Wide-temperature carbon monoxide shift catalyst and preparation method thereof

Abstract

The invention relates to a wide temperature type carbon monoxide shift catalyst and a preparation method thereof, and relates to the technical field of catalysts.The wide temperature type carbon monoxide shift catalyst mainly comprises, by mass, 35%-50% of CuO, 25%-40% of ZnO, 5%-15% of Al2O3 and an oxide of an auxiliary agent, and the auxiliary agent is composed of, by mass, 35%-50% of CuO, 25%-40% of ZnO and 5%-15% of Al2O3. And the mass content of oxide in the auxiliary agent is 5-12%. The preparation technology is simple, no environment-friendly waste water and the like are generated, and industrial popularization is facilitated. The additive is added and the form of alumina is changed, so that the structure of the catalyst is improved, the comprehensive performance of heat resistance and high selectivity of the catalyst is improved, and the catalyst can meet the requirements of various conversion processes and multi-component feed gas conversion reaction on the market.

Description

Technical Field

[0001] The present invention relates to the field of catalyst technology, and in particular to a wide-temperature carbon monoxide conversion catalyst and a preparation method thereof. Background Art

[0002] Carbon monoxide shift (referred to as shift) is an important part of modern coal chemical projects. It converts CO in the raw gas into H2 through shift reaction and adjusts the hydrogen-carbon ratio in the raw gas to meet the requirements of downstream equipment.

[0003] The shift reaction is a reversible exothermic reaction. Traditional shift technology generally uses multiple adiabatic shift reactors in series to achieve the required shift depth. With the continuous development of coal gasification technology, dry coal powder quenching process gasification technology has been widely used. The raw coal gas produced by this type of gasification technology has the "double high" characteristics of high water content and high CO content. If it is directly fed into the shift furnace for reaction, the catalyst bed temperature will reach over 500°C, seriously affecting the service life of the catalyst and the safe operation of the system. Traditional adiabatic shift technology generally uses high water-gas ratio or low water-gas ratio process to prevent the catalyst bed from overheating. However, neither high water-gas ratio process nor low water-gas ratio process can fundamentally solve the problem of using the catalyst at high temperature. In recent years, isothermal shift technology has received attention from many scientific research institutions and enterprises and has achieved breakthrough development.

[0004] In recent years, several companies have developed process packages that have entered the market. However, these packages were not specifically developed for the shift reaction, but rather directly applied to methanol isothermal reactors. Due to differences in the shift and methanol reaction kinetics, the shift reaction suffers from drawbacks such as concentrated reaction zones and insufficient effective heat exchange area. These drawbacks do not fundamentally address the catalyst bed overheating issue in the "double high" raw coal gas shift reaction. For example, the tail gas from an electric ferroalloy reduction furnace contains 60% to 80% CO by volume, and the peak temperature during the shift furnace reaction reaches 370°C or even higher.

[0005] Existing copper-based shift catalysts, primarily composed of copper, zinc, and aluminum, are generally only suitable for shift reactions at low temperatures (180°C to 220°C) and low CO content (<5% by volume). For shift reactions with higher CO content, the catalysts exhibit poor thermal stability and low selectivity. Some researchers are also experimenting with adding other additives to the system to improve catalyst performance, particularly enhancing thermal stability and selectivity.

[0006] Chinese patent CN105536803A discloses a copper-based carbon monoxide medium-temperature shift catalyst and its preparation method. The catalyst uses copper salt, zinc salt, and aluminum salt as active components and is prepared using a co-precipitation process and specialized equipment.

[0007] Chinese patent CN106179360A discloses a copper-zinc-aluminum catalyst and its preparation method. The catalyst is composed of CuO, ZnO, and Al2O3. Compared with traditional precipitation methods, it differs from traditional precipitation methods in that an organic solvent is added to the dissolution of the precipitant.

[0008] Chinese patent CN101786000A discloses a carbon monoxide shift catalyst and its preparation method. The catalyst composition is based on a copper-zinc-aluminum system with a boron compound added, and the catalyst is prepared by a coprecipitation method.

[0009] In existing research, the heat resistance of the catalyst has been improved to a certain extent, but the selectivity of the catalyst is still not high, which affects the market promotion and use of the catalyst products. It is urgent to develop a conversion catalyst with wide temperature range, strong heat resistance and selectivity to meet the requirements of the conversion reaction. Summary of the Invention

[0010] To solve the above problems, the present invention provides a wide-temperature carbon monoxide conversion catalyst and a preparation method thereof.

