Dry gas hydrogenation catalyst and method of making

Abstract

This invention discloses a dry gas hydrogenation catalyst and its preparation method, comprising an alumina support component, an active component consisting of Group VIB and Group VIII metals existing in a sulfide state, and an active additive consisting of one or more of Cu, Ag, Ni, Co, W, and Mo existing in a reduced state. The preparation method is as follows: (1) Boehmite dry adhesive powder A is calcined at high temperature in an oxygen-containing atmosphere to obtain dry adhesive powder B; (2) Dry adhesive powder B is impregnated with active component impregnation liquid 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; (3) Boehmite dry adhesive powder A is impregnated with active additive impregnation liquid D, dried, and calcined to obtain powder F; (4) Powder E and powder F are mixed, and after molding, drying, and calcination, a dry gas hydrogenation catalyst is obtained. The catalyst prepared by this method has good removal performance of impurities such as oxygen, CO, and CO2, and also has good hydrogenation performance of organic sulfur and olefins.

Description

Technical Field

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

[0002] my country has numerous refining and chemical enterprises, and abundant light hydrocarbon resources such as catalytic dry gas and coking dry gas. For example, coking dry gas has high levels of impurities such as oxygen, sulfur, CO, and CO2, and has no better uses than fuel and hydrogen production. However, by hydrogenating coking dry gas to saturate the dienes and olefins and remove impurities such as sulfur and oxygen, it can be used as a high-quality feedstock for olefin production, with a high yield of trienes. This not only makes up for the shortage of ethylene feedstock but also improves economic efficiency.

[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 the content of impurities such as oxygen, CO, and CO2 in dry gas affects the hydrogenation activity of organic sulfur and olefins in catalysts. Therefore, when the content of impurities such as oxygen, CO, and CO2 in dry gas is high, the catalyst must have good impurity removal performance. 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 removal performance of impurities such as oxygen, CO, and CO2, and also has good hydrogenation performance of organic sulfur and olefins.

[0008] The dry gas hydrogenation catalyst of the present invention comprises a support component, an active component, and an active promoter; the support component is alumina; the active component is a Group VIB or Group VIII metal, wherein the Group VIB metal is preferably Mo and / or W; the Group VIII metal is preferably Co and / or Ni; the active promoter is one or more of Cu, Ag, Ni, Co, W, and Mo; the active component exists on the catalyst in a sulfide state, the average number of lamellar layers of the sulfide is <1.5 layers, and the proportion of monolayers is 65%~80%; the active promoter exists on the catalyst in a metallic state; and the catalyst is used for catalytic... Based on the weight of the catalyst, Group VIB metal sulfides account for 1 wt% to 20 wt% of the total catalyst mass, and Group VIII metal sulfides account for 0.5 wt% to 10 wt% of the total catalyst mass; the content of active promoters in the catalyst is 0.1 wt% to 4 wt%, preferably 0.3 wt% to 4 wt%; the total acid content of the catalyst is 0.1 to 0.4 mmol / g, of which the content of strong acid at 400-500℃ is 5% to 15%, the content of medium-strength acid at 250-400℃ is 10% to 20%, and the content of weak acid at 150-250℃ is 65% to 85%.

[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 impregnation solution D, 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, the powder is shaped, dried and calcined to 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 in step (2) and the active auxiliary agent impregnation solution D in step (3) are both aqueous solutions prepared by conventional methods. For example, the active component impregnation solution C can be an aqueous solution prepared from salts such as ammonium molybdate, ammonium metatungstate, cobalt nitrate, nickel nitrate, basic cobalt carbonate, and basic nickel carbonate; the active auxiliary agent D can be an aqueous solution prepared from salts such as copper nitrate, silver nitrate, ammonium molybdate, ammonium metatungstate, cobalt nitrate, nickel nitrate, basic cobalt carbonate, and basic nickel carbonate. The selected metal salts are all water-soluble, but are not limited to the above-mentioned salts. The amount of each component added to 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) and (3) 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 forming process described in step (4) is a method well known in the art, such as adding an extrusion aid to the composite powder, mixing the adhesive solvent and water to form a plastic body, and then kneading and forming it. 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.

[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 selected from N2, He or Ar.

