A sulfur-tolerant shift catalyst, preparation method and application

Abstract

A sulfur-tolerant shift catalyst and a preparation method thereof are provided. The catalyst comprises a carrier, an active component, a first promoter and a second promoter, wherein the active component is uniformly dispersed in the carrier structure. Among them, the carrier comprises an alkaline multi-component composite metal oxide; the active component comprises a cobalt-containing compound and a molybdenum-containing compound; the first promoter comprises at least one selected from lanthanum element or cerium element; the second promoter comprises potassium element. The catalyst has good structural and activity stability, is suitable for shift conditions of low temperature, high pressure and high CO content, has low alkali metal loss and long service life, and has good economic benefits and application prospects.

Description

Technical Field

[0001] The present invention relates to the technical field of sulfur-tolerant shift for producing syngas from heavy raw materials such as residue oil, heavy oil, petroleum coke, and coal, and specifically relates to a sulfur-tolerant shift catalyst, a preparation method, and an application thereof. Background Art

[0002] In recent years, the development of coal gasification technology in the domestic chemical industry has become increasingly mature. Among them, the purpose of the CO shift is to react CO with steam through the shift reaction to generate H2 and CO2, and adjust the composition of the raw gas produced by the coal gasification device to meet the requirements of downstream devices. Different downstream products in coal chemical projects require different compositions of syngas, and the corresponding shift reaction depth and shift process are also different.

[0003] Currently, the common sulfur-tolerant shift processes include adiabatic sulfur-tolerant shift reaction process and isothermal sulfur-tolerant shift process.

[0004] The isothermal sulfur-tolerant shift process has the following advantages: (1) short process, few equipment, low investment, small plant area, and low system pressure drop; (2) can timely remove the reaction heat, effectively solve the problem of over-temperature in the shift furnace under high CO concentration conditions; (3) can maintain the catalyst bed layer to operate stably at a lower temperature, with a high CO conversion rate and less catalyst consumption in the device.

[0005] The application of the isothermal sulfur-tolerant shift process also poses new requirements for sulfur-tolerant shift catalysts: (1) when the process gas with a high CO content undergoes a shift reaction, the shift reaction heat increases significantly, especially during start-up gas introduction or process parameter fluctuations, it is easy to cause over-temperature, so the catalyst is required to have good temperature resistance; (2) the reaction heat inside the catalyst particles needs to be timely transferred to the catalyst surface to avoid adverse effects such as local over-temperature sintering and rapid decline in activity of the shift catalyst; (3) the catalyst should have good low-temperature shift activity and activity stability, especially good structural stability.

[0006] Currently, most industrial catalyst carriers adopt alumina and magnesium aluminate spinel structures. The alumina structure has a relatively high specific surface area, but it is easy to hydrate to form boehmite structure under low-temperature conditions, resulting in unstable catalyst structure and affecting its activity and service life. The magnesium aluminate spinel structure is stable, but due to its relatively harsh formation conditions and low specific surface area, it is not conducive to the dispersion of active components and affects the shift reaction activity of the catalyst. In the prior art, adding alkali metal promoters to the active components can greatly improve the low-temperature shift performance of the catalyst, but there are disadvantages such as easy loss of alkali metals and easy caking.

[0007] Therefore, a new isothermal sulfur-tolerant shift catalyst and its preparation method are needed to solve the above technical problems. Summary of the Invention

[0008] To this end, in view of the deficiencies of the prior art, the present invention provides a sulfur-tolerant shift catalyst, which catalyst comprises a carrier, an active component, a first promoter and a second promoter, and the active component is uniformly dispersed in the carrier structure, wherein:

[0009] The carrier comprises a basic multi-component composite metal oxide, and the basic multi-component composite metal oxide comprises a composite oxide composed of at least four of alumina, titanium oxide, zirconium oxide, magnesium oxide, calcium oxide, barium oxide, potassium oxide and sodium oxide;

[0010] The active component comprises a cobalt-containing compound and a molybdenum-containing compound ；

[0011] The first promoter comprises at least one selected from lanthanum element or cerium element;

[0012] The second promoter comprises potassium element.

[0013] Wherein, the carrier structure contains magnesium aluminate spinel and calcium aluminate.