[0011] In the first aspect, the present invention provides a wide-temperature carbon monoxide conversion catalyst, the main components of which include CuO, ZnO, Al2O3 and oxides of auxiliary agents, the mass content of CuO is 35% to 50%, the mass content of ZnO is 25% to 40%, the mass content of Al2O3 is 5% to 15%, and the mass content of oxides of the auxiliary agent is 5% to 12%.

[0012] Furthermore, the auxiliary agent is a mixture of one or more of Cr, Zr, Mn, Si, Ce and K.

[0013] Furthermore, the CuO mass content is 40% to 45%.

[0014] Furthermore, the ZnO mass content is 30% to 35%.

[0015] In a second aspect, the present invention provides a method for preparing the wide-temperature carbon monoxide conversion catalyst according to any one of the first aspects, such as Figure 1 As shown, the preparation method comprises the following steps:

[0016] The metal salt solution containing the additive 1 is added to the mixed solution containing copper nitrate and zinc nitrate, mixed evenly, and then added to the sodium carbonate solution at a uniform speed for a first neutralization precipitation, and aged to obtain the material 1;

[0017] The sodium hydroxide solution is uniformly added dropwise to the aluminum nitrate solution of the prepared concentration to perform a second neutralization precipitation to obtain a colloidal precipitate;

[0018] The colloidal precipitate is added to the material 1 and slurried. After slurrying, the material is washed and dried to obtain a filter cake;

[0019] Spraying a metal salt solution containing the additive 2 into the filter cake, and then grinding and granulating the material to obtain the material 2;

[0020] The material 2 is dried, calcined and tabletted to obtain the wide-temperature carbon monoxide conversion catalyst.

[0021] Furthermore, the metal salt solution of the auxiliary agent 1 is a soluble nitrate or carbonate solution corresponding to the metal, the temperature of the first neutralization precipitation is 78° C. to 80° C., and the time of the first neutralization precipitation is 20 min to 25 min.

[0022] Furthermore, the aging temperature is 80° C. to 82° C., and the aging time is 20 min to 25 min.

[0023] Furthermore, the aluminum nitrate solution contains Al 3+ The concentration is 22g / L~28g / L, and the pH value at the end of precipitation is controlled at 6.7~6.9.

[0024] Furthermore, the washing temperature is 60°C to 70°C, the washing time is 3h to 4h, the metal salt solution of the auxiliary agent 2 is a soluble carbonate or nitrate solution corresponding to its metal, the grinding time is 35min to 40min, the roasting temperature is 320°C to 360°C, and the roasting time is 3h to 4h.

[0025] Furthermore, the wide-temperature carbon monoxide conversion catalyst is suitable for conversion reactions using calcium carbide furnace tail gas, natural gas conversion gas, coke oven gas conversion gas, coal gas and blast furnace gas as raw gas.

[0026] The above technical solution provided by the embodiment of the present invention has at least the following advantages compared with the prior art:

[0027] The present invention provides a wide-temperature carbon monoxide conversion catalyst and its preparation method. Compared with the existing technology, the preparation process of the present invention is simple, no environmental wastewater is generated, and it is conducive to industrial promotion. The addition of additives and the change of the morphology of alumina improve the structure of the catalyst, enhance the comprehensive performance of the catalyst's heat resistance and high selectivity, and can meet the requirements of various conversion processes and multi-component feed gas conversion reactions on the market. Specifically:

[0028] 1) Adding an improved structural additive during the neutralization process improves the catalyst structure, effectively inhibits the occurrence of side reactions, and reduces the production of the main by-product methanol.

[0029] 2) Heat-resistant structural additives are added during the grinding process. The additive oxides are evenly dispersed in the catalyst, which can effectively inhibit the aggregation and growth of copper particles in a high temperature environment and enhance the heat resistance of the catalyst.

[0030] 3) Adding colloidal Al(OH)3 during slurrying effectively improves the structure of the carrier oxide, broadens the operating temperature range of the catalyst, and improves the applicability of the catalyst. It can be applied to the conversion reaction of calcium carbide furnace tail gas, natural gas conversion gas, coke oven gas conversion gas, coal gas and blast furnace gas as raw materials with high CO content (up to 80% by volume) and complex gas composition. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the invention and, together with the description, serve to explain the principles of the invention.

