Sulfided shift catalyst and method for its preparation

Abstract

The application discloses a sulfidation type shift catalyst and a preparation method thereof, and belongs to the technical field of sulfur-tolerant shift catalysts. Since the sulfidation state sulfur-tolerant shift catalyst has oxygen affinity, when it is exposed to an oxygen-containing environment, an exothermic reaction with oxygen occurs, temperature rises until combustion occurs, therefore, the sulfidation state shift catalyst needs to be passivated or pretreated. The carrier component of the application comprises a mixture of alumina, magnesia and titania, the active component comprises cobalt-molybdenum sulfide; and the surface is covered with a protective layer of one or more organic matters of n-heptane, ammonium sulfide and glyceride in any ratio. When used, the sulfidation process is avoided, the catalyst performance is not affected, the method for removing the protective component during start-up is simple, the protective agent has low content and does not affect the subsequent device system, the start-up time of the enterprise can be significantly reduced, and the application has good economic benefits and application prospect.

Description

Technical Field

[0001] A sulfur-based shift catalyst and its preparation method are disclosed, belonging to the field of sulfur-resistant shift catalyst technology. Background Technology

[0002] Cobalt-molybdenum based sulfur-resistant shift catalysts are widely used in chemical production processes such as hydrogen production, ammonia synthesis, methanol synthesis, gasoline synthesis, and city gas production. However, they must undergo a sulfidation process before use to convert their cobalt-molybdenum active components from the oxidized state to the sulfidated state, thus acquiring shift activity. Because sulfidated sulfur-resistant shift catalysts are oxygen-loving, they will undergo an exothermic reaction with oxygen when exposed to an oxygen-containing environment, leading to a temperature increase and even combustion. Therefore, sulfidated shift catalysts require passivation or other pretreatment.

[0003] Current pretreatment methods for sulfide-type shift catalysts mainly include three types: gas-phase passivation, liquid-phase passivation, and solid-phase passivation. Gas-phase passivation primarily uses O2 at a certain temperature to oxidize the surface of sulfide-type shift catalyst particles, forming a dense oxide film that isolates O2 from the air, achieving protection. This method is difficult to control, and poor control can easily affect catalyst performance. Liquid passivation mainly uses organic hydrocarbons, employing methods such as impregnation, spraying, and blending to form a protective layer on the catalyst surface. This passivation can be considered a simple physical protection process, but the catalyst needs to be removed under specific conditions before use, and large amounts of organic compounds can easily affect subsequent systems. Solid passivation utilizes the temperature difference between the passivator and the catalyst to form a protective film on the catalyst surface, effectively isolating it from air. This protective film is difficult to control, resulting in poor protection. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to overcome the shortcomings of the prior art and provide a sulfurized conversion catalyst and its preparation method that is simple to prepare, easy to implement, and can be stably stored, transported and loaded.

[0005] The technical solution adopted by the present invention to solve its technical problem is: a sulfide-type conversion catalyst, characterized in that: the support component includes a mixture of alumina, magnesium oxide and titanium oxide, the active component includes cobalt molybdenum sulfide; and the catalyst surface is covered with a protective layer of one or more organic substances in any proportion selected from n-heptane, ammonium sulfide and glycerol ester.

[0006] The catalyst preparation method is simple and easy to implement, combining the catalyst preparation process with protective treatment. The catalyst has a high sulfur content and uniformly dispersed active sulfides. It can be stored stably in air at room temperature, making it easy to transport and fill. It eliminates the need for sulfidation during use, and the protective components on the catalyst surface can be removed under normal start-up conditions without affecting the catalyst performance. The method for removing the protective components during start-up is simple and almost negligible. Furthermore, the low content of the protective agent will not affect subsequent equipment systems, significantly reducing the company's start-up time and demonstrating good economic benefits and application prospects.

[0007] Preferably, the composition includes 1.0~4.0 wt% Co metal content, 5~10 wt% Mo metal content, 2.0~7.0 wt% Mg metal content, 30.0~45.0 wt% Al metal content, 1.0~8.0 wt% Ti metal content, 3.0~6.0 wt% S content, 1.0~5.0 wt% C content, and the balance being oxygen.

