrogenated at 80 to 240 0} C in the presence of a hydrogenation catalyst according to claim 1 or 2 with hydrogen at a pressure of 1.013 «10 ^ to 2.7 * 10 ⁶ Pa, the duration of the reaction being selected according to the required composition of the fatty acids in the reaction product. 8. The method according to any one of claims 5 to 7 »characterized in that the 130038 / 097A Hydraulic catalyst in an amount from 0.01 "to 2 % By weight of metallic nickel, based on the weight of the raw material to be processed, is used. Process according to Claim 8, characterized in that the hydrogenation catalyst in an amount of from 0.02 to 0.06% by weight metallic Nickel, based on the weight of the raw material to be processed, is used. 130038/0974