Sulfur-tolerant shift catalyst, method for producing the same, and carbon monoxide shift method

Abstract

The present application relates to the field of synthesis gas, and discloses a sulfur-tolerant shift catalyst, a preparation method thereof and a carbon monoxide shift method. The catalyst contains oxides and / or sulfides of cobalt, molybdenum, aluminum, magnesium and zinc respectively or two or more of them together; at least part of the magnesium and aluminum form a spinel structure, and at least part of the zinc and aluminum form a spinel structure. The catalyst provided by the present application can still have considerable catalytic activity when the sulfur content of the raw material gas is as low as 100 ppm, and has higher strength and better industrial applicability.

Description

Technical Field

[0001] This invention relates to the field of syngas, specifically to a sulfur-resistant shift catalyst and its preparation method, as well as a carbon monoxide shift method. Background Technology

[0002] Cobalt-molybdenum based sulfur-resistant shift catalysts possess excellent sulfur resistance and high activity in CO shift reactions, and have been widely used in the coal chemical industry. With the clean development and increased utilization of coal resources, the sulfur content in raw coal has decreased, leading to a significant reduction in hydrogen sulfide content in the crude syngas from coal gasification. However, existing industrial sulfur-resistant shift catalysts are prone to sulfur loss and desulfurization under low hydrogen sulfide conditions, especially under high pressure, high CO content, and high water-to-gas ratios. This results in decreased catalyst activity, reduced resistance to operating condition fluctuations, and shortened service life. Consequently, coal chemical plants using these catalysts experience varying degrees of CO exceedances at the shift outlet during operation.

[0003] For example, US4389335A discloses a carbon monoxide conversion catalyst in an acidic gas, comprising an aluminum-containing catalyst support; catalytically active metal compounds, including oxides and sulfides of cobalt and molybdenum; a promoting amount of an alkali metal compound; and a promoting amount of oxides or sulfides of manganese. However, the catalyst is only effective at catalyzing the CO conversion reaction when the feed gas contains approximately 0.25% hydrogen sulfide.

[0004] Furthermore, with advancements in syngas processes, the content of oxidizing substances in syngas (such as oxygen, sulfur dioxide, and nitrogen oxides) has been effectively controlled, eliminating the need for additional antioxidants to protect the catalyst. Summary of the Invention

[0005] To overcome the shortcomings of existing catalysts that are not tolerant to low-sulfur conditions, this invention provides a sulfur-resistant shift catalyst, its preparation method, and a carbon monoxide shift method, which can improve the catalytic performance of the sulfur-resistant shift catalyst under low-sulfur conditions.

[0006] The first aspect of the present invention provides a sulfur-resistant conversion catalyst, said catalyst containing oxides and / or sulfides of cobalt, molybdenum, aluminum, magnesium and zinc, or two or more thereof;

[0007] At least a portion of the magnesium forms a spinel structure with aluminum, and at least a portion of the zinc forms a spinel structure with aluminum. A second aspect of the present invention provides a method for preparing the catalyst provided in the first aspect of the present invention, comprising the following steps:

[0008] (1) In the presence of a solvent, soluble cobalt source, molybdenum source, aluminum source, magnesium source and zinc source are mixed with a dispersant;

[0009] (2) The above mixture is aged, shaped, and heat-treated;

[0010] The dispersant comprises amino acid surfactants and nonionic surfactants;

[0011] The heat treatment conditions enable the magnesium and zinc sources to form spinel in the presence of the aluminum source.

[0012] A third aspect of the present invention provides a carbon monoxide conversion method, the method comprising contacting a raw material with a catalyst provided in the first aspect of the present invention under carbon monoxide conversion conditions;

[0013] The raw materials include CO, H2, H2O and H2S;

[0014] The molar ratio of CO, H2, and H2O is 1:0.5-1.5:1-4;

[0015] The contact temperature is 200-480℃ and the pressure is 2-6.5MPa.

