Dry gas hydrogenation catalyst and method of making

Abstract

This invention discloses a dry gas hydrogenation catalyst and its preparation method. The catalyst includes an alumina support component, active components consisting of Group VIB and Group VIII metal sulfides, and active agent a in a metallic state selected from one or more of Cu, Ag, Ni, Co, W, and Mo. Active agent b is in an oxidized state consisting of one or more of Li, Na, K, Cs, Mg, and Ca. The preparation method is as follows: Boehmite dry gel powder is calcined, impregnated with an active component impregnation solution, dried, calcined again, and then calcined in a mixed atmosphere of H2S and H2 to obtain powder E; the boehmite dry gel powder is impregnated with active agent a impregnation solution, dried, and calcined in a hydrogen atmosphere to obtain powder F; powder E and F are mixed, active agent b impregnation solution is added, and the mixture is shaped, dried, and calcined to obtain the dry gas hydrogenation catalyst. The catalyst prepared by this method exhibits good performance in removing impurities such as oxygen, CO, and CO2, and suitable olefin hydrogenation saturation performance, effectively improving catalyst lifetime.

Description

Technical Field

[0001] This invention relates to the field of hydrogenation refining of low-carbon hydrocarbons, and specifically to a dry gas hydrogenation catalyst and its preparation method. Background Technology

[0002] In the hydrogenation process of light hydrocarbons such as catalytic dry gas and coking dry gas, when the content of impurities such as oxygen, CO, and CO2 is low, it has little impact on the activity of the catalyst in hydrodesulfurization and olefin hydrogenation saturation. However, when the content of impurities such as oxygen, CO, and CO2 is high, it will significantly inhibit the activity of the catalyst in hydrodesulfurization and olefin hydrogenation saturation, and the activity of the catalyst will not increase significantly with increasing temperature.

[0003] CN200910230393.4 discloses a bifunctional hydrogenation catalyst for use in the hydrorefining process of high-olefin-content feedstocks such as coking dry gas or catalytic dry gas, exhibiting excellent performance in the hydrogenolysis of organic sulfur and olefin saturation. This catalyst utilizes a Co-Mo-Ni-Cu rare earth element active metal supported on titanium oxide-alumina, which can effectively hydrogenate organic sulfur and olefins in coking dry gas and catalytic dry gas.

[0004] CN201911052623.2 discloses a dry gas hydrodesulfurization catalyst, its preparation method, and its application. The catalyst comprises raspberry-shaped particles composed of an active component a, a structural aid b, and other aids c. The raspberry-shaped particles are hollow microspheres with a large pore on their surface. The hollow microspheres have a hollow structure inside, with the large pore communicating with the hollow structure to form a cavity open at one end. The active component a is selected from Ni and Mo as its metal element. The structural aid b is selected from one or more of alumina, silicon dioxide, titanium dioxide, and zirconium oxide. The other aid c is selected from one or more of Cu, La, Ce, W, Mn, and Zn as its metal element.

[0005] CN201911053316.6 discloses a dry gas hydrogenation catalyst for saturated olefins and desulfurization, its preparation method, and its application. The catalyst comprises a support and an active metal component supported on the support, wherein the active metal component comprises molybdenum and a Group VIII metal, with the molybdenum content (based on oxides and the catalyst itself) being 10-45 wt%; the Group VIII metal content being 1-10 wt%; and the support oxide content being 50-89 wt%, preferably 55-80 wt%.

[0006] Numerous studies and experiments have shown that removing high levels of impurities such as oxygen, CO, and CO2 is the most effective way to restore the activity of dry gas hydrogenation catalysts. Meanwhile, low-carbon olefins readily undergo hydrogenation, leading to excessively concentrated exothermic reactions and soaring temperatures. Thermodynamically, this affects the reaction equilibrium of olefin hydrogenation. Furthermore, at higher temperatures, olefins readily react with oxygen-containing impurities to form carbon deposits, resulting in catalyst deactivation and shortening catalyst lifespan. Summary of the Invention

[0007] To address the shortcomings of existing technologies, this invention proposes a dry gas hydrogenation catalyst and its preparation method. The catalyst prepared by this method has good performance in removing oxygen-containing impurities such as oxygen, CO, and CO2, and has appropriately low olefin hydrogenation saturation performance, which can effectively improve catalyst life.

