RU2712637C1 - Catalyst for combined hydrofining of a mixture of vegetable and petroleum hydrocarbon material and method of its preparation - Google Patents

Abstract

FIELD: technological processes.SUBSTANCE: invention relates to a massive catalyst for combined hydrofining of a mixture of vegetable and petroleum hydrocarbon material and a method for preparing it. Said catalyst contains molybdenum in amount of 55–65.0 wt%, sulfur in amount of 30–45 wt% and carbon in amount of 0–5.0 wt%. Catalyst has specific surface area of 50–150 m/g, specific pore volume of 0.1–0.5 cm/g. Disclosed catalyst enables combined hydrofining of a mixture of vegetable and petroleum hydrocarbon material. Invention also relates to a method of preparing a solid catalyst for combined hydrofining of a mixture of vegetable and petroleum hydrocarbon material, which involves the following steps: single impregnation of the porous support in the moisture capacity with an aqueous solution of the molybdenum compound, followed by drying, sulphurization and etching of the carrier with hydrofluoric acid.EFFECT: increased activity of the catalyst in the process of combined hydrofining of a mixture of vegetable and petroleum hydrocarbon material.7 cl, 2 tbl, 10 ex

Description

The invention relates to the field of chemistry, namely to the field of production of catalysts designed for hydrotreating vegetable and petroleum hydrocarbons, and can be used in the refining and petrochemical industries.

From 1974 to the present day, numerous energy crises [Licklider R. - International Studies Quarterly. - 1988. - V. 32. - P. 205-226.], As well as the need to reduce greenhouse gas emissions and sulfur oxides [Directive 2009/30 / EC of the European Parliament and of the Council of April 23, 2009.] increasing interest in bioenergy, especially in the use of processed plant materials as fuel or as additives to motor fuels [Czernik S., Bridgwater AV - Energy Fuel. - 2004. - V. 18. - P. 590-598. Mohan D., Pittman C.U., Steele P.H. - Energy Fuels. - 2006. - V. 20. - P. 848-889. Ingram L., Mohan D., Bricka M. et al. - Energy Fuels. - 2008. - V. 22. - P. 614-625. Azadi P., Inderwildi O.R., Farnood R. et al. - Renew. Sustain. Energy Rev. - 2013. - V. 21. - P. 506-523. Bridgwater A.V. - Biomass Bioenergy. - 2012. - V. 38. - P. 68-94. Furimsky E. - Catal. Today. - 2013. - V. 217. - P. 13-56.]. Disadvantages of biofuel 1 (biodiesel), such as higher viscosity compared to traditional motor fuels, the need to dispose of by-products of production (glycerin), low chemical and temperature stability due to the high oxygen content (35-40 wt%) and double bonds [ Czernik S., Bridgwater AV - Energy Fuel. - 2004. - V. 18. - P. 590-598.], Can be eliminated by hydrodeoxygenation (GDO) and hydrogenation (HYD) of the original plant material (in particular vegetable oils) to obtain a mixture of alkanes under the name "green diesel" (greendiesel) or supercetane (supercetane), which have high stability and a higher cetane number compared to biodiesel [Guzman A., Torres JE, Prada LP et al. - Catal. Today - 2010. - V. 156. - P. 38. Hancsok J., Krar M., Magyar S. et al. - Microporous Mesoporous Mater. - 2007. - V. 101. - P. 148. Kalnes T., Marker T., Shonnard D.R. - Int. J. Chem. React Eng. - 2007. - V. 5. - P. 48.]. Most often, GDO is carried out as on noble metals deposited on various carriers [Ardiyanti A.R., Gutierrez A., Honkela M.L. et al. - Appl. Catal. A gen - 2011. - V. 407. - P. 56-66.], And on sulfides of transition metals [Bejblova M., Zamostny P., Cerveny L. et al. - Appl. Catal. A gen - 2005. - V. 296. - P. 69. Bunch A., Ozkan U. - J. Catal. - 2002. - V. 206. - P. 177. Yang Y., Thue S., Smith K. - Catal. Commun. - 2008. - V. 9. - P. 1364. Senol O., Viljava T., Krause A. - Catal. Today. - 2005. - V. 106. - P. 186. Viljava T., Komulainen R., Krause A. - Catal. Today. - 2000. - V. 60. - P. 83. Whiffen V.M.L., Smith K.J. - Energy Fuel. - 2010. - V. 24. - P. 4728-4737. Zhang S., Yongjie Y., Li T. et al. - Bioresour. Technol. - 2004. - V. 96. - P. 545. Laurent E., Delmon B. - Ind. Eng. Chem. Res. - 1993. - V. 32. - P. 2516.]. Noble metals have high activity and selectivity in GDO, but roads and their use are difficult, because they can even be poisoned by trace amounts of sulfur, so the use of transition metal sulfides is preferable.