[0016] The technical solution provided by this invention has the following beneficial effects:

[0017] In this invention, the catalyst support has a composite structure of alumina, magnesium aluminum spinel, and zinc aluminum spinel. This structure enhances the bonding ability between the active component and the support, while also increasing the number of basic sites on the support, thereby improving its ability to capture and contain sulfur. Under low-sulfur conditions, when sulfur bound to the active component sites is lost, it can be replenished by sulfur bound to the support, thus improving the catalyst's tolerance to low sulfur. Specifically, the catalyst provided by this invention maintains considerable catalytic activity even when the sulfur content of the feed gas is as low as 100 ppm.

[0018] Meanwhile, the support with a composite structure of alumina, magnesium aluminum spinel and zinc aluminum spinel can suppress the pulverization of the catalyst under high temperature and high pressure conditions, improve the catalyst strength, enhance the industrial applicability of the catalyst, and has a suitable specific surface area and pore volume, which can enable the cobalt and molybdenum active components to be well dispersed.

[0019] In the preparation of the above-mentioned catalyst, the present invention adds amino acid surfactants and nonionic surfactants as dispersants. The synergistic effect of the two can better disperse cobalt, molybdenum, magnesium, zinc and aluminum compounds. On the one hand, it enhances the binding force between the active components and the support, and on the other hand, it enables spinel to form at a lower sintering temperature and reduces the formation of magnesium oxide and zinc oxide, thereby greatly improving the structural stability of the support. Attached Figure Description

[0020] Figure 1 The XRD patterns are for catalysts A1 and D1-D3. Detailed Implementation

[0021] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0022] The first aspect of the present invention provides a sulfur-resistant conversion catalyst, said catalyst containing oxides and / or sulfides of cobalt, molybdenum, aluminum, magnesium and zinc, or two or more thereof;

[0023] At least a portion of the magnesium and aluminum form a spinel structure, and at least a portion of the zinc and aluminum form a spinel structure. In this invention, the catalyst support has a composite structure of alumina, magnesium-aluminum spinel, and zinc-aluminum spinel. This structure enhances the bonding ability between the active component and the support, and also increases the number of basic sites on the support, thereby improving its ability to capture and contain sulfur. When sulfur bound to the active component sites is lost under low-sulfur conditions, it can be replenished by sulfur bound to the support, thus improving the catalyst's resistance to low-sulfur conditions.

[0024] In this invention, sulfidation can convert some or all of the oxides of metal elements in the catalyst into sulfides.

[0025] According to a preferred embodiment of the present invention, the molar ratio of aluminum, magnesium and zinc is 1:0.2-0.3:0.1-0.4 (based on elemental composition).

[0026] In this invention, when the molar ratio of aluminum, magnesium, and zinc is within the above-mentioned preferred range, the catalyst provided by this invention has better catalytic performance.

[0027] In this invention, the content of each element in the catalyst is calculated by the amount of feed.

[0028] More preferably, the molar ratio of aluminum, magnesium and zinc, in terms of elements, is 1:0.2-0.25:0.1-0.2.

[0029] According to the present invention, preferably, the mass ratio of cobalt to molybdenum, calculated as oxides, is 1:1-4.

[0030] In this invention, when the mass ratio of cobalt to molybdenum is within the above-mentioned range, the catalyst provided by this invention has better catalytic performance.

[0031] More preferably, the mass ratio of cobalt to molybdenum, calculated as oxides, is 1:1.5-2.5.

[0032] According to a preferred embodiment of the present invention, the content of cobalt and molybdenum, based on the mass of the catalyst and calculated as oxides, is 8-13 wt%.

[0033] In this invention, when the contents of the active component and the support are within the above-mentioned range, the active component has better dispersibility, and the catalyst has good strength.

[0034] More preferably, the content of cobalt and molybdenum is 10-12 wt%.

