RU2677654C1 - Method of mechanic chemical preparation of catalyst of hydrogenation reactions on the basis of nickel - Google Patents

Abstract

FIELD: chemistry.SUBSTANCE: invention relates to methods of mechanochemical preparation of a catalyst for nickel-based hydrogenation reactions for use in the reduction reactions of the main classes of industrially important organic compounds: production of caprolactam, aniline, alcohols and fats. Method for producing catalyst for Ni/SiOhydrogenation reactions is applied on a carrier (silica gel) in the form of dispersed powder of nickel oxides, reduction at 450–470 °C with a heating rate of 4 °C/min in a stream of hydrogen at a speed of 30 cm/ min, passivation by introducing it in hydrogen atmosphere in fatty monohydroxy alcohols Cat 80–100 °C, stirring and cooling the finished catalyst to room temperature, at the same time, nickel oxide (NiO) is directly applied to silica gel (carrier) directly in its original dry form using a planetary mill at an energy consumption of 0.08–3.94 kJ/gkat., which corresponds to 20–40 % of maximum power and time work 10–240 with a mass ratio (NiO:SiO) 1:2.36.EFFECT: technical result of the invention is to simplify the production method, reduce the cost of the production process, significantly reduce the amount of starting materials and by-products without the formation of harmful gases (strong oxidizing agents or greenhouse gases) and in the absence of an evaporation stage of aqueous and non-aqueous solutions.1 cl, 1 dwg, 2 tbl

Description

The invention relates to methods for mechanochemical production of a catalyst for nickel-based hydrogenation reactions for use in reduction reactions of the main classes of industrially important organic compounds: the preparation of caprolactam, aniline, alcohols and fats.

A known method of mechanochemical production of a nickel catalyst, a method for its preparation and a process for producing ferromagnetic graphitized carbon and hydrogen [RF patent No. 2042425, IPC B01J 23/78, B01J 37/34, C01B 31/04, C01B 3/26. The catalyst, the method of its preparation and the process of producing ferromagnetic graphitized carbon and hydrogen / Chesnokov V.V., Prokudina N.A., Buyanov R.A., Molchanov V.V .; Applicant and patent holder: Institute of Catalysis, SB RAS; No. 5065825, application. 1992-06-15; publ. August 27, 1995], in which the catalyst contains the following components, May. NiO 70-90%, CuO 2-16%, Al (OH) ₃ or Mg (OH) ₂ 8-14%. The catalyst preparation method includes mechanochemical activation of a double mixture of nickel and copper oxides, and then a triple mixture of nickel and copper with aluminum or magnesium hydroxide in a planetary centrifugal mill, followed by reduction of the mixture with hydrogen while heating to the temperature of the methane decomposition reaction.

Known mechanochemical method of preparing a catalyst for the selective hydrogenation of diene and acetylene hydrocarbons into olefins [RF patent No. 2087187, IPC B01J 35/06, B01J 23/74, B01J 21/18 Selective hydrogenation catalyst and method for its preparation / Molchanov V.V., Chesnokov V.V., Buyanov R.A., Zaitseva N.A .; applicant and patentee: Institute of Catalysis named after G.K. Boreskova SB RAS; No. 94017624; declared 05/10/1994]. The essence of the invention lies in the fact that a mixture of nickel oxide, copper oxide and magnesium hydroxide was subjected to mechanochemical activation in a centrifugal planetary mill, and then restored and subjected to coking in a mixture of methane and hydrogen at 600 ° C until deactivation with respect to coke formation. during coking of metals of the subgroup of iron and their alloys, filiform carbon is formed. At the ends of the threads is a particle of metal or alloy.

A known method of producing hydrogenation catalysts by impregnation methods [Patent No. 2102145 of the Russian Federation, IPC B01J 37/04. A method of producing a nickel hydrogenation catalyst / Kipnis M.A., Gazimzyanov N.R., Aleshin A.I., Agoronov B.C .; Applicant and patent holder of ZAO NPF Khimtek. - No. 96117610/04; application 09/05/1996; publ. 01/20/1998]. The essence of the invention is to obtain a nickel hydrogenation catalyst by mixing basic nickel carbonate with an alumina support (a mixture of high-temperature and low-temperature forms of aluminum oxide) in the presence of a peptizer of an aqueous solution of ammonia, followed by drying at 100-120 ° C and calcining at 350-500 ° C, grinding mixing with graphite and tableting. This leads to the formation of gaseous ammonia and carbon dioxide as waste.

