RU2050197C1 - Method to prepare catalyst for chemical processes of hydrogenation of ketones, nitro compositions and amination of alcohols - Google Patents

Abstract

FIELD: catalysts production. SUBSTANCE: method to prepare catalysts for chemical processes of hydrogenation of ketones, nitro compositions and amination of alcohols provides, that ammonium chromates of metals are produced by chromic acid mixing with copper, nickel or zinc or their mixture carbonates or oxides Produced compound is mixed with ammonium water. Chromates thermal decomposition is exercised. Catalyst is formed and reduced by hydrogen. In the process ammonium chromates of metals are mixed with oxides or hydrooxides, or carbonates, or chromates of copper and /or nickel, and /or cobalt, and /or metals of II-d group of chemical elements periodical system, and or aluminum. and /or manganese in presence of water or ammonium water. In the case, compositions of copper, nickel and cobalt are introduced in amount of 25 80 mol and composition of II-d group metals, aluminum and manganese are introduced in amount of 0,1 75,0 mol EFFECT: simplified technique. 3 cl, 1 tbl

Description

 The invention relates to the production of a catalyst for the hydrogenation and amination of compounds used in the chemical industry.

It is known to use as intermediates the formation of active and selective catalysts of ammonium metal chromates [1] Through ammonium chromates, in particular, catalysts for the production of furfuryl alcohol [2] hydrogenation of acetone [3] for the production of amino alcohols [4]
A known method of producing a catalyst through ammonium metal chromates by precipitation by ammonia from nitric salts of copper and chromic acid [1]
The disadvantage of this method is the formation of a large amount of wastewater (≈ 30 m ³ / t of catalyst) containing compounds Cr (YI), Cu (II), requiring special labor-intensive and expensive treatment.

A known method of producing a catalyst, comprising the interaction of a solution of a carbon ammonium complex of copper and copper chromate [5] This produces ammonium metal chromate of the general formula Cu (OH) (NH ₄ ) CrO ₄ . The method is non-waste.

 The disadvantages include the instability of the properties of the return filtrate, multi-stage and laboriousness.

The closest to the invention is a process for preparing multicomponent catalysts comprising forming an ammonium chromate mixing basic metal carbonates or oxides of copper, nickel or zinc chromic acid at 20 ^{100 °} C, followed by mixing the obtained paste chennoy with ammonia water [6] A method almost completely eliminates harmful effluents and air emissions. However, while ensuring satisfactory performance characteristics for a number of processes, the preparation method has its limitations associated with the impossibility of its use for the production of catalysts requiring an increased content of the active component (beyond the molar ratio of MOHNH ₄ CrO ₄ ), or the introduction of metals that do not form compounds of the MOHNH type ₄ CrO ₄ .

 The disadvantages of the method include low productivity, low life, insufficient mechanical strength of the resulting catalysts.

 The present invention is directed to the development of a method for producing active and selective multicomponent catalysts with an increased service life for hydrogenation of ketones, nitro compounds and amination of alcohols.

 The invention consists in the following.

In a first step ammonium chromates obtained by reacting the metal carbonates or the oxides of copper, nickel or zinc, or a mixture of chromic acid at 20 100 ^{° C} and then mixing the resulting paste with ammonia water. Further, the obtained ammonium chromates are mixed with insoluble compounds (oxides, hydroxides, carbonates and chromates) of active metals (copper and / or nickel, and / or zinc, and / or cobalt, and / or promoters of compounds of group II of the Periodic system of elements, and / or aluminum, and / or manganese) in the presence of water or ammonia water. After drying, heat treatment of the intermediate is carried out at 280 350 ^about C, the catalyst is tableted. Before use, the catalyst is reduced with hydrogen with a gradual increase in temperature from 20 to 250 450 ^about C, depending on the nature of the active component with exposure for 10 hours

The preparation of the catalyst by the proposed method completely eliminates harmful effluents and atmospheric emissions, since during the heat treatment of ammonium chromate, ammonia Cr (VI) is reduced to Cr (III) with the release of harmless nitrogen and water gases, and the excess ammonia released during the drying of the catalyst with molar the ratio of NH ₃ M> 1, is captured by water and returns to the stage of mixing of the starting materials. In the process of preparing the catalyst, it is advisable to use compounds of copper, zinc, cobalt or nickel in an amount of 25 to 80 mol. To increase stability, increase service life and mechanical strength, it is necessary to introduce compounds of metals of group II of the Periodic system of elements, manganese or aluminum in an amount of 0.1 to 75.0 mol.