[0008] The dry gas hydrogenation catalyst of the present invention comprises a support component, an active component, and two active promoters, a and b. The support component is alumina; the active component is a Group VIB metal sulfide and a Group VIII metal sulfide, wherein the Group VIB metal is preferably Mo and / or W; the Group VIII metal is preferably Co and / or Ni; the average number of lamellar layers of the sulfide is <1.5 layers, and the proportion of single layers is 65-80%; active promoter a is in a metallic state and is selected from one or more of Cu, Ag, Ni, Co, W, and Mo; active promoter b is in an oxidized state and is selected from one or more of Li, Na, K, Cs, Mg, and Ca; based on the weight of the catalyst, the Group VIB metal sulfide is the catalyst... The catalyst comprises 1 wt% to 20 wt% of its total mass, group VIII metal sulfides comprise 0.5 wt% to 10 wt% of its total mass, active agent a comprises 0.1 wt% to 4 wt% (preferably 0.3 wt%) based on elemental composition, and active agent b comprises 0.2 wt% to 2 wt% based on oxide composition; the total acid content of the catalyst is 0.05 to 0.3 mmol / g, of which strong acid at 400-500℃ accounts for 3 wt% to 10%, moderately strong acid at 250-400℃ accounts for 10 wt% to 20%, and weak acid at 150-250℃ accounts for 87 wt% to 70%.

[0009] The preparation method of the dry gas hydrogenation catalyst of the present invention includes the following:

[0010] (1) Take boehmite dry adhesive powder A and calcine it at high temperature in an oxygen-containing atmosphere to obtain alumina dry adhesive powder B;

[0011] (2) Alumina dry adhesive powder B is impregnated with active component impregnation solution C, dried, calcined at high temperature in an oxygen-containing atmosphere, and then calcined in a mixed atmosphere of H2S and H2 to obtain powder E;

[0012] (3) Impregnate pseudoboehmite dry adhesive powder A with active additive a impregnation solution, dry, and calcine in hydrogen atmosphere to obtain powder F;

[0013] (4) After mixing the powder E prepared in step (2) with the powder F prepared in step (3) evenly, add the active additive b impregnation liquid, and after molding, drying and calcining, obtain the dry gas hydrogenation catalyst.

[0014] In the method of the present invention, the pseudo-boehmite dry adhesive powder A mentioned in step (1) is a commonly used commodity on the market, which can be prepared by methods such as aluminum alkoxide method, sodium aluminate neutralization method, and carbonization method.

[0015] In the method of the present invention, the oxygen content in the oxygen-containing atmosphere in step (1) is 10v%~30v%, preferably an air atmosphere, and the high-temperature calcination conditions are: calcination temperature of 800~1100℃ and calcination time of 0.5~5 hours.

[0016] In the method of the present invention, the oxygen content in the oxygen-containing atmosphere in step (2) is 10v%~30v%, preferably an air atmosphere, and the high-temperature calcination conditions are: calcination temperature of 800~1100℃ and calcination time of 0.5~5 hours.

[0017] In the method of the present invention, the calcination conditions of the H2S and H2 mixed atmosphere in step (2) are: calcination temperature of 250~550℃ and calcination time of 3~8 hours; wherein the proportion of H2S in the H2S and H2 mixed atmosphere is 0.1v%~2v.

[0018] In the method of the present invention, the calcination conditions in the hydrogen atmosphere described in step (3) are: calcination temperature of 300~700℃ and calcination time of 2~5 hours.

[0019] In the method of this invention, the active component impregnation solution C mentioned in step (2), the active additive impregnation solution mentioned in step (3), and the active additive impregnation solution mentioned in step (4) are all aqueous solutions prepared by conventional methods. For example, the active component impregnation solution C can be an aqueous solution prepared with salts such as ammonium molybdate, ammonium metatungstate, cobalt nitrate, nickel nitrate, basic cobalt carbonate, and basic nickel carbonate; the active additive impregnation solution can be an aqueous solution prepared with salts such as copper nitrate, silver nitrate, ammonium molybdate, ammonium metatungstate, cobalt nitrate, nickel nitrate, basic cobalt carbonate, and basic nickel carbonate. The active additive impregnation solution can be an aqueous solution prepared with salts such as lithium nitrate, lithium carbonate, lithium bicarbonate, sodium nitrate, sodium carbonate, sodium bicarbonate, potassium nitrate, potassium carbonate, potassium bicarbonate, cesium nitrate, cesium carbonate, cesium bicarbonate, magnesium nitrate, and calcium nitrate. The selected metal salts are all water-soluble, but are not limited to the above-mentioned salts. The amount of each component added in the impregnation solution is calculated according to the content of each component on the catalyst.

[0020] In the method of the present invention, the impregnation method described in steps (2), (3) and (4) is saturated impregnation or supersaturated impregnation, which is well known to those skilled in the art; the drying process described is also well known to those skilled in the art, such as conventional drying or vacuum drying.

[0021] In the method of this invention, the catalyst molding in step (4) is a method well known in the art, such as adding an extrusion aid to a composite powder, mixing a peptide and water to form a plastic body, and then kneading, molding, drying, and calcining to obtain a carrier. The extrusion aid is one or more of methylcellulose, guar gum powder, starch, and polyvinyl alcohol. The peptide is one or more of dilute nitric acid, dilute phosphoric acid, and silicic acid.