[0014] Wherein, calculated as metal oxides, the carrier accounts for 80% - 90% of the total mass of the catalyst.

[0015] Wherein, the basic multi-component composite metal oxide comprises a first metal oxide and a second metal oxide, the first metal oxide is at least two selected from alumina, titanium oxide and zirconium oxide, and the second metal oxide is at least two selected from magnesium oxide, calcium oxide, barium oxide and potassium oxide, and the mass ratio of the first metal oxide to the second metal oxide is 2 - 4:1.

[0016] Wherein, the active component comprises cobalt oxide and molybdenum oxide, and calculated as mass percentage, cobalt accounts for 2.0 - 6.0% of the total mass of the catalyst in terms of CoO, and molybdenum accounts for 6.0 - 12.0% of the total mass of the catalyst in terms of MoO3.

[0017] Wherein, calculated as the oxides of the corresponding metal elements, the first promoter and the second promoter together account for 1.0 - 3.0% of the total mass of the catalyst.

[0018] Wherein, the sulfur-tolerant shift catalyst is an oxidized catalyst.

[0019] Wherein, the specific surface area of the sulfur-tolerant shift catalyst is 80 - 120m 2 / g, and the pore volume is not less than 0.30 mL / g.

[0020] Wherein, the appearance of the sulfur-tolerant shift catalyst is one of bar-shaped, clover-shaped, four-leaf clover-shaped and spherical.

[0021] The present invention also provides a preparation method of the above sulfur-tolerant shift catalyst, comprising:

[0022] (1) Add a certain amount of molybdenum source to a mixed solution of water and ethanol containing citric acid, and heat it to 40 - 60 °C to obtain solution A;

[0023] (2) Dissolve the first auxiliary agent raw material and cobalt source in water to obtain solution B;

[0024] (3) Under the condition of 40 - 60 °C, while stirring, slowly add solution B to solution A (for example, at a speed of 60 - 100 mL per minute), and keep the temperature constant for a certain period of time to obtain solution C;

[0025] (4) Mix the solid powder catalyst carrier raw materials, add them to solution C, stir and knead for a certain period of time, dry and crush to obtain powder D;

[0026] (5) Add a binder and an extrusion aid to powder D, mix evenly, extrude into shape, dry and calcine to obtain the sulfur - tolerant shift catalyst;

[0027] Among them, in the step (4), after mixing and adding the catalyst carrier raw materials to solution C, add a certain amount of solution containing the second auxiliary agent raw material, and then carry out the stirring and kneading described in step (4); or, in the step (5), after adding the binder and the extrusion aid to powder D, add a certain amount of solution containing the second auxiliary agent raw material, and then carry out the mixing evenly and extruding into shape described in step (5).

[0028] Among them, the mass ratio of the cobalt element content in the cobalt source to the molybdenum element content in the molybdenum source is 1:2 - 4.

[0029] Among them, the mass ratio of the citric acid content in the step (1) to the total amount of the molybdenum source and the cobalt source is 1:0.5 - 1.0.

[0030] Among them, in the step (1), in the mixed solution of water and ethanol containing citric acid, the ethanol content is 2 - 5 vol%.

[0031] Among them, in the step (1), the molybdenum source is selected from ammonium molybdate.

[0032] Among them, in the step (2), the first auxiliary agent raw material is at least one selected from lanthanum source and cerium source, the lanthanum source is selected from lanthanum nitrate, and the cerium source is selected from cerium nitrate.

[0033] Among them, in the step (2), the cobalt source is selected from cobalt nitrate.

[0034] Among them, in the step (3), the constant temperature time is 1 - 3 h.

[0035] Among them, in the step (4), the catalyst carrier raw materials include at least four selected from aluminum sources, magnesium sources, titanium sources, calcium sources, zirconium sources, barium sources, and potassium sources.

[0036] Among them, in the step (4), the catalyst carrier raw materials include a first carrier raw material and a second carrier raw material. The first carrier raw material includes at least two of aluminum sources, titanium sources, or zirconium sources; the second carrier raw material includes at least two of magnesium sources, calcium sources, barium sources, and potassium sources.

