Liquefied gas hydrogenation catalyst, its preparation method and application

Abstract

This invention proposes a liquefied petroleum gas (LPG) hydrogenation catalyst, its preparation method, and its application. The catalyst contains a support and an active metal component; the support is modified γ-alumina, and the modifying agent used in the modified γ-alumina is one or more of Si, Ti, Zr, P, and B; the active metal component is a Group VIB metal sulfide and / or a Group VIII metal sulfide, wherein the average number of lamellar layers of the Group VIB metal sulfide and / or the Group VIII metal sulfide is <1.5 layers, and the proportion of single layers is 70%–90%. The LPG hydrogenation catalyst uses modified γ-alumina as a support, has a low average number of lamellar layers of the active metal component, and a high proportion of single layers; the catalyst still exhibits good organic sulfur removal and olefin saturation performance after long-term operation under high-temperature conditions, demonstrating good stability.

Description

Technical Field

[0001] This invention belongs to the field of petrochemical technology and relates to a liquefied gas hydrogenation catalyst, its preparation method, and its application. Background Technology

[0002] With the rapid increase in my country's crude oil processing capacity, refining and chemical plants are producing large quantities of low-carbon hydrocarbons such as liquefied petroleum gas (LPG). These low-carbon hydrocarbons are high-quality feedstocks for ethylene cracking. However, apart from hydrocracking LPG, which has a high saturation level and can be directly used as ethylene cracking feedstock, the LPG produced by catalytic cracking and coking units contains a large amount of olefins. It must be hydrogenated to saturation before entering the ethylene cracking furnace; otherwise, the olefins will undergo polymerization and coking reactions in the cracking furnace. Furthermore, the presence of organic sulfur in LPG also limits its development and utilization as a chemical feedstock. Direct emission as industrial or domestic fuel would cause environmental pollution, so hydrogenation is also necessary to remove these organic sulfur compounds.

[0003] CN201210419417.2 discloses a sulfur-containing coking liquefied gas hydrogenation catalyst, its preparation method, and its application. The catalyst uses γ-alumina as a support, and the active components are molybdenum and nickel. Based on 100% of the total catalyst weight, it contains 10.0–20.0% Mo₂O₃ and 6.0–18.0% NiO. The catalyst is in the form of strips, cloverleaf shapes, or spheres with a diameter of 3×3–5 mm, and a specific surface area of ​​100–200 m². 2 / g. In the catalyst preparation process, molybdenum is first loaded, followed by nickel, and then dried and calcined to obtain the catalyst. The catalyst of this invention can be used for high-temperature hydrogenation saturation of coking liquefied gas and residual coking C4. The catalyst does not require pre-sulfurization; after reduction in a hydrogen atmosphere, it can be directly used for high-temperature hydrogenation of coking liquefied gas and residual coking C4. No pretreatment is required for the coking liquefied gas and residual coking C4. The feed temperature for the hydrogenation reaction is 180–230℃, the reaction temperature is 280–300℃, the reaction pressure is 2.3–3.5 MPa, and the volumetric liquid hourly space velocity is 1.5–8.0 h⁻¹. -1 The hydrogen / olefin molar ratio is 1.2 to 1.8:1, and the olefin content can be less than 1% after hydrogenation.

[0004] When the above-mentioned catalyst is used in the hydrogenation process of liquefied gas, the stability of the catalyst needs to be further improved. Summary of the Invention

[0005] During their research, the inventors discovered that high-temperature conditions are beneficial for the removal of organic sulfur from liquefied petroleum gas (LPG) and the hydrogenation saturation of unsaturated olefins. However, the multilayer metal sulfide active phase in the catalyst is prone to migration and aggregation under high-temperature conditions, which affects the stability of the LPG hydrogenation catalyst.

[0006] Based on the above research results, this invention proposes a liquefied petroleum gas (LPG) hydrogenation catalyst, its preparation method, and its application. The LPG hydrogenation catalyst uses modified γ-alumina as a support, exhibits a low average number of lamellar layers in the active metal component, and a high proportion of monolayers. Even after prolonged operation at high temperatures, the catalyst still demonstrates good organic sulfur removal and olefin saturation performance, exhibiting excellent stability.