[0008] The optimal content results in a good weight ratio of active component to support, which gives the final catalyst high catalytic activity.

[0009] Preferably, the catalyst surface is further covered with an oxide film generated by the reaction of cobalt-molybdenum sulfide and oxygen.

[0010] A partial oxide film is used to provide dual physical and chemical protection for the active center (the organic protective layer isolates the air, and the reaction of oxygen with sulfur components forms a film). This effectively compensates for the lack of complete coverage of the organic protective layer, improves the stability of the catalyst during storage and transportation, and, with the presence of the organic protective layer, the oxide film coverage area is small, which has little impact on the catalyst performance. Furthermore, it is easy to remove and activate the catalyst during the start-up phase.

[0011] A method for preparing the above-mentioned sulfurized shift catalyst is characterized in that: a mixed solution containing cobalt nitrate, organic acid, ammonium molybdate and sulfur-containing compound is added to the support, kneaded and molded, and calcined in an inert gas containing hydrogen; after calcination, a uniformly dispersed organic solution is sprayed on, and then purged with oxygen-containing carbon dioxide or an inert gas to obtain the sulfurized shift catalyst; wherein the solvent of the organic solution is an ethanol solution containing 0.5~5.0wt% diethyl ether, and the solute is one or more of n-heptane, ammonium sulfide and glycerol ester in any proportion, with a solute mass fraction of 1~8wt%.

[0012] A further preferred method is to add the mixed solution of cobalt nitrate, organic acid, ammonium molybdate, and sulfur-containing compound to the carrier as follows: cobalt nitrate and organic acid are dissolved in water to prepare a mixed solution, and ammonium molybdate and sulfur-containing compound are dissolved in water to prepare a mixed solution. The two mixed solutions are then added to the carrier separately. This preferred method avoids precipitation that may occur with conventional addition of cobalt nitrate and ammonium molybdate, facilitating rapid and uniform mixing.

[0013] After the active components are impregnated and loaded onto the support, they are activated by calcination with a hydrogen mixed gas to form an unstable sulfurized conversion catalyst with the highest catalytic activity. At this point, an organic protective layer is applied to maintain the catalyst's activity. After the organic coating, the surface is promptly purged with oxygen-containing gas, which not only quickly evaporates the solvent of the organic protective layer but also forms an oxide film on the catalyst surface, fully encapsulating the catalyst and greatly improving its stability.

[0014] Preferably, the carrier preparation method includes the following steps: adding aluminum-containing compound, light magnesium oxide and metatitanic acid to a binder and mixing them evenly.

[0015] More preferably, the aluminum-containing compound is one or more of boehmite, alumina, and aluminum colloid in any proportion.

[0016] More preferably, the adhesive comprises one or more of guar gum powder, water, citric acid, oxalic acid, and nitric acid in any proportion. The preferred adhesive here primarily functions as a binder and expands pores. Nitric acid provides the best bonding, but it is polluting and has poor pore-expanding ability. Acidic conditions favor physical bonding, and the decomposition of organic compounds during calcination creates larger pore structures.

[0017] Preferably, the sulfur-containing compound is one or a mixture of two of ammonium sulfide or ammonium thiosulfate in any proportion.

[0018] While providing good active sulfur elements for sulfide transformation, it avoids introducing more other impurity elements, and ammonium is easily removed in the subsequent roasting process.

[0019] Preferably, the hydrogen-containing inert gas has a hydrogen volume content of 10-40%; the calcination process includes first heating to 120-150°C and holding at that temperature for 1.5-2.5 hours, then heating to 220-280°C and holding at that temperature for 2.5-3.5 hours, then heating to 500-550°C and holding at that temperature for 0.5-1.5 hours, and finally cooling to room temperature.

[0020] Hydrogen reacts with sulfur-containing compounds to produce hydrogen sulfide. Under optimal conditions, it can be ensured that at different temperatures, the active component compounds decompose into oxides while the oxides and hydrogen sulfide undergo a sulfidation process simultaneously. Metal oxides are easier to sulfide, resulting in a better sulfidation effect.

