RU2691451C1 - Catalyst for liquid-phase synthesis of methanol and a method for production thereof - Google Patents

Abstract

FIELD: technological processes.SUBSTANCE: invention relates to production of heterogeneous catalysts for liquid-phase synthesis of methanol. Catalyst for liquid-phase synthesis of methanol contains a carrier and zinc as an active component. According to the invention, the support used is a super-cross-linked polystyrene with a cross-linking degree of 195–205 %, wherein content of zinc in catalyst is from 2 to 4 wt%, and content of super-cross-linked polystyrene is 96–98 wt%. Super-cross-linked polystyrene with functional tertiary amine groups, particle size 5–7 mcm, exchange capacity 0.5 mole/l, moisture content 55÷62 %, degree of swelling of ±5 %, relative density of 1.04 g/ml, inner surface area of 900÷1,100 m/g and granule size of 5–7 mcm. Method of producing a catalyst for liquid phase synthesis of methanol involves treatment of the support with a zinc salt solution, drying for 1 hour, washing with distilled water, drying and reduction with hydrogen for 2 hours. According to the invention, as zinc salt solution a zinc acetate solution with concentration of 2.8–2.9 wt% is used in tetrahydrofuran, distilled water and methanol, prepared under nitrogen flow, treatment of support with zinc acetate solution is carried out for 10±0.5 minutes, after which catalyst is dried at 75±5 °C for 1±0.05 hours, washed with distilled water with pH=6.4–7.0, dried again at 75±5 °C for 1±0.05 hours, placed in a tubular furnace, purged with nitrogen at rate of 30±5 ml/min for 30±5 minutes, is purged with hydrogen at rate of 30±5 ml/min for 30±5 minutes, reduced with hydrogen at 300±10 °C at rate of 30±5 ml/min for 2±0.1 hours, cooled to room temperature and purged with nitrogen at rate of 30±5 ml/min for 30±5 minutes. Super-cross-linked polystyrene is pre-treated with acetone, washed with distilled water and dried under vacuum for 24 hours.EFFECT: high activity, selectivity and operational stability of the heterogeneous catalyst in the reaction of liquid phase synthesis of methanol owing to use of an inert polymer support with a large surface area and high availability of the active metal (zinc).4 cl, 23 ex

Description

The invention relates to the chemical industry, namely, to the production of heterogeneous catalysts for the processes of liquid-phase methanol synthesis, and can be applied in the chemical industry to produce methanol, which is used for the synthesis of formaldehyde, esters of organic and inorganic acids, fuel additives, and also as a solvent and extractant.

The liquid-phase catalytic synthesis of methanol is actually carried out in a three-phase “gas-catalyst-solvent” system on a pulverized catalyst that is fluidized in a circulating stream of a liquid inert high-boiling hydrocarbon, which makes it possible to make the most of the catalytic properties of the catalyst (lowering the process temperature, uniform distribution of heat, liquid and gas, low catalyst losses, high methanol conversion).

There are several generations of catalysts for liquid-phase methanol synthesis. Initially, zinc-chromium high-temperature catalytic systems were used for methanol synthesis, the advantage of which was a relatively low sensitivity to catalytic poisons [Rozovsky A.Ya., Lin G.Ye. The theoretical basis of the process of methanol synthesis. M .: Chemistry. 1990. 272 p.]. The main disadvantage of this type of catalysts is the high content of impurities when using the catalyst in the process of methanol synthesis.

The second generation of methanol synthesis catalysts is zinc-copper-aluminum (30-70% mass. CuO, 15-50% mass. ZnO, 1-16% mass. Al ₂ O ₃ ) and zinc-copper-chromium (10-90% mass of CuO, 8-80% of mass. of ZnO, 2-30% of mass. of Cr ₂ O ₃ ) system [Rozovsky A.Ya., Lin G.E. The theoretical basis of the process of methanol synthesis. M .: Chemistry. 1990. 272 p.]. The advantages of copper-containing catalysts - the possibility of carrying out the process of methanol synthesis at relatively low temperatures and pressures, which can significantly reduce the content of impurities compared with zinc-chromium compositions. The main disadvantages of this type of catalysts are relatively low stability, a strong influence on the rate of methanol formation of the composition of the initial gas mixture, the catalyst and the method of its reduction.

