Normal-temperature gas-phase fine desulfurizer and preparation method thereof

Abstract

The application discloses a normal-temperature gas-phase fine desulfurizer and a preparation method thereof, and belongs to the field of gas purification and desulfurization. 2 The specific surface area of the normal-temperature gas-phase fine desulfurizer is greater than or equal to 168 m 2 / g, and the breakthrough sulfur capacity is greater than or equal to 20.6%. The normal-temperature gas-phase fine desulfurizer has high specific surface area and high breakthrough sulfur capacity, can deeply adsorb hydrogen sulfide, mercaptan and carbonyl sulfur in gas-phase materials such as natural gas and synthetic gas at normal temperature, reduces the sulfide in raw gas to below 5 ppb, and realizes excellent desulfurization effect. Moreover, the preparation method of the normal-temperature gas-phase fine desulfurizer is simple in operation and is beneficial to actual production.

Description

Technical Field

[0001] This invention belongs to the field of gas purification and desulfurization technology, and particularly relates to a room-temperature gas-phase fine desulfurizing agent and its preparation method. Background Technology

[0002] Natural gas, as a high-quality, efficient, low-carbon, and clean energy source, is playing an increasingly prominent role in chemical production and the energy structure, with global natural gas consumption steadily increasing. Natural gas is primarily composed of methane, but also contains small amounts of impurities such as hydrogen sulfide, mercaptans, carbonyl sulfide, thiophene, and other sulfur-containing compounds. Many industrial processes have strict requirements regarding the sulfur content of natural gas; for example, in natural gas-to-hydrogen production for subsequent fuel cell processes, the sulfide content in natural gas must reach the ppb level. However, existing desulfurizing agents cannot achieve desorption effects at the ppb level. Summary of the Invention

[0003] The purpose of this invention is to overcome the shortcomings of the prior art and provide a room-temperature gas-phase fine desulfurizing agent with a large specific surface area, high sulfur penetration capacity, and desulfurization effect at the ppb level, as well as its preparation method.

[0004] To achieve the above objectives, in a first aspect, the present invention provides a room-temperature gas-phase fine desulfurizing agent, wherein the specific surface area of ​​the room-temperature gas-phase fine desulfurizing agent is ≥168 m². 2 / g, breakthrough sulfur capacity ≥20.6%.

[0005] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0006] The ambient temperature gas-phase desulfurizing agent provided by this invention has a high specific surface area and a high sulfur penetration capacity. It can deeply adsorb hydrogen sulfide, mercaptans and carbonyl sulfide in gaseous materials such as natural gas and syngas at ambient temperature, reducing the sulfide in the raw gas to below 5 ppb, and achieving excellent desulfurization effect. Attached Figure Description

[0007] Figure 1 Diagram of the evaluation device used in desulfurization performance testing:

[0008] 1-Raw material bottle, 2-Pressure regulating valve, 3-Pressure reducing valve, 4-Mass flow meter, 5-Reaction tube fixed bed, 6-Chromatography;

[0009] Figure 2 The XRD pattern of the room-temperature gas-phase fine desulfurizer prepared in Example 1;

[0010] Figure 3 The image shows the SEM image of the room-temperature gas-phase fine desulfurizer prepared in Example 1. Detailed Implementation

[0011] To better illustrate the purpose, technical solution, and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments.

[0012] Unless otherwise specified, the reagents, methods and equipment used in this invention are all conventional reagents, methods and equipment in the field; and unless otherwise specified, the raw materials used in parallel experiments are from the same batch.

[0013] In a first aspect, the present invention provides a room-temperature gas-phase fine desulfurizing agent, wherein the specific surface area of ​​the room-temperature gas-phase fine desulfurizing agent is ≥168 m². 2 / g, breakthrough sulfur capacity ≥20.6%.

[0014] The ambient temperature gas-phase desulfurizing agent provided by this invention has a high specific surface area and a high sulfur penetration capacity. It can deeply adsorb hydrogen sulfide, mercaptans and carbonyl sulfide in gaseous materials such as natural gas and syngas at ambient temperature, reducing the sulfide in the raw gas to below 5 ppb, and achieving excellent desulfurization effect.

[0015] For example, the specific surface area of ​​the ambient temperature gas-phase desulfurizing agent can be ≥168m². 2 Any point value or any two points within the range of / g, for example, 168-210m. 2 / g、180-210m 2 / g, or 168m 2 / g、170m 2 / g、172m 2 / g、174m 2 / g、176m 2 / g、178m 2 / g、180m 2 / g、182m 2 / g、185m 2 / g、188m 2 / g、190m 2 / g、192m 2 / g、195m 2 / g、198m 2 / g、200m 2 / g、202m 2 / g、205m 2 / g、208m 2 / g、210m 2 / g etc.

[0016] For example, the breakthrough sulfur capacity of the ambient temperature gas phase desulfurizing agent can be any point value or any two points within a range of ≥20.6%, such as 20.6-28%, 23-28%, or 20.6%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, etc.

[0017] In some embodiments, the raw materials for preparing the gas-phase fine desulfurizing agent at room temperature include the following components in parts by weight: 70-90 parts of active component and 10-30 parts of carrier;

[0018] The active component includes manganese salt, and also includes at least one of copper salt, zinc salt, and nickel salt; the carrier includes at least one of boehmite powder, sepiolite, and montmorillonite.

[0019] The present invention has found that when the components within the above-mentioned mass range of the present invention are used to prepare the room temperature gas phase fine desulfurizer, the components have a relatively excellent synergistic effect. The prepared room temperature gas phase fine desulfurizer has a stable structure and can achieve excellent desulfurization activity, thus achieving a good desulfurization effect.