[0022] In the method of the present invention, the drying conditions described in steps (2), (3) and (4) are: drying time of 1 to 5 hours and drying temperature of 80 to 120°C.

[0023] In the method of this invention, the calcination conditions in step (4) are: calcination temperature of 200~350℃ and calcination time of 1~4 hours. The calcination atmosphere is an inert atmosphere, selected from one or more gases of N2, He or Ar.

[0024] The dry gas catalyst of the present invention is applied in a dry gas hydrogenation reaction under the following conditions: reaction pressure 0.1~10 MPa, gas hourly space velocity 300~10000 h⁻¹. -1 The reaction temperature is 150~400℃. Specific process conditions can be adjusted according to the differences in raw material quality.

[0025] The inventors discovered that when the interaction between the support and Group VIB and / or Group VIII active metals is weak, the metal sulfides formed after sulfidation have a multilayer structure. During dry gas hydrogenation, the rapid saturation of olefins and the resulting exothermic reaction lead to the migration and aggregation of these multilayered sulfides. Simultaneously, the strong acidity of the catalyst surface and the presence of impurities such as oxygen, CO, and CO2 can cause olefin polymerization and carbon deposition. These factors reduce the catalyst's desulfurization and olefin saturation activity. High-temperature treatment significantly reduces the acidity of the alumina dry powder. Impregnation with Group VIB and / or Group VIII active metals followed by high-temperature calcination strengthens the interaction between the alumina and the metals, resulting in a single-layer structure of the metal sulfides formed after sulfidation, thus improving the stability of the catalyst's desulfurization and olefin saturation activity.

[0026] Furthermore, when the content of impurities such as oxygen, CO, and CO2 in the dry gas is too high, it is necessary to appropriately increase the reaction temperature to improve the hydrogenation removal performance of the catalyst for these impurities. However, increasing the temperature will lead to more exothermic olefin hydrogenation reactions and more intense condensation reactions. The inventors used active additives such as Cu, Ag, Ni, Co, W, and Mo, which have the advantage of adsorbing impurities such as oxygen, CO, and CO2 to induce hydrogenation reactions. At the same time, compared with alumina powder treated at high temperatures, the pseudoboehmite powder that has not undergone high-temperature treatment has better colloidal solubility and can be directly molded into catalysts. The interaction between the active additives and the pseudoboehmite powder is weak, which is conducive to the reduction and dispersion of the active additives at low temperatures, thereby improving the performance of the active additives in hydrogenation removal of impurities such as oxygen, CO, and CO2. In addition, the catalyst has more weak acids and less strong acids. By adding additives such as Li, Na, K, Cs, Mg, and Ca, the acidity of the catalyst is further reduced, which can appropriately reduce the olefin hydrogenation reaction and the condensation reaction that produces carbon deposits, thus further improving the catalyst's lifespan. Attached Figure Description

[0027] Figure 1 The image shows the X-ray photoelectron (XPS) spectrum of the catalyst in Example 1. Detailed Implementation

[0028] The following examples further illustrate the solution and effects of the present invention, but do not constitute a limitation on the present invention.

[0029] In this invention, a commercially available boehmite dry adhesive powder purchased from Sinopec Catalyst Dalian Branch was selected. This boehmite dry adhesive powder has a specific surface area of ​​392 m². 2 / g, pore volume 0.95 cm³ 3 / g, pore size 9.7nm, dry basis 70%. The valence states of each active metal on the catalyst were characterized by XPS energy dispersive spectroscopy. The acidity of the catalyst was determined by the NH3-TPD method. The number of lamellar layers of sulfides on the catalyst was obtained by statistical analysis using TEM images. The components of the raw materials and products were obtained by normalization calculations based on chromatographic analysis.

[0030] Example 1

[0031] Take 18.0 g of ammonium heptamolybdate and 11.6 g of cobalt nitrate hexahydrate, dissolve them in an appropriate amount of water, and prepare a 70 mL aqueous solution C for the active component. Similarly, take 8.0 g of copper nitrate and 4.8 g of nickel nitrate hexahydrate, dissolve them in an appropriate amount of water, and prepare a 56 mL aqueous solution D for the auxiliary component. Then, take 3.1 g of sodium carbonate, dissolve it in an appropriate amount of water, and prepare a 50 mL aqueous solution X for the auxiliary component. Then, take a certain amount of the above-mentioned pseudoboehmite dry adhesive powder A and calcine it in air at 1000 °C for 2 h to obtain alumina dry adhesive powder B. Impregnate 100 g of the calcined alumina dry adhesive powder B with the loading solution C, dry it at 100 °C for 3 h, calcine it in air at 900 °C for 1.5 h, and then treat it at 350 °C in a mixed atmosphere of 1% H2S and H2 for 4 h to obtain powder E. 80g of pseudoboehmite dry adhesive powder A was impregnated with a loaded aqueous solution D, dried at 100℃ for 3h, and then calcined at 650℃ in a hydrogen atmosphere for 3h to obtain powder F. Powder E and powder F were mixed evenly, pulverized and sieved (200 mesh), and then 2g of guar gum powder, 15g of 10% nitric acid, aqueous solution X of the auxiliary component, and 100mL of deionized water were added. After molding, the mixture was dried at 100℃ for 3h and then calcined at 300℃ in a nitrogen atmosphere for 2h to obtain the final catalyst C-1. (Based on a search of the NIST XPS database, such as...) Figure 1 The metals shown are Mo in the +4 valence state (MoS2), Co in the +2 valence state (CoS), and Cu and Ni in the 0 valence state (metallic state).