[0024] The dry gas hydrogenation catalyst of the present invention is applied to the reaction of dry gas hydrogenation to produce low-carbon hydrocarbons, under the following reaction 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 organic sulfur in dry gas is mostly carbonyl sulfide, and metal sulfides with lower layer counts also exhibit good hydrodesulfurization activity. When alumina, as a support, has weak interaction with Group VIB and / or Group VIII active metals, the resulting metal sulfides 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 alumina and the metals. This significantly reduces the number of stacked metal sulfides after sulfidation and significantly increases the number of single layers, thereby improving the stability of the catalyst's desulfurization and olefin saturation activity.

[0026] Furthermore, if the dry gas contains excessive amounts of impurities such as oxygen, CO, and CO2, especially CO, these impurities will be adsorbed onto the active metal, reducing the catalyst's hydrogenation and desulfurization performance. The inventors utilize an active auxiliary metal, which has the advantage of adsorbing impurities such as oxygen, CO, and CO2 and removing them through a hydrogenation reaction. Simultaneously, the untreated boehmite powder has better colloidal solubility compared to high-temperature calcined alumina powder, allowing it to be directly molded with the high-temperature calcined alumina powder to prepare a catalyst. The resulting catalyst contains more weak acids and less strong acids. The weak interaction between the active auxiliary metal and the boehmite powder facilitates the reduction and dispersion of the active auxiliary metal at lower temperatures, thereby improving the hydrogenation performance of the active auxiliary metal in removing impurities such as oxygen, CO, and CO2. 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 invention's solution and effects, but do not constitute a limitation of the invention. In this invention, a commercially available boehmite dry adhesive powder purchased from Sinopec Catalyst Dalian Branch is 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.

[0029] Example 1

[0030] Take 17.2g of ammonium heptamolybdate and 18.8g of cobalt nitrate hexahydrate, dissolve them in an appropriate amount of water, and prepare a 70mL aqueous solution C of the active component. Similarly, take 5.8g of copper nitrate and 10.4g of nickel nitrate hexahydrate, dissolve them in an appropriate amount of water, and prepare a 70mL aqueous solution D of the auxiliary component. Then, take a certain amount of the above-mentioned pseudoboehmite dry adhesive powder A and calcine it in air at 1000℃ for 1.5h 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 100℃ for 3h, calcine it in air at 1000℃ for 1.5h, and then treat it at 350℃ in a mixed atmosphere of 1% H2S and H2 for 6h to obtain powder E. 100g 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 4h 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, it was dried at 100℃ for 3h and then calcined at 350℃ in a nitrogen atmosphere for 2h to obtain the final catalyst C-1. According to the NIST XPS database, as follows... 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).

[0031] Example 2

[0032] Take 29.0 g of ammonium heptamolybdate and 26.0 g of nickel nitrate hexahydrate, dissolve them in an appropriate amount of water, and prepare a 90 mL aqueous solution C for the active component. Similarly, take 3.2 g of silver nitrate and 6.3 g of ammonium metatungstate, dissolve them in an appropriate amount of water, and prepare a 42 mL aqueous solution D for the auxiliary component. Then, take a certain amount of the above-mentioned boehmite dry adhesive powder A and calcine it at 900 °C for 3 h in an air atmosphere to obtain alumina dry adhesive powder B. Impregnate 120 g of the calcined alumina dry adhesive powder B with the loading aqueous solution C, dry it at 110 °C for 3 h, calcine it at 1050 °C in an air atmosphere for 1 h, and then treat it at 400 °C in a mixed atmosphere of 1% H2S and H2 for 5 h to obtain powder E. Impregnate 60 g of boehmite dry adhesive powder A with the loading aqueous solution D, dry it at 110 °C for 3 h, and calcine it at 550 °C in a hydrogen atmosphere for 3 h to obtain powder F. Powder E and powder F were mixed evenly, pulverized and sieved (200 mesh), and then 2.5g of guar gum powder, 17g of 10% nitric acid and 190mL of deionized water were added. After molding, the mixture was dried at 110℃ for 3h and then calcined at 250℃ in a nitrogen atmosphere for 2h to obtain the final catalyst C-2.

[0033] Example 3

[0034] Take 19.1g of ammonium metatungstate, 7.3g of ammonium heptamolybdate, and 10.6g 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 1.6g of cobalt nitrate and 2.5g of nickel nitrate, dissolve them in an appropriate amount of water, and prepare a 35mL aqueous solution D for the auxiliary component. Then, take a certain amount of the above-mentioned boehmite dry adhesive powder A and calcine it at 800℃ for 5h in an air atmosphere to obtain alumina dry adhesive powder B. Impregnate 100g of the calcined alumina dry adhesive powder B with the loading aqueous solution C, dry it at 110℃ for 2h, calcine it at 900℃ in an air atmosphere for 4h, and then treat it at 500℃ in a mixed atmosphere of 1% H2S and H2 for 4h to obtain powder E. Impregnate 50g of boehmite dry adhesive powder A with the loading aqueous solution D, dry it at 110℃ for 2h, and then calcine it at 450℃ 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 2.5g of guar gum powder, 17g of 10% nitric acid and 170mL 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.