[0035] According to the present invention, preferably, the combined content of magnesium oxide and zinc oxide does not exceed 30 wt%.

[0036] In this invention, if the content of magnesium oxide and zinc oxide in the support exceeds the above-mentioned range, the catalyst strength will be significantly reduced, which is detrimental to industrial applications. The side pressure strength of the sulfur-resistant shift catalyst for industrial applications should not be less than 120 N / cm.

[0037] According to the present invention, preferably, the XRD pattern of the catalyst has diffraction peaks at 2θ = 31.3°, 36.8°, 44.8°, 59.4°, and 66.8°.

[0038] A second aspect of the present invention provides a method for preparing a catalyst, comprising the following steps:

[0039] (1) In the presence of a solvent, a cobalt source, a molybdenum source, an aluminum source, a magnesium source, and a zinc source are mixed with a dispersant;

[0040] (2) The above mixture is aged, shaped, and heat-treated;

[0041] The dispersant comprises amino acid surfactants and nonionic surfactants;

[0042] The heat treatment conditions enable the magnesium and zinc sources to form spinel in the presence of the aluminum source.

[0043] The above method can be used to prepare the catalyst provided in the first aspect of the present invention.

[0044] In this invention, the above-mentioned amino acid surfactants and nonionic surfactants are beneficial for obtaining spinel structures at lower heat treatment temperatures, reducing the content of magnesium oxide and zinc oxide in the heat-treated support, and resulting in catalysts with better catalytic performance.

[0045] The present invention does not particularly limit the specific type of solvent, and those skilled in the art can choose it conventionally. For example, the solvent can be water.

[0046] According to the present invention, preferably, the amount of the amino acid surfactant added is 1-3 parts by mass, and the amount of the nonionic surfactant added is 0.5-2 parts by mass.

[0047] In this invention, when the amount of amino acid surfactant and nonionic surfactant added is within the above range, the content of magnesium oxide and zinc oxide in the heat-treated carrier can be further reduced.

[0048] More preferably, the mass ratio of the amino acid surfactant to the nonionic surfactant is 1:0.5-0.8.

[0049] According to the present invention, preferably, the amino acid surfactant comprises at least one of serine, glutamic acid and glycine.

[0050] In this invention, when the specific type of the amino acid surfactant is within the above-mentioned range, the heat treatment temperature for obtaining the spinel structure can be further reduced.

[0051] More preferably, the amino acid surfactant is glycine.

[0052] According to the present invention, preferably, the nonionic surfactant is selected from at least one of polyoxyethylene type, polyol type, alkanolamide type, polyether type and alkyl polyglycoside type nonionic surfactants.

[0053] In this invention, when the specific type of the nonionic surfactant is within the above-mentioned range, the heat treatment temperature for obtaining the spinel structure can be further reduced.

[0054] More preferably, the nonionic surfactant is polyethylene glycol.

[0055] More preferably, the number average molecular weight of polyethylene glycol is 400-800 g / mol.

[0056] According to a preferred embodiment of the present invention, based on oxides, relative to 1 part by mass of the cobalt source:

[0057] The amount of molybdenum source added is 1-4 parts by weight;

[0058] The amount of zinc source added is 3-9 parts by weight;

[0059] The amount of aluminum source added is 10-30 parts by weight;

[0060] The amount of magnesium source added is 1-8 parts by mass.

[0061] In this invention, when the amounts of cobalt source, molybdenum source, zinc source, aluminum source and magnesium source added are within the above range, a catalyst with better catalytic performance can be obtained.

[0062] More preferably, based on oxides, relative to 1 part by mass of the cobalt source:

[0063] The amount of molybdenum source added is 2-4 parts by weight;

[0064] The amount of zinc source added is 4-8 parts by weight;

[0065] The amount of aluminum source added is 15-25 parts by weight;

[0066] The amount of magnesium source added is 3-6 parts by mass.