[0007] The first aspect of this invention provides a liquefied gas hydrogenation catalyst, the catalyst comprising a support and an active metal component; the support is modified γ-alumina, wherein the modifying agent used in the modified γ-alumina is one or more of Si, Ti, Zr, P and B; the active metal component is a Group VIB metal sulfide and / or a Group VIII metal sulfide, wherein the average number of lamellar layers of the Group VIB metal sulfide and / or the Group VIII metal sulfide is <1.5 layers, and the proportion of a single layer is 70% to 90%.

[0008] In the above-mentioned liquefied gas hydrogenation catalyst, based on the mass of the liquefied gas hydrogenation catalyst, the content of the modified additive, calculated as oxide, is 1.5wt% to 15wt%.

[0009] In the above-mentioned liquefied gas hydrogenation catalyst, the Group VIB metal sulfides are Mo metal sulfides and / or W metal sulfides; based on the mass of the liquefied gas hydrogenation catalyst, the Group VIB metal sulfides account for 3wt% to 20wt% of the total mass of the catalyst.

[0010] In the above-mentioned liquefied gas hydrogenation catalyst, the Group VIII metal sulfide is one or more of Ni metal sulfide, Fe-Ni metal sulfide, Co-Ni metal sulfide and Fe-Co-Ni metal sulfide; based on the mass of the liquefied gas hydrogenation catalyst, the Group VIII metal sulfide accounts for 3 to 10 wt% of the total mass of the catalyst, of which Ni metal sulfide accounts for at least 3 wt% of the total mass of the catalyst.

[0011] In the above-mentioned liquefied gas hydrogenation catalyst, the total acid content of the liquefied gas hydrogenation catalyst is 0.02-0.3 mmol / g, of which the content of strong acid at 400-500℃ accounts for 5-15%, the content of medium-strength acid at 250-400℃ accounts for 10-20%, and the balance is weak acid at 150-250℃; the ratio of Brønsted acid to Lewis acid is not less than 0.3.

[0012] In the above-mentioned liquefied gas hydrogenation catalyst, the specific surface area of ​​the liquefied gas hydrogenation catalyst is 100-400 m². 2 / g, pore volume is 0.2-1.0mL / g, and average pore size is 4-15nm.

[0013] A second aspect of this invention provides a method for preparing a liquefied gas hydrogenation catalyst, the method comprising the following:

[0014] (1) The γ-alumina carrier was impregnated with an impregnation solution containing a modifying agent, and then dried and calcined at high temperature in an oxygen-containing atmosphere to obtain the modified γ-alumina carrier.

[0015] (2) The modified γ-alumina support obtained in step (1) is impregnated with an impregnation solution containing quaternary ammonium salt compounds and active components. After drying, it is calcined at high temperature in an oxygen-containing atmosphere and then calcined in an H2S+H2 atmosphere to obtain the final liquefied gas hydrogenation catalyst.

[0016] In the above preparation method, the modifying agent in step (1) is one or more of Si, Ti, Zr, P, and B; the modifying agent used in the impregnation solution containing the modifying agent is derived from one or more of methyl orthosilicate, ethyl orthosilicate, tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, tetrabutyl titanate, tetraisopropoxide, zirconium isopropoxide, tetrapropyl zirconate, tetrabutyl zirconate, zirconium acetylacetonate, hypophosphorous acid, phosphorous acid, phosphoric acid, pyrophosphoric acid, boron oxide, and boric acid; the impregnation solution containing the modifying agent is an aqueous solution or alcohol solution prepared using conventional methods in the art, and the alcohol used in the alcohol solution is one or more of methanol, ethanol, propanol, ethylene glycol, propylene glycol, and glycerol.

[0017] In the above preparation method, the γ-alumina support in step (1) can be an existing commercial support, or it can be prepared according to common knowledge in the field as needed.

[0018] In the above preparation method, the oxygen content in the oxygen-containing atmosphere in step (1) is 10v% to 30v%, preferably an air atmosphere.

[0019] In the above preparation method, the operating conditions of the high-temperature calcination treatment in step (1) are as follows: the calcination temperature is 800-1100℃ and the calcination time is 0.5-5h.