[0032] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, for ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative labor.

[0033] Figure 1 A schematic flow chart of a method for preparing a wide-temperature carbon monoxide conversion catalyst provided in an embodiment of the present invention. DETAILED DESCRIPTION

[0034] To make the objectives, technical solutions, and advantages of the embodiments of the present invention more clear, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts shall fall within the scope of protection of the present invention.

[0035] Unless otherwise specified, various raw materials, reagents, instruments and equipment used in the present invention can be purchased from the market or prepared by existing methods.

[0036] The present invention will be further described below in conjunction with specific examples. It should be understood that these examples are intended to illustrate the present invention only and are not intended to limit the scope of the invention. The experimental methods in the following examples where specific conditions are not specified are generally measured in accordance with national standards. If there are no corresponding national standards, then the methods are carried out in accordance with general international standards, conventional conditions, or the conditions recommended by the manufacturer.

[0037] Example 1:

[0038] In a neutralization barrel equipped with a stirring paddle and water bath heating, add 6L of 0.5mol / L sodium carbonate solution and use nitrate to prepare Cu 2+ The concentration is 43.5g / L, Zn 2+ The concentration is 30.0g / L, Mn 2+ The concentration is 2.5g / L and Zr 3+ 1.5L of the mixed solution with a concentration of 3.0g / L was uniformly added to the sodium carbonate solution at a temperature of 78℃ for neutralization. The neutralization time was 20min and the end pH value was 7.5. The mixture was stirred and aged at 80℃ for 20min to obtain material 1. The sodium hydroxide solution was uniformly added dropwise to the Al 3+ A gel precipitate was obtained from a 25 g / L aluminum nitrate solution with an end point pH of 6.8. The gel precipitate was added to material 1 for slurrying, and then washed at 65 ° C for 3.5 h. After drying, a filter cake was obtained. 140 mL of a 50 ° C Cr 3+ A 50.1 g / L chromium nitrate solution was mixed evenly and ground for 35 minutes. The material was granulated, dried, and then calcined at 330°C for 3.5 hours. Graphite and water were added and the material was formed into sheets to obtain a catalyst sample, which was marked as Z-1.

[0039] Example 2:

[0040] In a neutralization barrel equipped with a stirring paddle and water bath heating, add 6L of 0.5mol / L sodium carbonate solution and use nitrate to prepare Cu 2+ The concentration is 41.5g / L, Zn 2+ The concentration is 33.0g / L, Ce 2+ The concentration is 4.0g / L and Zr 3+ 1.5L of the mixed solution with a concentration of 3.5g / L was uniformly added to the sodium carbonate solution at a temperature of 80℃ for neutralization. The neutralization time was 22min and the end pH value was 7.4. The mixture was stirred and aged at 80℃ for 25min to obtain material 1. The sodium hydroxide solution was uniformly added dropwise to the Al 3+ A gel precipitate was obtained from a 26 g / L aluminum nitrate solution with an end point pH of 6.9. The gel precipitate was added to material 1 for slurrying, and then washed at 65 ° C for 3.5 h. After drying, a filter cake was obtained. 140 mL of a 50 ° C, Cr 3+ A 50.0 g / L chromium nitrate solution was mixed evenly and ground for 40 minutes. The material was granulated and dried, and then calcined at 335° C. for 3.0 hours. Graphite and water were added and the material was formed into sheets to obtain a catalyst sample, which was marked as Z-2.

[0041] Example 3:

[0042] In a neutralization barrel equipped with a stirring paddle and water bath heating, add 6L of 0.5mol / L sodium carbonate solution and use nitrate to prepare Cu 2+ The concentration is 46.5g / L, Zn 2+ The concentration is 28.5g / L, Zr 4+ The concentration is 5.5g / L and K + 1.5L of the mixed solution with a concentration of 1.0g / L was uniformly added to the sodium carbonate solution at a temperature of 78℃ for neutralization. The neutralization time was 20min and the end pH value was 7.5. The mixture was stirred and aged at 80℃ for 20min to obtain material 1. The sodium hydroxide solution was uniformly added dropwise to the Al 3+ A gel precipitate was obtained from a 24 g / L aluminum nitrate solution with an end point pH of 6.7. The gel precipitate was added to material 1 for slurrying, and then washed at 70 ° C for 3.0 h. After drying, a filter cake was obtained. 145 mL of a 50 ° C, Cr 3+ The mixture was mixed evenly with a 49.2 g / L chromium nitrate solution and ground for 37 minutes. The mixture was granulated, dried, and then calcined at 330°C for 3.5 hours. Graphite and water were added and the mixture was formed into tablets to obtain a catalyst sample, which was labeled Z-3.