[0035] Example 4

[0036] Take 24.4g of ammonium metatungstate, 9.3g of ammonium heptamolybdate, and 13.5g 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 9.3g of copper nitrate, dissolve it in an appropriate amount of water, and prepare a 70mL aqueous solution D for the auxiliary component. Then, take a certain amount of the above-mentioned boehmite dry adhesive powder A and calcine it at 900℃ for 5h in an air atmosphere to obtain alumina dry adhesive powder B. Impregnate 100g of the calcined alumina dry adhesive powder B with the loading aqueous solution C, dry it at 90℃ for 4h, calcine it at 850℃ in an air atmosphere for 4h, and then treat it at 300℃ in a mixed atmosphere of 1% H2S and H2 for 7h to obtain powder E. Impregnate 100g of the boehmite dry adhesive powder A with the loading aqueous solution D, dry it at 90℃ for 4h, and calcine it 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 2.5g of guar gum powder, 20g of 10% nitric acid and 210mL of deionized water were added. After molding, the mixture was dried at 90℃ for 4h and then calcined at 300℃ in a nitrogen atmosphere for 2h to obtain the final catalyst C-4.

[0037] Comparative Example 1

[0038] The preparation method of Example 1 was followed, but without the addition of any auxiliary components. 17.2 g of ammonium heptamolybdate and 18.8 g of cobalt nitrate hexahydrate were dissolved in an appropriate amount of water to prepare a 120 mL aqueous solution C of the active component. A certain amount of the above-mentioned boehmite dry adhesive powder A was calcined at 1000°C for 1.5 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 1000°C in air for 1.5 h, and then treated at 350°C in a mixed atmosphere of 1% H2S and H2 for 6 h to obtain powder E. Powder E and 100g 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 and 150mL of deionized water were added. After molding, the mixture was dried at 100℃ for 3h and then calcined at 350℃ in a nitrogen atmosphere for 2h to obtain the final catalyst D-1.

[0039] Comparative Example 2

[0040] The preparation method of Example 1 was followed, but the boehmite powder was not subjected to high-temperature calcination during the preparation process. 13.7 g of ammonium heptamolybdate and 14.9 g of cobalt nitrate hexahydrate were dissolved in an appropriate amount of water to prepare a 100 mL aqueous solution C of the active component. Similarly, 4.6 g of copper nitrate and 8.2 g of nickel nitrate hexahydrate were dissolved in an appropriate amount of water to prepare a 70 mL aqueous solution D of the auxiliary component. Then, 142.9 g of boehmite dry adhesive powder A was impregnated with the loading solution C, dried at 100°C for 3 h, calcined at 1000°C in air for 1.5 h, and then treated at 350°C in a mixed atmosphere of 1% H2S and H2 for 6 h to obtain powder E. 100 g of boehmite dry adhesive powder A was impregnated with the loading solution D, dried at 100°C for 3 h, and then calcined at 650°C in a hydrogen atmosphere for 4 h 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 350℃ in a nitrogen atmosphere for 2h to obtain the final catalyst D-2.

[0041] Comparative Example 3

[0042] 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 obtain γ-alumina. 13.7g of ammonium heptamolybdate and 14.9g of cobalt nitrate hexahydrate were dissolved in an appropriate amount of water to prepare a 100mL aqueous solution C of the active component. Similarly, 4.6g of copper nitrate and 8.2g of nickel nitrate hexahydrate were dissolved in an appropriate amount of water to prepare a 70mL aqueous solution D of the auxiliary component. Then, a certain amount of pseudoboehmite dry adhesive powder A was calcined at 550°C for 3h in an air atmosphere to obtain γ-alumina dry adhesive powder. 100g of γ-alumina powder was then impregnated with loading solution C, dried at 100°C for 3h, calcined in an air atmosphere at 1000°C for 1.5h, and then treated at 350°C in a mixed atmosphere of 1% H2S and H2 for 6h to obtain powder E. 100g 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 4h 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 shaping, the mixture was dried at 100℃ for 3h and then calcined at 350℃ in a nitrogen atmosphere for 2h to obtain the final catalyst D-3.

