Multifunctional synthetic gas desulfurization iron protective agent and use thereof
By using a multifunctional protective agent with CuO/Cu and ZnO/Zn active centers supported on an aluminosilicate molecular sieve carrier in syngas, the problem of removing sulfur and its sulfides and carbonyl iron-nickel in syngas was solved, improving the stability and product purity of the methanol synthesis catalyst, making it suitable for large-scale methanol production.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- CHINA PETROLEUM & CHEMICAL CORP
- Filing Date
- 2024-12-27
- Publication Date
- 2026-06-30
AI Technical Summary
The lack of a multifunctional protective agent in the current technology that can simultaneously and efficiently remove sulfur and its sulfides and carbonyl iron-nickel from the synthesis gas leads to a decrease in the activity of methanol synthesis catalysts and a reduction in product purity.
By loading CuO/Cu and ZnO/Zn active centers onto aluminosilicate molecular sieve support, a multifunctional syngas desulfurization iron protectant is prepared through physical adsorption and catalytic decomposition, achieving efficient removal of sulfur and its sulfides, as well as carbonyl iron-nickel.
It improves the long-term operational stability and product purity of methanol synthesis catalysts, making it suitable for large-scale methanol production plants, especially industrial production at the million-ton level.
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Abstract
Description
Technical Field
[0001] This invention belongs to the field of catalytic material preparation technology, specifically relating to a multifunctional syngas desulfurization iron protection agent and its applications. Background Technology
[0002] Methanol is an important organic chemical raw material, used in the production of chemical products such as formaldehyde, dimethyl ether, and acetic acid. It can also be used as a fuel and solvent. To more effectively reduce the production cost per unit of methanol, Lurgi pioneered the concept of large-scale methanol production in 1997, making large-scale methanol synthesis plants the direction of development for the methanol industry.
[0003] Common medium- and low-pressure methanol synthesis catalysts are copper-based catalysts. This type of catalyst is extremely sensitive to poisons. The known poisons are mainly: (1) sulfur and sulfur compounds; (2) chlorine and chlorine compounds; (3) trace amounts of ammonia; (4) trace amounts of arsenic and arsenides; and (5) carbonyl iron and carbonyl nickel. With the trend of large-scale production plants, the amount of these poisons in the synthesis gas to be processed is large, the processing procedures are complex and varied, and the side effects are also very obvious.
[0004] The presence of sulfur and its sulfides in the synthesis gas has a serious, even fatal, impact on methanol synthesis catalysts. A few hundred ppm of sulfur is enough to completely deactivate the methanol synthesis catalyst. Similarly, 1500 ppm of carbonyl iron-nickel can reduce the reaction rate of the methanol catalyst by 50%, and 3000 ppm of carbonyl iron-nickel on the methanol catalyst itself is enough to completely deactivate the methanol catalyst.
[0005] Sulfur and its sulfides can chemically react with active components in catalysts (such as copper or zinc) to form stable sulfides, thereby reducing the activity of methanol catalysts. This leads to a slower and slower methanol synthesis reaction rate, resulting in a gradual decrease in production efficiency. Furthermore, the presence of sulfur and its sulfides also affects the purity of the final methanol product. Excessive sulfur content leads to increased impurities in the methanol, failing to meet market demands and industry standards.
[0006] The effects of iron carbonyl and nickel carbonyl on methanol synthesis are closely related to the reaction conditions. Although only carbon, hydrogen, and oxygen participate in the methanol synthesis reaction, reaction conditions such as temperature, pressure, space velocity, catalyst, and impurities in the reactant and vaporizing agent can deviate from the main reaction direction, generating various byproducts that become impurities in the methanol. The presence of these impurities not only complicates the distillation and extraction purification processes but also affects product quality. The presence of iron carbonyl and nickel carbonyl can induce many side reactions, such as the formation of hydrocarbons and paraffinic hydrocarbons, thus affecting product purity.