[0043] Example 4:

[0044] In a neutralization barrel equipped with a stirring paddle and water bath heating, add 6L of 0.5mol / L sodium carbonate solution and use nitrate to prepare Cu 2+ The concentration is 40.0g / L, Zn 2+ The concentration is 35.5g / L, Zr 4+ The concentration is 3.0g / L and K + 1.5L of the mixed solution with a concentration of 1.0g / L was uniformly added to the sodium carbonate solution at a temperature of 79℃ for neutralization. The neutralization time was 25min and the end pH value was 7.3. The mixture was stirred and aged at 80℃ for 25min to obtain material 1. The sodium hydroxide solution was uniformly added dropwise to the Al 3+ A gel precipitate was obtained by adding aluminum nitrate solution with a concentration of 28 g / L. The pH value was controlled at 6.8 after precipitation. The gel precipitate was added to material 1 for pulping. After washing at 65 ° C for 4.0 h and drying, a filter cake was obtained. 140 mL of Cr 3+ A 50.0 g / L chromium nitrate solution was mixed evenly and ground for 37 minutes. After granulation and drying, the mixture was calcined at 330°C for 3.5 hours. Graphite and water were added and tablets were formed to obtain a catalyst sample, which was marked as Z-4.

[0045] Example 5:

[0046] In a neutralization barrel equipped with a stirring paddle and water bath heating, add 6L of 0.5mol / L sodium carbonate solution and use nitrate to prepare Cu 2+ The concentration is 38.5g / L, Zn 2+ The concentration is 37.5g / L, K+ concentration is 1.0g / L, Mn 2+ The concentration is 2.0g / L and Zr 4+ 1.5L of the mixed solution with a concentration of 2.5g / L was uniformly added to the sodium carbonate solution at a temperature of 78°C for neutralization. The neutralization time was 20min and the end pH value was 7.5. The mixture was stirred and aged at 80°C for 20min to obtain material 1. The sodium hydroxide solution was uniformly added dropwise to the Al 3+ A gel precipitate was obtained from a 22 g / L aluminum nitrate solution with an end point pH of 6.7. The gel precipitate was added to material 1 for slurrying, and then washed at 65 ° C for 3.5 h and dried to obtain a filter cake. 150 mL of 50 ° C Cr 3+ The material was mixed evenly with a 49.9 g / L chromium nitrate solution and ground for 35 minutes. After granulation and drying, it was calcined at 330°C for 3.5 hours. After adding graphite and water, it was formed into sheets to obtain a catalyst sample, which was marked as Z-5.

[0047] Example 6:

[0048] In a neutralization barrel equipped with a stirring paddle and water bath heating, add 6L of 0.5mol / L sodium carbonate solution and use nitrate to prepare Cu 2+ The concentration is 36.5g / L, Zn 2+ The concentration is 40.0g / L, K + The concentration is 0.8g / L, Si 4+ 1.5L of the mixed solution with a concentration of 3.5g / L was uniformly added to the sodium carbonate solution at a temperature of 78℃ for neutralization. The neutralization time was 20min and the end pH value was 7.5. The mixture was stirred and aged at 80℃ for 20min to obtain material 1. The sodium hydroxide solution was uniformly added dropwise to the Al 3+ A gel precipitate was obtained from a 24 g / L aluminum nitrate solution with an end point pH of 6.9. The gel precipitate was added to material 1 for slurrying, and then washed at 68 ° C for 3.5 h and dried to obtain a filter cake. 150 mL of 50 ° C Cr 3+ The material was mixed evenly with a 49.8 g / L chromium nitrate solution and ground for 35 minutes. After granulation and drying, it was calcined at 330°C for 3.5 hours. After adding graphite and water, it was formed into tablets to obtain a catalyst sample, which was marked as Z-6.