[0037] The aluminum source includes one selected from pseudo-boehmite, alumina, and aluminum gel, and preferably pseudo-boehmite;

[0038] The magnesium source includes one selected from light magnesium oxide, magnesium carbonate, and magnesium hydroxide, and preferably light magnesium oxide;

[0039] The titanium source includes one selected from metatitanic acid and titanium oxide, and preferably metatitanic acid;

[0040] The calcium source includes one selected from calcium oxide, calcium carbonate, and calcium hydroxide, and preferably calcium oxide;

[0041] The zirconium source is selected from nano-zirconia;

[0042] Among them, in the step (4), stir and knead for 10 - 30 min (preferably 20 min), the drying temperature is 110 - 130 °C (preferably 120 °C), and crush to 200 - 250 mesh.

[0043] Among them, in the step (5), the binder is at least one selected from water, acetic acid, citric acid, oxalic acid, or nitric acid, preferably citric acid and / or oxalic acid. Based on the mass of the catalyst, the addition amount of the binder is 1 - 5 wt%, preferably 2 - 4 wt%. The binder is well compatible with the main catalyst components, ensuring that the catalyst has high strength and good stability.

[0044] Among them, in the step (5), the extrusion aid is at least one selected from sesbania powder, citric acid, starch, or sucrose, preferably sesbania powder. Based on the mass of the catalyst, the addition amount of the extrusion aid is 2 - 8 wt%, preferably 3 - 6 wt%.

[0045] Among them, the second auxiliary raw material is at least one selected from potassium citrate, potassium carbonate, or potassium bicarbonate, preferably potassium citrate. Based on the mass of the catalyst, the addition amount of the second auxiliary raw material is 0.1 - 3.0 wt%, preferably 1.0 - 2.0 wt%.

[0046] Among them, in the step (5), the extrusion molding is strip extrusion molding.

[0047] The present invention also provides the application of the sulfur-tolerant shift catalyst, and the sulfur-tolerant shift catalyst is used in the sulfur-tolerant shift process.

[0048] The present invention has the following beneficial technical effects:

[0049] (1) The present invention provides a novel isothermal sulfur-tolerant shift catalyst and a preparation process. The catalyst has good structural and activity stability, is suitable for shift conditions of low temperature, high pressure and high CO content, has low alkali metal loss and long service life, and has good economic benefits and application prospects.

[0050] (2) At least two of the auxiliary agents cerium, lanthanum and potassium elements are added to the catalyst carrier or the active component of the present invention. When preparing the sulfur-tolerant shift catalyst of the present invention, the active component complex is uniformly coated on the surface of the carrier material according to the ratio. At the same time, its skeleton material (such as calcium aluminate and magnesium aluminate spinel) is modified with a water resistance auxiliary agent (such as calcium oxide), and then mixed and formed with other material compounds of the carrier. That is, the active components of the catalyst are mixed together in the form of a solution, form a complex in the environment of citric acid and ethanol, and are mixed with the carrier material. During the calcination process, while the carrier structure is formed, the active components are dispersed in the inner pores of the carrier according to the ratio. Thus, while the magnesium aluminate spinel and calcium aluminate structures are in-situ generated in the catalyst carrier, the active components are uniformly dispersed in the carrier structure, which makes the dispersion of the active components better.

[0051] (3) In the catalyst of the present invention, the catalyst carrier is a self-made magnesium aluminate spinel-calcium aluminate composite. Since the carrier contains alkaline earth metal calcium as a structural auxiliary agent for structural modification, the dosage of potassium compounds is reduced, so that the catalyst has good low-temperature reaction activity at low potassium content; at the same time, the excess structural auxiliary agent forms calcium molybdate with the active component molybdenum, improving the surface alkalinity of the catalyst. On the premise of ensuring its low-temperature shift activity, the dosage of alkali metals (such as potassium) can also be appropriately reduced, thereby further reducing alkali metal loss.

[0052] (4) The preparation method of the catalyst of the present invention is simple, has high and low temperature activities, high activity stability and wide activity temperature range; it also has good water resistance performance and structural stability.

[0053] Brief description of the drawings

[0054] Figure 1 XRD pattern of the catalyst obtained in Example 1.