Also known is a method for the selective hydrogenation of phenylacetylene in the presence of styrene using a composite layer [Patent No. 2492160 of the Russian Federation, IPC С07С 7/167, С07С 5/09, С07С 15/46, B01J 23/755, B01J 23/72, B01J 23/44 . The method of selective hydrogenation of phenylacetylene in the presence of styrene using a composite layer / LJ Yuntao, ZhU Yunhua, KUAI Yun, ZHU Zhiyan, LI Sicin; applicant and patent holder CHINA PETROLEUM AND KEMIKAL CORPORATION (CN), SHANGHAI RISERCH INSTITUTE OF PETROKEMIKAL TECHNOLOGY SINOPEC (CN), application No. 2011129678/04 ,; declared 12/17/2009; publ. 09/10/2013; Bull. No. 25]. In this method, when preparing the catalyst, there are the following steps: slowly add a certain amount of a water-soluble nickel salt, for example, nickel nitrate, to an aqueous solution of a dilute acid (for example, nitric acid) and mix to dissolve the nickel salt; then impregnate a certain amount of carrier, for example alumina, with the resulting solution for, for example, more than 8 hours; and then dried and calcined. In this method, a poisonous gas, nitrogen dioxide, is released as a by-product.

The closest to the present patent in essence and technical result is a method of producing a catalyst for hydrogenation reactions, which consists in applying to a carrier (silica gel) in the form of a dispersed powder of nickel oxides, reduction at 470-500 ° C in a stream of hydrogen at a speed of 20-40 cm ³ / min, passivation by introducing it in a hydrogen atmosphere into C _16-18 fatty monohydric alcohols at 80-100 ° C, stirring and cooling the finished catalyst to room temperature [RF Patent No. 2604093, IPC B01J 23/755, 37/00. A method of producing a catalyst for hydrogenation reactions / Osadchaya T.Yu., Afineevsky A.V., Prozorov D.A .; patent holder: Federal State Budgetary Educational Institution of Higher Professional Education "Ivanovo State University of Chemical Technology"(IGHTU); No. 2015143251 application. 10/09/2015; publ. 12/10/2016, Bull. No. 34]

The disadvantages of the known methods for the synthesis of catalytic systems based on transition metals by impregnation methods (including the previously mentioned) are: the relatively high cost of the starting components, the complexity, during the synthesis, the formation of a large number of by-products (waste), including such as nitrogen oxides, which carry a high environmental hazard or greenhouse gases.

The technical result of the invention is to simplify the production process, to reduce the cost of the production process, to significantly reduce the amount of starting materials and by-products without the formation of harmful gases (strong oxidizing agents or greenhouse gases), as well as in the absence of a stage of evaporation of aqueous and non-aqueous solutions.

The specified result is achieved by the fact that in the method for producing a catalyst for the reaction of hydrogenation of Ni / SiO ₂ , which consists in applying to a carrier (silica gel) in the form of a dispersed powder of nickel oxides, reduction at 450-470 ° C, with a heating rate of 4 ° C / min, in a stream of hydrogen at a speed of 30 cm ³ / min, passivation by introducing it in a hydrogen atmosphere into C _16-18 fatty monohydric alcohols at 80-100 ° C, stirring and cooling the finished catalyst to room temperature, according to the invention, is applied to silica gel (carrier) nickel oxide (NiO) directly Actually in its original dry form using a planetary mill at an energy consumption of 0.08-3.94 kJ / g.cat., which corresponds to 20-40% of the maximum power and operating time 10-240 s in the ratio (NiO: SiO ₂ ) 1: 2.36.

The technical result is achieved by reducing the number of cooking operations, which simplifies and reduces the cost of the process, by eliminating the process of temperature decomposition of nickel salts, which produce harmful gases (strong oxidizing agents or greenhouse gases), carrying out the process without the use of solutions, which reduces water consumption and eliminates the need for evaporation of moisture.

To implement the invention using the following equipment:

Mill "Activator-2SL" with the technical characteristics:

The rotation speed of the central axis is 993 rpm (max), 904 rpm (cf.), 828 rpm (min).