[0020] In the above preparation method, the preparation process of the impregnation solution containing quaternary ammonium salt compounds and active components in step (2) is as follows: add the active components and quaternary ammonium salt compounds to water, and the pH value of the resulting impregnation solution is 8.5 to 11.5.

[0021] In the above preparation method, the active component is a Group VIB and / or Group VIII metal, preferably Mo and / or W, and preferably one or more of Ni, Fe-Ni, Co-Ni, and Fe-Co-Ni. Specifically, in this invention, the active component is derived from one or more of metal salts such as ammonium molybdate, ammonium metatungstate, cobalt nitrate, nickel nitrate, basic cobalt carbonate, and basic nickel carbonate. These metal salts are all water-soluble, but are not limited to the aforementioned metal salts.

[0022] In the above preparation method, the quaternary ammonium salt compound has 4 to 19 carbon atoms, such as one or more of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, dodecyltrimethylammonium hydroxide, and hexadecyltrimethylammonium hydroxide.

[0023] In the above preparation method, the conditions for high-temperature calcination in an oxygen-containing atmosphere in step (2) are as follows: the oxygen content in the oxygen-containing atmosphere is 10v% to 30v%, preferably an air atmosphere; the calcination temperature is 800 to 1100℃, and the calcination time is 0.5 to 5h.

[0024] In the above preparation method, the conditions for calcination in H2S+H2 atmosphere in step (2) are: the proportion of H2S in H2S+H2 atmosphere is 0.1-2v%; the calcination temperature is 250-550℃; and the calcination time is 3-8h.

[0025] In the above preparation method, the impregnation in steps (1) and (2) can be carried out by an impregnation method known to those skilled in the art, preferably by a saturated impregnation method or a supersaturated impregnation method.

[0026] In the above preparation method, the drying process described in steps (1) and (2) is also well known to those skilled in the art, for example, conventional drying or vacuum drying can be used.

[0027] A third aspect of the present invention provides a liquefied gas hydrogenation catalyst obtained by the above preparation method.

[0028] The fourth aspect of the present invention provides an application of the above-mentioned liquefied gas hydrogenation catalyst in the liquefied gas hydrogenation process.

[0029] In the above applications, the reaction conditions for the liquefied gas hydrogenation process are: reaction pressure of 0.5–10 MPa, preferably 1.5–8.0 MPa; reaction temperature of 120–280 °C, preferably 140–260 °C; and liquid hourly space velocity of 0.1–10.0 h⁻¹. -1 The hydrogen / liquefied petroleum gas molar ratio is 200–1500. Specific process conditions can be adjusted according to variations in raw material quality.

[0030] Compared with the prior art, the present invention has the following advantages:

[0031] 1. In the catalyst of this invention, the average number of lamellar layers of metal sulfides is low, and the proportion of single layers is high. By reducing the proportion of multilayer metal sulfides, the migration and aggregation of the multilayer metal sulfide active phase with weak interaction with the support under high-temperature conditions are avoided, thus preventing a decrease in catalyst activity and improving catalyst stability. Furthermore, the total acid content in the catalyst is low, and the proportion of strong acids is relatively low, which can inhibit the polymerization of olefins and dienes in liquefied gas to form carbon precursors, thereby improving catalyst lifespan.

[0032] 2. In the preparation method of the catalyst of the present invention, the γ-alumina support is modified with a modifying agent and then calcined at high temperature in an oxygen-containing atmosphere; then, it is impregnated with an impregnation solution containing quaternary ammonium salt compounds and active components, and the catalyst is calcined in an oxygen-containing atmosphere and then in an H2S+H2 atmosphere. The resulting catalyst has a low average number of lamellar layers of active metal components, a high proportion of monolayers, and a low total acid content and a low proportion of strong acids. The catalyst exhibits good stability in the hydrogenation reaction of liquefied gas. Attached Figure Description

[0033] Figure 1 The image shows the TEM spectrum of the catalyst prepared in Example 1. Detailed Implementation

[0034] The following examples further illustrate the solution and effects of the present invention, but do not constitute a limitation on the present invention.

[0035] In this invention, the number of lamellar layers of metal sulfides on the catalyst is obtained by statistical analysis using TEM images. The specific statistical formula is as follows:

[0036]

[0037] In the formula, N is the average number of wafer stack layers; N i n is the number of stacking layers for the i-th wafer; i Indicates the statistical N i The number.