[0055] Figure 2 Schematic diagram of the process flow of the pressurized evaluation device. Detailed implementation manners

[0056] To make the objectives, technical solutions and advantages of the present invention more clearly understood, the present invention will be further described in detail below in conjunction with specific embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0057] Example 1

[0058] Dissolve 11 g of citric acid and 2 mL of absolute ethanol in 100 mL of deionized water, add 12.3 g of ammonium molybdate, heat the solution to 60 °C to dissolve and form solution A. Dissolve 11.7 g of cobalt nitrate and 0.66 g of lanthanum nitrate in deionized water to obtain solution B. Under the condition of heating to 60 °C, slowly drop solution B into solution A, stir while adding at 60 °C, and keep the temperature constant for 2 h to obtain solution C. Mix 64 g of pseudo-boehmite powder, 15 g of light magnesium oxide, 18.5 g of metatitanic acid, 3.5 g of nano-zirconia and 8 g of calcium oxide evenly, add solution C, stir and knead for 20 minutes, then add a potassium-containing solution (the potassium-containing solution is a solution formed by dissolving 5.5 g of potassium citrate in 30 mL of deionized water), stir and knead for 20 minutes, dry at 120 °C, and crush to 220 mesh. Add 2 mL of acetic acid and 3 g of citric acid to 26 mL of deionized water to obtain solution E. Add 2 g of sesbania powder and 2 g of starch to the above-mentioned 220-mesh powder and mix evenly, then add solution E and knead for 30 minutes, extrude into shape, dry naturally, heat up to 230 °C and calcine for 1 h, and then heat up to 500 °C and calcine for 3 h to obtain the oxidized catalyst D1. The physical and chemical structure is as Figure 1 shown. It can be seen from the XRD results that there are magnesium aluminate spinel, calcium aluminate, and calcium molybdate phases in the obtained catalyst.

[0059] Example 2

[0060] Dissolve 10 g of citric acid and 5 mL of absolute ethanol in 100 mL of deionized water, add 9.8 g of ammonium molybdate, heat the solution to 60 °C to dissolve and form solution A. Dissolve 7.8 g of cobalt nitrate, 1.32 g of cerium nitrate and 0.66 g of lanthanum nitrate in deionized water to obtain solution B. Under the condition of heating to 60 °C, slowly drip solution B into solution A, stir while adding at 60 °C, and keep the temperature constant for 3 h to obtain solution C. Mix 100 g of powdered aluminosilicate, 20 g of light magnesium oxide, 10.5 g of metatitanic acid, 7.0 g of nano-zirconia and 4 g of calcium oxide evenly, add solution C, stir and knead for 20 minutes, then add a potassium-containing solution (the potassium-containing solution is a solution formed by dissolving 1.8 g of potassium carbonate in 25 mL of deionized water), stir and knead for 20 minutes, dry at 120 °C, and crush to 240 mesh. Add 2 mL of dilute nitric acid and 3 g of citric acid to 28 mL of deionized water to obtain solution E. Add 3 g of sesbania powder to the above 240-mesh powder and mix evenly, then add solution E and knead for 30 minutes, extrude into shape, dry naturally, heat to 230 °C and calcine for 2 h, then heat to 500 °C and calcine for 3 h to obtain the oxidized catalyst D2.

[0061] Example 3

[0062] Dissolve 8 g of citric acid and 4 mL of absolute ethanol in 100 mL of deionized water, add 7.4 g of ammonium molybdate, heat the solution to 60 °C to dissolve and form solution A. Dissolve 11.7 g of cobalt nitrate and 0.66 g of lanthanum nitrate in deionized water to obtain solution B. Under the condition of heating to 60 °C, slowly drip solution B into solution A, stir while adding at 60 °C, and keep the temperature constant for 2 h to obtain solution C. Mix 52 g of powdered alumina, 19 g of light magnesium oxide, 14.3 g of metatitanic acid and 20 g of calcium carbonate evenly, add solution C, stir and knead for 20 minutes, then add a potassium-containing solution (the potassium-containing solution is a solution formed by dissolving 6.0 g of potassium citrate in 30 mL of deionized water), stir and knead for 20 minutes, dry at 120 °C, and crush to 250 mesh. Add 3 g of oxalic acid and 4 g of citric acid to 35 mL of deionized water to obtain solution E. Add 3 g of sesbania powder and 3 g of starch to the above 250-mesh powder and mix evenly, then add solution E and knead for 30 minutes, extrude into shape, dry naturally, heat to 220 °C and calcine for 2 h, then heat to 500 °C and calcine for 3 h to obtain the oxidized catalyst D3.