[0007] Currently, desulfurization protective agents and decarbonylation iron-nickel protective agents exist independently, presenting themselves in the application market as two major product categories, resulting in a wide variety of products. In the existing protective agent market, there is currently no multifunctional protective agent product that integrates desulfurization and decarbonylation iron-nickel removal functions, achieving excellent desulfurization and deironization effects. Summary of the Invention
[0008] Purpose of the Invention: The purpose of this invention is to provide a multifunctional syngas desulfurization iron protectant and its applications. This invention first synthesizes an aluminosilicate molecular sieve support for preparing the multifunctional syngas desulfurization iron protectant. This invention utilizes the desulfurization characteristics of copper-zinc dual components, with single or multiple layers precisely distributed on the support, resulting in an eggshell-type or protein-type protectant product. Furthermore, it leverages the large specific surface area and numerous micropores of the molecular sieve support to fully physically adsorb or retain carbonyl iron and nickel, which are then deposited after catalytic dissociation at the copper-zinc active centers.
[0009] This invention provides a protective agent to remove sulfur and its sulfides from the synthesis gas during methanol production, as well as carbonyl iron-nickel formed during the reaction, thereby enhancing the agent's functionality. Without affecting the main methanol process, it protects the activity and lifespan of the methanol synthesis catalyst in subsequent processes, better meeting the production requirements for long-term stable operation of industrial plants.
[0010] Technical solution: The objective of this invention is achieved through the following technical solution:
[0011] This invention provides a silicate-aluminate molecular sieve support for preparing a multifunctional syngas desulfurization iron protectant, which is prepared by using water glass solution, structure directing agent solution, aluminum sulfate solution, sodium aluminate solution and silicate-aluminate gel solution as raw materials, and carrying out gelation reaction, aging and post-treatment.
[0012] Preferably, after the gelation reaction is completed, the solution is washed with water, and the conductivity of the washing endpoint solution is controlled to be ≤10μs / cm.
[0013] Preferably, in the gelation reaction, the molar ratio of Na2O, Al2O3, and SiO2 is controlled to be 2-3.5:1:8-10.
[0014] Preferably, the gelation reaction is carried out at a temperature of 30–80°C for 20–80 min.
[0015] Preferably, the aging process conditions are: aging at 90-100℃ for 16-40 hours.
[0016] Preferably, the structure-directing agent solution is prepared as follows: sodium aluminate solution and sodium hydroxide solution are mixed and stirred evenly, then water glass solution is added, and the mixture is allowed to stand and age at 15-40°C for 8-24 hours to obtain the solution.
[0017] This invention also provides a multifunctional syngas desulfurization iron protectant prepared from the above-mentioned aluminosilicate molecular sieve support.
[0018] The chemically active centers of the protective agent are composed of CuO / Cu and ZnO / Zn, and the carrier of the protective agent is an aluminosilicate molecular sieve. The components of the protective agent, by mass percentage, are copper oxide or copper content of 1.0% to 20.0%, zinc oxide or zinc content of 1.0% to 20.0%, and aluminosilicate molecular sieve content of 75.0% to 94.0%.
[0019] The copper-zinc based protective agent supported by molecular sieves of this invention exhibits good desulfurization and decarbonylation iron-nickel activity and high iron capacity. Its metal active centers include Cu and Zn, and the support is composed of molecular sieves with a high silica-to-alumina ratio. The metal active centers in this system exist in the form of basic complex salts, uniformly distributed among the molecular sieve supports, and alternately and cyclically attached to the supports.
[0020] Preferably, the copper oxide or copper content is 3% to 15%, and the zinc oxide or zinc content is 5% to 15%.
[0021] The present invention also provides a method for preparing the above-mentioned protective agent, comprising the following steps:
[0022] (1) Aluminosilicate gel-like carrier was prepared by hydrothermal synthesis and then formed to obtain aluminosilicate molecular sieve carrier;
[0023] (2) The active precursor of the protective agent was prepared by co-precipitation with a precipitant and a copper-zinc mixture;
[0024] (3) Mix the aluminosilicate molecular sieve support obtained in step (1) and the active precursor of the protective agent obtained in step (2), slurry, let stand, filter, dry and granulate to obtain the protective agent.