Also known are bimetallic catalysts for the synthesis of methanol based on copper using zinc, lanthanum, vanadium, yttrium, chromium and manganese as the second metal [Matsuda T., Shizuta M, Yoshizawa J., Kikushi E. Liquid-phase methanol synthesis by Cu-based ultrafine particles prepared by chemical deposition in liquid phase // Appl. Catal. A - Gen. 1995. Vol. 125. pp. 293-302]. The most effective of these catalysts are Cu-Zn (70/30) and Cu-V (98.5 / 1.5) - at a temperature of 250 ° C, a pressure of 3.0 MPa and the composition of the gas mixture H ₂ : CO (2: 1) allow to obtain 195 and 486 g of methanol per kg of catalyst per hour, respectively. Catalysts for liquid-phase methanol synthesis based on palladium on inorganic carriers are also known [Barrandeguy J., Chiavassa DL, Collins SE, Bonivardi AL, Baltanas MA and J. Gallium-palladium-supported catalysts // J. Catal. 2002. Vol. 211. pp. 252-264; Collins SE, Delgado JJ, Mira C , Calvino JJ, Bernal S., Chiavassa DL, Baltanas MA, Bonivardi AL The role of Pd-Ga bimetallic particles in the bifunctional mechanism of selective methanol synthesis via CO ₂ hydrogenation on a Pd / Ga ₂ O ₃ catalyst // J. Catal. 2012. Vol. 292. pp. 90-98; Collins SE, Baltanas MA, Bonivard AL Pd / β-Ga ₂ O ₃ , an infrared study of intermediates // J. Catal. 2004. Vol. 226. pp. 410-421; Ali SH, JG Impact of Resorption of Corrosive Effects and Synthesis on Pd / SiO ₂ / J. Catal. 1997. Vol. 171. pp. 339-344]. A common disadvantage of these types of catalysts is low activity (not more than 600 g of methanol per kg of catalyst per hour) and low selectivity for methanol.

Closest to the proposed catalyst is a catalyst for methanol synthesis obtained by the method of mixing-precipitation, including oxides of copper, zinc, chromium, manganese, magnesium, aluminum and barium, characterized in that the catalyst has the following molar ratio: CuO: ZnO: Cr ₂ O ₃ : MnO: MgO: Al ₂ O ₃ : BaO = 1: 0.3: (0.15-0.2) :( 0.05-0.1) :( 0.05-0.1) :( 0 , 25-0.3): 0.05 (Patent RU 2175886, B01J 23/72 (2000.01), B01J 23/80 (2000.01), B01J 23/86 (2000.01), B01J 23/887 (2000.01), B01J 21 / 04 (2000.01), B01J 21/10 (2000.01), C07C 31/04 (2000.01), Application: 2000103275/04, February 14, 2000, Published: November 20, 2001, Bulletin No. 32).

The disadvantages of the catalyst are the complexity of the composition of the catalyst, insufficient activity on methanol, as well as a large number of by-products formed during the synthesis of methanol, which significantly reduces the efficiency of the use of the catalyst.

A method of obtaining a zinc-copper-aluminum catalyst for methanol synthesis using liquid-phase reduction [Schimpf S., Rittermeier A., Zhang X., Li Z.-A., Spasova M., van den Berg MWE, Farle M., Wang Y ., Fischer RA, Muhler M. Stearate-Based Cu Colloids in Methanol Synthesis: Structural Changes Driven by Strong Metal-Support Interactions // Chem. Cat. Chem. 2010. Vol. 2. pp. 214-222]. First, the catalyst was heated to 110 ° C under nitrogen to remove residual water, then heating continued to 180 ° C at a heating rate of 1 ° C / min in 5% H ₂ and kept for 14 hours. Next, the temperature was raised to 190 ° C and kept for 3 hours. At the last stage, the temperature and hydrogen content were increased in 3 stages: 200 ° C and 10% H ₂ , 210 ° C and 15% H ₂ , 220 ° C and 20% H ₂ at a heating rate of 1 ° C / min and a holding time of 3 hours at each stage. The reduced catalyst was tested in liquid-phase methanol synthesis on a mixture of the composition H ₂ : CO: CO ₂ : N ₂ (72: 103: 4: 14) at a temperature of 220 ° C and a pressure of 2.6 MPa. The resulting rate of formation of methanol - 199 g of methanol per kg of catalyst per hour.