[0063] Example 4

[0064] Dissolve 10 g of citric acid and 3 mL of absolute ethanol in 90 mL of deionized water, add 11.0 g of ammonium molybdate, heat the solution to 50 °C to dissolve and form solution A. Dissolve 13.6 g of cobalt nitrate and 0.66 g of lanthanum nitrate in deionized water to obtain solution B. Under the condition of heating to 50 °C, slowly drip solution B into solution A, stir while adding at 50 °C, and keep the temperature constant for 3 h to obtain solution C. Mix 70 g of pseudo-boehmite powder, 20 g of light magnesium oxide, 10.5 g of titanium oxide and 12.5 g of calcium carbonate evenly, add solution C, stir and knead for 30 minutes, then add a potassium-containing solution (the potassium-containing solution is a solution formed by dissolving 4.4 g of potassium carbonate in 35 mL of deionized water), stir and knead for 30 minutes, dry at 120 °C, and crush to 200 mesh. Add 2 g of sucrose and 6 g of citric acid to 30 mL of deionized water to obtain solution E. Add 5 g of sesbania powder to the above 200-mesh powder and mix evenly, then add solution E and knead for 30 minutes, extrude into shape, dry naturally, heat to 220 °C and calcine for 2 h, and then heat to 550 °C and calcine for 3 h to obtain the oxidized catalyst D4.

[0065] Example 5

[0066] Dissolve 9 g of citric acid and 4 mL of absolute ethanol in 90 mL of deionized water, add 10.4 g of ammonium molybdate, heat the solution to 50 °C to dissolve and form solution A. Dissolve 15.5 g of cobalt nitrate and 0.99 g of lanthanum nitrate in deionized water to obtain solution B. Under the condition of heating to 50 °C, slowly drip solution B into solution A, stir while adding at 50 °C, and keep the temperature constant for 3 h to obtain solution C. Mix 86 g of aluminum gel powder, 20 g of magnesium carbonate, 28 g of metatitanic acid, 4 g of zirconium oxide and 9.0 g of calcium hydroxide evenly, add solution C, stir and knead for 30 minutes, then add a potassium-containing solution (the potassium-containing solution is a solution formed by dissolving 3.4 g of potassium bicarbonate in 30 mL of deionized water), stir and knead for 30 minutes, dry at 120 °C, and crush to 220 mesh. Add 3 mL of acetic acid and 4 g of oxalic acid to 30 mL of deionized water to obtain solution E. Add 4 g of sesbania powder and 2 g of starch to the above 220-mesh powder and mix evenly, then add solution E and knead for 30 minutes, extrude into shape, dry naturally, heat to 230 °C and calcine for 2 h, and then heat to 550 °C and calcine for 3 h to obtain the oxidized catalyst D5.

[0067] Example 6

[0068] Dissolve 8.5 g of citric acid and 3.5 mL of absolute ethanol in 80 mL of deionized water, add 6.4 g of ammonium molybdate, heat the solution to 45 °C to dissolve and form solution A. Dissolve 10.5 g of cobalt nitrate and 0.33 g of lanthanum nitrate in deionized water to obtain solution B. Under the condition of heating to 45 °C, slowly drip solution B into solution A, add and stir at 45 °C, and keep the temperature constant for 3 h to obtain solution C. Mix 74.5 g of pseudo-boehmite in powder form, 14 g of light magnesium oxide, 14.3 g of metatitanic acid, 7.5 g of zirconia and 6.0 g of calcium oxide evenly, add solution C, stir and knead for 20 minutes, then add a potassium-containing solution (the potassium-containing solution is a solution formed by dissolving 4.8 g of potassium carbonate in 35 mL of deionized water), stir and knead for 30 minutes, dry at 120 °C, and crush to 250 mesh. Add 3 mL of dilute nitric acid and 3 g of citric acid to 30 mL of deionized water to obtain solution E. Add 2 g of sesbania powder and 4 g of starch to the above 250-mesh powder and mix evenly, then add solution E and knead for 30 minutes, extrude into shape, dry naturally, heat to 230 °C and calcine for 2 h, then heat to 550 °C and calcine for 3 h to obtain the oxidized catalyst D6.