[0032] Example 2

[0033] Take 11.6g of ammonium metatungstate, 13.3g of ammonium heptamolybdate, and 12.9g of nickel nitrate hexahydrate, dissolve them in an appropriate amount of water, and prepare an 80mL aqueous solution C for the active component. Similarly, take 7.9g of cobalt nitrate hexahydrate, dissolve it in an appropriate amount of water, and prepare a 70mL aqueous solution D for the auxiliary component. Then, take 2.1g of potassium bicarbonate, dissolve it in an appropriate amount of water, and prepare a 40mL aqueous solution X for the auxiliary component. Then, take a certain amount of the above-mentioned pseudoboehmite dry adhesive powder A and calcine it in air at 850℃ for 5h to obtain alumina dry adhesive powder B. Impregnate 100g of the calcined alumina dry adhesive powder B with the loading solution C, dry it at 110℃ for 3h, calcine it in air at 940℃ for 4h, and then treat it at 400℃ in a mixed atmosphere of 1% H2S and H2 for 4h to obtain powder E. 100g of pseudoboehmite dry adhesive powder A was impregnated with a loading aqueous solution D, dried at 110℃ for 3h, and then calcined at 550℃ in a hydrogen atmosphere for 2h to obtain powder F. Powder E and powder F were mixed evenly, pulverized and sieved (200 mesh), and then 1.8g of guar gum powder, 14g of 10% nitric acid, aqueous solution X of the auxiliary component, and 120mL of deionized water were added. After molding, the mixture was dried at 110℃ for 3h and then calcined at 350℃ in a nitrogen atmosphere for 2h to obtain the final catalyst C-2.

[0034] Example 3

[0035] Take 32.1g of ammonium heptamolybdate and 28.8g of nickel nitrate hexahydrate, dissolve them in an appropriate amount of water, and prepare a 90mL aqueous solution C for the active component. Similarly, take 3.5g of silver nitrate and 22.1g of cobalt nitrate hexahydrate, dissolve them in an appropriate amount of water, and prepare a 56mL aqueous solution D for the auxiliary component. Then, take 12.4g of magnesium nitrate, dissolve it in an appropriate amount of water, and prepare a 40mL aqueous solution X for the auxiliary component. Then, take a certain amount of the above-mentioned pseudoboehmite dry adhesive powder A and calcine it at 900℃ for 3h in an air atmosphere to obtain alumina dry adhesive powder B. Impregnate 100g of the calcined alumina dry adhesive powder B with the loading solution C, dry it at 110℃ for 2h, calcine it at 1050℃ in an air atmosphere for 1h, and then treat it at 400℃ in a mixed atmosphere of 1% H2S and H2 for 5h to obtain powder E. 100g of pseudoboehmite dry adhesive powder A was impregnated with a loading aqueous solution D, dried at 110℃ for 2h, and then calcined at 450℃ in a hydrogen atmosphere for 3h to obtain powder F. Powder E and powder F were mixed evenly, pulverized and sieved (200 mesh), and then 1.6g of guar gum powder, 12g of 10% nitric acid, aqueous solution X of the auxiliary component, and 130mL of deionized water were added. After molding, the mixture was dried at 110℃ for 2h and then calcined at 300℃ in a nitrogen atmosphere for 2h to obtain the final catalyst C-3.

[0036] Example 4

[0037] Take 19.5g of ammonium metatungstate, 7.4g of ammonium heptamolybdate, and 10.8g of nickel nitrate hexahydrate, dissolve them in an appropriate amount of water, and prepare an 80mL aqueous solution C for the active component. Similarly, take 4.9g of copper nitrate, dissolve it in an appropriate amount of water, and prepare a 35mL aqueous solution D for the auxiliary component. Then, take 2.3g of sodium nitrate and 3.1g of magnesium nitrate, dissolve them in an appropriate amount of water, and prepare a 50mL aqueous solution X for the auxiliary component. Then, take a certain amount of the above-mentioned pseudoboehmite dry adhesive powder A and calcine it at 950℃ for 3h in an air atmosphere to obtain alumina dry adhesive powder B. Impregnate 100g of the calcined alumina dry adhesive powder B with the loading solution C, dry it at 90℃ for 4h, calcine it at 950℃ in an air atmosphere for 3h, and then treat it at 350℃ in a mixed atmosphere of 1% H2S and H2 for 6h to obtain powder E. 50g of pseudoboehmite dry adhesive powder A was impregnated with a loading aqueous solution D, dried at 90℃ for 4h, and then calcined at 600℃ in a hydrogen atmosphere for 3h to obtain powder F. Powder E and powder F were mixed evenly, pulverized and sieved (200 mesh), and then 1.4g of guar gum powder, 10g of 10% nitric acid, aqueous solution X of the auxiliary component, and 120mL of deionized water were added. After molding, the mixture was dried at 90℃ for 4h and then calcined at 250℃ in a nitrogen atmosphere for 2h to obtain the final catalyst C-4.