A method of obtaining a zinc-copper-aluminum catalyst for methanol synthesis using liquid-phase reduction in a mixture of H ₂ (10%) and N ₂ (90%) at a pressure of 0.3 MPa, while during the recovery, the temperature rose to 270 ° C with a speed 2 ° C / min, the catalyst was kept at this temperature for 7 hours, then cooled to 240 ° C [Zhang X., Zhong L. Guo Q., Fan H., Zheng H., Xie K. Influence of the calcination on the activity and stability of the Cu / ZnO / Al ₂ O ₃ catalyst in liquid phase methanol synthesis // Fuel . 2010. Vol. 89. pp. 1348-1352]. The reduced catalyst was tested in liquid-phase methanol synthesis using a mixture of the composition H ₂ : CO: CO ₂ (68: 24: 5) at a temperature of 240 ° C and a pressure of 4.0 MPa. The resulting rate of formation of methanol - 173 g of methanol per kg of catalyst per hour.

A common drawback of these methods is the insufficient recovery depth of the active metals, which reduces the activity of the catalyst in the methanol synthesis reaction.

Also known is a method of preparing a catalyst for methanol synthesis, which includes precipitating on a pre-precipitated stabilizer copper, zinc and aluminum nitrate salts from solutions of copper, zinc and aluminum nitrates with sodium carbonate solution at a given temperature and pH, followed by precipitation, washing, drying, calcining and tableting , moreover, the deposition is carried out on pre-precipitated copper-aluminum (Cu-Al), or copper-zinc-aluminum (Cu-Zn-Al), or zinc-aluminum stabilizer, and after the stages of drying and / or calcining reinforcing additives are introduced into the catalyst mass — talum (a mixture of calcium mono- and dialuminate) or calcium oxide, and / or promoting alkali metal additives (RU Patent 2500470, B01J 37/03 (2006.01), Application: 2012149492/04, 20.11.2012, Published: 10/12/2013 Bul.№34).

The disadvantage of this method is the impossibility of ensuring the stabilization of the active metals on the surface of the catalyst, as well as the absence of a stage for their reduction, which significantly impairs the catalytic activity of the catalyst for methanol and operational stability.

Closest to the proposed method is a method of obtaining a zinc-copper-aluminum catalyst for methanol synthesis using gas-phase reduction with a mixture of N ₂ (95%) and H ₂ (5%) with a temperature rise from 122 to 207 ° С [Lee S., Sardesai A Liquid phase methanol and dimethyl ether synthesis from syngas // Topics in Catalysis. 2005. Vol. 32, Iss. 3-4, pp. 197-207]. The reduced catalyst was tested in liquid-phase methanol synthesis in a mixture of composition H ₂ : CO: CO ₂ : CH ₄ (37.4: 46.3: 7.7: 8.6) at a temperature of 237 ° C and a pressure of 6.3 MPa. The resulting rate of formation of methanol - 979 g of methanol per kg of catalyst per hour.

The disadvantage of this method is the lack of recovery of active metals, which reduces the activity of the catalyst in the reaction of methanol synthesis.

The technical problem solved by the creation of the present invention is the development of a highly active, stable and selective heterogeneous catalyst for the reaction of liquid-phase methanol synthesis for multiple uses and a method for preparing a catalyst for the reaction of methanol synthesis with optimal catalytic properties.