[0025] Preferably, in step (2), the molar ratio of copper to zinc ions in the copper-zinc mixture is 1:2 to 2:1, and the molar concentration of the copper-zinc mixture is 0.1 mol / L to 5 mol / L.
[0026] Preferably, in step (2), the precipitant is a sodium carbonate solution, sodium bicarbonate solution, potassium carbonate solution, potassium bicarbonate solution, or ammonia water, with a molar concentration of 0.01 mol / L to 4.0 mol / L.
[0027] Preferably, in step (2), the temperature of the coprecipitation is 20 to 90°C, and the final pH value of the coprecipitation is 6.5 to 8.5.
[0028] Further, in step (2), at a temperature of 20 to 90°C, a precipitant with a concentration of 0.1 mol / L to 3.0 mol / L is added to a Cu and Zn mixed nitrate solution to carry out a coprecipitation reaction. The final pH value is controlled at 6.5 to 8.0, and the mixture is aged for 10 to 120 minutes. After washing with water, the active precursor of the protective agent is obtained.
[0029] In step (2) of this invention, the control of preparation technical parameters includes, but is not limited to, feeding rate, precipitation temperature, process pH value, and precipitation endpoint pH value.
[0030] Preferably, in step (3), the drying temperature is 100℃~120℃ and the drying time is 20~80min.
[0031] This invention also provides the use of the above-mentioned multifunctional syngas desulfurization iron protectant for removing sulfur and its sulfides and carbonyl iron-nickel formed in the syngas during the methanol production process.
[0032] Beneficial effects:
[0033] (1) The desulfurization and desulfurization of its sulfides and decarbonyl iron-nickel protective agents prepared using the silicate molecular sieve carrier of the present invention have two processes: chemical reaction desulfurization, physical adsorption and catalytic decomposition deposition deironization. The protective agent has the characteristics of good desulfurization and deironization activity, high removal accuracy, high sulfur capacity and carbonyl iron-nickel capacity.
[0034] (2) The desulfurization and its sulfides and decarbonylation iron-nickel protective agents prepared by this invention can better protect the long-term operation of methanol synthesis catalysts. They are particularly suitable for use in large-scale methanol synthesis plants with medium and low pressure, especially in the now common million-ton-level large-scale methanol industrial production plants. Detailed Implementation
[0035] The technical solution of the present invention will be described in detail below through specific embodiments, but the scope of protection of the present invention is not limited to the embodiments described.
[0036] Example 1
[0037] (1) Preparation of aluminosilicate molecular sieve supports
[0038] Preparation of sodium aluminate solution: 500 ml of 32.8% sodium hydroxide solution and 223.8 g of aluminum hydroxide powder with an Al2O3 content of 63.7% were added to a stirred reactor. The reaction pressure was 0.2 MPa, the reaction temperature was 125℃, and the reaction time was 6 hours to prepare sodium aluminate solution.
[0039] Preparation of aluminosilicate gel solution: Filtered qualified material with SiO2 concentration of 46.8 g / L and Na2O concentration of 25.3 g / L was reacted with aluminum sulfate solution with Al2O3 concentration of 90.2 g / L. After filtration and washing, aluminosilicate gel solution was prepared. The composition of the aluminosilicate gel was: SiO2 61.8%, Al2O3 16.5%, Na2O 13.8%, solid content 11.8%, and density 1.0965.