[0038] Comparative Example 1

[0039] The preparation method of Example 1 was followed, but without the addition of auxiliary component a. 18.0 g of ammonium heptamolybdate and 11.6 g of cobalt nitrate hexahydrate were dissolved in an appropriate amount of water to prepare a 70 mL aqueous solution C of the active component. Similarly, 3.1 g of sodium carbonate was dissolved in an appropriate amount of water to prepare a 50 mL aqueous solution X of the auxiliary component. Then, a certain amount of the above-mentioned pseudoboehmite dry adhesive powder A was calcined at 1000 °C for 2 h in air to obtain alumina dry adhesive powder B. 100 g of the calcined alumina dry adhesive powder B was impregnated with the loading solution C, dried at 100 °C for 3 h, calcined at 900 °C in air for 1.5 h, and then treated at 350 °C in a mixed atmosphere of 1% H2S and H2 for 4 h to obtain powder E. Powder E and 80g of pseudoboehmite dry adhesive powder A were mixed evenly, pulverized and sieved (200 mesh), and then 2g of guar gum powder, 15g of 10% nitric acid, aqueous solution of auxiliary component X and 100mL of deionized water were added. After molding, the mixture was dried at 100℃ for 3h and then calcined at 300℃ in a nitrogen atmosphere for 2h to obtain the final catalyst D-1.

[0040] Comparative Example 2

[0041] The preparation method of Example 1 was followed, but without the addition of auxiliary component b. 18.0 g of ammonium heptamolybdate and 11.6 g of cobalt nitrate hexahydrate were dissolved in an appropriate amount of water to prepare a 70 mL aqueous solution C of the active component. Similarly, 8.0 g of copper nitrate and 4.8 g of nickel nitrate hexahydrate were dissolved in an appropriate amount of water to prepare a 56 mL aqueous solution D of the auxiliary component. Then, a certain amount of the above-mentioned pseudoboehmite dry adhesive powder A was calcined at 1000 °C for 2 h in air to obtain alumina dry adhesive powder B. 100 g of the calcined alumina dry adhesive powder B was impregnated with the loading solution C, dried at 100 °C for 3 h, calcined at 900 °C in air for 1.5 h, and then treated at 350 °C in a mixed atmosphere of 1% H2S and H2 for 4 h to obtain powder E. 80g of pseudoboehmite dry adhesive powder A was impregnated with a loaded aqueous solution D, dried at 100℃ for 3h, and then calcined at 650℃ in a hydrogen atmosphere for 3h to obtain powder F. Powder E and powder F were mixed evenly, pulverized and sieved (200 mesh), and then 2g of guar gum powder, 15g of 10% nitric acid, and 150mL of deionized water were added. After molding, the mixture was dried at 100℃ for 3h and then calcined at 300℃ in a nitrogen atmosphere for 2h to obtain the final catalyst D-2.

[0042] Comparative Example 3

[0043] The preparation method of Example 1 was followed, but the pseudoboehmite powder was not subjected to high-temperature calcination during the preparation process. 18.0 g of ammonium heptamolybdate and 11.6 g of cobalt nitrate hexahydrate were dissolved in an appropriate amount of water to prepare a 70 mL aqueous solution C for the active component. Similarly, 8.0 g of copper nitrate and 4.8 g of nickel nitrate hexahydrate were dissolved in an appropriate amount of water to prepare a 56 mL aqueous solution D for the auxiliary component. 3.1 g of sodium carbonate was dissolved in an appropriate amount of water to prepare a 50 mL aqueous solution X for the auxiliary component. Then, 142.9 g of pseudoboehmite dry adhesive powder A was impregnated with the loading solution C, dried at 100°C for 3 h, calcined at 900°C in air for 1.5 h, and then treated at 350°C in a 1% H2S + H2 atmosphere for 4 h to obtain powder E. 80g of pseudoboehmite dry adhesive powder A was impregnated with a loading aqueous solution D, dried at 100℃ for 3h, and then calcined at 650℃ in a hydrogen atmosphere for 3h to obtain powder F. Powder E and powder F were mixed evenly, pulverized and sieved (200 mesh), and then 2g of guar gum powder, 15g of 10% nitric acid, aqueous solution X of the auxiliary component, and 100mL of deionized water were added. After molding, the mixture was dried at 100℃ for 3h and then calcined at 300℃ in a nitrogen atmosphere for 2h to obtain the final catalyst D-3.