[0069] Comparative Example 1 - Using magnesium aluminate spinel as the aluminum source and magnesium source in the carrier

[0070] Dissolve 11 g of citric acid and 2 mL of absolute ethanol in 100 mL of deionized water, add 12.3 g of ammonium molybdate, heat the solution to 60 °C to dissolve and form solution A. Dissolve 11.7 g of cobalt nitrate and 0.66 g of lanthanum nitrate in deionized water to obtain solution B. Under the condition of heating to 60 °C, slowly drip solution B into solution A, add and stir at 60 °C, and keep the temperature constant for 2 h to obtain solution C. Mix 60 g of magnesium aluminate spinel in powder form, 18.5 g of metatitanic acid, 3.5 g of nano-zirconia and 8 g of calcium oxide evenly, add solution C, stir and knead for 20 minutes, then add a potassium-containing solution (the potassium-containing solution is a solution formed by dissolving 5.5 g of potassium citrate in 30 mL of deionized water), stir and knead for 20 minutes, dry at 120 °C, and crush to 220 mesh. Add 2 mL of acetic acid and 3 g of citric acid to 26 mL of deionized water to obtain solution E. Add 2 g of sesbania powder and 2 g of starch to the above 220-mesh powder and mix evenly, then add solution E and knead for 30 minutes, extrude into shape, dry naturally, heat to 230 °C and calcine for 1 h, then heat to 500 °C and calcine for 3 h to obtain the oxidized catalyst D-1.

[0071] Comparative Example 2 - Using magnesium aluminate spinel and calcium aluminate as the aluminum source and magnesium source in the carrier

[0072] Dissolve 11 g of citric acid and 2 mL of absolute ethanol in 100 mL of deionized water, add 12.3 g of ammonium molybdate, heat the solution to 60 °C to dissolve and form solution A. Dissolve 11.7 g of cobalt nitrate and 0.66 g of lanthanum nitrate in deionized water to obtain solution B. Under the condition of heating to 60 °C, slowly drip solution B into solution A, stir while adding at 60 °C, and keep the temperature constant for 2 h to obtain solution C. Mix 35 g of magnesium aluminate spinel powder, 33 g of calcium aluminate, 18.5 g of metatitanic acid and 3.5 g of nano-zirconia evenly, add solution C, stir and knead for 30 minutes, then add a potassium-containing solution (the potassium-containing solution is a solution formed by dissolving 5.5 g of potassium citrate in 30 mL of deionized water), stir and knead for 30 minutes, dry at 120 °C, and crush to 230 mesh. Add 2 mL of dilute nitric acid and 3 g of citric acid to 30 mL of deionized water to obtain solution E. Add 2 g of sesbania powder and 2 g of starch to the above 230-mesh powder and mix evenly, then add solution E and knead for 30 minutes, extrude into shape, dry naturally, heat to 230 °C and calcine for 1 h, and then heat to 500 °C and calcine for 3 h to obtain the oxidized catalyst D-2.

[0073] Comparative Example 3 - The content of pseudoboehmite in the carrier raw material is too low, and the content of calcium oxide is too high, that is, the mass ratio of the first metal oxide and the second metal oxide in the carrier raw material does not meet 2 - 4:1