[0038] In this invention, the acidity of the catalyst was tested using the NH3-TPD method. The Brønsted (B) and Lewis (L) acid content of the catalyst was tested using the pyridine infrared adsorption method.

[0039] In this invention, the composition and content of raw materials and products are obtained after normalization calculation through chromatographic analysis.

[0040] In this invention, the γ-alumina support used in the examples and comparative examples was purchased from Sinopec Catalysts Dalian Co., Ltd. This γ-alumina support has a specific surface area of ​​364.9 m². 2 / g, pore volume 0.62cm 3 / g, with a pore size of 6.8nm.

[0041] Example 1

[0042] 12.7 g of titanium isopropoxide was dispersed in 60 g of ethanol. Then, 100 g of γ-alumina support was impregnated with the titanium isopropoxide solution. After drying at 110 °C for 5 h, it was calcined at 1000 °C for 2 h in air to obtain a modified γ-alumina support. 10.5 g of ammonium heptamolybdate, 19.1 g of nickel nitrate hexahydrate, and 10 g of tetraethylammonium hydroxide were dissolved in water to prepare a 70 mL impregnation solution with a pH of 9.6. The modified alumina support was impregnated with this impregnation solution and dried at 110 °C for 4 h. After calcination at 1000 °C in air for 1.5 h, it was then treated at 350 °C in an H2S+H2 atmosphere (H2S volume fraction 1 v%) for 6 h to obtain the finished catalyst C-1.

[0043] Example 2

[0044] 20.9 g of tetraethyl orthosilicate was dispersed in 80 g of ethylene glycol. Then, 100 g of γ-alumina support was impregnated with the tetraethyl orthosilicate solution. After drying at 110 °C for 5 h, it was calcined at 900 °C for 3 h in air to obtain a modified γ-alumina support. 7.7 g of cobalt nitrate hexahydrate, 9.3 g of ammonium heptamolybdate, 11.6 g of nickel nitrate hexahydrate, and 8 g of tetramethylammonium hydroxide were dissolved in water to prepare a 70 mL impregnation solution with a pH of 10.9. The modified alumina support was impregnated with this impregnation solution and dried at 100 °C for 5 h. Afterward, it was calcined at 1050 °C in air for 1 h, and then treated at 400 °C in an H2S+H2 atmosphere (H2S volume fraction 1.5 v%) for 5 h to obtain the finished catalyst C-2.

[0045] Example 3

[0046] 3.8 g of phosphoric acid (85 wt%) was dispersed in 90 g of water. Then, 100 g of γ-alumina support was impregnated with the phosphoric acid solution. After drying at 110 °C for 5 h, it was calcined at 850 °C for 4 h in air to obtain a modified γ-alumina support. 8.2 g of ammonium metatungstate, 22.6 g of nickel nitrate hexahydrate, and 11 g of tetrapropylammonium hydroxide were dissolved in water to prepare a 70 mL impregnation solution with a pH of 9.0. The modified alumina support was impregnated with this impregnation solution and dried at 120 °C for 3 h. It was then calcined at 900 °C in air for 3 h, and finally treated at 300 °C in an H2S+H2 atmosphere (H2S volume fraction 1.5 v%) for 7.5 h to obtain the finished catalyst C-3.

[0047] Example 4

[0048] 4.3 g of boric acid was dispersed in 90 g of water, and then 100 g of γ-alumina support was impregnated with the above phosphoric acid solution. After drying at 110 °C for 5 h, it was calcined at 1050 °C for 1 h in air to obtain a modified γ-alumina support. 2.8 g of ferric nitrate, 7.2 g of ammonium metatungstate, 30.9 g of nickel nitrate hexahydrate, and 13 g of tetrabutylammonium hydroxide were dissolved in water to prepare a 70 mL impregnation solution with a pH of 9.3. The modified alumina support was impregnated with this impregnation solution and dried at 110 °C for 5 h. Then, it was calcined at 850 °C in air for 4 h, and finally treated at 450 °C in an H2S+H2 atmosphere (H2S volume fraction 1.5 v%) for 4 h to obtain the finished catalyst C-4.