[0040] Preparation of the directing agent solution: 135.6 ml of sodium aluminate solution with Al2O3 concentration of 150.5 g / L and Na2O concentration of 180.3 g / L and 270.6 ml of sodium hydroxide solution with a concentration of 31% were added to a stirred reactor and stirred evenly. Then, 718.2 ml of water glass solution with SiO2 concentration of 250.6 g / L and modulus of 3.25 was added. The aging temperature was controlled at 28℃ and the solution was allowed to stand for aging for 20 hours. After aging, 169 ml of chemical water was added. The resulting product is the directing agent solution.
[0041] 255.9 ml of the prepared aluminosilicate gel solution, 294.2 ml of water glass solution with SiO2 concentration of 250.6 g / L and modulus of 3.25, 52.8 ml of sodium aluminate solution, 50 ml of directing agent solution, and 65.8 ml of aluminum sulfate solution with Al2O3 concentration of 90.5 g / L were added concurrently to the gelation reactor. The gelation reaction was carried out at 40°C with stirring for 40 minutes. The temperature was then raised to 98°C, and the mixture was allowed to stand for 28 hours for aging. After washing and filtration, the aluminosilicate molecular sieve support was obtained.
[0042] (2) 200 mL of 0.1 mol / L sodium carbonate solution was added to 40 mL of 0.5 mol / L Cu and Zn (molar ratio of 1:2) mixed nitrate aqueous solution to carry out coprecipitation reaction at 40 °C. The parent precipitate was washed with deionized water and the final pH value of the filtrate was 6.5. After aging at 40 °C for 60 min, the parent precipitate slurry was obtained.
[0043] (3) Mix the above-mentioned parent precipitate slurry and carrier, let stand for 20 minutes, filter, dry and granulate, and press into tablets to make desulfurization and decarbonylation iron-nickel protective agent sample C1.
[0044] Example 2
[0045] (1) Preparation of aluminosilicate molecular sieve supports
[0046] Preparation of sodium aluminate solution: 500 ml of 31.8% sodium hydroxide solution and 218.61 g of aluminum hydroxide powder with an Al2O3 content of 64.2% were added to a stirred reactor. The reaction pressure was 0.2 MPa, the reaction temperature was 125℃, and the reaction time was 6 hours to prepare sodium aluminate solution.
[0047] Preparation of silica-alumina gel solution: Filtered qualified materials with SiO2 concentrations of 45.8 g / L and 25.2 g / L were reacted with aluminum sulfate solution with an Al2O3 concentration of 90.2 g / L. After filtration and washing, a silica-alumina gel solution was prepared. The composition of the silica-alumina gel was: SiO2 61.9%, Al2O3 16.6%, Na2O 13.7%, solid content 11.9%, and density 1.096.
[0048] Preparation of the directing agent solution: 137.6 ml of sodium aluminate solution with Al2O3 concentration of 148.2 g / L and Na2O concentration of 181.6 g / L and 261.8 ml of sodium hydroxide solution with a concentration of 31.8% were added to a stirred reactor and stirred evenly. Then, 712.6 ml of water glass solution with SiO2 concentration of 252.6 g / L and modulus of 3.23 was added. The aging temperature was controlled at 25℃ and the mixture was allowed to stand for 22 hours. After aging, 200.2 ml of chemical water was added. The resulting product is the directing agent solution.
[0049] 255.9 ml of the prepared aluminosilicate solution, 291.2 ml of water glass solution with a SiO2 concentration of 252.6 g / L and a modulus of 3.23, 52.6 ml of sodium aluminate solution, 49.6 ml of directing agent solution, and 67.2 ml of aluminum sulfate solution with an Al2O3 concentration of 91.6 g / L were added concurrently to the gelation reactor. The gelation reaction was carried out at 50°C with stirring for 60 minutes. After the addition was complete, the temperature was raised to 98°C, and the mixture was allowed to stand for aging for 28 hours before being washed and filtered to obtain the aluminosilicate molecular sieve support.
[0050] (2) 300 mL of 0.5 mol / L sodium bicarbonate solution was added to 30 mL of 1 mol / L Cu and Zn (molar ratio of 1:1) mixed nitrate aqueous solution to carry out coprecipitation reaction at 60 °C. The parent precipitate was washed with deionized water and the final pH value of the filtrate was 7.2. After aging at 60 °C for 100 min, the parent precipitate slurry was obtained.