[0021] Preferably, the oxygen-containing carbon dioxide or inert gas is carbon dioxide containing 10-30% air by volume, and the purge air velocity is 100-200 h⁻¹. -1 Furthermore, the catalyst surface temperature during the purging process is less than or equal to 50°C.

[0022] During the oxygen-containing gas purging process, an oxidation film formation reaction occurs on the catalyst surface, which generates a certain amount of heat. Excessive heat may lead to the oxidation of too many active catalyst components. Therefore, by controlling the catalyst surface temperature below 50°C, the degree of oxidation can be effectively controlled, forming a protective film on the catalyst while avoiding affecting its performance.

[0023] Compared with existing technologies, the beneficial effects of this invention are: combining the catalyst preparation process and the sulfidation process, significantly shortening the catalyst sulfidation time; employing a special organic mixed solution and protective process, the preparation method is simple, safe, and easy to implement; providing dual physical and chemical protection for its active centers without affecting the dispersion of active sulfides; the prepared pre-sulfidated sulfur-resistant conversion catalyst has a high sulfur content and uniform dispersion of active sulfides; it can exist stably in air at room temperature, facilitating transportation and storage; and the catalyst can be used directly in industrial applications without the need for a sulfidation process, significantly reducing equipment start-up time and demonstrating good economic benefits and application prospects. Detailed Implementation

[0024] The present invention will be further described below with reference to the embodiments, of which embodiment 5 is the preferred embodiment of the present invention.

[0025] Example 1

[0026] A sulfide-type shift catalyst and its preparation method are disclosed. The method involves uniformly mixing 94.3g of boehmite powder, 8.0g of light magnesium oxide powder, 6.0g of guar gum powder, and 8.5g of metatitanic acid powder. Then, 3g of citric acid, 2g of oxalic acid, and 16.1g of cobalt nitrate are dissolved in 18mL of deionized water and added to the above powder mixture. The mixture is kneaded until homogeneous. Next, 9.8g of ammonium heptamolybdate and 10.6g of ammonium sulfide are dissolved in 30mL of deionized water and added to the wet mixture. The mixture is kneaded until homogeneous, extruded into strips, and air-dried. The mixture is then placed in a CO2 mixture containing 20% ​​(v / v) hydrogen and heated at a rate of 40℃ / h. The temperature is first increased to 140℃ and held for 2 hours, then increased to 250℃ and held for 3 hours, then increased to 520℃ and held for 1 hour. The temperature is then lowered to room temperature to obtain a semi-finished product containing 2.5% hydrogen. An ethanol solution containing wt% diethyl ether (anhydrous ethanol) was used as the solvent. 0.5% n-heptane and 4.0% ammonium sulfide (by mass of the total organic mixture) were added. After complete dissolution, the organic mixture was uniformly sprayed onto the catalyst until adsorption saturation and the surface became wet. A CO2 mixture containing 20% ​​(v / v) air was then used at a flow rate of 200 h⁻¹. -1 The catalyst is prepared by air purging at a speed not exceeding 40°C until the catalyst surface is dry and no longer generates heat.

[0027] The obtained sulfide-type shift catalyst contains 1.0~4.0 wt% Co, 5~10 wt% Mo, 2.0~7.0 wt% Mg, 30.0~45.0 wt% Al, 1.0~8.0 wt% Ti, 3.0~6.0 wt% S, 1.0~5.0 wt% C, with the balance being oxygen.