Thus, the hallmarks of this method of preparation of the catalyst are:
mixing ammonium chromates of copper and / or nickel and / or zinc with insoluble metal compounds in the presence of water or ammonia water;
the presence of ammonium chromates of copper and / or nickel, and / or zinc in the intermediate in the first stage of preparation of the catalyst.

 The proposed method allows to obtain a number of catalysts by varying in a wide range the ratio of active components and promoting and stabilizing additives, depending on the intended purpose. In this case, the presence of ammonium metal chromate ensures in all cases the presence of a solid-phase reducing agent (complex bound ammonia) at the stage of heat treatment of the obtained complex oxides, carbonates, and chromates, which leads to a significant development of the active surface due to heat treatment at low temperatures.

Example 1. 0.800 kg of chromic anhydride, 0.800 kg of basic copper carbonate, 0.157 kg of barium carbonate are mixed in a paddle mixer for 0.05 hours. Water and 646 ml of ammonia water with a density of 0.904 g / ml are then added. Stirring was continued for 0.5 hours. The slurry discharged from the mixer and dried in an oven at a temperature of 100 ± 10 ° ^C. The thus obtained powder of ammonium chromate, which is subjected to heat treatment at 280 290 ^{° C,} is tabletted into tablets of 4.5 mm diameter and a height of 4.5 mm. The result is a catalyst corresponding to the General formula 9 (CuO ˙ CuCr ₂ O ₄ ) 2BaCrO ₄ and containing, by weight. CuO 42.8; Cr ₂ O ₃ 45.5; BaO 11.8. The bulk density of the catalyst is 1.5 kg / l; specific surface area 56 m ² / g and mechanical strength 45 kg / table. Before use, the catalyst is reduced with a nitrogen-hydrogen mixture with an initial hydrogen content of 0.5 to 100 vol. by slowly increasing the temperature (15 20 ^{° C} per hour) to 250 ^{° C;} the catalyst is maintained at a final temperature and in pure hydrogen for 10 hours

In the hydrogenation of furfural to furfuryl alcohol is at a temperature of 120 ^C, atmospheric pressure, a contact load of 0.2 kg furfural / kg furfural conversion catalyst when using this catalyst is 99.9% selectivity at 98% furfural alcohol catalyst life 1500 hours.

PRI me R 2. 1.00 kg Cr ₂ O ₃ , 1.15 kg NiCO ₃ x xNi (OH) ₂ , 0.11 kg CuCO ₃ ˙ Cu (OH) ₂ x CuCO ₃ x Cu (OH) ₂ , 0.020 kg of barium carbonate is mixed in a paddle mixer for 0.1 h; 1 liter of distilled water is added, stirring is continued for 3 hours. Then, 808 ml of ammonia water (25%) is added to the paste and stirred for 0.5 hours. The paste is dried in an oven for 10 hours at a temperature of 100 ± 10 ^о С. at a temperature of 300 ± 10 ^about C. The powder is tabletted with the addition of 1% graphite by weight. A catalyst corresponding to the general formula is obtained:
9 (NiO ˙ NiCr ₂ O ₄ ) ˙ CuO ˙ CuCr ₂ O ₄ .

Bulk density 1.3 kg / l, specific surface area 200 m ² / g, mechanical strength 35 kg / table. Before use the catalyst was reduced at 450 ^C. When the amination of ethanol was hydrogenated in a pilot plant continuous operation at 225 ^{° C,} the contact load of 0.9 ml of ethanol / ml cat h ˙ and ammiakspirt ratio equal to 1 April, the conversion was 95.5% in during 2500 hours of work.