[0049] Example 7:

[0050] In a neutralization barrel equipped with a stirring paddle and water bath heating, add 6L of 0.5mol / L sodium carbonate solution and use nitrate to prepare Cu 2+ The concentration is 47.5g / L, Zn 2+ The concentration is 28.0g / L and Zr 3+ 1.5L of the mixed solution with a concentration of 3g / L was uniformly added to the sodium carbonate solution at a temperature of 78℃ for neutralization. The neutralization time was 20min and the end pH value was 7.5. The mixture was stirred and aged at 80℃ for 20min to obtain material 1. The sodium hydroxide solution was uniformly added dropwise to the Al 3+ A gel precipitate was obtained from a 27 g / L aluminum nitrate solution with an end point pH of 6.8. The gel precipitate was added to material 1 for slurrying, and then washed at 65 ° C for 3.5 h and dried to obtain a filter cake. 140 mL of 50 ° C Cr was added to the filter cake. 3+ A 30.5 g / L chromium nitrate solution was mixed evenly and ground for 40 minutes. The material was granulated, dried, and then calcined at 330° C. for 4 hours. Graphite and water were added and tablets were formed to obtain a catalyst sample, which was marked as Z-7.

[0051] Example 8:

[0052] In a neutralization barrel equipped with a stirring paddle and water bath heating, add 6L of 0.5mol / L sodium carbonate solution and use nitrate to prepare Cu 2+ The concentration is 42.5g / L, Zn 2+ The concentration is 33.5g / L and Zr 3+ 1.5L of the mixed solution with a concentration of 3g / L was uniformly added to the sodium carbonate solution at a temperature of 78℃ for neutralization. The neutralization time was 20min and the end pH value was 7.4. The material 1 was obtained by stirring and aging at 82℃ for 20min. The sodium hydroxide solution was uniformly added dropwise to the Al 3+ A gel precipitate was obtained from a 26 g / L aluminum nitrate solution with an end point pH of 6.9. The gel precipitate was added to material 1 for slurrying, and then washed at 65 ° C for 3.5 h and dried to obtain a filter cake. 140 mL of 50 ° C Cr 3+ A 40.0 g / L chromium nitrate solution was mixed evenly and ground for 35 minutes. The material was granulated, dried, and then calcined at 330° C. for 3.5 hours. Graphite and water were added and tablets were formed to obtain a catalyst sample, which was marked as Z-8.

[0053] Comparative Example 1: prepared with reference to Example 2 of patent CN108114724A.

[0054] (1) Weigh 4.274g of sodium carbonate into a 100mL volumetric flask, add distilled water and shake to volume, and use it as a precipitant. Weigh 1.155g of zinc sulfate (ZnSO4·7H2O) into a 100mL beaker, add 50mL of distilled water to dissolve it, and then add 0.105g of industrial-grade γ-alumina (γ-Al2O3). Slowly add the sodium carbonate solution dropwise to the above-mentioned zinc salt solution at room temperature and continue stirring until the end point reaches pH = 9. Stop the addition and obtain a zinc hydroxide suspension. Continue stirring for 40 minutes after the addition is complete. (2) Weigh 0.945 g of copper nitrate (Cu(NO3)2·3H2O) into a 100 mL beaker and dissolve it in 50 mL of distilled water. Slowly add the precipitant sodium carbonate solution and the above-mentioned Cu salt solution to the zinc hydroxide suspension at the same time, stirring continuously during the addition process, and controlling the pH to about 8; after the copper salt is added, continue to add the precipitant sodium carbonate solution until the pH is 9; the resulting suspension is stirred in a 60°C water bath for 2 h, then filtered and washed with distilled water until the pH is 7; the solid is dried in an 80°C oven for 12 to 24 h to obtain a precipitate precursor; the precipitate precursor is calcined at 400°C in an air atmosphere for 2 h to obtain comparative sample 1, marked as D-1.

[0055] Comparative Example 2: prepared with reference to Example 1 of patent CN106179360A.

[0056] Take 73.5g of sodium carbonate and dissolve it in 800mL of water, marked as solution I. Add 200mL of methanol to solution I.

[0057] mL to obtain solution II, which was heated to 55°C; 72.9g of copper nitrate (Cu(NO3)2·3H2O) and 73.1g of zinc nitrate (Zn(NO3)2·6H2O) were weighed and dissolved in 500mL of water, recorded as solution III, and solution III was added to solution II, changing from dropwise addition to stirring; after precipitation, 9.2g of aluminum hydroxide (Al(OH)3) was added, filtered, washed, and dried, and then calcined at 350°C for 5h. The calcined product was granulated, mixed with 3% graphite, and pressed into tablets to obtain comparative sample 2, marked as D-2.