[0067] According to the present invention, preferably, the molar ratio of aluminum, magnesium and zinc in the added aluminum source, magnesium source and zinc source is 1:0.1-0.3:0.1-0.4.

[0068] In this invention, when the molar ratio of aluminum, magnesium, and zinc in the added aluminum, magnesium, and zinc sources is within the above-mentioned range, the content of alumina and spinel in the catalyst can be balanced, while the content of magnesium oxide and zinc oxide can be controlled, thereby enabling the catalyst to have both good catalytic performance and higher mechanical strength.

[0069] More preferably, the molar ratio of aluminum, magnesium and zinc in the added aluminum source, magnesium source and zinc source is 1:0.2-0.25:0.1-0.2, based on elements.

[0070] The present invention does not particularly limit the specific types of the cobalt source, molybdenum source, zinc source, aluminum source and magnesium source, and those skilled in the art can choose them conventionally.

[0071] For example, the cobalt source can be one or more of cobalt nitrate, cobalt sulfate, and cobalt acetate;

[0072] The molybdenum source can be one or more of ammonium molybdate and molybdic acid;

[0073] The zinc source can be one or more of zinc nitrate, zinc acetate, and zinc chloride;

[0074] The aluminum source can be one or more of aluminum nitrate, aluminum sulfate, aluminum hydroxide, and boehmite;

[0075] The magnesium source can be one or more of magnesium nitrate, magnesium oxide, magnesium hydroxide, and magnesium carbonate.

[0076] The present invention does not impose any particular limitation on aging conditions, and those skilled in the art can make conventional selections.

[0077] According to the present invention, preferably, the aging temperature is 50-70°C and the time is 3-6 hours.

[0078] In this invention, aging conditions within the above-mentioned range are more conducive to the stability of the catalyst structure.

[0079] More preferably, the aging temperature is 55-65°C and the time is 4-5 hours.

[0080] According to the present invention, preferably, the aging process further includes drying the aged material at a temperature of 100-120°C for 2-5 hours.

[0081] According to a preferred embodiment of the present invention, the molding process involves pulverizing the aged material, adding a binder in the presence of a solvent, and extruding it.

[0082] According to the present invention, preferably, the adhesive is citric acid and / or dilute nitric acid.

[0083] According to a preferred embodiment of the present invention, the heat treatment temperature is 530-560°C and the time is 2-4 hours.

[0084] In this invention, the heat treatment temperature is lower than that of conventional heat treatment in the art, resulting in a catalyst with better catalytic performance.

[0085] According to a particularly preferred embodiment of the present invention, the catalyst is prepared by mixing a cobalt source, a zinc source, and a surfactant in the presence of a solvent to obtain mixture A. A molybdenum source is prepared into mixture B in the presence of a solvent. An aluminum source and a magnesium source are mixed, added to mixture B, and then added to mixture A.

[0086] A third aspect of the present invention provides a carbon monoxide conversion method, the method comprising contacting a raw material with a catalyst according to any one of claims 1-3 under carbon monoxide conversion conditions;

[0087] The raw materials include CO, H2, H2O and H2S;

[0088] The molar ratio of CO, H2, and H2O is 1:0.5-1.5:1-4;

[0089] The contact temperature is 200-480℃ and the pressure is 2-6.5MPa.

[0090] More preferably, the molar ratio of CO, H2 and H2O is 1:0.8-1.2:1.5-2.5, the contact temperature is 280-400℃, and the pressure is 3.5-4.5MPa.

[0091] According to a preferred embodiment of the present invention, the raw material further contains oxygen, wherein the volume concentration of oxygen does not exceed 500 ppm.

[0092] In this invention, the oxygen content in the raw materials is low, especially not exceeding 2000 ppm, so the catalyst provided by this invention does not require the addition of antioxidants.

[0093] According to the present invention, preferably, the volume concentration of H2S is 200-600 ppm.