EXAMPLE EXAMPLE 3 800 g of chromic anhydride, 769 g of basic nickel carbonate and 212 g of basic copper carbonate, 16 g of barium carbonate was stirred, was added 900 ml of distilled water and stirring was continued for 3 hours. The slurry was cooled to 30 ^{° C.} was added 650 ml of ammonia water, stirred for 0.5 hours. Then, the paste was dried in an oven at 100 ± 10 ^{° C,} calcined at 300 ± 10 ° ^C is tabletted to tablets 4.5 x 4.5 mm. Get the catalyst corresponding to the formula: 3 (NiO x NiCr ₂ O ₄ ) CuO ˙ CuCr ₂ O ₄ . The bulk density of the catalyst is 1.3 kg / l, the specific surface is 190 m ² / g, and the mechanical strength is 35 kg / table.

Before use the catalyst was reduced ^at 400 ° C in a stream of hydrogen. The amination reaction polioksipropilenola polyoxypropylene in the pilot plant under a pressure of 5 to 10 MPa, temperature of 160 200 ^{° C} and the contact load of the original polioksipropilenolu 0.1 0.2 l / l cat h ˙ achieved degree of conversion of 92 95% for 5000 hours. the process of liquid-phase hydrogenation of acetone to isopropyl alcohol in a flow unit with a contact load of 1.0 kg of acetone / kg cat кат h conversion is 45.6% per pass.

EXAMPLE EXAMPLE 4. 0.450 kg of CrO _3, 0.500 g of RCM stirred in a paddle mixer for 0.1 h. Then 450 ml of distilled water and stirring was continued at 70 80 ^{° C} for 1 hour. After this paste was cooled ^to 25 ° C, was added 385 ml of ammonia water (24%) and stirring was continued for 0.5 hours. Then is added 0.580 kg of basic nickel carbonate, is stirred 0.5 h. The paste was dried in an oven at a temperature of 100 ± ± 10 ° ^C Then the paste is unloaded, subjected to heat treatment at 290 300 ^about C, tableted in tablets with a diameter of 4.5 mm and a height of 4.5 mm This gives a catalyst corresponding to the general formula: 2NiO (CuO x CuCr ₂ O ₄ ) and containing, by weight. CuO 34.6, Cr ₂ O ₃ 33.0, NiO 32.4. The bulk density of the catalyst is 1.5 kg / l, the specific surface area is 120 m ² / g and the mechanical strength is 50 kg / table. Before use, the catalyst is reduced with a nitrogen-hydrogen mixture with an initial hydrogen content of 0.5 to 10 vol. with gradually increasing temperature (15 20 ^{° C} per hour) to 300 ^{° C} and finish reduction in hydrogen at ²⁰⁰ ° C was held for 10 hours.

When the gas-phase hydrogenation of acetone to isopropyl alcohol at flow unit with a contact load of 10.0 kg of acetone / kg cat h ˙ in the presence of the catalyst obtained conversion was 84.8% (80 ^{° C,} the hydrogen flow rate to 50 l / g) per pass. In the hydrogenation of diethyl trinitrobenzene dietiltriaminobenzol in contact with a load of 0.05 h ^-1, temperature of 100 ^C, a pressure of 50 atm, conversion was 98% for 3 hours.

PRI me R 5. 1,100 kg of chromic anhydride, 1,210 kg of basic carbon dioxide of copper is stirred, adding 700 ml of distilled water, stirring is continued for 15 hours. Then, 890 ml of ammonia water (25%) is introduced into the chromate paste, stirred for 0.5 hours. Thereafter, the resulting mass is injected 0.224 kg of aluminum oxide and stirring continued for 0.5 hours. After drying in an oven at 100 ± 10 ° ^C was calcined at 300 ± 10 ^{° C} for 10 hours. tabletted in tablets 4.5 x 4.5 mm. Restore analogously to example 1. The specific surface area of the catalyst 236 m ² / year Mechanical strength 55 kg / table. bulk density of 1.3 kg / l. The catalyst is reduced in hydrogen at 280 ° ^C. In the process of gas-phase hydrogenation of acetone to isopropyl alcohol at flow unit with a contact load of 10.0 kg of acetone / kg cat h ˙ temperature ^of 100 C was 49.4% per pass.

