RU2095136C1 - Nickel hydrogenation catalyst on carrier and method of preparing modified nickel hydrogenation catalyst on carrier - Google Patents

Abstract

FIELD: catalysts for organic syntheses. SUBSTANCE: palladium-modified nickel catalyst on carrier is provided in which nickel concentration is 0.08-0.5 wt %, Ni/Pd ratio 1:(1.5 ± 0.2), and iron content not higher than 0.3 wt %. Catalyst is prepared by adsorption on carrier of active metals from their aqueous solutions, adsorption of nickel salt being accomplish at pH 10-12, iron salt at pH 8-10, and, as palladium compound solution, palladium chlorohydroxo complexes solution being used prepared by alkali hydrolysis of palladium chloride at alkali metal hydroxide to palladium weight ratio (0.25-0.65: 1. Catalyst manifests high activity and selectivity in processes of reducing aromatic polynitro compounds, hydroxylamines, and nitriles into primary amines, ethers into alcohols, hydrogenating acetylenes into olefins and paraffins, and hydrogenolysis of phenylhalides with detachment of halogen. EFFECT: increased activity and selectivity of catalysts. 2 cl, 1 tbl

Description

 The invention relates to catalytic chemistry, in particular to supported nickel catalysts for the hydrogenation processes of various organic compounds, as well as to a method for producing such catalysts, and can be used in the chemical industry.

 Supported nickel catalysts (aluminum, silicon, magnesium, calcium oxides, activated carbons, diatomite) are widely used in hydrogenation practice.

So, for the reduction of nitro compounds into amines, catalysts have been proposed where nickel is the main active component or promoter with a nickel content on the support of 70 to 0.2% [1-5] Moreover, the catalyst may contain other metals, for example cobalt [3] vanadium [4] copper, alkaline earth metal [5]
When hydrogenating olefin and acetylene bonds (including for the selective hydrogenation of acetylene bonds to olefin), nickel catalysts are used on various supports with a nickel content of 10-90% [6] 55-56% [7] 0.1-10% [8] modified with metals of groups VII and VIII of the Periodic system [6] or silver, palladium, copper, chromium [7] salts with germanium, tin or lead [8] and Raney nickel in the presence of 3-15% copper salts [9]
In the hydrogenolysis of oxiranes, for example, phenyl-oxirane (styrene oxide) to β-phenylethyl alcohol, a nickel catalyst (in the form of Raney nickel) is used as an additive (very substantial) to 1-5% palladium on activated carbon to achieve the desired process direction, because . when using various nickel, palladium, platinum, etc. The catalysts form many impurities specific for each of the listed catalysts. The use of a combined catalyst (Pd / C + Ni Raney) with a ratio of nickel: palladium equal to (10 ⁴ 10) 1, and nickel: styrene oxide 1 (10 100), allows to achieve high (≈96.7%) selectivity for b - phenylethyl alcohol. The hydrogenation process is carried out in two stages: with a mild regime (≈3 at, 30-40 ^o C) in the first stage and more stringent (> 10 at, 100 ^o C) in the second [10]
It is also known to use a supported nickel-chromium catalyst in this process (graphite) with a nickel content of 48-60% [11]. The catalyst operates at a hydrogen pressure> 50 at.

 Said supported nickel catalysts are active in a specific hydrogenation process, i.e. the scope of each catalyst is often limited to one particular process. Information about more universal supported nickel catalysts successfully used in several hydrogenation processes, for example, reduction of aromatic polynitro compounds, hydroxylamines or nitriles to primary amines, ethers to alcohols, hydrogenation of acetylenes to olefins or paraffins, hydrogenolysis of phenyl halides with halogen cleavage, etc. not identified.

The supported nickel catalysts are prepared by adsorption of the active metal precursor compound by a carrier, followed by drying and / or calcination and reduction [4,12]
A disadvantage of the known methods is the complexity of the cooking process, including the stages of drying and / or calcination, high-temperature recovery.