By the end of the 20th century, all the main ways to increase the activity of catalysts based on transition metal sulfides promoted by cobalt or nickel have reached the limit of their capabilities. One of the solutions to this problem was the creation of massive catalysts consisting entirely of the active phase. The most famous were obtained by coprecipitation of the precursor salts of the polymetallic Ni-Mo-W massive highly dispersed catalysts of the NEBULA® series. Such catalysts are highly effective in many hydrogenation processes [Eijsbouts S., MayoS.W., Fujita K. - Appl. Catal. A: General. - 2007. - V. 322. - P. 58-66.].

The main disadvantages of using such catalysts in co-hydrotreating reactions of vegetable and petroleum feedstocks are their low selectivity for direct hydrogenation reactions compared to decarbonylation and decarboxylation, which leads to the release of CO or CO ₂ , which, adsorbed on active centers, prevent the occurrence of target hydrodesulfurization reactions ( GDS) and hydrogenation (GID), i.e. exhibit an inhibitory effect [Lappas A.A., Bezergianni S., Vasalos LA. - Catal. Today. - 2009. - V. 145. - P. 55-62.]. The technical solution of the present invention is the use of hydrofluoric acid to remove the media when creating a massive catalyst for the combined hydrotreatment of petroleum and vegetable raw materials, which allows to increase the selectivity along the hydrogenation route, compared with traditional catalytic systems obtained by the decomposition of molybdenum thiosols.

The closest in its technical essence and the achieved effect to the proposed technical solution is a massive hydrotreating catalyst described in US patent 7,223,713 B2.

This system is a MoS ₂ molybdenum disulfide or MoS _2-x C _x carbon-containing molybdenum disulfide obtained by decomposition of a salt of the precursor composition A _x MoS ₄ (where A is an ammonium, tetra-alkylammonium or diamine ion) under hydrothermal conditions. The main disadvantage of the above catalyst is the use of decomposition of molybdenum thiosols as a synthesis method, which leads to low selectivity under conditions of combined hydrotreatment of plant and oil feedstocks.

The technical result of the present invention is the creation of a new massive catalyst for the combined hydrotreatment of petroleum and plant materials, which has increased activity and is selective along the hydrogenation route, compared with traditional catalytic systems by synthesizing a massive catalyst by removing the carrier with hydrofluoric acid. The technical result is achieved due to the massive catalyst for the joint hydrotreating of vegetable and petroleum hydrocarbons, containing Mo - 55-65.0% wt., S - 30-45% wt., C - 0-5.0% wt .; the catalyst has a specific surface area of 50-150 m ² / g, specific pore volume of 0.1-0.5 cm ³ / g

A method of preparing a massive catalyst for joint hydrotreating of vegetable and petroleum hydrocarbon feeds involves a single impregnation of one of the precursors of the active components ((NH ₄ ) ₆ Mo ₇ O ₂₄ , (NH ₄ ) ₃ [Co (OH) ₆ Mo ₆ O ₁₈ ], H with an aqueous solution ₅ [BMo ₁₂ O ₄₀ ], (NH ₄ ) ₃ [Ni (OH) ₆ Mo ₆ O ₁₈ ], H ₇ [PMo ₁₁ CoO ₄₀ ], H ₃ [PMo ₁₂ O ₄₀ ], H ₃ [SiMo ₁₂ O ₄₀ ]), a vacuum carrier (aluminum oxide, silicon oxide or their composites with a carbon content of 0-5 wt.%) for moisture capacity; drying at temperatures from the range of 100-150 ° C; sulfidation with a gas mixture of H ₂ S / H ₂ (1-10% vol. H ₂ S) at a temperature from the range of 120-400 ° C and pressure from the range of 0.1-4.0 MPa; etching the carrier with HF hydrofluoric acid according to the procedure [Varakin AN, Mozhaev AV, Pimerzin A.A. et al. - Appl. Catal. In: Environ. - 2018 - V. 238 - P. 498-508.] At a temperature from the range of 20-80 ° C and holding time from the range of 2-8 hours.