[0043] Comparative Example 4

[0044] 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. 13.7 g of ammonium heptamolybdate and 14.9 g of cobalt nitrate hexahydrate were dissolved in an appropriate amount of water to prepare a 100 mL aqueous solution C of the active component. Similarly, 4.6 g of copper nitrate and 8.2 g of nickel nitrate hexahydrate were dissolved in an appropriate amount of water to prepare a 70 mL aqueous solution D of the auxiliary component. A certain amount of the above-mentioned pseudoboehmite dry adhesive powder A was calcined at 1000 °C for 1.5 h in air to obtain alumina dry adhesive powder B. Then, 100 g of 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 6 h to obtain powder E. 100g 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 4h 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 shaping, the mixture was dried at 100℃ for 3h and then calcined at 350℃ in a nitrogen atmosphere for 2h to obtain the final catalyst D-4.

[0045] Comparative Example 5

[0046] 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. A certain amount of the above-mentioned boehmite dry adhesive powder A was calcined at 1000°C for 1.5 hours in air to obtain alumina dry adhesive powder B. Then, 100g of the calcined alumina dry adhesive powder B was mixed evenly with 100g of boehmite dry adhesive powder A, 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, it was dried at 100°C for 3 hours and then calcined at 250°C in air for 2 hours to obtain the catalyst carrier. 13.7g of ammonium heptamolybdate and 14.9g of cobalt nitrate hexahydrate were dissolved in an appropriate amount of water to prepare a 70mL aqueous solution C of the active component. Similarly, 4.6g of copper nitrate and 8.2g of nickel nitrate hexahydrate were dissolved in an appropriate amount of water to prepare a 35mL aqueous solution D of the auxiliary component. The prepared support was impregnated with the loaded solution C, dried at 100℃ for 3 h, calcined at 1000℃ in air for 1.5 h, and then treated at 350℃ in a mixed atmosphere of H2S and H2 (1% H2S) for 6 h to obtain a first-stage catalyst E. The first-stage catalyst E was then impregnated with the loaded aqueous solution D, dried at 100℃ for 3 h, and calcined at 350℃ in a nitrogen atmosphere for 2 h to obtain the final catalyst D-5.

[0047] The component content and properties of each catalyst are listed in Table 1.

[0048] Table 1. Catalyst component content and properties in the examples and comparative examples

[0049] C-1 C-2 C-3 C-4 D-1 D-2 D-3 D-4 D-5 Group VIB sulfides, wt% 8.0 13.0 16.0 16.0 8.2 8.0 8.0 8.0 8.0 Group VIII sulfides, wt% 3.0 4.0 2.0 2.0 3.1 3.0 3.0 3.0 3.0 Active ingredient c, wt% 2.0 3.0 0.5 1.5 0 2.0 2.0 2.0 2.0 Total acid content, mmol / g 0.38 0.25 0.15 0.32 0.36 0.47 0.45 0.35 0.08 Strong acid content at 400-500℃, % 6.8 9.4 13.2 13.6 7.2 19.8 17.4 10.5 4.2 Medium strength acidity at 250-400℃, % 17.6 12.2 15.5 14.1 16.3 27.5 35.7 19.4 10.4 Average number of lamellar layers of sulfides 1.2 1.3 1.3 1.3 1.2 1.4 1.6 1.8 1.6 Sulfide monolayer percentage, % 78 72 70 68 76 60 47 40 50

[0050] The above catalyst was subjected to an activity evaluation test in a 10 mL reaction apparatus at a reaction pressure of 3.0 MPa, a reaction temperature of 190 °C, and a gas hourly space velocity of 700 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.

[0051] Table 2 Composition of Coking Dry Gas Feedstock

[0052] composition Content, mol% <![CDATA[H2]]> 9.135 <![CDATA[O2]]> 0.092 <![CDATA[N2]]> 0.026 CO 0.238 <![CDATA[CO2]]> 0.516 <![CDATA[CH4]]> 13.762 Alkanes (C2~C5) 70.483 Alkenes (C2~C4) 5.596 <![CDATA[H2S]]> 0.099 carbonyl sulfide 0.038 <![CDATA[H2O]]> 0.015 total 100

[0053] Table 3. Composition of the product after hydrogenation 500 h after reaction