[0044] Comparative Example 4

[0045] The preparation method of Example 1 was followed, but the high-temperature calcination in step (1) was omitted, and instead, the pseudoboehmite powder was calcined at low temperature to form γ-alumina. 18.0 g of ammonium heptamolybdate and 11.6 g of cobalt nitrate hexahydrate were dissolved in an appropriate amount of water to prepare a 70 mL aqueous solution C of the active component. Similarly, 8.0 g of copper nitrate and 4.8 g of nickel nitrate hexahydrate were dissolved in an appropriate amount of water to prepare a 56 mL aqueous solution D of the auxiliary component. 3.1 g of sodium carbonate was dissolved in an appropriate amount of water to prepare a 50 mL aqueous solution X of the auxiliary component. Then, a certain amount of the above-mentioned boehmite dry adhesive powder A was calcined at 550°C for 3 hours in air to obtain γ-alumina dry adhesive powder. 100g of γ-alumina powder was then impregnated with a loading solution C, dried at 100°C for 3 hours, calcined at 900°C in air for 1.5 hours, and then treated at 350°C in a mixed atmosphere of 1% H2S and H2 for 4 hours to obtain powder E. 80g of boehmite dry adhesive powder A was impregnated with a loading aqueous solution D, dried at 100°C for 3 hours, and then calcined at 650°C in a hydrogen atmosphere for 3 hours to obtain powder F. Powder E and powder F were mixed evenly, pulverized and sieved (200 mesh), and then 2g of guar gum powder, 15g of 10% nitric acid, aqueous solution X of auxiliary component and 100mL of deionized water were added. After molding, the mixture was dried at 100℃ for 3h and then calcined at 300℃ in a nitrogen atmosphere for 2h to obtain the final catalyst D-4.

[0046] Comparative Example 5

[0047] The preparation method of Example 1 was followed, but the powder impregnated with Group VIB and / or Group VIII metals was not subjected to high-temperature calcination during the preparation process. 18.0 g of ammonium heptamolybdate and 11.6 g of cobalt nitrate hexahydrate were dissolved in an appropriate amount of water to prepare a 70 mL aqueous solution C of the active component. Similarly, 8.0 g of copper nitrate and 4.8 g of nickel nitrate hexahydrate were dissolved in an appropriate amount of water to prepare a 56 mL aqueous solution D of the auxiliary component. 3.1 g of sodium carbonate was dissolved in an appropriate amount of water to prepare a 50 mL aqueous solution X of the auxiliary component. Then, a certain amount of the above-mentioned pseudoboehmite dry adhesive powder A was calcined at 1000 °C for 2 h in air to obtain alumina dry adhesive powder B. 100 g of the calcined alumina dry adhesive powder B was impregnated with the loading solution C, dried at 100 °C for 3 h, and then treated at 350 °C in a mixed atmosphere of 1% H2S and H2 for 4 h to obtain powder E. 80g of pseudoboehmite dry adhesive powder A was impregnated with a loading aqueous solution D, dried at 100℃ for 3h, and then calcined at 650℃ in a hydrogen atmosphere for 3h to obtain powder F. Powder E and powder F were mixed evenly, pulverized and sieved (200 mesh), and then 2g of guar gum powder, 15g of 10% nitric acid, aqueous solution X of the auxiliary component, and 100mL of deionized water were added. After molding, the mixture was dried at 100℃ for 3h and then calcined at 300℃ in a nitrogen atmosphere for 2h to obtain the final catalyst D-5.

[0048] Comparative Example 6

[0049] The preparation method of Example 1 was followed, but the carrier was prepared first, followed by stepwise impregnation of the active metal component and the auxiliary component. 3.1 g of sodium carbonate was dissolved in an appropriate amount of water to prepare a 50 mL aqueous solution of the auxiliary component X. A certain amount of the above-mentioned boehmite dry adhesive powder A was then calcined in air at 1000°C for 2 hours to obtain alumina dry adhesive powder B. Then, 100 g of the calcined alumina dry adhesive powder B was mixed evenly with 80 g of boehmite dry adhesive powder A, pulverized and sieved (200 mesh), and then 2 g of guar gum powder, 15 g of 10% nitric acid, the auxiliary component aqueous solution X, and 100 mL of deionized water were added. After molding, the mixture was dried at 100°C for 3 hours and then calcined in air at 300°C for 2 hours to obtain the catalyst carrier. 18.0 g of ammonium heptamolybdate and 11.6 g of cobalt nitrate hexahydrate were dissolved in an appropriate amount of water to prepare a 70 mL aqueous solution of the active component C. Similarly, 8.0 g of copper nitrate and 4.8 g of nickel nitrate hexahydrate were dissolved in an appropriate amount of water to prepare a 56 mL aqueous solution D of the auxiliary component. The prepared support was impregnated with the loading solution C, dried at 100 °C for 3 h, calcined at 900 °C in air for 1.5 h, and then treated at 350 °C in a mixed atmosphere of 1% H2S and H2 for 4 h to obtain a first-stage catalyst E. Then, the first-stage catalyst E was impregnated with the loading aqueous solution D, dried at 100 °C for 3 h, and calcined at 350 °C in a nitrogen atmosphere for 3 h to obtain the final catalyst D-6.