The starting compounds for the preparation of the impregnating solution, the properties of the carrier and the composition of the catalysts are given in table. 1.

Сущность изобретения иллюстрируется следующими примерами.

The invention is illustrated by the following examples.

Example 1

The composition of the catalyst and the method of its preparation according to the well-known technical solution - the prototype.

To 75 ml of deionized water was added 10 g of ammonium tetratiomolybdate, placed in an autoclave reactor. The autoclave was purged twice with hydrogen to remove air oxygen. After heating to 300 ° C at a stirring speed of 300 rpm, the autoclave was held for 2 hours. After cooling, the resulting black precipitate was taken and washed with isopropanol.

The massive catalyst in a stream calcined in a stream of H ₂ S / H ₂ (10% vol. H ₂ S) at a temperature of 400 ° C for 4 hours contains, wt. %: Mo - 57.70; has a specific surface area of 45 m ² / g, pore volume of 0.08 cm ³ / g (table. 1).

Examples 2-10 illustrate the proposed technical solution.

Example 2

To prepare an impregnating solution, 42.8 g of H ₃ PMO ₁₂ O ₄₀ × 5H ₂ O are dissolved in 83.2 cm ^{3 of} water at 60 ° C with stirring.

The carrier, γ-Al ₂ O ₃ alumina, with a mass of 100 g is kept in a vacuum for 30 minutes, then it is poured with an impregnating solution having a temperature of 40 ° C. The carrier is kept in an impregnating solution for 15 minutes. The resulting catalyst was dried in air at room temperature, and then at 160 ° C for 3 hours, then sulfidized in a stream of H ₂ S / H ₂ (10% vol. H ₂ S) at a temperature of 400 ° C for 6 hours

The support was etched from the deposited sulfidated catalyst using HF hydrofluoric acid according to the procedure: 100 g of the catalyst was placed in a plastic bottle, then 474 g of distilled water and 193 g of hydrofluoric acid were added. After 4 hours at 50 ° С and stirring constantly, the black solution was filtered and washed with distilled water.

The catalyst contains, by weight. %: Mo - 57.7 has a specific surface area of 121 m ² / g, a pore volume of 0.21 cm ³ / g (Table 1).

Example 3

To prepare an impregnating solution, 68.1 g of (NH ₄ ) ₃ [Co (OH) ₆ Mo ₆ O ₁₈ ] is dissolved in 88.3 cm ^{3 of} water at 40 ° C with stirring.

The carrier - carbonized alumina γ-Al ₂ O ₃ (2% wt. Carbon) - weighing 100 g is kept in vacuum for 30 minutes, then pour in an impregnating solution having a temperature of 40 ° C. The carrier is kept in an impregnating solution for 15 minutes. The resulting catalyst was dried in air at room temperature, and then at 120 ° C for 4 hours, and then sulfidized in a stream of H ₂ S / H ₂ (10% vol. H ₂ S) at a temperature of 350 ° C for 5 hours

The support was etched from the deposited sulfidated catalyst using HF hydrofluoric acid according to the procedure: 100 g of the catalyst was placed in a plastic bottle, then 474 g of distilled water and 193 g of hydrofluoric acid were added. After 6 hours at 30 ° C with constant stirring, the black solution was filtered and washed with distilled water.

The catalyst contains, by weight. %: Mo - 56.6, has a specific surface area of 143 m ² / g, pore volume 0.17 cm ³ / g (Table 1).

Example 4

To prepare an impregnating solution, 58.9 g of H ₅ [BMo ₁₂ O ₄₀ ] are dissolved in 76.8 cm ^{3 of} water at 50 ° C with stirring.

Carrier - carbonized alumina γ-Al ₂ O ₃ (5% wt. Carbon) - weighing 100 g is kept in vacuum for 30 minutes, then fill in with an impregnating solution having a temperature of 40 ° C. The carrier is kept in an impregnating solution for 15 minutes. The resulting catalyst was dried in air at room temperature, and then at 150 ° C for 3 hours, and then sulfidized in a stream of H ₂ S / H ₂ (10% vol. H ₂ S) at a temperature of 400 ° C for 5 hours

The support was etched from the deposited sulfidated catalyst using HF hydrofluoric acid according to the procedure: 100 g of the catalyst was placed in a plastic bottle, then 474 g of distilled water and 193 g of hydrofluoric acid were added. After 5 hours at a temperature of 50 ° C and constant stirring, the black solution was filtered and washed with distilled water.