This task is achieved due to the fact that in the catalyst for liquid-phase methanol synthesis, containing a carrier and zinc as an active component, super-linked polystyrene with a degree of crosslinking of 195 ÷ 205% is used as a carrier, while the zinc content in the catalyst is from 2 to 4 mass. %, and the content of supercrosslinked polystyrene - 96 ÷ 98 mass. % At the same time, ultracrosslinked polystyrene with functional tertiary amino groups, particle size 5-7 μm, exchange capacity 0.5 mol / l, humidity 55 ÷ 62%, swelling degree ± 5%, relative density 1.04 g / ml inner surface area 900 is used. ÷ 1100 m ² / g and granule size 5 ÷ 7 microns. In the method of producing a catalyst for liquid-phase methanol synthesis, which includes processing the carrier with a solution of zinc salt, drying for 1 hour, washing with distilled water, drying, and reducing with hydrogen for 2 hours, a zinc acetate solution of 2.8 ÷ 2 is used as a solution of zinc salt, 9% by weight, in tetrahydrofuran, distilled water and methanol, prepared under a stream of nitrogen, the carrier is treated with a solution of zinc acetate for 10 ± 0.5 minutes, after which the catalyst is dried at 75 ± 5 ° C for 1 ± 0.0 5 hours, washed with distilled water with pH = 6.4 ÷ 7.0, dried again at 75 ± 5 ° С for 1 ± 0.05 hours, placed in a tube furnace, purged with nitrogen at a rate of 30 ± 5 ml / min. 30 ± 5 minutes, rinsed with hydrogen at a flow rate of 30 ± 5 ml / min for 30 ± 5 minutes, reduced with hydrogen at 300 ± 10 ° C at a flow rate of 30 ± 5 ml / min for 2 ± 0.1 hours, cooled to room temperature and flushed with nitrogen at a flow rate of 30 ± 5 ml / min for 30 ± 5 minutes. The supercrosslinked polystyrene is pretreated with acetone, washed with distilled water and dried under vacuum for 24 hours.

The technical result of the invention is to increase the activity, selectivity and operational stability of a heterogeneous catalyst in the reaction of liquid-phase methanol synthesis by using an inert polymeric carrier with a large surface area and increasing the availability of the active metal (zinc).

The proposed catalyst has the following advantages compared with existing analogues:

high availability of the active metal (zinc) due to the use of the inner surface of the polymer, over which the active metal is distributed;

- a more uniform distribution of the active metal (zinc) over the surface of the carrier and the absence of its leaching (and, accordingly, loss) during the reaction due to the large surface area;

- a small amount of by-products in the reaction of methanol synthesis in the presence of the proposed catalyst due to the inertness of the polymer carrier.

Inclusion in the catalyst of each of these components is mandatory and none of them can be excluded from this system, as well as change their proportion, as this will lead to a significant decrease in the activity, stability and selectivity of the catalyst in the methanol synthesis reaction.

The use of supercrosslinked polystyrene (ATP) as a carrier for the zinc catalyst for methanol synthesis is due to its spatial structure, ideal for the formation of metal-polymer catalysts. The catalyst synthesis is based on the formation of metal nanoparticles in the micro cavities of the SPS polymer matrix. Polystyrene is formed by crosslinking the phenyl rings of linear polystyrene with methylene bridges between themselves, which ensures a strong structure and the formation of a large inner surface (90 ÷ 1100 m ² / g), as well as the ability to swell in a liquid medium. When using ATP with a degree of crosslinking of less than 195%, the strength of fixing zinc in the pores of the carrier decreases, which significantly reduces the stability of the catalyst and degrades the quality of the products obtained due to their contamination with zinc leached from the pores of the carrier. The use of ATP with a degree of crosslinking of more than 205% is impractical, since it does not lead to an improvement in the catalytic properties of the catalyst, but it requires additional costs. When using ATP with an internal surface area of less than 900 m ² / g, the zinc carrier capacity is reduced, which leads to a significant loss of catalytic activity of the catalyst. The use of ATP with an internal surface area of more than 1,100 m ² / g is impractical, since it does not lead to an improvement in the catalytic properties of the catalyst, but it also requires additional costs. When using ATP granules with a size of less than 5 microns, it is much more difficult to work with the carrier and its loss during processing increases. When using ATP granules with a size of more than 7 microns, the effectiveness of applying an active metal (zinc) to the polymer surface decreases.

The ratio of components (ATP and zinc) was chosen experimentally. The total zinc content relative to ATP is less than 3% by weight, it significantly reduces the catalyst activity in the methanol synthesis reaction of glucose, and an increase in its content is above 3% by weight, which is impractical, since according to the experimental results, this does not lead to a significant increase in catalyst activity in the methanol synthesis reaction.

Processing pre-prepared ATP zinc acetate solution is necessary for uniform deposition of the active metal (zinc) on the surface of the polymer carrier (ATP).

Use as a solution of zinc salt of zinc acetate due to better penetration of the substance into the pores of ATP, compared with other zinc salts.