[0028] Example 2

[0029] A sulfide-type shift catalyst and its preparation method are disclosed. The method involves uniformly mixing 70.0 g of boehmite powder, 26.0 g of alumina gel, 10 g of light magnesium oxide powder, 6.5 g of guar gum powder, and 7.2 g of metatitanic acid powder. 6 g of citric acid and 12.0 g of cobalt nitrate are dissolved in 15 mL of deionized water and then added to the above powder mixture. The mixture is kneaded until homogeneous. Then, 12.2 g of ammonium heptamolybdate and 14.0 g of ammonium thiosulfate are dissolved in 40 mL of deionized water and added to the wet mixture. The mixture is kneaded until homogeneous, extruded into strips, and air-dried. The mixture is then placed in a CO2 mixture containing 20% ​​(v / v) hydrogen and heated at a rate of 40 °C / h. The temperature is first increased to 140 °C and held for 2 h, then increased to 250 °C and held for 3 h, then increased to 520 °C and held for 1 h. The temperature is then lowered to room temperature to obtain a semi-finished product. A sample containing 5.0% hydrogen is taken. Using an anhydrous ethanol solution of wt% diethyl ether as a solvent, 1.5% (w / w) of glycerol ester was added to the total organic mixture solution. After complete dissolution, the organic mixture solution was obtained. This organic mixture solution was then uniformly sprayed onto the catalyst semi-finished product until adsorption saturation. A CO2 mixture containing 10% (v / v) air was then used at a concentration of 100 h⁻¹. -1 The catalyst is prepared by air purging at a speed not exceeding 50°C until the catalyst surface is dry and no longer generates heat.

[0030] The obtained sulfide-type shift catalyst contains 1.0~4.0 wt% Co, 5~10 wt% Mo, 2.0~7.0 wt% Mg, 30.0~45.0 wt% Al, 1.0~8.0 wt% Ti, 3.0~6.0 wt% S, 1.0~5.0 wt% C, with the balance being oxygen.

[0031] Example 3

[0032] A sulfide-type shift catalyst and its preparation method are disclosed. The method involves uniformly mixing 85.7g of boehmite powder, 22g of γ-alumina, 5.0g of light magnesium oxide powder, 4.0g of guar gum powder, and 1.5g of metatitanic acid powder. 6g of oxalic acid and 8.2g of cobalt nitrate are dissolved in 16mL of deionized water and then added to the above powder mixture. The mixture is kneaded until homogeneous. 7.4g of ammonium heptamolybdate and 6.5g of ammonium sulfide are dissolved in 40mL of deionized water and added to the wet mixture. The mixture is kneaded until homogeneous, extruded into strips, and air-dried. The mixture is then placed in a CO2 mixture containing 20% ​​(v / v) hydrogen and heated at a rate of 40℃ / h. The temperature is first increased to 140℃ and held for 2h, then increased to 250℃ and held for 3h, then increased to 520℃ and held for 1h. The temperature is then lowered to room temperature to obtain a semi-finished product. A sample containing 0.5% hydrogen is taken. Using an anhydrous ethanol solution of diethyl ether as a solvent, 2.0% glycerol ester and 3.0% ammonium sulfide (by mass) of the total organic mixture were added. After complete dissolution, an organic mixture was obtained. This organic mixture was then uniformly sprayed onto the catalyst semi-finished product until adsorption saturation. A CO2 mixture containing 25% (v / v) air was then used at a concentration of 200 h⁻¹. -1 The catalyst is prepared by air purging at a speed not exceeding 40°C until the catalyst surface is dry and no longer generates heat.

[0033] The obtained sulfide-type shift catalyst contains 1.0~4.0 wt% Co, 5~10 wt% Mo, 2.0~7.0 wt% Mg, 30.0~45.0 wt% Al, 1.0~8.0 wt% Ti, 3.0~6.0 wt% S, 1.0~5.0 wt% C, with the balance being oxygen.

[0034] Example 4

[0035] A sulfide-type shift catalyst and its preparation method are disclosed. The method involves uniformly mixing 85.7g of boehmite powder, 12.0g of light magnesium oxide powder, 3.0g of guar gum powder, and 11.5g of metatitanic acid powder. Then, 3g of citric acid, 2mL of dilute nitric acid, and 20.0g of cobalt nitrate are dissolved in 15mL of deionized water and added to the above powder mixture. The mixture is kneaded until homogeneous. Next, 14.6g of ammonium heptamolybdate and 11.5g of ammonium thiosulfate are dissolved in 45mL of deionized water and added to the wet mixture. The mixture is kneaded until homogeneous, extruded into strips, and air-dried. The mixture is then placed in a CO2 mixture containing 20% ​​(v / v) hydrogen and heated at a rate of 40℃ / h. The temperature is first increased to 140℃ and held for 2 hours, then increased to 250℃ and held for 3 hours, and finally increased to 520℃ and held for 1 hour. The temperature is then lowered to room temperature to obtain a semi-finished product containing 2.5% hydrogen. An ethanol solution containing wt% diethyl ether (anhydrous ethanol) was used as the solvent. 0.5% n-heptane and 4.0% glycerol esters (by mass of the total organic mixture) were added. After complete dissolution, the resulting organic mixture was uniformly sprayed onto the catalyst semi-finished product until adsorption saturation. A CO2 mixture containing 20% ​​(v / v) air was then used at a flow rate of 200 h⁻¹. -1 The catalyst is prepared by air purging at a speed not exceeding 40°C until the catalyst surface is dry and no longer generates heat.