[0049] Comparative Example 1

[0050] The preparation method of Example 1 was followed, but the γ-alumina support was not modified and was directly calcined at high temperature. 100g of the γ-alumina support was calcined at 1000℃ for 2h in air to obtain a modified γ-alumina support. 10.1g of ammonium heptamolybdate, 18.4g of nickel nitrate hexahydrate, and 10g of tetraethylammonium hydroxide were dissolved in water to prepare a 70mL impregnation solution with a pH of 9.6. The modified alumina support was impregnated with this impregnation solution and dried at 110℃ for 4h. Then, it was calcined at 1000℃ in air for 1.5h, and then treated at 350℃ in an H2S+H2 (H2S volume fraction 1v%) atmosphere for 6h to obtain the finished catalyst D-1.

[0051] Comparative Example 2

[0052] The preparation method of Example 1 was followed, but the γ-alumina support was not subjected to high-temperature calcination, but rather calcined at a lower temperature. 12.7 g of titanium isopropoxide was dispersed in 60 g of ethanol, and then 100 g of the γ-alumina support was impregnated with the above titanium isopropoxide solution. After drying at 110 °C for 5 h, it was calcined at 500 °C for 2 h in air to obtain the modified γ-alumina support. 10.5 g of ammonium heptamolybdate, 19.1 g of nickel nitrate hexahydrate, and 10 g of tetraethylammonium hydroxide were dissolved in water to prepare a 70 mL impregnation solution with a pH of 9.6. The modified alumina support was impregnated with this impregnation solution, dried at 110 °C for 4 h, calcined at 1000 °C in air for 1.5 h, and then treated at 350 °C in an H2S+H2 (H2S volume fraction 1 v%) atmosphere for 6 h to obtain the finished catalyst D-2.

[0053] Comparative Example 3

[0054] The preparation method of Example 1 was followed, but without the addition of quaternary ammonium salt compounds to the Mo-Ni impregnation solution. 12.7 g of titanium isopropoxide was dispersed in 60 g of ethanol, and then 100 g of γ-alumina support was impregnated with the above titanium isopropoxide solution. After drying at 110 °C for 5 h, it was calcined at 1000 °C for 2 h in air to obtain a modified γ-alumina support. 10.5 g of ammonium heptamolybdate and 19.1 g of nickel nitrate hexahydrate were dissolved in water to prepare a 70 mL impregnation solution. The modified alumina support was impregnated with this impregnation solution, dried at 110 °C for 4 h, calcined at 1000 °C in air for 1.5 h, and then treated at 350 °C in an H2S+H2 (H2S volume fraction 1 v%) atmosphere for 6 h to obtain the finished catalyst D-3.

[0055] Comparative Example 4

[0056] Following the preparation method of Example 1, the modified γ-alumina support impregnated with the active component was dried but not subjected to high-temperature calcination; instead, calcination was performed at a lower temperature. 12.7 g of titanium isopropoxide was dispersed in 60 g of ethanol, and then 100 g of the γ-alumina support was impregnated with the titanium isopropoxide solution. After drying at 110°C for 5 h, it was calcined at 1000°C for 2 h in air to obtain the modified γ-alumina support. 10.5 g of ammonium heptamolybdate, 19.1 g of nickel nitrate hexahydrate, and 10 g of tetraethylammonium hydroxide were dissolved in water to prepare a 70 mL impregnation solution with a pH of 9.6. The modified alumina support was impregnated with the impregnation solution, dried at 110℃ for 4 hours, calcined in air at 500℃ for 3 hours, and then treated in H2S+H2 (H2S volume fraction 1v%) atmosphere at 350℃ for 6 hours to obtain the finished catalyst D-4.