The drying temperature at 75 ± 5 ° С of the obtained catalyst and the drying time of 1 ± 0.05 hours were chosen experimentally. The decrease in temperature below 70 ° C leads to a decrease in the efficiency of the catalyst due to insufficient removal of moisture from the pores, and an increase above 80 ° C does not lead to a significant increase in the efficiency of the catalyst, and requires additional energy consumption. Reducing the drying time of less than 0.95 hours leads to a decrease in the efficiency of the catalyst due to insufficient removal of moisture from the pores, and an increase of more than 1.05 hours does not lead to a significant increase in the efficiency of the catalyst, while requiring additional energy consumption.

The reduction of the catalyst with hydrogen at 300 ± 10 ° С with a flow rate of 30 ± 5 ml / min is necessary for the transfer of zinc from the ionic to the metallic state (zinc in the metallic state exhibits much more catalytic activity in the methanol synthesis reaction). The reduction temperature of 300 ± 10 ° С was chosen experimentally. Reducing the temperature below 290 ° C leads to underestimation of zinc and, accordingly, to a significant decrease in the efficiency of the catalyst in the reaction of methanol synthesis. An increase in temperature above 310 ° C does not lead to a significant increase in the efficiency of the catalyst, and requires additional energy consumption. The recovery time of the catalyst 2 ± 0.1 hours was chosen experimentally. Reducing the recovery time of less than 1.9 hours leads to underestimation of zinc and, accordingly, to a significant decrease in the efficiency of the catalyst in the reaction of methanol synthesis, and an increase above 2.1 hours does not lead to a significant increase in the efficiency of the catalyst, while requiring additional energy costs. The consumption of hydrogen in the recovery of 30 ± 5 ml / min is determined by the calculation method, based on the amount of active metal in the catalyst. Reducing the consumption of hydrogen below 25 ml / min leads to underestoration of zinc and, accordingly, to a significant decrease in the efficiency of the catalyst in the reaction of methanol synthesis. An increase in the consumption of hydrogen of more than 35 ml / min does not lead to a significant increase in the efficiency of the catalyst, and this requires additional costs of hydrogen.

Pretreatment of the ATP with acetone followed by drying is necessary to clean the polymer pores from residues of non-specifically bound components.

The catalyst is prepared as follows.

Example 1

3 g of ATP with functional tertiary amino groups, exchange capacity 0.5 mol / l, humidity 55 ÷ 62%, degree of swelling ± 5%, relative density 1.04 g / ml, internal surface area 900 ÷ 1100 m ² / g and size particles of 5 ÷ 7 μm, prewashed with acetone, double-distilled water and dried under vacuum for 24 hours, were introduced into the solution prepared by mixing under a stream of nitrogen 0.245 g of zinc acetate with 5 ml of tetrahydrofuran, 3 ml of distilled water and 1 ml of methanol. The suspension was stirred for 10 minutes to allow the solution to be adsorbed by the ATP polymer beads. Then the catalyst was dried at 75 ° C for 1 hour, washed with distilled water with pH = 6.4 ÷ 7.0 and dried again at 75 ° C. Next, the catalyst was placed in a tubular furnace and purged with nitrogen at a flow rate of 30 ml per minute for 30 minutes to remove residual oxygen. After that, the catalyst was purged with hydrogen in a tube furnace at a flow rate of 30 ml per minute for 30 minutes to remove residual nitrogen. Next, the tube furnace was heated to 300 ° C, the catalyst was reduced for 2 hours, then the tube furnace was cooled to room temperature. After that, the catalyst was purged with nitrogen for a flow rate of 30 ml per minute for 30 minutes. As a result, a catalyst was formed with the following ratio of components, mass%: ATP - 97, zinc - 3.

The activity of the synthesized catalyst in the reaction of methanol synthesis was investigated in a laboratory setup including a stainless steel reactor (internal volume 450 ml) with a propeller stirrer (stirring speed 1450 rpm) connected to gas cylinders equipped with a pressure gauge under the following conditions: catalyst weight - 1.5 g; the volume of isopropyl alcohol is 150 ml, the gas pressure is 15 atm, the gas temperature is 150 ° C, the flow rate of the gas mixture is 270 ml / min. Before the experiment, an initial gas mixture (synthesis gas: 80% H _2. 20% CO) was prepared, for which gases were fed from a gas cylinder with pure gases through a gas distribution device into a buffer cylinder, the filling of which was controlled using a pressure gauge. The exact composition of the gas mixture was determined by gas chromatography. Analysis of the products of methanol synthesis was performed by gas chromatography, while calculating the conversion of the starting materials to methanol (concentration of the reacted starting materials divided by the initial amount of starting substances, in percent) and selectivity (concentration of the target product - methanol divided by the concentration of all products, in percent ).