The rotation speed of the drums is 1490 rpm (max), 1356 rpm (cf.), 1242 rpm (min).

The ratio of the radii (central and drums) is 1.5.

Radius of planetary rotation - 52.5 mm

The inner radius of the drums is 35 mm.

The volume of the drums is 220 cm ³ .

Power consumption - 1.7 kW, 380 V / 3 phases.

Grinding bodies:

small grinding media - diameter 5 mm, weight 0.499 g,

large grinding media - diameter 8 mm, weight 2.713 g,

Loading in each drum grinding media and powder:

small grinding bodies - 90 pcs.

large grinding bodies - 90 pcs.

Powder - 41.369 g.

To adjust the power used inverter TOSVERT VF-S11 firm Toshiba. The following power adjustments were used: 20%, 30%, 40%.

For the implementation of the invention using the following substances:

1. Nickel (II) oxide (NiO) "ChDA" TU-6-09-4125-80, supplier of "Spectrum-chemical" LLC.

2. Maleic acid diethyl ether (DEMK) TU 6-09-3932-87 “ChCH”, supplier of Crystal-Center LLC, ρ = 1,064 g / cm ³ ..

3. Silica gel grade L 5/40 microns (SiO ₂ ) "ChP".

4. Hydrogen electrolytic grade B GOST 3022-80.

5. Distilled water GOST 6709-72.

6. Cetylstearyl alcohol, supplier KurskKhimProm LLC KurskKhimProm.

The method is as follows:

For all examples, a weighed portion of the powder weighing 41.37 g is prepared by simple mixing of 12.32 g of NiO and 29.05 g of SiO ₂ , then this mixture is designated as (NiO + SiO ₂ ). This allows you to get a catalyst composition of Ni / SiO ₂ with w (Ni) = 25%.

Example 1

A mixture of (NiO + SiO ₂ ) is charged into the mill drum. Mechanical activation is carried out at 40% of the maximum power on the TOSVERT inverter for 120 s, which corresponds to 1.97 kJ / g.kat. energy spent.

Activation (recovery) of the catalyst is as follows. The carrier (substrate) with nickel deposited is placed in a tubular furnace and reduced in a stream of hydrogen at a speed of 30 cm ³ / min at t = 450 ° C. The temperature rise is carried out from 30 ° C to 450 ° C with a heating rate of 4 ° C / min. Upon reaching the indicated temperature, the catalyst is cooled to 80 ° C. At this stage, the resulting Ni / SiO ₂ catalyst already has significant activity, however, passivation is used for long-term storage. The activated catalyst is introduced in a hydrogen atmosphere into C _16-18 fatty monohydric alcohols at a temperature of 80 ° C, in the ratio of alcohol: catalyst - 3: 1 by weight. The resulting mass is stirred and then cooled to room temperature.

Example 2

It differs from example 1 in that it is reduced at t = 470 ° C.

Example 3

It differs from example 1 in that it is reduced at t = 470 ° C. The temperature rise is carried out from 30 ° C to 470 ° C with a heating rate of 4 ° C / min., And then kept for 15 minutes at this temperature before cooling.

Example 4

A mixture of (NiO + SiO ₂ ) is charged into the mill drum. Mechanical activation is carried out at 40% power on the TOSVERT inverter for 30 s, which corresponds to 0.49 kJ / g. energy spent.

Activation (recovery) of the catalyst is as follows. The carrier (substrate) with nickel deposited is placed in a tube furnace and reduced in a stream of hydrogen at a speed of 30 cm ³ / min at t = 470 ° C. The temperature rise is carried out from 30 ° C to 470 ° C with a heating rate of 4 ° C / min. Upon reaching the indicated temperature, the catalyst is cooled to 80 ° C. At this stage, the resulting Ni / SiO ₂ catalyst already has significant activity, however, passivation is used for long-term storage. The activated catalyst is introduced in a hydrogen atmosphere into C _16-18 fatty monohydric alcohols at a temperature of 100 ° C in the alcohol: catalyst ratio of 3: 1 by weight. The resulting mass is stirred and then cooled to room temperature.

Example 5

It differs from example 4 in that it performs mechanical activation for 60 s, which corresponds to 0.98 kJ / g. energy spent.