[0036] The obtained sulfide-type shift catalyst contains 1.0~4.0 wt% Co, 5~10 wt% Mo, 2.0~7.0 wt% Mg, 30.0~45.0 wt% Al, 1.0~8.0 wt% Ti, 3.0~6.0 wt% S, 1.0~5.0 wt% C, with the balance being oxygen.

[0037] Example 5

[0038] A sulfide-type shift catalyst and its preparation method are disclosed. The method involves uniformly mixing 102.0 g of boehmite powder, 3.0 g of light magnesium oxide powder, 6 g of guar gum powder, and 11.4 g of metatitanic acid powder. Then, 6 g of citric acid and 4.0 g of cobalt nitrate are dissolved in 15 mL of deionized water and added to the above powder mixture, kneading until homogeneous. Finally, 12.2 g of ammonium heptamolybdate and 9.3 g of ammonium thiosulfate are dissolved in 30 mL of water. Add mL of deionized water to the above wet material, knead evenly, extrude into strips, air dry naturally, and place in a CO2 mixture containing 20% ​​(v / v) hydrogen. Heat at a rate of 40℃ / h, first to 140℃, hold for 2h, then to 250℃, hold for 3h, then to 520℃, hold for 1h, and then cool to room temperature to obtain a catalyst semi-finished product. Use an ethanol solution containing 3.0wt% diethyl ether as a solvent (ethanol is a 95.5% ethanol aqueous solution), add 0.5% ammonium sulfide and 5.0% n-heptane (total organic mixture content), and after complete dissolution, obtain an organic mixture solution. Spray this organic mixture solution evenly onto the catalyst semi-finished product until adsorption saturation. Then, use a CO2 mixture containing 30% (v / v) air at a rate of 150h... -1 The catalyst is prepared by air purging at a speed not exceeding 45°C until the catalyst surface is dry and no longer generates heat.

[0039] The obtained sulfide-type shift catalyst contains 1.0~4.0 wt% Co, 5~10 wt% Mo, 2.0~7.0 wt% Mg, 30.0~45.0 wt% Al, 1.0~8.0 wt% Ti, 3.0~6.0 wt% S, 1.0~5.0 wt% C, with the balance being oxygen.

[0040] Comparative Example 1

[0041] A sulfurized shift catalyst and its preparation method are disclosed. 94.3g of boehmite powder, 8.0g of light magnesium oxide powder, 6.0g of guar gum powder, and 8.5g of metatitanic acid powder are mixed evenly. 3g of citric acid, 2g of oxalic acid, and 16.1g of cobalt nitrate are dissolved in 18mL of deionized water and then added to the above powder mixture. The mixture is kneaded evenly. 9.8g of ammonium heptamolybdate is dissolved in 30mL of deionized water and added to the wet mixture. The mixture is kneaded evenly, extruded into strips, and air-dried to obtain an oxidized sulfur-resistant shift catalyst, which is neither sulfurized nor protected by a protective component coating.

[0042] Comparative Example 2

[0043] A sulfide-type shift catalyst and its preparation method are disclosed. The method involves uniformly mixing 94.3g of boehmite powder, 8.0g of light magnesium oxide powder, 6.0g of guar gum powder, and 8.5g of metatitanic acid powder. Then, 3g of citric acid, 2g of oxalic acid, and 16.1g of cobalt nitrate are dissolved in 18mL of deionized water and added to the above powder mixture. The mixture is kneaded until homogeneous. Next, 9.8g of ammonium heptamolybdate and 10.6g of ammonium sulfide are dissolved in 30mL of deionized water and added to the wet mixture. The mixture is kneaded until homogeneous, extruded into strips, and air-dried. The mixture is then placed in a CO2 mixture containing 20% ​​(v / v) hydrogen and heated to 520℃ at a rate of 40℃ / h, held at that temperature for 4h, and then cooled to room temperature to obtain a catalyst semi-finished product. Finally, the catalyst is subjected to a CO2 mixture containing 20% ​​(v / v) air for 200h... -1 The catalyst is prepared by air purging at a speed not exceeding 40°C until the catalyst surface is dry and no longer generates heat.