Closest to the proposed catalyst is a hydrogenation catalyst containing 10-90 wt. nickel, 0.05-5 wt. palladium or rhodium or a mixture thereof and 0.03-10 wt. carrier rhenium [13]
The catalyst is prepared by immersing the carrier in an aqueous solution of nickel salt, followed by drying and calcination, during which the salt is converted to nickel oxide, after which the carrier containing nickel oxide is impregnated with an aqueous solution of palladium or rhodium salt (or a mixture thereof), dried, calcined and treated with a solution of a rhenium compound. Before use in the hydrogenation reaction, the catalyst is reduced with increasing hydrogen concentration and increasing temperature.

 The catalyst is used to hydrogenate compounds containing an unsaturated carbon-carbon bond or carbonyl group.

The disadvantages of the known catalyst are:
significant metal content (the minimum value of the total amount of metals is>10%);
the complexity of the preparation, including the intermediate stages of drying, calcination and high-temperature recovery;
limited scope.

 The purpose of the invention is the preparation of an active and selective supported nickel catalyst for the reduction of aromatic polynitro compounds, hydroxylamines or nitriles to primary amines, esters to alcohols, hydrogenation of acetylenes to olefins or paraffins, hydrogenolysis of phenyl halides with halogen cleavage, etc.

 Such a catalyst is a supported palladium-modified nickel catalyst in which the concentration of nickel on the carrier is 0.08 0.5 wt. with a ratio of nickel palladium equal to 1 (1.5 - 0.2), and containing iron with a concentration on the carrier of not more than 0.3 wt.

 The catalyst is obtained by the proposed method, which includes adsorption of nickel, palladium and iron compounds from their aqueous solutions, the adsorption of nickel salts being carried out at pH 10 12, iron salts at pH 8 10, and a solution of its chlorohydroxocomplexes obtained by alkaline hydrolysis is used as a solution of the palladium compound palladium chloride at a mass ratio of alkali metal hydroxide and palladium equal to (0.25 - 0.65) 1.

As a carrier in the proposed catalyst and method for its preparation, known carriers with a developed surface of at least 250 m ² / g (S _beats ) are used.

 New in the proposed Nickel hydrogenation catalyst modified with palladium, compared with the prototype, is that the concentration of Nickel on the carrier is 0.08 to 0.5 wt. the ratio of nickel palladium is 1 (1.5 0.2) and the catalyst contains iron with a concentration on the support of not more than 0.3 wt.

 New in the proposed method for the preparation of a modified nickel hydrogenation catalyst, including the adsorption of active metal compounds by the carrier from their aqueous solutions, is that the nickel salt is adsorbed at pH 10-12, the iron salt at pH 8 10, and its solution is used as a palladium compound solution chlorohydroxocomplexes obtained by alkaline hydrolysis of palladium chloride at a mass ratio of alkali metal hydroxide and palladium equal to (0.25 0.65) 1.

 The catalyst obtained under the proposed conditions is a universal hydrogenation catalyst, since possesses high activity and selectivity in a number of hydrogenation processes.

 Thus, when reducing aromatic polynitro compounds to polyamines, the low-percentage nickel catalysts of the present invention exhibit an activity that is 2 3 times higher than the activity of palladium catalysts (with an equal precious metal content), while being more selective.

 Known nickel catalysts on supports with the same nickel content (≅ 0.5 wt.) Are generally inactive in the hydrogenation of aromatic polynitro compounds such as 2'4'4 trinitrobenzanilide, bis (2,4 dinitroanilide) tere- and isophthalic acid, 4, 4'-dinitrotriphenylamine, polynitro (di, tri and tetra) diphenyl oxides, 4,4'-bis- (p-nitrophenyl) diphenylpropanedioxide, 1,3-bis- (p-nitrophenyl) phenylenedioxide and the like.

 The increased activity and selectivity of the proposed catalysts allows to reduce (compared with the known catalysts) the ratio of the palladium nitro compound while achieving the same high quality hydrogenation product.

 The proposed catalyst is less temperature sensitive and operates stably at such a temperature regime when it is not possible to complete the hydrogenation process on palladium catalysts (with an equal and high precious metal content) due to a sharp drop in their activity as a result of intense gumming at elevated temperatures.