[0074] Dissolve 11 g of citric acid and 2 mL of absolute ethanol in 100 mL of deionized water, add 12.3 g of ammonium molybdate, heat the solution to 60 °C to dissolve and form solution A. Dissolve 11.7 g of cobalt nitrate and 0.66 g of lanthanum nitrate in deionized water to obtain solution B. Under the condition of heating to 60 °C, slowly drip solution B into solution A, stir while adding at 60 °C, and keep the temperature constant for 2 h to obtain solution C. Mix 38 g of pseudoboehmite, 15 g of light magnesium oxide, 18.5 g of metatitanic acid, 3.5 g of nano-zirconia and 33 g of calcium oxide evenly, add solution C, stir and knead for 20 minutes, then add a potassium-containing solution (the potassium-containing solution is a solution formed by dissolving 5.5 g of potassium citrate in 30 mL of deionized water), stir and knead for 20 minutes, dry at 120 °C, and crush to 220 mesh. Add 2 mL of acetic acid and 3 g of citric acid to 26 mL of deionized water to obtain solution E. Add 2 g of sesbania powder and 2 g of starch to the above 220-mesh powder and mix evenly, then add solution E and knead for 30 minutes, extrude into shape, dry naturally, heat to 230 °C and calcine for 1 h, and then heat to 500 °C and calcine for 3 h to obtain the oxidized catalyst D-3.

[0075] Comparative Example 4 - Add the potassium source in solution B, and do not mix solution A and solution B in advance before mixing with the carrier raw material

[0076] Dissolve 12.3 g of ammonium molybdate in 100 mL of deionized water, heat to 60 °C to form solution A. Dissolve 11.7 g of cobalt nitrate, 5.5 g of potassium citrate and 0.66 g of lanthanum nitrate in deionized water and heat to 60 °C to form solution B. Mix 64 g of pseudo-boehmite powder, 15 g of light magnesium oxide, 18.5 g of metatitanic acid, 3.5 g of nano-zirconia and 8 g of calcium oxide evenly, add solution A, stir and knead for 20 minutes, then add solution B, stir and knead for 20 minutes, dry at 120 °C, and crush to 220 mesh. Add 2 mL of acetic acid and 3 g of citric acid to 26 mL of deionized water to obtain solution E. Add 2 g of sesbania powder and 2 g of starch to the above 220-mesh powder and mix evenly, then add solution E and knead for 30 minutes, extrude into shape, dry naturally, heat to 230 °C and calcine for 1 h, then heat to 500 °C and calcine for 3 h to obtain the oxidized catalyst D-4.

[0077] Use a pressurized evaluation device to test the physical and chemical properties of the catalysts in the examples and comparative examples of the present invention and the CO conversion rate at 230 °C. The specific process of the pressurized evaluation device is as Figure 2 shown, where each reference numeral is: 1, raw gas purifier; 2, pressure reducer; 3, mixer; 4, pressure gauge; 5, shutdown valve; 6, heating furnace; 7, reaction tube; 8, internal heat thermocouple tube; 9, condenser; 10, separator; 11, drainer; 12, wet gas flowmeter; 13, vaporizer; 14, water tank; 15, water metering pump.

[0078] The test conditions are:

[0079] Composition of raw gas: CO content: 50.0%; CO2 content: 3.0%;

[0080] H2S content: 0.2% - 0.3%; Remainder: H2;

[0081] Catalyst loading: 50 mL;

[0082] Sulfidation process: Use nitrogen to heat to 250 °C, then start to switch to process gas and start process gas sulfidation. Do not add water during sulfidation. Sulfidation pressure: 2.0 MPa; Dry gas space velocity: 2000 h -1 ; Sulfidation inlet temperature: Maintain at 250 °C for 10 h, heat up to 300 °C and maintain for 6 h, heat up to 350 °C and maintain for 2 h.

[0083] Catalyst pressurized evaluation conditions:

[0084] Inlet temperature: 230 °C; Pressure: 4.0 MPa; Water / gas: 1.2;

[0085] Dry gas space velocity: 3000 h -1 ; H2S content: 0.2% - 0.3%; Time: 40 h.

[0086] The test results are shown in Table 1.

[0087] Table 1 Pressure Activity and Sulfur Content of the Catalysts in the Examples and Comparative Examples

[0088]

[0089] It can be seen from the evaluation results in Table 1 that the comprehensive physical and chemical properties of the catalysts in the examples of the present invention and the CO conversion rate at 230 °C are significantly better than those of the comparative examples.

[0090] Obviously, the above examples are only illustrations for clear explanation and are not limitations on the implementation manners. For those of ordinary skill in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to enumerate all the implementation manners here. And the obvious changes or modifications derived therefrom are still within the protection scope of the present invention.