[0094] The catalyst provided by this invention still exhibits good catalytic performance even when the H2S content in the feed is as low as 100 ppm.

[0095] The present invention will be described in detail below through embodiments.

[0096] In the following examples, the lateral compressive strength was measured using a DL-Ⅱ type particle strength tester, referring to HG / T2782-2024 "Determination of Crushing Resistance of Chemical Catalyst Particles";

[0097] The sulfur content of the catalyst was determined by X-ray fluorescence (XRF) elemental analysis;

[0098] The phase structure of the catalyst was determined using a Smartlab3 X-ray diffractometer manufactured by Rigaku Corporation of Japan, with a scanning range of 10°-70° and a scanning speed of 10° / min.

[0099] Unless otherwise specified, all reagents and raw materials are commercially available.

[0100] Examples 1-8

[0101] Cobalt nitrate and zinc nitrate were dissolved in sufficient deionized water, glycine was added and stirred evenly, and then polyethylene glycol 600 was added and stirred evenly to obtain solution A; ammonium molybdate was dissolved in sufficient deionized water to form solution B; pseudoboehmite and light magnesium oxide powder were mixed evenly, added to solution B and stirred evenly, and then solution A was added dropwise to the above materials while stirring. The mixture was aged at 65℃ for 5 hours, dried at 120℃, and then pulverized to 200 mesh. Five parts by mass of 0.5 mol / L citric acid aqueous solution were added, kneaded evenly, extruded, and air-dried naturally. The mixture was then heat-treated at 530℃ for 3 hours to obtain catalysts A1-A8.

[0102] Comparative Example 1

[0103] The catalyst was prepared according to the method of Example 1, except that zinc was not added, resulting in catalyst D1.

[0104] Comparative Example 2

[0105] The catalyst was prepared in accordance with the method of Example 1, except that glycine was not added, resulting in catalyst D2.

[0106] Comparative Example 3

[0107] The catalyst was prepared according to the method of Example 1, except that polyethylene glycol 600 was not added, resulting in catalyst D3.

[0108] In the above embodiments and comparative examples, the amounts of cobalt, molybdenum, aluminum, magnesium, and zinc added, as well as the amount of dispersant added, are shown in Table 1, based on oxides.

[0109] Table 1

[0110]

[0111]

[0112] Example 9

[0113] The catalyst was prepared in the manner described in Example 1, except that the heat treatment temperature was 750°C, resulting in catalyst A9.

[0114] Example 10

[0115] The catalyst was prepared in the manner described in Example 1, except that glycine was replaced with glutamic acid and polyethylene glycol 600 was replaced with polyethylene glycol 200, resulting in catalyst A10.

[0116] Test Example 1

[0117] The side pressure strength and phase structure of the above-mentioned catalyst were determined according to the method described in the specific embodiments of this invention. The results are shown in Table 2. The XRD patterns of catalysts A1 and D1-D3 are shown in Table 2. Figure 1 As shown.

[0118] like Figure 1 As shown, the XRD pattern of catalyst A1 exhibits characteristic peaks at 2θ = 18.9°, 31.2°, 36.6°, 44.9°, 59.4°, and 65.6°. Therefore, the phases in A1 are mainly alumina, magnesium aluminum spinel, and zinc aluminum spinel.

[0119] The characteristic peak positions of the XRD spectrum of catalyst D1 are basically the same as those of A1. Since no zinc source was added during the preparation of D1, the phases in D1 are mainly alumina and magnesium aluminum spinel.

[0120] The XRD pattern of catalyst D2 exhibits characteristic peaks at 2θ = 31.2°, 36.6°, 44.9°, 47.9°, 55.2°, 59.4°, 62.5°, and 65.6°. The main phases of catalyst D2 are alumina, magnesium aluminum spinel, and zinc aluminum spinel. Furthermore, the weak peaks at 47.9°, 55.2°, and 62.5° indicate the presence of a certain amount of zinc oxide in the sample.