PRI me R 6. 0.011 kg of basic carbon dioxide of copper, 0.010 kg of chromic anhydride, 20 ml of water is stirred in a paddle mixer for 0.5 h at a temperature of 70 80 ^about C. Then the paste is cooled to 30 ^about C, add 8 ml ammonia water, mix the mass for 10 minutes. Thereafter, when working blades in a mixer at a temperature of 25 30 ^C is introduced 0,650 kg of ground carbon nickel, 0.183 kg of basic carbonic copper, 0.377 kg of basic magnesium carbonate, was added 1820 ml of ammonia water (ρ 0,904 g / m), stirred for 0, 5 hours. Then the temperature was raised in the mixer to 70 ^{° C} and 80 carried predrying paste, while stirring. After this paste is dried in an oven at 100 ± 10 ° ^C. The heat treatment of the powder is carried out at 350 ± 10 ^° C is tabletted into tablets of 4.5 mm diameter and 4.5 mm height. The catalyst was then reduced with hydrazoic mixture having a hydrogen content of 5% with a gradual increase in temperature at a rate ^of 30 C / h to 250 ^{° C} and finish recovery, maintaining at the final temperature for 8 hours. The prepared catalyst composition, wt. 47.3 NiO; 17.4 CuO; 34.4 MgO; 1 Cr ₂ O ₃ . Bulk density 0.9 kg / l, specific surface 160 m ² / g, mechanical strength 70 kg / table.

 When liquid-phase hydrogenation of acetone to isopropyl alcohol in a flow unit with a contact load of 1.0 kg of acetone / kg cat ˙ h using the obtained catalyst, the conversion is 93.8% per passage.

In the preparation of linear polyethylene amines (diethylenetriamine, triethylenetriamine, etc.) Of monoethanolamine and ethylenediamine to flow apparatus at 160 200 ^{° C,} a pressure of 20 MPa and a contact load of 1.0 kg of the mixture of monoethanolamine and ethylenediamine / kg cat h ˙ conversion is 60% selectivity 70 % for 2000 hours

PRI me R 7. 0.011 kg of basic carbon dioxide of copper, 0.010 kg of chromic anhydride, 20 ml of water is stirred in a paddle mixer for 0.5 h at a temperature of 70 80 ^about C. The paste is cooled to a temperature of 25 ^about C, make 8 ml ammonia water, mix the mass for 30 minutes. Then at a temperature of 25 30 ^C in the mixer make 0.432 kg of basic nickel carbonate, 0.366 kg of basic copper carbonate, 0.270 kg of magnesium oxide, was added 1820 ml of ammonia water (26%), the mixture stirred for 0.5 hours. The catalyst is dried in a mixer by feeding hot water to the mixer shirt. The paste was then discharged onto a tray and dried in an oven at a temperature of 100 ± 10 ° ^C. The heat treatment is conducted at 350 360 ^° C is tabletted in a tablet height 4 mm, diameter 6 mm. The catalyst is reduced with a mixture of nitric hydrogen content of 10% by gradually increasing the temperature at a rate ^of 30 C / h to 250 ° ^C. Complete delayed reduction in hydrogen at 250 ^{° C} for 8 hours. The prepared catalyst composition, wt. 31.3 NiO; 34.3 CuO; 33.4 MgO; 1 Cr ₂ O ₃ . Bulk density 0.95 g / ml, specific surface 140 m ² / g, mechanical strength 65 kg / table.