[0051] (3) Mix the above-mentioned parent precipitate slurry and carrier, let stand for 30 minutes, filter, dry and granulate, and press into tablets to make desulfurization and decarbonylation iron-nickel protective agent sample C2.
[0052] Example 3
[0053] (1) Preparation of aluminosilicate molecular sieve supports
[0054] Preparation of sodium aluminate solution: 500 ml of 30.5% sodium hydroxide solution and 207.99 g of aluminum hydroxide powder with Al2O3 content of 64% were added to a stirred reactor. The reaction pressure was 0.2 MPa, the reaction temperature was 125℃, and the reaction time was 6 hours to prepare sodium aluminate solution.
[0055] Preparation of silica-alumina gel solution: Filtered qualified materials with SiO2 concentrations of 45.8 g / L and 25.2 g / L were reacted with aluminum sulfate solution with an Al2O3 concentration of 90.2 g / L. After filtration and washing, silica-alumina gel was prepared. The composition of the silica-alumina gel was: SiO2 61.9%, Al2O3 16.6%, Na2O 13.7%, solid content 11.9%, and density 1.096.
[0056] Preparation of the directing agent solution: 134.2 ml of sodium aluminate solution with Al2O3 concentration of 152.0 g / L and Na2O concentration of 178.2 g / L and 276.3 ml of sodium hydroxide solution with a concentration of 30.5% were added to a stirred reactor and stirred evenly. Then, 724 ml of water glass solution with SiO2 concentration of 248.6 g / L and modulus of 3.25 was added. The aging temperature was controlled at 28℃ and the solution was allowed to stand for 20 hours. After aging, 204.8 ml of chemical water was added. The resulting product is the directing agent solution.
[0057] 255.9 ml of the prepared aluminosilicate gel solution, 295.8 ml of water glass solution with a SiO2 concentration of 248.6 g / L and a modulus of 3.25, 52.6 ml of sodium aluminate solution, 50 ml of directing agent solution, and 65.0 ml of aluminum sulfate solution with an Al2O3 concentration of 89.2 g / L were added concurrently to the gelation reactor. The gelation reaction was carried out at 80°C with stirring for 25 minutes. After the addition was complete, the temperature was raised to 98°C, and the mixture was allowed to stand for aging for 28 hours before being washed and filtered to obtain the aluminosilicate molecular sieve support.
[0058] (2) Add 200 mL of 1.5 mol / L potassium hydroxide solution to 150 mL of 2.0 mol / L Cu and Zn (molar ratio of 1.5:1) mixed nitrate aqueous solution to carry out coprecipitation reaction at 70 °C. The parent precipitate is washed with deionized water and the final pH value of the filtrate is 7.2. The parent precipitate slurry is obtained by aging at 90 °C for 10 min.
[0059] (3) Mix the above-mentioned parent precipitate slurry and carrier, let stand for 50 minutes, filter, dry and granulate, and press into tablets to make desulfurization and decarbonylation iron-nickel protective agent sample C3.
[0060] Example 4
[0061] (1) Preparation of aluminosilicate molecular sieve supports
[0062] Preparation of sodium aluminate solution: 500 ml of 31.0% sodium hydroxide solution and 213.066 g of aluminum hydroxide powder with Al2O3 content of 63.5% were added to a stirred reactor. The reaction pressure was 0.2 MPa, the reaction temperature was 125℃, and the reaction time was 6 hours to prepare sodium aluminate solution.
[0063] Preparation of silica-alumina gel solution: Filtered qualified materials with SiO2 concentrations of 45.8 g / L and 25.2 g / L were reacted with aluminum sulfate solution with an Al2O3 concentration of 90.2 g / L. After filtration and washing, silica-alumina gel was prepared. The composition of the silica-alumina gel was: SiO2 61.95%, Al2O3 16.6%, Na2O 13.7%, solid content 11.9%, and density 1.096.