[0057] Comparative Example 5

[0058] The preparation method of Example 1 was followed, but instead of calcination in an H2S+H2 atmosphere, wet sulfidation was used. 12.7 g of titanium isopropoxide was dispersed in 60 g of ethanol, and then 100 g of γ-alumina support was impregnated with the titanium isopropoxide solution. After drying at 110°C for 5 h, it was calcined at 1000°C for 2 h in air to obtain a modified γ-alumina support. 10.5 g of ammonium heptamolybdate, 19.1 g of nickel nitrate hexahydrate, and 10 g of tetraethylammonium hydroxide were dissolved in water to prepare a 70 mL impregnation solution with a pH of 9.6. The modified alumina support was impregnated with this impregnation solution, dried at 110°C for 4 h, and then calcined at 1000°C in air for 1.5 h. The catalyst was then sulfided using a commercially available wet sulfidation method, employing straight-run kerosene containing 1.5 wt% DMDS as the sulfiding oil. The specific operating conditions are as follows: sulfidation pressure is 1.5 MPa. The catalyst bed temperature is first raised to 120°C at a rate of 10°C / min, with a liquid hourly space velocity (LHSV) of 2.0 h⁻¹. -1 Sulfated oil was introduced at a rate of [missing information] to fully wet the catalyst bed for 2 hours. Then, the catalyst bed temperature was raised to 320°C at a rate of 25°C / min and held at that temperature for 8 hours. During this period, the injection rate of sulfated oil was maintained at a liquid hourly space velocity (LHSV) of 2.0 h. -1 This allows us to obtain the finished catalyst D-5.

[0059] Comparative Example 6

[0060] The catalyst was prepared according to the method in Example 1 of CN201210419417.2. 60 g of the shaped strip-shaped γ-alumina support was weighed, and ammonium molybdate tetrahydrate and nickel nitrate hexahydrate were weighed quantitatively according to the final catalyst content of 8.0 wt% MoS2 and 5.0 wt%, and a 90 mL solution was prepared. The support was immersed in the solution for 12 hours at room temperature, filtered, dried at 125 °C, and then calcined at 400 °C for 6 hours. The prepared catalyst was D-6.

[0061] The properties of the catalysts obtained in the examples and comparative examples are listed in Table 1.

[0062] Table 1. Properties of catalysts obtained from the examples and comparative examples.

[0063]

[0064] The above catalyst was subjected to activity evaluation tests in a 10 mL reaction apparatus at a reaction pressure of 1.5 MPa, a reaction temperature of 180 °C, and a liquid hourly space velocity of 4.0 h⁻¹. -1 The hydrogen / liquefied petroleum gas molar ratio is 500. The feedstock is 20 vol% total olefins and 203 mg / m³ total sulfur content. 3 The coking liquefied gas. The evaluation results after 500 h of reaction are shown in Table 2, and the amount of carbon deposited on the catalyst after 500 h of reaction is shown in Table 3.

[0065] Table 2. Composition of the product obtained after 500 hours of reaction.

[0066]

[0067]

[0068] Table 3. Catalyst carbon deposition after 500 hours of reaction.

[0069] C-1 C-2 C-3 C-4 D-1 D-2 D-3 D-4 D-5 D-6 Carbon deposits, wt% 2.44 2.12 2.38 2.23 3.56 3.84 3.92 3.66 3.73 4.03

[0070] The evaluation results in Table 2 and the amount of carbon deposit on the catalyst after hydrogenation in Table 3 demonstrate that the catalyst of the present invention has better olefin saturation and desulfurization activity than the comparative catalyst, and the amount of carbon deposit is also lower after 500 hours of reaction, indicating that the catalyst has better stability.

Claims

1. A liquefied gas hydrogenation catalyst, characterized in that: The catalyst contains a support and an active metal component; the support is modified γ-alumina, and the modifying agent used in the modified γ-alumina is one or more of Si, Ti, Zr, P and B; the active metal component is a Group VIB metal sulfide and / or a Group VIII metal sulfide, wherein the average number of lamellar layers of the Group VIB metal sulfide and / or the Group VIII metal sulfide is <1.5 layers, and the proportion of a single layer is 70%~90%; Based on the mass of the liquefied petroleum gas hydrogenation catalyst, the content of the modified additive, calculated as oxides, is 1.5 wt% to 15 wt%. Based on the mass of the liquefied gas hydrogenation catalyst, Group VIB metal sulfides account for 3 wt% to 20 wt% of the total catalyst mass; Group VIII metal sulfides account for 3 wt% to 10 wt% of the total catalyst mass, of which Ni metal sulfides account for at least 3 wt% of the total catalyst mass. The total acid content of the LPG hydrogenation catalyst is 0.02~0.3 mmol / g, of which 5~15% is strong acid at 400-500℃, 10~20% is medium-strength acid at 250-400℃, and the remainder is weak acid at 150-250℃; the ratio of Brønsted acid to Lewis acid is not less than 0.3; the acid content is tested by the NH3-TPD method; the ratio of Brønsted acid to Lewis acid is tested by the pyridine infrared adsorption method.