[0058] Test Case

[0059] The relevant performance test results of the samples prepared in the eight embodiments of the present invention and the comparative examples are shown in the following table.

[0060] Catalyst performance test conditions:

[0061] (1) Fixed bed reactor: catalyst particle size 0.85 mm to 2.0 mm, catalyst loading 40 mL, feed gas composition (v / v%): CO 20%, CO 5% to 10%, H 55% to 70%, CH 5% to 15%, steam-gas ratio (water vapor / dry gas molar ratio) 0.40, reaction pressure 3.0 MPa, space velocity 2000 h -1 , inlet temperature 200℃~280℃.

[0062] (2) Isothermal bed reactor (with steam drum for heat transfer): original catalyst particle size, catalyst loading 40 mL, feed gas composition (v / v%): CO 20%-75%, CO2 5%-10%, H2 5%-10%, N2 5%-15%, steam-gas ratio (water vapor / dry gas molar ratio) 0.40, reaction pressure 3.0 MPa, space velocity 2000 h -1 , inlet temperature 200℃~220℃.

[0063] (3) Catalyst activation: reducing atmosphere: N2 / H2 mixed gas (H2 accounts for 10%, the rest is N2); reducing pressure: normal pressure; reducing space velocity: 800h -1 The temperature was programmed to rise slowly to 230°C and held for 2.0 h (heating rate 1.5°C / 3 min). Heat-resistant conditions: raw gas atmosphere, normal pressure, 400°C, 5.0 h.

[0064] CO conversion rate calculation formula: Where: E: CO conversion rate, %; Φ1: CO volume fraction in the inlet gas (raw gas), %; Φ2: CO volume fraction in the outlet gas (product gas), %.

[0065] The physical and chemical data of the sample catalysts prepared in the examples and comparative examples are shown in Table 1 below.

[0066] Table 1: Physical and chemical data of samples prepared in Examples and Comparative Examples

[0067]

[0068]

[0069] It can be seen from the data in Table 1 that the catalyst prepared by the present invention has a more suitable structure, a relatively larger comparative area and pore volume, which is beneficial to the shift reaction, and the grain size of CuO and ZnO is larger than that of the control sample, which is beneficial to improving the heat resistance of the catalyst.

[0070] Referring to the above catalyst performance test conditions, performance tests were conducted on the example and comparative catalysts in a fixed bed reactor. The specific results are shown in Tables 2, 3 and 4 below.

[0071] Table 2 Performance comparison data of examples and comparative examples

[0072] catalyst Inlet temperature ℃ Hot spot temperature ℃ CO content% CO conversion rate % Alcohol content ppm Z-1 200 275 15 94.5 1870 Z-2 200 278 15 94.3 1800 Z-3 200 276 15 94.5 1790 Z-4 200 277 15 94.0 1900 Z-5 200 278 15 94.1 1950 Z-6 200 275 15 93.9 1890 Z-7 200 277 15 93.8 1900 Z-8 200 277 15 94.0 2000 D-1 200 275 15 94.2 2250 D-2 200 275 15 92.5 2500

[0073] Table 3 Performance comparison data of examples and comparative examples

[0074]

[0075]

[0076] Table 4 Performance comparison data of examples and comparative examples

[0077] catalyst Inlet temperature ℃ Hot spot temperature ℃ CO content% CO conversion rate % Alcohol content ppm Z-1 300 365 15 90.7 2450 Z-2 300 368 15 89.9 2430 Z-3 300 365 15 90.5 2470 Z-4 300 369 15 89.5 2490 Z-5 300 367 15 90.3 2450 Z-6 300 365 15 90.1 2490 Z-7 300 366 15 90.2 2500 Z-8 300 364 15 89.9 2485 D-1 300 360 15 84.9 3000 D-2 300 360 15 85.5 3900

[0078] Referring to the above catalyst performance test conditions, performance tests were conducted on the example and comparative catalysts in an isothermal bed reactor. The specific results are shown in Table 5 below.

[0079] Table 5 Performance comparison data of examples and comparative examples

[0080]

[0081]

[0082] It can be seen from the data in Tables 2, 3, 4 and 5 that the catalyst prepared by the present invention has excellent performance and a wider operating temperature range. The addition of the auxiliary agent and the change of the alumina morphology can significantly improve the heat resistance of the strong catalyst, which is suitable for the requirements of the high-CO content feed gas shift reaction. The addition of the auxiliary agent can inhibit side reactions and effectively reduce the amount of alcohols produced in the liquid phase product of the shift reaction.