 The use of the proposed catalyst in the hydrogenolysis of styrene oxide allows the process to be carried out, in contrast to known methods with high selectivity with a ratio of nickel (and palladium) styrene oxide equal to (0.001 0.002) 100, in one step and to obtain the target product b-phenylethyl alcohol used in perfumes, which determines the increased requirements for its purity.

 The proposed modified nickel catalyst can be used both for the selective hydrogenation of an acetylene bond, for example, in 1,4-butynediol to olefinic, and for its exhaustive hydrogenation to a paraffin diol, the direction of the hydrogenation process is determined by the content and ratio of the metals on the support and the process conditions. In the process of hydrogenation of 1,4-butynediol to 1,4-butanediol, the proposed catalyst combines the advantages of skeletal nickel catalysts known in this field, exhibiting high selectivity, and highly active palladium supported catalysts.

 With the selective hydrogenation of 1,4-butynediol to 1,4-butenediol, the proposed low-percentage modified nickel catalyst allows, compared with the Lindlar catalyst used in hydrogenation practice with a palladium content on the support of ≥ 2%, to sharply (by an order or more) reduce the consumption of precious metal, while providing high (> 96%) selectivity for the formation of 1,4-butenediol with a fairly high speed.

 The advantage of the proposed catalyst is also high stability during long-term storage: it does not lose its properties within a year after preparation.

 The proposed catalyst makes it possible to achieve high performance hydrogenation processes for a number of unsaturated compounds at minimal cost, since it allows hydrogenation to be carried out at high rates typical for precious metal catalysts, but with a much lower content (≅ 0.5%).

 An advantage of the proposed method for preparing the catalyst is the absence of a preliminary high-temperature reduction stage of the catalyst (i.e., the proposed catalyst does not need to be reduced at all).

 The invention is illustrated by the following examples.

Example 1. The catalyst is prepared on the installation, consisting of an enameled synthesis reactor with a capacity of 160 dm ³ , equipped with a jacket for heating, stirrer and cooler suction filter and a glass container-dispenser.

With stirring, 50-70 dm ^{3 of} distilled water and 5 kg (in terms of dry weight) of active ACB-O cellolignin having S _{beats are} loaded _. 630 m ² / g. The suspension is heated to 65-70 ^o C and adjusted to pH 10.5 with a dosage of ≈ 27 dm ^{3 of a} 0.25 sodium hydroxide solution. Then, a solution of nickel acetate, obtained by dissolving 42.4 g of Ni (CH ₃ COO) ₂ • 4 H ₂ O in 1.4 dm ^{3 of} distilled water, is metered into the reactor from the metering tank slowly, over ≈ 10 min. The suspension is maintained at 65-70 ^o C for 30 minutes, then cooled to 30-40 ^o C.

For 20-30 minutes, a solution of iron chloride (17 g of FeCl ₂ in 5.7 dm ^{3 of} distilled water) is poured into the suspension, and to precipitate iron, first a solution of sodium carbonate (50 g of Na ₂ CO ₃ in 5 dm ^{3 of} distilled water) , then a solution of sodium bicarbonate (2 kg of NaHCO ₃ in 20 dm ^{3 of} distilled water) to establish a pH of 9.0.

After 15 minutes of exposure to the suspension at room temperature, 1 dm ^{3 of a} solution of palladium chlorohydroxocomplexes (CGCPd) is dosed slowly over 10 minutes.

To obtain a solution of CGCR in a container with a stirrer of 2 dm ^3, 17 g of palladium chloride, 11 g of sodium chloride in 500 cm ^{3 of} distilled water, acidified with 1.3 cm ^{3 of} hydrochloric acid are dissolved by heating to 60-70 ^° C, after which the solution is cooled to 40-50 ^o C and hydrolyzed with 0.25 N sodium hydroxide solution to a mass ratio of NaOH Pd of 0.5 to 1.