2. The catalyst according to claim 1, characterized in that: Group VIB metal sulfides are Mo metal sulfides and / or W metal sulfides.

3. The catalyst according to claim 1, characterized in that: The group VIII metal sulfides are one of Ni metal sulfides, Fe-Ni metal sulfides, Co-Ni metal sulfides, and Fe-Co-Ni metal sulfides.

4. The catalyst according to claim 1, characterized in that: The liquefied gas hydrogenation catalyst has a specific surface area of ​​100~400 m². 2 / g, pore volume is 0.2-1.0mL / g, and average pore size is 4~15nm.

5. A method for preparing a liquefied gas hydrogenation catalyst according to any one of claims 1-4, characterized in that: The method includes the following: (1) The γ-alumina carrier is impregnated with an impregnation solution containing a modifying agent, dried, and then calcined at high temperature in an oxygen-containing atmosphere to obtain a modified γ-alumina carrier; the operating conditions of the high-temperature calcination treatment are as follows: the calcination temperature is 800~1100℃; (2) The modified γ-alumina support obtained in step (1) is impregnated with an impregnation solution containing quaternary ammonium salt compounds and active metal components. After drying, it is calcined at high temperature in an oxygen-containing atmosphere and then calcined in an H2S+H2 atmosphere to obtain the final liquefied gas hydrogenation catalyst.

6. The method according to claim 5, characterized in that: The modifying agent used in the impregnation solution containing the modifying agent in step (1) is derived from one or more of the following: methyl orthosilicate, ethyl orthosilicate, tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, tetrabutyl titanate, tetraisopropoxide, zirconium isopropoxide, tetrapropyl zirconate, tetrabutyl zirconate, zirconium acetylacetonate, hypophosphorous acid, phosphorous acid, phosphoric acid, pyrophosphoric acid, boron oxide, and boric acid; the impregnation solution containing the modifying agent is an aqueous solution or an alcohol solution, and the alcohol used in the alcohol solution is one or more of the following: methanol, ethanol, propanol, ethylene glycol, propylene glycol, and glycerol.

7. The method according to claim 5, characterized in that: The oxygen content in the oxygen-containing atmosphere described in step (1) is 10v%~30v.

8. The method according to claim 7, characterized in that: The oxygen-containing atmosphere mentioned in step (1) is an air atmosphere.

9. The method according to claim 5, characterized in that: The operating conditions for the high-temperature roasting treatment in step (1) are as follows: roasting time is 0.5~5h.

10. The method according to claim 5, characterized in that: The preparation process of the impregnation solution containing quaternary ammonium salt compounds and active metal components in step (2) is as follows: add the active metal components and quaternary ammonium salt compounds to water, and the pH value of the resulting impregnation solution is 8.5~11.

5.

11. The method according to claim 5, characterized in that: The quaternary ammonium salt compound is one or more of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, dodecyltrimethylammonium hydroxide, and hexadecyltrimethylammonium hydroxide.

12. The method according to claim 5, characterized in that: The conditions for high-temperature calcination in step (2) in an oxygen-containing atmosphere are: the oxygen content in the oxygen-containing atmosphere is 10v%~30v; the calcination temperature is 800~1100℃; and the calcination time is 0.5~5h.

13. The method according to claim 12, characterized in that: In step (2), the oxygen-containing atmosphere is an air atmosphere.

14. The method according to claim 5, characterized in that: The conditions for calcination in step (2) in an H2S+H2 atmosphere are: the H2S content in the H2S+H2 atmosphere is 0.1~2v%; the calcination temperature is 250~550℃; and the calcination time is 3~8h.

15. The method according to claim 5, characterized in that: The impregnation in steps (1) and (2) is performed using either saturated impregnation or supersaturated impregnation.

16. The use of the liquefied gas hydrogenation catalyst according to any one of claims 1-4 in the liquefied gas hydrogenation process.

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