[0044] Comparative Example 3

[0045] A sulfide-type shift catalyst and its preparation method are disclosed. The method involves uniformly mixing 94.3 g of boehmite powder, 8.0 g of light magnesium oxide powder, 6.0 g of guar gum powder, and 8.5 g of metatitanic acid powder. Then, 3 g of citric acid, 2 g of oxalic acid, and 16.1 g of cobalt nitrate are dissolved in 18 mL of deionized water and added to the above powder mixture. The mixture is kneaded until homogeneous. Finally, 9.8 g of ammonium heptamolybdate and 10.6 g of ammonium sulfide are dissolved in 30 mL of water. Add mL of deionized water to the above wet material, knead evenly, extrude into strips, air dry naturally, and place in a CO2 mixture containing 20% ​​(v / v) hydrogen. Heat at a rate of 40℃ / h, first to 140℃, hold for 2h, then to 250℃, hold for 3h, then to 520℃, hold for 1h, and then cool to room temperature to obtain a catalyst semi-finished product. Use an ethanol solution containing 2.5% diethyl ether as a solvent (anhydrous ethanol), add 0.5% n-heptane and 4.0% hexadecylamine to the total organic mixture solution. After complete dissolution, obtain an organic mixture solution. Spray this organic mixture solution evenly onto the catalyst semi-finished product until adsorption saturation. Then, use air at a rate of 200 h... -1 The catalyst is prepared by air purging at a speed not exceeding 60°C until the catalyst surface is dry and no longer generates heat.

[0046] Comparative Example 4

[0047] A sulfurized conversion catalyst and its preparation method are described. Based on Example 1, the solute component in the organic mixed solution is replaced with 4.5% hexadecylamine, and other conditions are the same as in Example 1.

[0048] After drying, the catalyst exhibits severe adhesion and a decrease in specific surface area, requiring a dispersion process. After dispersion, the active components of the catalyst are exposed and the temperature rises.

[0049] Performance testing

[0050] The pressure activity tests of the sulfurized shift catalysts obtained in the above examples and comparative examples were conducted using the following methods:

[0051] The oxidized QCS-03 and Comparative Example 1 were treated with in-cabin sulfidation to become fully sulfidated catalysts. The sulfidation conditions were: pressure 2.0 MPa, dry gas space velocity 2000 h⁻¹. -1 The H2S concentration in the sulfidation gas was 0.3% (v / v). Sulfidation was carried out at 250℃ for 10 hours, then increased to 300℃ for another 5 hours, and finally increased to 350℃ for another 5 hours. After sulfidation within the apparatus, the catalyst was not removed and directly subjected to pressure activity testing to evaluate its oxidized state. Completely sulfidated catalysts inevitably come into contact with oxygen after removal, and if not treated promptly, their activity will be significantly affected. Sulfidation-type shift catalysts do not require a sulfidation process and can be directly heated to the test temperature for pressure activity evaluation.

[0052] Overall process flow: A pressurized activity evaluation device was used to simulate industrial operating conditions and compare the catalyst's shift activity. Industrial syngas was selected as the feed gas (composition: CO content: 50.0%; H2S content: 0.2%, balance hydrogen). A certain amount of water was added according to different water-to-gas ratio requirements. After high-temperature gasification, the water was introduced into the reaction tube along with the feed gas for water-to-gas shift reaction. The tail gas after the reaction was analyzed by chromatography. The catalyst testing conditions were: inlet temperature 250℃; pressure 4.0 MPa; water / gas ratio 1.0; dry gas hourly space velocity 3000 h⁻¹. -1 The H2S content was 0.2%; the time was 20 hours.