[0054] Product composition, mol% C-1 C-2 C-3 C-4 D-1 D-2 D-3 D-4 D-5 <![CDATA[H2]]> 2.823 2.383 2.408 2.854 4.414 5.403 6.186 5.623 4.415 <![CDATA[O2]]> 0 0 0 0 0.004 0.002 0.002 0.002 0.004 <![CDATA[N2]]> 0.027 0.026 0.027 0.027 0.026 0.026 0.026 0.026 0.026 CO 0 0 0 0 0.073 0.005 0.006 0.005 0.038 <![CDATA[CO2]]> 0 0 0.001 0 0.104 0.006 0.006 0.005 0.055 <![CDATA[CH4]]> 15.294 15.594 16.146 15.888 14.837 14.667 14.047 13.843 14.659 Alkanes (C2~C5) 79.532 79.811 79.251 79.066 77.48 77.576 77.137 78.013 78.465 Alkenes (C2~C4) 0.699 0.636 0.633 0.63 1.787 1.022 1.332 1.128 1.033 <![CDATA[H2S]]> 0.14 0.144 0.132 0.132 0.111 0.12 0.125 0.11 0.126 Organic sulfur 0 0 0 0 0 0 0 0 0.002 <![CDATA[H2O]]> 1.485 1.406 1.402 1.403 1.164 1.173 1.133 1.245 1.177 total 100 100 100 100 100 100 100 100 100

[0055] Table 4. Carbon deposits on the catalyst after hydrogenation

[0056] C-1 C-2 C-3 C-4 D-1 D-2 D-3 D-4 D-5 Carbon deposits, wt% 2.47 2.04 1.93 2.29 2.98 3.24 3.43 2.99 2.96

[0057] 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 an active additive; the support component is alumina; the active component is a Group VIB or Group VIII metal; the active additive is one or more of Cu, Ag, Ni, Co, W, and Mo; the active component exists on the catalyst in a sulfide state, with an average number of lamellar layers <1.5 layers and a single layer ratio of 65%–80%; the active additive exists on the catalyst in a reduced state; based on the weight of the catalyst, Group VIB metal sulfides account for 1 wt%–20 wt% of the total catalyst mass, and Group VIII metal sulfides account for 0.5 wt%–10 wt% of the total catalyst mass; the active additive content in the catalyst is 0.1 wt%–4 wt%; the total acid content of the catalyst is 0.1–0.4 mmol / g, of which strong acid at 400–500℃ accounts for 5%–15%, and moderately strong acid at 250–400℃ accounts for 10%–20%. The proportion of weak acid at 150-250℃ is 65%~85%; the acidity of the catalyst is tested by NH3-TPD method; the preparation method of the dry gas hydrogenation catalyst includes the following: (1) taking boehmite dry adhesive powder A, calcining it at high temperature in an oxygen-containing atmosphere to obtain alumina dry adhesive powder B; (2) impregnating alumina dry adhesive powder B with active component impregnation liquid C, drying it, calcining it at high temperature in an oxygen-containing atmosphere, and then in a mixed atmosphere of H2S and H2. (2) Powder E is obtained by calcination in the middle; (3) Powder A is impregnated with active additive impregnation liquid D, dried, and calcined in a hydrogen atmosphere to obtain powder F; (4) Powder E prepared in step (2) is mixed evenly with powder F prepared in step (3), and then shaped, dried and calcined to obtain dry gas hydrogenation catalyst; The high temperature calcination temperature in step (1) is 800~1100℃; The high temperature calcination temperature in step (2) is 800~1100℃.

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 auxiliary agent impregnation liquid D, 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, and then shape, dry and calcine it to obtain a dry gas hydrogenation catalyst.

4. The method according to claim 3, characterized in that: The oxygen content in the oxygen-containing atmosphere described in step (1) is 10v%~30v%; the conditions for high-temperature roasting are: roasting temperature of 800~1100℃ and roasting 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%; 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) and (3) are saturated impregnation or supersaturated impregnation.

9. The method according to claim 3, characterized in that: The molding process in step (4) involves adding extrusion aid, adhesive solvent and water to the composite powder to form a plastic body, and then kneading and molding it. 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 for 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 for step (4) are: calcination temperature of 200~350℃, calcination time of 1~4 hours; and calcination atmosphere of 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 the reaction of dry gas hydrogenation to produce low-carbon hydrocarbons, characterized in that... The reaction conditions are: reaction pressure 0.1~10MPa, gas hourly space velocity 300~10000h⁻¹ -1 The reaction temperature is 150~400℃.

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