After dosing the HCHR solution, the suspension is kept for 1 h, then it is filtered on a suction filter under vacuum and the catalyst paste ≈ 25 dm ^{3 of} distilled water is washed off to the absence of chlorine ions in the wash water.

 The finished catalyst is a paste with a moisture content of 40-50 wt. containing according to the analysis by atomic absorption method (calculated on the weight of the dry product): 0.18% nickel, 0.16% palladium and 0.17% iron.

Example 2. The catalyst is prepared in a pilot plant, consisting of a reactor for the synthesis of catalyst with a capacity of 6.3 m ³ , a reactor for preparing a HGCR solution with a capacity of 0.63 m ³ , reactors for preparing an alkali solution with a capacity of 0.4 m ³ and a nickel salt solution with a capacity of 0 , 1 m ³ , and for filtering and washing the catalyst filter press type FPAKM.

Desalted water in the amount of 3.5-4.0 m ^{3 is} pumped into the catalyst synthesis reactor from the measuring unit and ≈1000 kg of OUB coal (S _beats = 700 m ² / g) with a moisture content of ≈ 50 wt. and an iron content of 0.03 wt. The coal suspension is heated to 60-70 ^o C, then an IN aqueous solution of sodium hydroxide (180-200 dm ³ ) is dosed to establish a pH ≥ 10, after which a solution of nickel chloride (4 kg NiCl ₂ • 6 N ₂ O in 60-80 dm ³ desalted water) and hold for 30 minutes at 60-70 ^o C. Then the contents of the reactor are cooled to 30-40 ^o C and the HCGd solution is dosed for 1 hour.

The CGCR solution is prepared by loading 100-120 dm ³ desalted water, 130-140 cm ³ hydrochloric acid, 1.7 kg of palladium chloride and 0.6 kg of sodium chloride into the reactor with stirring. The mixture is heated to 60-70 ^o C and maintained at this temperature and stirring until the palladium salt is completely dissolved. The solution is cooled to 30-40 ^o C, after which the IN solution of sodium hydroxide is slowly dosed to a mass ratio of NaOH Pd 0.45 1.

 After dosing the HCHR solution, the suspension is kept in the synthesis reactor for 1 h, then it is filtered in PFACM and the precipitate is washed with ten times the amount of water.

 The finished catalyst is a paste with a moisture content of 40-50 wt. containing (according to analysis) 0.22% nickel, 0.18% palladium and 0.03% iron, based on the weight of the dry product.

Example 3. The catalyst is prepared in a laboratory setup, which is a three-necked round-bottom flask with a capacity of 0.5 dm ³ equipped with a stirrer, thermometer, dropping funnel and a refrigerator, heated with a mantle heater, as well as a Bunsen flask with a funnel for filtering under vacuum.

In a three-necked flask, with stirring, 100 cm ^{3 of} distilled water and 10 g (calculated on dry weight) of finely dispersed chromatographic g-alumina (S _beats = 200 m ² / g) are loaded. The suspension is heated to 60-70 ^o C and dosed to it with stirring, first an IN solution of sodium hydroxide to establish a pH of 10, and then a solution of nickel sulfate (0.047 g of NiSO ₄ • 7 H ₂ O in 1.6 cm ^{3 of} distilled water). The suspension is maintained at 60-70 ^o C and stirring for 30 minutes, cooled to ≈ 50 ^o C, after which the solution of CGCR is dosed.

A solution of CGCR was prepared by dissolving 0.017 g of palladium chloride (59.5% palladium) in an acidified aqueous solution of sodium chloride (0.011 g of NaCl, 0.5 cm ^{3 of} distilled water and ≈ 0.001 cm ^{3 of} hydrochloric acid) when heated to 60-70 ^o C and stirring, after which the solution is cooled to 30-40 ^o C and add IN solution of sodium hydroxide to a mass ratio of NaOH Pd of 0.5 to 1.