[0064] Preparation of the directing agent solution: 134.4 ml of sodium aluminate solution with Al2O3 concentration of 151.8 g / L and Na2O concentration of 181.5 g / L and 268.7 ml of sodium hydroxide solution with a concentration of 31% were added to a stirred reactor and stirred evenly. Then, 728.4 ml of water glass solution with SiO2 concentration of 247.1 g / L and modulus of 3.20 was added. The aging temperature was controlled at 25℃ and the solution was allowed to stand for 22 hours. After aging, 203.8 ml of chemical water was added. The resulting product is the directing agent solution.
[0065] 255.9 ml of the prepared aluminosilicate solution, 294.2 ml of water glass solution with a SiO2 concentration of 247.1 g / L and a modulus of 3.20, 52.2 ml of sodium aluminate solution, 49.8 ml of directing agent solution, and 65.8 ml of aluminum sulfate solution with an Al2O3 concentration of 90.1 g / L were added concurrently to the gelation reactor. The gelation reaction was carried out at 30°C with stirring for 80 minutes. After the addition was complete, the temperature was raised to 98°C, and the mixture was allowed to stand for aging for 28 hours before being washed and filtered to obtain the aluminosilicate molecular sieve support.
[0066] (2) Add 250 mL of 2.5 mol / L sodium bicarbonate solution to 100 mL of 2.5 mol / L Cu and Zn (molar ratio of 2:1) mixed nitrate aqueous solution to carry out coprecipitation reaction at 80 °C. The parent precipitate is washed with deionized water and the final pH value of the filtrate is 8.0. The precipitate is aged at 30 °C for 100 min to obtain the parent precipitate slurry.
[0067] (3) Mix the above-mentioned parent precipitate slurry and carrier, let stand for 80 minutes, filter, dry and granulate, and press into tablets to make desulfurization and decarbonylation iron-nickel protective agent sample C4.
[0068] Comparative Example 1
[0069] Aluminum nitrate and sodium silicate soluble salts were mixed at a mass percentage of 8% for co-precipitation. The final pH value was adjusted to 8.0 according to the different ionization constants of the metal precipitates. The temperature of the mixed solution was controlled at 70℃. After aging and washing, the carrier slurry was obtained.
[0070] 100 mL of a 4.0 mol / L ammonia solution was added to 50 mL of a 3.0 mol / L Cu and Zn (molar ratio 2:1) mixed nitrate solution to carry out a coprecipitation reaction at 70 °C. The parent precipitate was washed with deionized water, and the final pH of the filtrate was 8.0. The precipitate was aged at 40 °C for 60 min to obtain a slurry of parent precipitate.
[0071] The above-mentioned parent precipitate slurry and carrier slurry were mixed and pulped, allowed to stand for 120 minutes, filtered, dried and granulated, and then molded to obtain the comparative sample C5 of desulfurization and decarbonylation iron-nickel protective agent.
[0072] Comparative Example 2
[0073] Aluminum nitrate and sodium hydroxide were mixed at a mass percentage of 13% for co-precipitation. The final pH value was adjusted to 8.5 according to the different ionization constants of the metal precipitates. The temperature of the mixed solution was controlled at 70℃. After aging and washing, the carrier slurry was obtained.
[0074] 150 mL of a 3.0 mol / L sodium carbonate solution was added to 50 mL of a 2.0 mol / L Cu and Zn (molar ratio 1:1) mixed nitrate aqueous solution to carry out a coprecipitation reaction at 80 °C. The parent precipitate was washed with deionized water, and the final pH of the filtrate was 8.0. The precipitate was aged at 40 °C for 60 min to obtain a slurry of the parent precipitate.