[0121] The characteristic peak positions of the XRD spectrum of catalyst D3 are basically the same as those of D2. Therefore, D3 also contains alumina, magnesium aluminum spinel and zinc aluminum spinel, as well as a certain amount of zinc oxide.

[0122] The XRD patterns of catalysts A1 and D1-D3 do not show obvious diffraction peaks for CoO and MoO3, indicating that the active material exists uniformly in the catalyst bulk phase in a highly dispersed or amorphous state.

[0123] Table 2

[0124] catalyst Lateral compressive strength N / cm carrier phase structure A1 132 <![CDATA[Al2O3 / MgAl2O4 / ZnAl2O4]]> A2 130 <![CDATA[Al2O3 / MgAl2O4 / ZnAl2O4]]> A3 131 <![CDATA[Al2O3 / MgAl2O4 / ZnAl2O4 <!-- 6 -->]]> A4 128 <![CDATA[Al2O3 / MgAl2O4 / ZnAl2O4]]> A5 127 <![CDATA[Al2O3 / MgAl2O4 / ZnAl2O4]]> A6 124 <![CDATA[Al2O3 / MgAl2O4 / ZnAl2O4]]> A7 126 <![CDATA[Al2O3 / MgAl2O4 / ZnAl2O4]]> A8 129 <![CDATA[Al2O3 / MgAl2O4 / ZnAl2O4]]> A9 123 <![CDATA[Al2O3 / MgAl2O4 / ZnAl2O4]]> A10 120 <![CDATA[Al2O3 / MgAl2O4 / ZnAl2O4]]> D1 127 <![CDATA[Al2O3 / MgAl2O4]]> D2 82 <![CDATA[ZnO / Al2O3 / MgAl2O4 / ZnAl2O4]]> D3 86 <![CDATA[ZnO / Al2O3 / MgAl2O4 / ZnAl2O4]]>

[0125] Test Example 2

[0126] At 2.0 MPa, the above catalyst was sulfided using sulfiding gas at 250 °C for 4 h, then sulfided at 300 °C for 3 h, and finally sulfided at 350 °C for 2 h. The volume composition of the sulfiding gas was CO: 50%, H2S: 0.3%, and the balance being H2. The gas space velocity (HSV) was 1000 h⁻¹. -1 .

[0127] The catalytic performance of the sulfidated catalyst for the carbon monoxide conversion reaction was tested at a sulfur content of 300 ppm in the feed gas.

[0128] The reaction temperature was 270℃, and the pressure was 4.0 MPa. The reactant gases consisted of dry gas and water vapor. The volume composition of the dry gas was CO: 50%, H2S: 300 ppm, and the balance being H2. Based on the catalyst volume, the dry gas volume hourly space velocity (VHSV) was 3000 h⁻¹. -1 The volume ratio of dry gas to water vapor is 1:1.

[0129] The CO conversion rate and sulfur content of the catalyst after 20 hours of reaction are shown in Table 3.

[0130] Table 3

[0131] catalyst Sulfur content / wt% CO conversion rate / % A1 6.8 92.5 A2 6.5 92.4 A3 6.6 92.4 A4 6.4 92.1 A5 6.3 92.2 A6 6.2 92.0 A7 6.4 91.8 A8 6.2 91.9 A9 6.0 91.7 A10 6.1 91.6 D1 3.9 91.5 D2 5.8 90.4 D3 5.7 89.8

[0132] Test Example 3

[0133] The sulfidation method of the catalyst is the same as that in Test Example 2.

[0134] The catalytic performance of the sulfidated catalyst for the carbon monoxide shift reaction was tested at a sulfur content of 100 ppm in the feed gas.

[0135] The reaction temperature was 270℃, and the pressure was 4.0 MPa. The reactant gases consisted of dry gas and water vapor. The volume composition of the dry gas was CO: 50%, H2S: 100 ppm, and the balance being H2. Based on the catalyst volume, the dry gas volume hourly space velocity (VHSV) was 3000 h⁻¹. -1 The volume ratio of dry gas to water vapor is 1:1.