The catalyst contains, by weight. %: Mo - 54.8, has a specific surface area of 150 m ² / g, pore volume 0.15 cm ³ / g (Table 1).

Example 5

To prepare an impregnating solution, 60.6 g of (NH ₄ ) ₆ Mo ₇ O _{24 are} dissolved in 148.2 cm ^{3 of} water at 50 ° C with stirring.

Carrier SiO ₂ weighing 100 g is kept in vacuum for 30 minutes, then fill in with an impregnating solution having a temperature of 40 ° C. The carrier is kept in an impregnating solution for 15 minutes. The resulting catalyst was dried in air at room temperature, and then at 160 ° C for 2 hours, and then sulfidized in a stream of H ₂ S / H ₂ (10% vol. H ₂ S) at a temperature of 360 ° C for 5 hours

The support was etched from the deposited sulfidated catalyst using HF hydrofluoric acid according to the procedure: 100 g of the catalyst was placed in a plastic bottle, then 474 g of distilled water and 193 g of hydrofluoric acid were added. After 4 hours at 40 ° С with constant stirring, the black solution was filtered and washed with distilled water.

The catalyst contains, by weight. %: Mo - 57.7 has a specific surface area of 105 m ² / g, a pore volume of 0.35 cm ³ / g (Table 1).

Example 6

To prepare an impregnating solution, 68.1 g of (NH ₄ ) ₃ [Ni (OH) ₆ Mo ₆ O ₁₈ ] is dissolved in 99.8 cm ^{3 of} water at 60 ° C with stirring.

The carrier is a carbonized mixture of alumina γ-Al ₂ O ₃ and 5% by weight of SiO ₂ (2% by weight of carbon) - 100 g in weight are kept in vacuum for 30 minutes, then filled with an impregnating solution having a temperature of 40 ° C. The carrier is kept in an impregnating solution for 15 minutes. The resulting catalyst was dried in air at room temperature, and then at 160 ° C for 3 hours, and then sulfidized in a stream of H ₂ S / H ₂ (10% vol. H ₂ S) at a temperature of 400 ° C for 6 hours

The support was etched from the deposited sulfidated catalyst using HF hydrofluoric acid according to the procedure: 100 g of the catalyst was placed in a plastic bottle, then 474 g of distilled water and 193 g of hydrofluoric acid were added. After 6 hours at 30 ° C with constant stirring, the black solution was filtered and washed with distilled water.

The catalyst contains, by weight. %: Mo - 56.5, has a specific surface area of 95 m ² / g, pore volume 0.31 cm ³ / g (Table 1).

Example 7

To prepare an impregnating solution, 58.9 g of H ₅ [BMo ₁₂ O ₄₀ ] are dissolved in 97.4 cm ^{3 of} water at 90 ° C with stirring.

The carrier is a carbonized mixture of alumina γ-Al ₂ O ₃ and 5% wt. SiO ₂ (5% wt. Carbon) - weighing 100 g is kept in vacuum for 30 minutes, then fill in with an impregnating solution having a temperature of 40 ° C. The carrier is kept in an impregnating solution for 15 minutes. The resulting catalyst was dried in air at room temperature, and then at 150 ° C for 3 hours, and then sulfidized in a stream of H ₂ S / H ₂ (10% vol. H ₂ S) at a temperature of 400 ° C for 6 hours

The support was etched from the deposited sulfidated catalyst using HF hydrofluoric acid according to the procedure: 100 g of the catalyst was placed in a plastic bottle, then 474 g of distilled water and 193 g of hydrofluoric acid were added. After 5 hours at a temperature of 50 ° C and constant stirring, the black solution was filtered and washed with distilled water.

The catalyst contains, by weight. %: Mo - 54.8, has a specific surface area of 90 m ² / g, pore volume 0.28 cm ³ / g (Table 1).

Example 8

To prepare an impregnating solution, 59.6 g of H ₇ [PMo ₁₁ CoO ₄₀ ] are dissolved in 96.0 cm ^{3 of} water at 50 ° C with stirring.