[0075] The above-mentioned parent precipitate slurry and carrier slurry were mixed and pulped, allowed to stand for 100 minutes, filtered, dried and granulated, and then shaped to obtain the comparative sample C6 of desulfurization and decarbonylation iron-nickel protective agent.
[0076] The molded protective agent was crushed into 20-40 mesh particles, and 2 ml of the sample was placed in a reactor for reduction treatment. The reduction atmosphere was an NH mixed gas containing 5% hydrogen by volume, and the reduction temperature was 210℃. The carbonyl iron and sulfur removal reaction temperatures were set according to Table 1, and the synthesis gas space velocity was 12000 h⁻¹. -1The inlet synthesis gas contains 10 ppm carbonyl iron-nickel and 4 ppm sulfur. After desulfurization and deironization by the protective agent in the reactor, it passes through the methanol catalyst reactor. After the furnace is dismantled, the iron content of the desulfurization iron protective agent and the methanol catalyst body is analyzed.
[0077] Table 1. Physicochemical data and carbonyl iron-nickel removal performance of the protective agent samples.
[0078]
[0079] Note: For the breakthrough sulfur capacity test method, please refer to standard HG / T 4198-2011 "Analytical Methods for Chemical Composition of Methanol Synthesis Catalysts".
[0080] As shown in Table 1, all the protective agents exhibit desulfurization and decarbonyl iron-nickel removal properties, with a sulfur penetration capacity greater than 10%. The desulfurization performance is even better when copper-zinc active components are loaded onto the silica-alumina molecular sieve, with a sulfur penetration capacity reaching as high as 23%. Similarly, the carbonyl iron-nickel removal rate of the protective agents of this invention is above 98%, reaching a maximum of 99.96%. Furthermore, under the porous physical adsorption of the molecular sieve support, the copper-zinc protective agent loaded on the silica-alumina molecular sieve exhibits better activity and higher desulfurization and iron removal capacity. Using the desulfurization agent and its sulfides, as well as the decarbonyl iron-nickel removal protective agent prepared according to this invention in the protective bed of the methanol synthesis reaction can effectively ensure the longer operation of the methanol synthesis catalyst.
[0081] As described above, although the invention has been shown and described with reference to specific preferred embodiments, it should not be construed as limiting the invention itself. Various changes in form and detail may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims
1. An aluminosilicate molecular sieve support for preparing a multifunctional syngas desulfurization iron protectant, characterized in that, The aluminosilicate molecular sieve carrier is prepared by using water glass solution, structure guiding agent solution, aluminum sulfate solution, sodium aluminate solution and aluminosilicate gel solution as raw materials, and by carrying out gelation reaction, aging and post-treatment.
2. The aluminosilicate molecular sieve support according to claim 1, characterized in that, After the gelation reaction is completed, the solution is washed with water, and the conductivity of the washing endpoint solution is controlled to be ≤10μs / cm.
3. The aluminosilicate molecular sieve support according to claim 1, characterized in that, In the gelation reaction, the molar ratio of Na2O, Al2O3, and SiO2 is controlled to be 2–3.5:1:8–10.
4. The aluminosilicate molecular sieve support according to claim 1, characterized in that, The gelation reaction is carried out at a temperature of 30–80°C for 20–80 minutes.
5. The aluminosilicate molecular sieve support according to claim 1, characterized in that, The aging process conditions are: aging at 90-100℃ for 16-40 hours.
6. The aluminosilicate molecular sieve support according to claim 1, characterized in that, The method for preparing the structure-directing agent solution is as follows: mix sodium aluminate solution and sodium hydroxide solution, stir evenly, then add water glass solution, and let it stand and age at 15-40℃ for 8-24 hours to obtain the solution.
7. A multifunctional syngas desulfurization iron protectant prepared from a silicate molecular sieve support as described in any one of claims 1-6.
8. The use of the multifunctional syngas desulfurization iron protectant according to claim 7 for removing sulfur and its sulfides and carbonyl iron-nickel formed in the syngas during the methanol production process.