[0136] The CO conversion rates after 20 h and 500 h of reaction are shown in Table 4.

[0137] Table 4

[0138]

[0139]

[0140] The results above show that the catalyst provided by the present invention can better tolerate low sulfur conditions compared with the comparative technical solution, has a higher CO conversion rate under low sulfur conditions, and also has good strength.

[0141] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A sulfur-resistant shift catalyst, characterized in that, The catalyst contains oxides and / or sulfides of cobalt, molybdenum, aluminum, magnesium and zinc, or two or more of them. At least a portion of the magnesium forms a spinel structure with the aluminum, and at least a portion of the zinc forms a spinel structure with the aluminum.

2. The catalyst according to claim 1, wherein, The molar ratio of aluminum, magnesium, and zinc, based on elemental composition, is 1:0.1-0.3:0.1-0.4, preferably 1:0.2-0.25:0.1-0.2; Preferably, the mass ratio of cobalt to molybdenum, calculated as oxides, is 1:1-4, more preferably 1:1.5-2.

5.

3. The catalyst according to claim 1 or 2, wherein, Based on catalyst mass, the content of cobalt and molybdenum, calculated as oxides, is 8-13 wt%. Preferably, the combined content of magnesium oxide and zinc oxide in the catalyst does not exceed 30 wt%.

4. A method for preparing a catalyst, characterized in that, Includes the following steps: (1) In the presence of a solvent, a cobalt source, a molybdenum source, an aluminum source, a magnesium source, and a zinc source are mixed with a dispersant; (2) The above mixture is aged, shaped, and heat-treated; The dispersant comprises amino acid surfactants and nonionic surfactants; The heat treatment conditions enable the magnesium and zinc sources to form spinel in the presence of the aluminum source.

5. The method according to claim 4, wherein, The amount of amino acid surfactant added is 1-3 parts by mass relative to 1 part by mass of cobalt source based on oxide, and the amount of nonionic surfactant added is 0.5-2 parts by mass.

6. The method according to claim 4 or 5, wherein, Based on oxides, relative to 1 part by mass of the cobalt source: The amount of molybdenum source added is 1-4 parts by weight; The amount of zinc source added is 3-9 parts by weight; The amount of aluminum source added is 10-30 parts by weight; The amount of magnesium source added is 1-8 parts by weight; Preferably, the molar ratio of aluminum, magnesium and zinc in the added aluminum source, magnesium source and zinc source is 1:0.1-0.3:0.1-0.4, and more preferably 1:0.2-0.25:0.1-0.

2.

7. The method according to any one of claims 4-6, wherein, The aging temperature is 50-70℃, and the time is 3-6 hours; Preferably, the aging process further includes drying the aged material at a temperature of 100-120°C for 2-5 hours.

8. The method according to any one of claims 4-7, wherein, The molding process involves pulverizing the aged material, adding a binder in the presence of a solvent, and then extruding it into shape. Preferably, the adhesive is citric acid and / or dilute nitric acid; And / or, the heat treatment temperature is 500-600℃ and the time is 2-4h.

9. The catalyst prepared by the method according to any one of claims 4-8.

10. A carbon monoxide conversion method, characterized in that, The method includes contacting the feedstock with the catalyst according to any one of claims 1-3 under carbon monoxide conversion conditions; The raw materials include CO, H2, H2O and H2S; Preferably, the molar ratio of CO, H2, and H2O is 1:0.5-1.5:1-4; Preferably, the contact temperature is 200-480℃ and the pressure is 2-6.5MPa; Preferably, the raw material also contains oxygen, and the volume concentration of said oxygen does not exceed 500 ppm; preferably, the volume concentration of H2S is 200-600 ppm.

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