The carrier, γ-Al ₂ O ₃ alumina, with a mass of 100 g is kept in a vacuum for 30 minutes, then it is poured with an impregnating solution having a temperature of 40 ° C. The carrier is kept in an impregnating solution for 15 minutes. The resulting catalyst was dried in air at room temperature, and then at 120 ° C for 4 hours, and then sulfidized in a stream of H ₂ S / H ₂ (10% vol. H ₂ S) at a temperature of 360 ° C for 5 hours

The support was etched from the deposited sulfidated catalyst using HF hydrofluoric acid according to the procedure: 100 g of the catalyst was placed in a plastic bottle, then 474 g of distilled water and 193 g of hydrofluoric acid were added. After 4 hours at 40 ° С with constant stirring, the black solution was filtered and washed with distilled water.

The catalyst contains, by weight. %: Mo - 57.5, has a specific surface area of 85 m ² / g, pore volume 0.41 cm ³ / g (Table 1).

Example 9

To prepare an impregnating solution, 57.3 g of H ₃ [SiMo ₁₂ O ₄₀ ] is dissolved in 107.2 cm ^{3 of} water at 60 ° C with stirring.

The carrier is a carbonized mixture of alumina γ-Al ₂ O ₃ and 10% by weight of SiO ₂ (2% by weight of carbon) - 100 g in weight are kept in vacuum for 30 minutes, then filled with an impregnating solution having a temperature of 40 ° C. The carrier is kept in an impregnating solution for 15 minutes. The resulting catalyst was dried in air at room temperature, and then at 160 ° C for 3 hours, and then sulfidized in a stream of H ₂ S / H ₂ (10% vol. H ₂ S) at a temperature of 400 ° C for 6 hours

The support was etched from the deposited sulfidated catalyst using HF hydrofluoric acid according to the procedure: 100 g of the catalyst was placed in a plastic bottle, then 474 g of distilled water and 193 g of hydrofluoric acid were added. After 5 h at 40 ° C and constant stirring, the black solution was filtered and washed with distilled water.

The catalyst contains, by weight. %: Mo - 64.6, has a specific surface area of 77 m ² / g, pore volume 0.36 cm ³ / g (Table 1).

Example 10

To prepare an impregnating solution, 65.0 g of (NH ₄ ) ₆ Mo ₇ O _{24 are} dissolved in 104.7 cm ^{3 of} water at 80 ° C with stirring.

The carrier is a carbonized mixture of alumina γ-Al ₂ O ₃ and 10% wt. SiO ₂ (5% wt. Carbon) - weighing 100 g is kept in vacuum for 30 minutes, then fill in with an impregnating solution having a temperature of 40 ° C. The carrier is kept in an impregnating solution for 15 minutes. The resulting catalyst was dried in air at room temperature, and then at 120 ° C for 6 hours, and then sulfidized in a stream of H ₂ S / H ₂ (10% vol. H ₂ S) at a temperature of 400 ° C for 5 hours

The support was etched from the deposited sulfidated catalyst using HF hydrofluoric acid according to the procedure: 100 g of the catalyst was placed in a plastic bottle, then 474 g of distilled water and 193 g of hydrofluoric acid were added. After 6 hours at 30 ° C with constant stirring, the black solution was filtered and washed with distilled water.

The catalyst contains, by weight. %: Mo - 54.8 has a specific surface area of 75 m ² / g, a pore volume of 0.30 cm ³ / g (Table 1).

Testing of the catalysts was carried out in the process of hydrotreating vegetable and petroleum hydrocarbons. As a mixed raw material used: a mixture of straight-run diesel fraction (90%) and vegetable oil (10%) (sulfur content of 0.88% wt.).

4 cm ^{3 of} catalyst diluted with SiC were charged into a tubular reactor. Sulfidation was carried out in a stream of H ₂ S / H ₂ (10% vol. H ₂ S) at a temperature of 400 ° C for 4 hours

Test conditions: hydrogen pressure 4.0 MPa, the hydrogen circulation rate of 500 nl / l of raw materials, the volumetric feed rate of 0.5 h ^-1 and 1.0 h ^-1 , the temperature in the reactor 360 ° C. Hydrogenates were separated from hydrogen in high and low pressure separators, then they were treated with 10% NaOH solution for 15 minutes, washed with distilled water until the washings were neutral, dried over calcined CaCl ₂ . The sulfur content in the feed and the resulting hydrogenates was determined according to GOST R 52660. The stability of the catalyst was evaluated under harsh conditions by the accelerated degree of deactivation: hydrogen pressure 1.0 MPa, hydrogen circulation rate of 150 nl / l of feed, bulk feed rate 2.0 h ¹ , temperature in the reactor 380 ° C, the process was conducted for 50 hours. The activity of the catalysts in the GDS was evaluated by the formula:

- содержание серы в сырье, (ppm); C_S - содержание серы в гидрогенизате (ppm).where GDS is the degree of hydrodesulfurization (%);

- sulfur content in raw materials, (ppm); C _S is the sulfur content in the hydrogenate (ppm).