Claims

1. A sulfur-tolerant shift catalyst, the catalyst comprising a support, an active component, a first promoter and a second promoter, the active component being uniformly dispersed in the support structure, wherein: The carrier includes basic multi-component composite metal oxides, which include a first metal oxide and a second metal oxide. The first metal oxide includes at least two selected from alumina, titanium oxide, and zirconium oxide and at least includes alumina. The second metal oxide includes at least two selected from magnesium oxide, calcium oxide, barium oxide, and potassium oxide and at least includes magnesium oxide and calcium oxide; Among them, while magnesium aluminate spinel and calcium aluminate structures are in-situ generated in the carrier, the active components are uniformly dispersed in the carrier structure; The active components include a cobalt-containing compound and a molybdenum-containing compound; The first promoter includes at least one selected from lanthanum element or cerium element; The second promoter includes potassium element.

2. The sulfur-tolerant shift catalyst according to claim 1, wherein the mass ratio of the first metal oxide to the second metal oxide is 2-4:

1.

3. The sulfur-tolerant shift catalyst according to claim 1, wherein, The specific surface area of the sulfur-tolerant shift catalyst is 80 - 120 m 2 / g, and the pore volume is not less than 0.30 mL / g.

4. The sulfur-tolerant shift catalyst according to claim 1, wherein, Calculated as metal oxides, the carrier accounts for 80% - 90% of the total mass of the catalyst; calculated as mass percentage, cobalt calculated as CoO accounts for 2.0 - 6.0% of the total mass of the catalyst, and molybdenum calculated as MoO3 accounts for 6.0 - 12.0% of the total mass of the catalyst; calculated as oxides of the corresponding metal elements, the first promoter and the second promoter together account for 1.0 - 3.0% of the total mass of the catalyst.

5. A method for preparing the sulfur-tolerant shift catalyst according to any one of claims 1-4, comprising: (1) Add a certain amount of molybdenum source to a mixed solution of water and ethanol containing citric acid, and heat to 40 - 60 °C to obtain solution A; (2) Dissolve the first promoter raw material and cobalt source in water to obtain solution B; (3) Under the condition of 40 - 60 °C, while stirring, drop solution B into solution A and keep it at a constant temperature for a certain period of time to obtain solution C; (4) Mix the solid powder catalyst carrier raw materials, add them to solution C, stir and knead for a certain time, dry and crush to obtain powder D; (5) Add a binder and an extrusion aid to powder D, mix evenly, extrude into shape, dry and calcine to obtain the sulfur-tolerant shift catalyst; Among them, in step (4), after mixing the catalyst carrier raw materials and adding them to solution C, add a certain amount of solution containing the second promoter raw material, and then carry out the stirring and kneading described in step (4); or, in step (5), after adding a binder and an extrusion aid to powder D, add a certain amount of solution containing the second promoter raw material, and then carry out the mixing evenly and extrusion into shape described in step (5); Among them, the catalyst carrier raw materials include a first carrier raw material and a second carrier raw material. The first carrier raw material includes at least two of an aluminum source, a titanium source, or a zirconium source and at least includes an aluminum source; the second carrier raw material includes at least two of a magnesium source, a calcium source, a barium source, and a potassium source and at least includes a magnesium source and a calcium source.

6. The method for preparing the sulfur-tolerant shift catalyst according to claim 5, wherein, The mass ratio of the cobalt element content in the cobalt source to the molybdenum element content in the molybdenum source is 1:2 - 4.

7. The method for preparing the sulfur-tolerant shift catalyst according to claim 5, wherein, The calcium source is one selected from calcium oxide, calcium carbonate, and calcium hydroxide.

8. The method for preparing the sulfur-tolerant shift catalyst according to claim 7, wherein, The aluminum source is one selected from pseudo-boehmite, alumina, and aluminum gel.

9. The method for preparing the sulfur-tolerant shift catalyst according to claim 7, wherein, The magnesium source is one selected from light magnesium oxide, magnesium carbonate, and magnesium hydroxide.

10. Use of the sulfur-tolerant shift catalyst according to any one of claims 1-4 in a sulfur-tolerant shift process.

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