[0050] The component content and properties of each catalyst are listed in Table 1.

[0051] Table 1. Catalyst component content and properties in the examples and comparative examples

[0052] C-1 C-2 C-3 C-4 D-1 D-2 D-3 D-4 D-5 D-6 Group VIB sulfides, wt% 9.0 12.0 13.0 16.0 9.2 9.1 9.0 9.0 9.0 9.0 Group VIII sulfides, wt% 2.0 2.0 4.0 2.0 2.1 2.0 2.0 2.0 2.0 2.0 Active ingredient c, wt% 2.0 0.8 3.0 1.0 0 2.0 2.0 2.0 2.0 2.0 Active additive d, wt% 1.0 0.5 1.5 1.0 1.0 0 1.0 1.0 1.0 1.0 Total acid content, mmol / g 0.27 0.21 0.13 0.17 0.22 0.37 0.31 0.30 0.16 0.23 Strong acid content at 400-500℃, % 4.4 8.2 3.6 6.7 4.9 7.7 5.3 5.0 6.0 6.4 Medium strength acidity at 250-400℃, % 18.3 14.2 13.7 16.1 15.6 17.3 24.1 26.8 22.6 17.7 Average number of lamellar layers of sulfides 1.2 1.3 1.3 1.3 1.3 1.4 1.7 1.8 1.8 1.6 Sulfide monolayer percentage, % 78 68 71 70 69 63 44 42 41 48

[0053] The above catalyst was subjected to an activity evaluation test in a 10 mL reaction apparatus at a reaction pressure of 3.5 MPa, a reaction temperature of 200 °C, and a gas hourly space velocity of 800 h⁻¹. -1 The properties of the raw materials are shown in Table 2, the evaluation results after 500 hours of reaction are shown in Table 3, and the amount of carbon deposited on the catalyst is shown in Table 4.

[0054] Table 2 Composition of Coking Dry Gas Feedstock

[0055] composition Content, mol% <![CDATA[H2]]> 10.435 <![CDATA[O2]]> 0.192 <![CDATA[N2]]> 0.026 CO 0.538 <![CDATA[CO2]]> 0.816 <![CDATA[CH4]]> 12.762 Alkanes (C2~C5) 70.483 Alkenes (C2~C4) 4.596 <![CDATA[H2S]]> 0.099 carbonyl sulfide 0.038 <![CDATA[H2O]]> 0.015 total 100

[0056] Table 3. Composition of the product after hydrogenation 500 h after reaction

[0057] Product composition, mol% C-1 C-2 C-3 C-4 D-1 D-2 D-3 D-4 D-5 D-6 <![CDATA[H2]]> 2.24 2.286 2.728 2.936 4.087 4.697 5.231 4.852 4.825 5.304 <![CDATA[O2]]> 0 0 0 0 0.005 0.004 0.004 0.004 0.005 0.005 <![CDATA[N2]]> 0.028 0.026 0.026 0.026 0.026 0.026 0.026 0.026 0.026 0.026 CO 0 0 0 0 0.103 0.073 0.077 0.084 0.096 0.107 <![CDATA[CO2]]> 0 0 0 0 0.169 0.099 0.109 0.095 0.114 0.136 <![CDATA[CH4]]> 14.118 14.325 14.984 14.246 13.989 13.639 13.496 13.865 13.596 13.473 Alkanes (C2~C5) 80.118 79.997 78.985 79.492 78.748 78.534 77.827 77.605 77.922 77.655 Alkenes (C2~C4) 0.604 0.615 0.638 0.605 1.253 1.287 1.623 1.843 1.832 1.642 <![CDATA[H2S]]> 0.143 0.137 0.137 0.131 0.117 0.123 0.119 0.124 0.108 0.133 Organic sulfur 0 0 0 0 0 0 0 0 0.003 0.004 <![CDATA[H2O]]> 2.749 2.614 2.502 2.564 1.503 1.518 1.488 1.502 1.473 1.515 total 100 100 100 100 100 100 100 100 100 100

[0058] Table 4. Carbon deposits on the catalyst after hydrogenation

[0059] C-1 C-2 C-3 C-4 D-1 D-2 D-3 D-4 D-5 D-6 Carbon deposits, wt% 1.82 1.97 2.12 2.03 2.91 3.73 3.42 3.55 3.38 3.65

[0060] The evaluation results in Table 3 and the amount of carbon deposit on the catalyst after hydrogenation in Table 4 demonstrate that the catalyst of the present invention has better activity in olefin saturation and removal of impurities such as sulfur, oxygen, CO, and CO2, and the amount of carbon deposit is also lower after 500 hours of reaction, indicating that the catalyst has better stability.