The measured rate of formation of methanol - 2103.3 g / (kg (Zn) h.

Example 2

The example was carried out similarly to the above example 1, but used the mass of zinc acetate - 0.123 g

The measured rate of methanol formation is 1443.5 g / (kg (Zn) h.

Example 3

The example was carried out similarly to the above example 1, however, used the mass of zinc acetate - 0,368,

The measured formation rate of methanol is 1987.9 g / (kg (Zn) h.

According to the results of experiments, the optimal content of zinc acetate is 0.245 g per 3 g of ATP.

Example 4

The example was carried out similarly to the above example 1, however, the suspension was stirred for 5 minutes.

The measured formation rate of methanol is 1766.0 g / (kg (Zn) h.

Example 5

The example was carried out similarly to the above example 1, but the suspension was stirred for 15 minutes.

The measured formation rate of methanol is 1912.2 g / (kg (Zn) h.

According to the results given in examples 1, 4 and 5, the optimal mixing time of the suspension is 10 minutes.

Example 6

The example was carried out similarly to the above example 1, however, the drying temperature of the catalyst is 85 ° C.

The measured formation rate of methanol is 1339.7 g / (kg (Zn) h.

Example 7

The example was carried out similarly to the above example 1, however, the drying temperature of the catalyst was 65 ° C.

The measured formation rate of methanol is 1781.2 g / (kg (Zn) h.

According to the results given in examples 1, 6 and 7, the optimum temperature for drying the catalyst is 75 ° C.

Example 8

The example was carried out similarly to the above example 1, however, the drying time of the catalyst is 0.5 hours.

The measured formation rate of methanol is 1659.5 g / (kg (Zn) h.

Example 9

The example was carried out similarly to the above example 1, however, the drying time of the catalyst is 1.5 hours.

The measured rate of formation of methanol - 2076.1 g / (kg (Zn) h.

According to the results given in examples 1, 8 and 9, the optimal drying time of the catalyst is 1 hour.

Example 10

The example was carried out similarly to the above example 1, however, the temperature of the recovery of the catalyst with hydrogen was equal to 280 ° C.

The measured formation rate of methanol is 1755.0 g / (kg (Zn) h.

Example 11

The example was carried out similarly to the above example 1, however, the temperature of the recovery of the catalyst with hydrogen was equal to 320 ° C.

The measured rate of methanol formation is 1870.1 g / (kg (Zn) h.

According to the results given in examples 1, 10 and 11, the optimum temperature for the reduction of the catalyst is 10 minutes.

Example 12

The example was carried out similarly to the above example 1, however, the recovery time of the catalyst with hydrogen for 1.5 hours.

The measured formation rate of methanol is 1986.6 g / (kg (Zn) h.

Example 13

The example was carried out similarly to the above example 1, however, the recovery time of the catalyst with hydrogen for 2.5 hours.

The measured formation rate of methanol is 2056.4 g / (kg (Zn) h.

According to the results given in examples 1, 12 and 13, the optimal recovery time of the catalyst is 2 hours.

Example 14

The example was carried out similarly to the above example 1, however, the consumption of hydrogen during the recovery of the catalyst was 15 ml / min.

The measured formation rate of methanol is 1344.1 g / (kg (Zn) h.

Example 15

The example was carried out similarly to the above example 1, however, the consumption of hydrogen in the recovery of the catalyst was equal to 45 ml / min.

The measured formation rate of methanol is 2014.5 g / (kg (Zn) h.

According to the results given in examples 1, 14 and 15, the optimal consumption of hydrogen during catalyst recovery is 30 ml / min.

Example 16

The example was carried out similarly to the above example 1, however, the temperature of the reaction mixture during the synthesis of methanol is equal to 130 ° C.

The measured formation rate of methanol is 1086.7 g / (kg (Zn) h.