After dosing the solution of HCHR, the suspension is kept for 15 minutes, then a solution of ferrous sulfate (0.025 g of FeSO ₄ • 7 H ₂ O in 6.5 cm ^{3 of} distilled water) is dosed to it, the pH is adjusted to 8 with a 1% solution of sodium carbonate. 0 and maintain the suspension for 30 minutes, after which they are filtered under vacuum on a Buchner funnel and the precipitate is washed with distilled water until there are no chlorine ions in the wash water. The catalyst contains (based on the weight of the dry product): 0.08% nickel, 0.09% palladium and 0.06% iron.

Example 4. The catalyst is prepared in the experimental setup described in example 1. In the synthesis reactor, 80-100 dm ^{3 of} distilled water and 10 kg (based on dry weight) of activated carbon OUB are loaded with stirring. A solution of iron nitrate, obtained by dissolving 31 g of Fe (NO ₃ ) ₃ • 6 H ₂ O in 3 dm ^{3 of} distilled water, is dosed to the suspension for 20 minutes, then the pH is adjusted to 8 with an IN solution of sodium hydroxide, and after heating to 60-70 ^o C to pH 10. Then, a solution of nickel nitrate (49.5 g Ni (NO ₃ ) ₂ • 6 H ₂ O in 1.6 dm ^{3 of} distilled water) is dosed to the suspension for -10 min, followed by a 30-minute exposure, after which the contents of the reactor are cooled to 50 ^° C. and 320 cm ³ of a CGCR solution are slowly dosed.

A solution of CGCR was prepared in a flask with a stirrer with a capacity of 0.5 dm ³ , dissolving at 60-70 ^o C 8.5 g of palladium chloride in 250 cm ^{3 of} distilled water in the presence of 5.6 g of sodium chloride and 0.6 cm ^{3 of} hydrochloric acid. The resulting solution was cooled to 30-40 ^o C and hydrolyzed IN solution of sodium hydroxide to a mass ratio of NaOH Pd of 0.5 to 1.

After dosing the HGCRd solution, the suspension was incubated for 1 h at 50 ^° C, then the precipitate was filtered and washed as described in Example 1. The finished catalyst was a paste with a humidity of 40-50 wt. containing (based on the dry weight of the product): 0.11% nickel, 0.04% palladium and 0.07% iron.

 Example 5. The catalyst is prepared in a laboratory setup described in example 3.

While stirring, 100 cm ^{3 of} distilled water and 10 g (calculated on dry weight) of Sibunit carbon powder carrier (S _beats = 300 m ² / g) are loaded into the flask, and a solution of iron chloride (0.145 g FeCl _{3 is} dosed to the resulting suspension) • 6 H ₂ O in 1.5 cm ^{3 of} distilled water), then a pH of 9.5 is adjusted with a 0.25 N sodium hydroxide solution and the suspension is maintained for 30 minutes, after which the pH is adjusted to 12 with a 0.25 N sodium hydroxide solution and the suspension is heated up to 90 ^o C and meter a solution of nickel chloride (0.202 g NiCl ₂ • 6 H ₂ O in 8 cm ^{3 of} distilled water), followed by exposure to 30 min at 65-70 ^o C.

To a suspension cooled to 30-40 ^° C, a solution of HCGCd is prepared, prepared as follows: dissolved at 60-70 ^° C with stirring, 0.084 g of palladium chloride and 0.055 g of sodium chloride in 2.5 cm ^{3 of} distilled water, 0.006 cm ^{3 of} hydrochloric acid are added , cool the resulting solution to 50 ^o C and hydrolyze with 0.25 N sodium hydroxide solution to a mass ratio of NaOH Pd of 0.4 1.

After dosing the HCHR solution, the suspension is kept under stirring for 30 minutes, then the catalyst is filtered off and washed as described in Example 3. The finished catalyst contains (based on the dry weight of the product): 0.5% nickel, 0.45% palladium, and iron 0.3%
Example 6. The catalyst is prepared in a laboratory setting using a flask with a capacity of 1 DM ³ .