Upon receipt of ethylenediamine from monoethanolamine and ammonia at flow apparatus at a temperature of 160 ¹⁷⁰ ° C, the contact load of 0.52 kg of monoethanolamine / kg cat h ˙ a pressure of 20.0 MPa in the presence of the catalyst the conversion obtained was 50% ethylenediamine yield 70% yield of diethylenetriamine 6 % The service life of the catalyst without loss of activity of 1200 hours

PRI me R 8. 0.011 kg of basic carbon dioxide of copper, 0.010 kg of chromic anhydride, 20 ml of distilled water is stirred in a paddle mixer for 0.5 h at a temperature of 70 80 ^about C. In the paste make 8 ml of ammonia water (25% ), the mixture stirred for 0.2 hours. Then, the paste is cooled to a temperature of 30 ° ^C, 0.864 kg making basic nickel carbonate, 0.377 kg of basic magnesium carbonate and poured in 1820 ml of ammonia water (having a density 0.904 g / ml). Conducted by stirring for 0.5 hours. The jacket of the mixer and dried steam is fed into the paste mixer for 6 hours. The calcined at a temperature of 300 ± 10 ^{° C} and tableted on a rotary press. This gives a catalyst containing, by weight. CuO 1; Cr ₂ O ₃ 1; NiO 63.8; MgO 34.2. The mechanical strength of the catalyst is 65 kg / table.

Before use the catalyst is reduced in flowing hydrogen at 450 ° ^C. The process of liquid-phase hydrogenation of acetone to isopropyl alcohol at flow unit with a contact load of 100 kg acetone / kg cat h ˙ conversion is 72.6% per pass.

PRI me R 9 (comparative). 1000 kg of chromic anhydride, 1136 kg of basic copper carbonate are mixed in a mixer, water and 810 ml of ammonia water are added and stirring is continued. Then the paste was dried, the powder was heat treated at ³⁰⁰ ° C and tabletted into tablets of 4.5 mm diameter and 4.5 mm height. This gives a catalyst corresponding to the formula: CuO ˙ CuCr ₂ O ₄ . The bulk density of the catalyst is 1.5 kg / l, the specific surface is 60 m ² / g, and the mechanical strength is 30 kg / table. Before use, the catalyst is reduced with a nitrogen-hydrogen mixture with a hydrogen content of 0.5 to 10 vol. at 250 ^C. In the process the hydrogenation of furfural to furfuryl alcohol is at ¹²⁰ ° C, atmospheric pressure and the contact load of 0.2 kg furfural / kg cat h ˙ furfural conversion of 99.9% the selectivity to 98% furfuryl alcohol catalyst life time 800 hours. in the process of gas-phase hydrogenation of acetone to isopropyl alcohol at flow unit with a contact load of 10.0 kg of acetone / kg cat h ˙ conversion is 35% (at ⁸⁰ ° C, a hydrogen flow rate of 50 l / h per pass.

 Physico-mechanical and operational properties of the catalysts prepared by the methods described in examples 1 to 9 are presented in the table.

Claims (3)

1. METHOD FOR PREPARING THE CATALYST FOR THE CHEMICAL PROCESSES OF HYDROGENATION OF KETONS, NITRO COMPOUNDS AND AMINATION OF ALCOHOLS, including the preparation of ammonium metal chromates of the formula
M (OH) / (NH ₄ ) CrO ₄ ,
where M is copper and / or nickel and / or zinc,
by mixing chromic acid with carbonates or oxides of copper, nickel or zinc, or a mixture thereof, followed by mixing the resulting paste with ammonia water, thermal decomposition of chromates, molding and reduction with hydrogen, characterized in that the ammonium chromates of metals are mixed with oxides or hydroxides or carbonates , or chromates of copper and / or nickel and / or cobalt and / or metals of group II of the Periodic system of elements and / or aluminum and / or manganese in the presence of water or ammonia water.  2. The method according to claim 1, characterized in that the compounds of copper, Nickel, zinc and cobalt are administered in an amount of 25 to 80 mol. 3. The method according to claim 1, characterized in that the compounds of metals of group II of the Periodic system of elements, aluminum and manganese are introduced in an amount of 0.1
75.0 mol

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