Example 17

The example was carried out similarly to the above example 1, however, the temperature of the reaction mixture during the synthesis of methanol is 140 ° C.

The measured rate of methanol formation is 1506.7 g / (kg (Zn) h.

Example 18

The example was carried out similarly to the above example 1, however, the temperature of the reaction mixture during the synthesis of methanol is 160 ° C.

The measured formation rate of methanol is 1940.0 g / (kg (Zn) h.

Example 19

The example was carried out similarly to the above example 1, however, the temperature of the reaction mixture during the synthesis of methanol is equal to 170 ° C.

The measured formation rate of methanol is 1753.3 g / (kg (Zn) h.

According to the results given in examples 1, 16-19, the optimal temperature for methanol synthesis in the presence of a catalyst is 150 ° C.

Example 20

The example was carried out similarly to the above example 1, but the catalyst was used after the first cycle of methanol synthesis. The measured formation rate of methanol is 2012.4 g / (kg (Zn) h.

Example 21

The example was carried out similarly to the above example 1, but the catalyst was used after the second cycle of methanol synthesis. The measured formation rate of methanol is 1989.7 g / (kg (Zn) h.

Example 22

The example was carried out similarly to the above example 1, but the catalyst was used after the third cycle of methanol synthesis. The measured formation rate of methanol is 1965.5 g / (kg (Zn) h.

Example 23

The example was carried out similarly to the above example 1, but the catalyst was used after the fourth cycle of methanol synthesis.

The measured formation rate of methanol is 1911.0 g / (kg (Zn) h.

The results given in examples 1, 20-21, it is obvious that the catalyst practically does not reduce the activity in the first 5 cycles of use in the synthesis of methanol.

Thus, the introduction of the active metal (zinc) into the polymer matrix (ATP) followed by reduction significantly increases the activity of the catalyst, its selectivity with respect to the target product (methanol), and operational stability.

The results indicate that the use of a zinc-based catalyst in an ultra-crosslinked polystyrene matrix is a promising option for the synthesis of methanol, a raw material for the chemical industry.

Claims (4)

1. A catalyst for liquid-phase methanol synthesis containing a carrier and zinc as an active component, characterized in that super-linked polystyrene with a degree of crosslinking of 195 ÷ 205% is used as a carrier, while the zinc content in the catalyst is from 2 to 4 mass. %, and the content of supercrosslinked polystyrene - 96 ÷ 98 mass. % 2. The catalyst according to claim 1, characterized in that they use supercrosslinked polystyrene with functional tertiary amino groups, a particle size of 5-7 μm, an exchange capacity of 0.5 mol / l, a humidity of 55 ÷ 62%, a swelling degree of ± 5%, a relative density 1.04 g / ml, inner surface area 900 ÷ 1100 m ² / g and granule size 5 ÷ 7 microns. 3. A method of producing a catalyst for liquid-phase methanol synthesis according to claim 1, comprising treating the carrier with a solution of zinc salt, drying for 1 hour, washing with distilled water, drying, recovering with hydrogen for 2 hours, characterized in that a solution of zinc salt is used as a solution of zinc salt Zinc acetate with a concentration of 2.8 ÷ 2.9% of the mass, in tetrahydrofuran, distilled water and methanol, prepared under a stream of nitrogen, the carrier is treated with a solution of zinc acetate for 10 ± 0.5 minutes, after which the catalyst su at 75 ± 5 ° С for 1 ± 0.05 hours, washed with distilled water with pH = 6.4 ÷ 7.0, dried again at 75 ± 5 ° С for 1 ± 0.05 hours, placed in a tubular the furnace is flushed with nitrogen at a flow rate of 30 ± 5 ml / min for 30 ± 5 minutes, flushed with hydrogen at a flow rate of 30 ± 5 ml / min for 30 ± 5 minutes, reduced with hydrogen at 300 ± 10 ° C with a flow rate of 30 ± 5 ml / min for 2 ± 0.1 hours, cool to room temperature and purge with nitrogen at a flow rate of 30 ± 5 ml / min for 30 ± 5 minutes. 4. The method according to p. 3, characterized in that the supercrosslinked polystyrene is pre-treated with acetone, washed with distilled water and dried under vacuum for 24 hours.