While stirring, 200 cm ^{3 of} distilled water and 20 g of finely dispersed silica "KSK" (S _beats 325 m ² / g) are loaded into the flask, the pH is adjusted to 10 with a potassium hydroxide solution, the suspension is heated to 65-70 ^° C and the solution is metered nickel chloride (0.405 g NiCl ₂ • 6 H ₂ O in 16 cm ^{3 of} distilled water). After a 30-minute exposure, the contents of the flask are cooled to 30-40 ^° C and the HCGCd solution is dosed, prepared as follows: by heating to 60-70 ^° C and stirring, 0.0336 g of palladium chloride (59.5% palladium) is dissolved, 0, 0285 g of potassium chloride in 1 cm ^{3 of} distilled water, acidified with 0.0025 cm ^{3 of} hydrochloric acid; after cooling the resulting solution to 40-50 ^o C it is hydrolyzed by slowly adding IN potassium hydroxide solution to a mass ratio of KOH Pd of 0.65 1.

After dosing the HGCRd solution, the suspension is kept for 15 min, then a solution containing iron chlorides 0.045 g FeCl ₂ and 0.097 g FeCl ₃ • 6 H ₂ O in 2 cm ^{3 of} distilled water) is slowly added, which are then hydrolyzed with a dosage of 1% carbonate solution in turn sodium (≈20 cm ³ ) and 10% sodium bicarbonate solution (≈100 cm ³ ) to a pH of 10, followed by a 30-minute exposure. After that, the catalyst precipitate was separated by filtration and washed with water, as described in example 3.

 The resulting catalyst contains (based on the dry weight of the product): 0.45% nickel, 0.09% palladium, 0.22% iron.

Example 7. The catalyst is prepared in the laboratory setup described in example 3. In a flask of 0.5 dm ³ capacity, 10 g (calculated on dry weight) of finely dispersed chromatographic alumina containing 0.10% is suspended in 100 cm ^{3 of} distilled water. iron (S _beats. 200 m ² / g). The suspension is heated to 65-70 ^o C, using IN solution of sodium hydroxide the pH is adjusted to 11 and a solution of nickel nitrate (0.149 g Ni (N0 ₃ ) ₂ • 6 H ₂ O in 4.8 cm ^{3 of} distilled water) is metered into it, then incubated at 65-70 ^o C for 30 minutes

After the mixture has cooled to 50 ^° C, a solution of CGCR is dosed into it, prepared as follows: 0.084 g of palladium chloride, 0.028 g of sodium chloride are dissolved by heating to 60-70 ^° C and stirring with a magnetic stirrer in 2.5 cm ^{3 of} distilled water, acidified with 0.006 cm ³ hydrochloric acid; after cooling the solution to 40-50 ^o C add IN solution of sodium hydroxide to a mass ratio of NaOH Pd of 0.5 to 1.

After dosing with HGCrd, the suspension was kept at 50 ^° C for 30 minutes, then filtered, as described in Example 3, and the catalyst precipitate was washed with ten times the amount of distilled water. The finished catalyst contains (in terms of the dry weight of the product): 0.32% nickel, 0.48% palladium, 0.10% iron.

Example 8. The catalyst is prepared on the experimental setup described in example 1. 80-100 dm ^{3 of} distilled water and 10 kg (in terms of dry weight) of activated carbon OUB are loaded into the reactor with the stirrer turned on. To the resulting suspension at ambient temperature, a solution of iron chloride (48.3 g of FeCl ₃ • 6 H ₂ O in 16 dm ^{3 of} distilled water) is slowly poured over 30-40 minutes, after which hydrolysis is carried out by pouring IN solution of sodium hydroxide to pH 8.5. Then the suspension is heated to 65-70 ^o C and using IN solution of sodium hydroxide the pH is adjusted to 10 and a solution of nickel chloride (40.5 g NiCl ₂ • 6 H ₂ O in 1.6 dm is slowly dosed for ≈ 10 min) ³ distilled water) followed by a 30-minute exposure. The contents of the reactor are cooled to 50 ^o C and for 5-7 minutes are the dosage of the solution CGCR. A solution of HCHR is prepared by heating to 65-70 ^o C with stirring a mixture of 17 g of palladium chloride, 11 g of sodium chloride, 1.3 cm ^{3 of} hydrochloric acid in 500 cm ^{3 of} distilled water, followed by cooling of the resulting solution to 50 ^o C and a dosage of IN solution sodium hydroxide to a mass ratio of NaOH Pd 0.4 1.