The stability of the catalyst was evaluated by the degree of accelerated deactivation and calculated by the formula:

- содержание серы в стабильном гидрогенизате, полученном при ОСПС 1 ч^-1 и температуре Т°С до ускоренной дезактивации, ppm;

- содержание серы в стабильном гидрогенизате, полученном при ОСПС 1 ч^-1 и температуре 360°С после ускоренной дезактивации, ppm.Where

- sulfur content in the stable hydrogenate obtained at the ISPS 1 h ^-1 and temperature T ° C until accelerated deactivation, ppm;

- sulfur content in the stable hydrogenate obtained at the ISPS 1 h ^-1 and a temperature of 360 ° C after accelerated deactivation, ppm.

The degree of hydrodeoxygenation (GDO) of vegetable oils was evaluated by the change in the concentration of triglycerides of fatty acids, determined by IR spectroscopy.

The test results of the catalysts are presented in table. 2.

Заявляемые катализаторы превосходят по активности и стабильности прототип в процессе совместной гидроочистки растительного и нефтяного углеводородного сырья. Показатели процесса совместной гидроочистки позволяют сделать вывод об эффективности заявляемых катализаторов и способов их приготовления.

The inventive catalysts are superior in activity and stability to the prototype in the process of joint hydrotreatment of vegetable and petroleum hydrocarbons. The performance of the process of joint hydrotreating allows us to conclude about the effectiveness of the claimed catalysts and methods for their preparation.

Claims (7)

1. A massive catalyst for joint hydrotreating a mixture of vegetable and petroleum hydrocarbon feedstocks, including molybdenum, sulfur and carbon, characterized in that it contains: Mo - 55-65.0% wt., S - 30-45% wt., C - 0-5.0% wt .; the catalyst has a specific surface area of 50-150 m ² / g, specific pore volume of 0.1-0.5 cm ³ / g 2. A method of preparing a massive catalyst for co-hydrotreating a mixture of vegetable and petroleum hydrocarbon feeds according to claim 1, including a single impregnation of a porous carrier in terms of moisture capacity with an aqueous solution of a molybdenum compound, followed by drying / calcination, sulfidation and etching of the carrier with hydrofluoric acid. 3. A method of preparing a bulk catalyst according to claim 2, characterized in that aluminum oxide, silicon oxide or their composites with a carbon content of 0-5 wt.% Are used as a porous carrier. % 4. A method of preparing a bulk catalyst according to claim 2, characterized in that one of the series: (NH ₄ ) ₆ Mo ₇ O ₂₄ , (NH ₄ ) ₃ [Co (OH) ₆ Mo ₆ O ₁₈ ] is used as the molybdenum compound , H ₅ [BMO ₁₂ O ₄₀ ], (NH ₄ ) ₃ [Ni (OH) ₆ Mo ₆ O ₁₈ ], H ₇ [PMo ₁₁ CoO ₄₀ ], H ₃ [PMo ₁₂ O ₄₀ ], H ₃ [SiMo ₁₂ O ₄₀ ]. 5. A method of preparing a bulk catalyst according to claim 2, characterized in that the drying is carried out at a temperature of 100-150 ° C in a stream of air or nitrogen. 6. A method of preparing a bulk catalyst according to claim 2, characterized in that the sulfidation is carried out by passing through a layer of once impregnated and dried porous carrier of hydrogen-containing gas and hydrogen sulfide with a concentration of H ₂ S in the range of 1-10% vol. when heated from 120 to 400 ° C and pressure from the range of 0.1-4.0 MPa. 7. A method of preparing a massive catalyst according to claim 2, characterized in that the etching of the carrier is carried out at a temperature from a range of 20-80 ° C and a holding time from a range of 2-8 hours