[0053] The final test results are shown in Table 1 below. The CO conversion rate reflects the activity of the catalyst. The higher the conversion rate, the better the catalyst activity.

[0054] Table 1 Performance test results.

[0055] .

[0056] Among them, the QSC-03 catalyst is an oxidized industrial catalyst produced by Shandong Qilu Keli Chemical Co., Ltd. The catalysts in the examples and comparative examples did not exhibit temperature rise when placed in air. The catalysts obtained in Examples 1-5 do not require a sulfidation process in actual use. Comparative Example 1 and the QSC-03 catalyst require a sulfidation process before use, and the sulfidated state generates heat in air, making them unsuitable for storage and transportation.

[0057] According to the test results in Table 1, the sulfurized conversion catalyst obtained in the examples has a high conversion efficiency, which can exceed the catalytic effect of QSC-03 catalyst after sulfurization. Moreover, the sulfurized conversion catalyst obtained in the examples does not need to be sulfurized before use and can be stored stably.

[0058] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention in any other way. Any person skilled in the art may make changes or modifications to the above-disclosed technical content to create equivalent embodiments. However, any simple modifications, equivalent changes, and modifications made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the protection scope of the present invention.

Claims

1. A method for producing a sulfurized shift catalyst, characterized by: The carrier component includes a mixture of aluminum oxide, magnesium oxide and titanium oxide, and the active component includes cobalt-molybdenum sulfide; and the catalyst surface is covered with a protective layer of organic matter in any proportion of one or more of n-heptane, ammonium sulfide and glyceride; A mixed solution containing cobalt nitrate, organic acid, ammonium molybdate and sulfur-containing compound is added to the carrier, kneaded into a shape, and calcined in an inert gas containing hydrogen; After calcination, a uniformly dispersed organic solution is sprayed, and then purged with carbon dioxide containing 10-30% by volume of air to obtain a sulfided shift catalyst; wherein the organic solution solvent is an ethanol solution containing 0.5-5.0wt% diethyl ether, and the solute is a mixture of one or more of n-heptane, ammonium sulfide and glyceride in any proportion, and the solute mass fraction is 1-8wt%.

2. The preparation method of the sulfidation shift catalyst according to claim 1, characterized by: The components include Co metal content of 1.0-4.0wt%, Mo metal content of 5-10wt%, Mg metal content of 2.0-7.0wt%, Al metal content of 30.0-45.0wt%, Ti metal content of 1.0-8.0wt%, S content of 3.0-6.0wt%, C content of 1.0-5.0wt%, and the balance is oxygen.

3. The method for producing a sulfurated shift catalyst according to claim 1, characterized by: The catalyst surface is also covered with an oxide film generated by the reaction of cobalt-molybdenum sulfide with oxygen.

4. The method for producing a sulfurated shift catalyst according to claim 1, characterized by: The carrier preparation method includes the following steps: adding an aluminum-containing compound, light magnesium oxide and metatitanic acid to a binder and mixing uniformly.

5. The method for producing a sulfurization-type shift catalyst according to claim 4, characterized by: The aluminum-containing compound is a mixture of one or more of pseudo-boehmite, aluminum oxide and aluminum gel in any proportion.

6. The method for producing a sulfurated shift catalyst according to claim 4, characterized by: The binder includes a mixture of one or more of amaranth powder, citric acid and oxalic acid in any proportion.

7. The method for producing a sulfur-forming shift catalyst according to claim 1, characterized by: The sulfur-containing compound is a mixture of one or both of ammonium sulfide and ammonium thiosulfate in any proportion.

8. The method for producing a sulfur-forming shift catalyst according to claim 1, characterized by: The inert gas containing hydrogen has a hydrogen volume content of 10-40%; the calcination process includes first heating to 120-150℃, holding for 1.5-2.5h, then heating to 220-280℃, holding for 2.5-3.5h, then heating to 500-550℃, holding for 0.5-1.5h, and then reducing the temperature to room temperature.

9. The method for producing a sulfur-forming shift catalyst according to claim 1, characterized by: The purge air speed is 100-200h -1 and the purge process catalyst surface temperature is less than or equal to 50°C.