After dosing the HCHR solution, the suspension is held at 50 ^° C for 30 minutes, then the catalyst precipitate is filtered and washed, as described in Example 1.

 The finished catalyst contains (based on the dry weight of the product): 0.11% nickel, 0.09% palladium, 0.12% iron.

Example 9. The catalyst is prepared in a laboratory setting. In a flask with a capacity of 1 DM ³ load with stirring 200 cm ^{3 of} distilled water and 20 g (calculated on dry weight) of activated carbon OUB. A solution of iron chloride (0.096 g of FeCl ₃ • 6 H ₂ O in 27 cm ^{3 of} distilled water) is dosed slowly to the suspension with stirring for 2-3 minutes, then the pH is adjusted to 8 using an IN potassium hydroxide solution (≈ 4 cm ³ ). 5. The suspension is heated to 65-70 ^o C, the pH of the solution of potassium hydroxide (≈ 4 cm ³ ) is adjusted to pH 10.5, then the solution of nickel chloride (0.08 g NiCl ₂ • 6 H ₂ O in 1.6 cm is slowly poured ³ distilled water), maintain the suspension for 30 minutes, cool to 50 ^o C, and then slowly add a solution of CGCR, which is prepared by dissolving 0.0336 g of palladium chloride (59.5% palladium) and 0.0285 g of potassium chloride in 2 cm ³ of distilled water with the addition of 0.0025 cm ^{3 of} hydrochloric acid with heating to 60-70 ^o C and stirring with a magnetic stirrer, followed by hydrolysis cooled to 30-40 ^o C impurity IN solution of potassium hydroxide KOH to a weight ratio of Pd 0,25 1.

 After dosing the HCHR solution, the suspension is held for 30 minutes, after which the catalyst is filtered off with suction and washed from chlorine ions with distilled water. The finished catalyst contains (based on the weight of the dry product): 0.12% nickel, 0.09% palladium, 0.10% iron.

 The resulting catalysts were tested in the hydrogenation reactions of various unsaturated compounds.

 The conditions and test results are shown in the table.

Information sources:
1. Economic patent GDR N 251550, MKI C 07 C 87/50, 1987

 2. Copyright certificate NRB N 43558, MKI B 01 J 23/74, 1988

 3. USSR author's certificate N 1200968, MKI B 01 J 23/78, 1985

 4. Copyright certificate of the USSR N 285689, MKI B 01 J 37/08, 1985

 5. Copyright certificate NRB N 38516, MKI B 01 J 23/78, 1986

 6. US patent N 4885410, NKI 5682 861, 1989.

 7. Patent of Czechoslovakia N 211004, MKI B 01 J 23/74, 1985

 8. French Patent N 2539647, B 01 J 37/04, 1983

 9. US patent N 2953605, NKI 260-635, 1960

 10. US patent N 3579593, NKI 568-814, 1971.

 11. Copyright certificate of the USSR N 954384, MKI C 07 C 33/22, 1982

 12. J. Anderson. The structure of metal catalysts. M.1978

 13. US patent N 4795733, NKI 502-327, 1989 (prototype).

Claims (2)

 1. Nickel hydrogenation catalyst on a carrier modified with palladium, characterized in that the concentration of nickel on the carrier is 0.08 to 0.5 wt. when the ratio of nickel palladium 1 (1.5 0.2), and the catalyst contains iron with a concentration on the carrier of not more than 0.3 wt.  2. A method of preparing a modified nickel hydrogenation catalyst on a support, comprising adsorption of active metal compounds from their aqueous solutions, characterized in that the adsorption of nickel salts is carried out at pH 10 12, iron salts at pH 8 10, and its solution is used as a solution of palladium compounds chlorohydroxocomplexes obtained by alkaline hydrolysis of palladium chloride at a mass ratio of alkali metal hydroxide and palladium (0.25 0.65) 1.

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