Claims

1. A dry gas hydrogenation catalyst, characterized in that: The catalyst comprises a support component, an active component, and two active agents, a and b. The support component is alumina, and the active components are Group VIB and Group VIII metal sulfides. The average number of lamellar layers in the sulfides is <1.5, with a single-layer ratio of 65-80%. Active agent a is in a metallic state, selected from one or more of Cu, Ag, Ni, Co, W, and Mo. Active agent b is in an oxidized state, selected from one or more of Li, Na, K, Cs, Mg, and Ca. Based on the weight of the catalyst, the Group VIB metal sulfides account for 1 wt% to 20% of the total catalyst mass. The total acid content of the catalyst is 0.5 wt% to 10 wt% of the total mass of Group VIII metal sulfides, 0.1 wt% to 4 wt% of active promoter a (based on elemental composition), and 0.2 wt% to 2 wt% of active promoter b (based on oxide composition). The total acid content of the catalyst is 0.05 to 0.3 mmol / g, of which 3% to 10% is strong acid at 400-500℃, 10% to 20% is moderately strong acid at 250-400℃, and 87% to 70% is weak acid at 150-250℃. The acid content of the catalyst is tested using the NH3-TPD method.

2. The catalyst according to claim 1, characterized in that: Group VIB metals are Mo and / or W; Group VIII metals are Co and / or Ni.

3. A method for preparing the dry gas hydrogenation catalyst according to claim 1 or 2, characterized in that... The following are included: (1) Take boehmite dry adhesive powder A and calcine it at high temperature in an oxygen-containing atmosphere to obtain alumina dry adhesive powder B; (2) Impregnate alumina dry adhesive powder B with active component impregnation liquid C, dry it, calcine it at high temperature in an oxygen-containing atmosphere, and then calcine it in a mixed atmosphere of H2S and H2 to obtain powder E; (3) Impregnate boehmite dry adhesive powder A with active additive a impregnation liquid, dry it, and calcine it in a hydrogen atmosphere to obtain powder F; (4) Mix the powder E prepared in step (2) with the powder F prepared in step (3) evenly, add active additive b impregnation liquid, and after molding, drying and calcining, obtain dry gas hydrogenation catalyst.

4. The method according to claim 3, characterized in that: The oxygen content in the oxygen-containing atmosphere in step (1) is 10v%~30v%, and the conditions for high-temperature calcination are: calcination temperature of 800~1100℃ and calcination time of 0.5~5 hours.

5. The method according to claim 3, characterized in that: The oxygen content in the oxygen-containing atmosphere in step (2) is 10v%~30v%, and the conditions for high-temperature roasting are: roasting temperature of 800~1100℃ and roasting time of 0.5~5 hours.

6. The method according to claim 3, characterized in that: The calcination conditions for the H2S and H2 mixed atmosphere in step (2) are: calcination temperature of 250~550℃ and calcination time of 3~8 hours; wherein the proportion of H2S in the H2S and H2 mixed atmosphere is 0.1v%~2v.

7. The method according to claim 3, characterized in that: The calcination conditions in step (3) in a hydrogen atmosphere are: calcination temperature of 300~700℃ and calcination time of 2~5 hours.

8. The method according to claim 3, characterized in that: The impregnation methods in steps (2), (3) and (4) are saturated impregnation or supersaturated impregnation.

9. The method according to claim 3, characterized in that: The molding process described in step (4) involves adding extrusion aid, adhesive solvent and water to the composite powder to form a plastic body, and then kneading, molding, drying and calcining to obtain a dry gas hydrogenation catalyst. The extrusion aid is one or more of methylcellulose, guar gum powder, starch, and polyvinyl alcohol; the adhesive solvent is one or more of dilute nitric acid, dilute phosphoric acid, and silicic acid.

10. The method according to claim 3, characterized in that: The drying conditions described in steps (2), (3) and (4) are: drying time of 1 to 5 hours and drying temperature of 80 to 120°C.

11. The method according to claim 3, characterized in that: The calcination conditions in step (4) are as follows: the calcination temperature is 200~350℃, the calcination time is 1~4 hours, and the atmosphere is an inert atmosphere, selected from one or more gases of N2, He or Ar.

12. The application of the dry gas hydrogenation catalyst according to claim 1 or 2 in a dry gas hydrogenation reaction.

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