[0083] Various embodiments of the present invention may be presented in the form of a range; it should be understood that the description in a range format is only for convenience and brevity and should not be construed as an inflexible limitation on the scope of the invention; therefore, the range description should be considered to have specifically disclosed all possible subranges and single numerical values within the range. For example, the description of a range from 1 to 6 should be considered to have specifically disclosed subranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as 1, 2, 3, 4, 5, and 6, regardless of the range. In addition, whenever a numerical range is indicated herein, it is intended to include any cited numeral (fractional or integer) within the indicated range.

[0084] The foregoing description is intended only to provide specific embodiments of the present invention, which will enable those skilled in the art to understand and implement the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention is not intended to be limited to the embodiments shown herein, but is intended to be accorded the widest scope consistent with the principles and novel features claimed herein.

Claims

1. A wide temperature carbon monoxide conversion catalyst, characterized in that: The wide-temperature carbon monoxide conversion catalyst mainly comprises CuO, ZnO, Al2O3 and oxides of the auxiliary agent, wherein the mass content of CuO is 35% to 50%, the mass content of ZnO is 25% to 40%, the mass content of Al2O3 is 5% to 15%, and the mass content of the oxide of the auxiliary agent is 5% to 12%.

2. The wide-temperature carbon monoxide conversion catalyst according to claim 1, characterized in that The auxiliary agent is a mixture of one or more of Cr, Zr, Mn, Si, Ce and K.

3. The wide-temperature carbon monoxide conversion catalyst according to claim 1, characterized in that The CuO mass content is 40% to 45%.

4. The wide-temperature carbon monoxide conversion catalyst according to claim 1, characterized in that The ZnO mass content is 30% to 35%.

5. A method for preparing a wide-temperature carbon monoxide conversion catalyst according to any one of claims 1 to 4, characterized in that: The preparation method comprises the following steps: The metal salt solution containing the additive 1 is added to the mixed solution containing copper nitrate and zinc nitrate, mixed evenly, and then added to the sodium carbonate solution at a uniform speed for a first neutralization precipitation, and aged to obtain the material 1; The sodium hydroxide solution is uniformly added dropwise to the aluminum nitrate solution of the prepared concentration to perform a second neutralization precipitation to obtain a colloidal precipitate; The colloidal precipitate is added to the material 1 and slurried. After slurrying, the material is washed and dried to obtain a filter cake; Spraying a metal salt solution containing the additive 2 into the filter cake, and then grinding and granulating the material to obtain the material 2; The material 2 is dried, calcined and tabletted to obtain the wide-temperature carbon monoxide conversion catalyst.

6. The method for preparing a wide-temperature carbon monoxide conversion catalyst according to claim 5, characterized in that: The metal salt solution of the auxiliary agent 1 is a soluble nitrate or carbonate solution corresponding to the metal thereof. The temperature of the first neutralization precipitation is 78° C. to 80° C., and the time of the first neutralization precipitation is 20 min to 25 min.

7. The method for preparing a wide-temperature carbon monoxide conversion catalyst according to claim 5, characterized in that: The aging temperature is 80℃~82℃, and the aging time is 20min~25min.

8. The method for preparing a wide-temperature carbon monoxide conversion catalyst according to claim 5, characterized in that: The aluminum nitrate solution contains Al 3+ The concentration is 22g / L~28g / L, and the pH value at the end of precipitation is controlled at 6.7~6.

9.

9. The method for preparing a wide-temperature carbon monoxide conversion catalyst according to claim 5, characterized in that: The washing temperature is 60℃~70℃, the washing time is 3h~4h, the metal salt solution of the auxiliary agent 2 is a soluble carbonate or nitrate solution corresponding to its metal, the grinding time is 35min~40min, the roasting temperature is 320℃~360℃, and the roasting time is 3h~4h.

10. The method for preparing a wide-temperature carbon monoxide conversion catalyst according to claim 5, characterized in that: The wide-temperature carbon monoxide conversion catalyst is suitable for conversion reactions using calcium carbide furnace tail gas, natural gas conversion gas, coke oven gas conversion gas, coal gas and blast furnace gas as raw gas.

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