Example 6

Differs from example 4 in that they perform mechanical activation for 10 s, this corresponds to 0.16 kJ / g. energy spent.

Example 7

It differs from example 4 in that it is mechanically activated at 30% power on a TOSVERT inverter for 10 s, this corresponds to 0.12 kJ / g. energy spent.

Example 8

It differs from Example 4 in that it is mechanically activated at 30% power on a TOSVERT inverter for 240 s, which corresponds to 2.95 kJ / g.kat. energy spent.

Example 9

It differs from Example 4 in that it is mechanically activated at 30% power on a TOSVERT inverter for 120 s, which corresponds to 1.47 kJ / g. energy spent.

Example 10

It differs from example 4 in that it is mechanically activated at 30% power on a TOSVERT inverter for 60 s, this corresponds to 0.74 kJ / g.kat. energy spent.

Example 11

It differs from Example 4 in that it is mechanically activated at 20% power on a TOSVERT inverter for 240 s, which corresponds to 1.97 kJ / g.kat. energy spent.

Example 12

It differs from Example 4 in that it is mechanically activated at 20% power on a TOSVERT inverter for 120 s, which corresponds to 0.98 kJ / g. energy spent.

Example 13

It differs from example 4 in that it performs mechanical activation for 240 s, which corresponds to 3.94 kJ / g.kat. energy spent.

The invention is illustrated by the drawing, which shows the kinetic curves of hydrogen absorption for hydrogenation of sodium maleate, this process is taken as an example of the use of a catalyst. The dependence of the rate of the hydrogenation reaction of maleic acid diethyl ether on the degree of conversion in water on supported Ni / SiO ₂ nickel catalysts, conditions of mechanochemical synthesis:

1-120 s., 1.97 kJ / g.cat., Reduction temperature 450 ° С;

2-120 s., 1.97 kJ / g.cat., Reduction temperature 470 ° С;

3-120 s., 1.97 kJ / g.cat., Reduction temperature 470 ° С (exposure 15 minutes);

4-30 s., 0.49 kJ / g.cat., Reduction temperature 470 ° С;

5-60 s., 0.98 kJ / g.cat., Reduction temperature 470 ° С;

6-240 s., 3.94 kJ / g.cat., Reduction temperature 470 ° С. Conditions for the reduction reaction: temperature 30 ° C., atmospheric pressure, stirrer rotation speed of 3000 rpm.

Table 1 shows the preparation conditions of the catalysts in examples 1-13.

Table 2 shows the characteristics for the activity of the catalysts obtained according to the indicated examples (1-13). The rate of the hydrogenation reaction of sodium maleate and maleic acid diethyl ether in water at a temperature of 30 ° С and atmospheric pressure of hydrogen per 1 gram of metal was taken as catalytic activity. These compounds were chosen as model ones since the hydrogenation reaction proceeds in one stage without the formation of intermediate products and the kinetics of these processes has been well studied. Also in table 2 shows the half-life for these hydrogenation reactions. Kinetic curves of hydrogen absorption are shown in the drawing.

The proposed method allows to obtain a catalyst with comparable or similar characteristics, while obtaining a catalyst requires less time and labor. Eliminates the need to use aqueous or non-aqueous solutions for applying metal to a carrier. With this method, there is no emission of by-products such as gases - strong oxidizing agents, or as greenhouse gases. By reducing the number of cooking stages, cooking time and eliminating the need to collect and process by-products, the manufacture of the catalyst is cheaper.

Claims (1)

The method of mechanochemical preparation of a catalyst for nickel-based hydrogenation reactions, which is applied to a support (silica gel) in the form of a dispersed powder of nickel oxides (NiO), reduction at 450-470 ° C with a heating rate of 4 ° C / min in a stream of hydrogen at a speed of 30 cm ³ / min, passivation by introducing it in a hydrogen atmosphere into C _16-18 fatty monohydric alcohols at 80-100 ° C, stirring and cooling the finished catalyst to room temperature, characterized in that nickel oxide (NiO) is applied to a carrier (silica gel) directly in and . Khodnev dry form using a planetary mill at a rate of 0,08-3,94 energy kJ / g.kat that corresponds to 20-40% of maximum power and operation time 10-240 seconds at a weight ratio (NiO: SiO ₂₎ 1: 2.36.

Images