[0020] In some embodiments, the molar ratio of manganese to the total molar ratio of copper, zinc and nickel is (0.5-3.5):1.

[0021] For example, the ratio of the mole of manganese to the total mole of copper, zinc and nickel can be any point value or any two points within the range of (0.5-3.2):1, such as 0.5:1, 0.8:1, 1:1, 1.2:1, 1.5:1, 1.8:1, 2:1, 2.2:1, 2.5:1, 2.8:1, 3:1, 3.2:1, etc.

[0022] This invention has found that selecting a ratio of the molar amount of manganese to the total molar amount of copper, zinc, and nickel within the aforementioned range allows for a reasonable combination of metal elements in the ambient temperature gas-phase desulfurizing agent, thereby achieving a synergistic effect and excellent desulfurization.

[0023] In some embodiments, the carrier is boehmite powder, and the specific surface area of ​​the boehmite powder is 350-400 m². 2 / g, pore volume 0.8-1.2m 3 / g.

[0024] It should be noted that the specific surface area of ​​the pseudoboehmite powder was obtained from the BET standard data of the sample, and the instrument used was a Micron Tristar-II plus, 3030. First, the sample was pretreated by vacuum at 350℃, and then nitrogen adsorption was performed at liquid nitrogen temperature. The specific surface area and pore volume of the sample were then determined by desorption.

[0025] For example, the specific surface area of ​​the pseudo-boehmite powder can be 350-400 m². 2 Any point value or any two points within a range of / g, for example, 350m 2 / g、360m 2 / g、370m 2 / g、380m 2 / g、390m 2 / g、400m 2 / g etc.

[0026] For example, the pore volume of the pseudo-boehmite powder can be 0.8-1.2 μm. 3 Any point value or any two points within a range of / g, for example, 0.8m. 3 / g, 0.9m 3 / g, 1.0m 3 / g, 1.1m 3 / g, 1.2m 3 / g etc.

[0027] The present invention has found that further selecting boehmite powder as a carrier and limiting the specific surface area and pore volume of boehmite powder within the above-mentioned range can effectively help improve the specific surface area of ​​the prepared room temperature gas phase fine desulfurizer, while also being conducive to the uniform dispersion of metal elements, improving the desulfurization activity of the room temperature gas phase fine desulfurizer, and achieving excellent desulfurization effect.

[0028] In some embodiments, the preparation method of the ambient temperature gas-phase fine desulfurizing agent includes the following steps:

[0029] (1) Add manganese salt and at least one of copper salt, zinc salt and nickel salt to water and mix to obtain a mixed salt solution;

[0030] (2) Add the dispersant aqueous solution to the mixed salt solution to obtain mixed solution A;

[0031] (3) Add the carrier to the alkaline aqueous solution to obtain mixed solution B;

[0032] (4) Mixed solution A and sodium carbonate aqueous solution are added to mixed solution B in parallel to carry out coprecipitation reaction. After the reaction is completed, the mixture is filtered, the filter residue is collected, washed and dried to obtain filter cake.

[0033] (5) After the filter cake and carrier are mixed evenly, the additives are added and extruded into shape. Then, the mixture is dried and calcined to obtain a room temperature gas phase fine desulfurizing agent.

[0034] In some embodiments, the molar concentration of the solute in the mixed salt solution is 0.4-1 mol / L.

[0035] For example, in the mixed salt solution, the molar concentration of the solute can be any point value or any two points between 0.4-1 mol / L, such as 0.4 mol / L, 0.45 mol / L, 0.5 mol / L, 0.55 mol / L, 0.6 mol / L, 0.65 mol / L, 0.7 mol / L, 0.75 mol / L, 0.8 mol / L, 0.85 mol / L, 0.9 mol / L, 0.95 mol / L, 1 mol / L, etc.

[0036] In some embodiments, the dispersant comprises 5-10% by mass of the active component.

[0037] For example, the mass percentage of the dispersant, based on the mass of the active component, can be any point value or any two-point range value between 5% and 10%, such as 5%, 6%, 7%, 8%, 9%, 10%, etc.

[0038] In one embodiment, the mass-volume concentration of the dispersant in the dispersant solution is (60-100) g / L.

[0039] For example, the mass-volume concentration of the dispersant in the dispersant solution can be any point value or any two-point range value between (60-100) g / L, such as 60 g / L, 70 g / L, 80 g / L, 90 g / L, 100 g / L, etc.

[0040] In some embodiments, the pH value of the alkaline aqueous solution is 8-10.

[0041] For example, the pH value of the alkaline aqueous solution can be any point value or any two points between 8 and 10, such as 8, 8.5, 9, 9.5, 10, etc.

[0042] The present invention has found that selecting an alkaline aqueous solution with a pH of 8-10 can ensure that the salt solution and sodium carbonate solution are evenly dispersed in the initial stage of co-precipitation, and that the precipitate forms uniform nucleation in the initial stage, thereby improving the desulfurization effect of the prepared room temperature gas phase fine desulfurizer.

[0043] In some embodiments, the sodium carbonate aqueous solution has a sodium carbonate mass concentration of 5-10%.

[0044] For example, in an aqueous solution of sodium carbonate, the mass concentration of sodium carbonate can be any point value or any two-point range between 5% and 10%, such as 5%, 6%, 7%, 8%, 9%, 10%, etc.

[0045] In some embodiments, the coprecipitation reaction is carried out at a temperature of 30-60°C for 15-30 minutes and at a pH of 8-10.

[0046] For example, the temperature of the coprecipitation reaction can be any point value or any two points within the range of 30-60℃, such as 30℃, 35℃, 40℃, 45℃, 50℃, 55℃, 60℃, etc.; the time can be any point value or any two points within the range of 15-30min, such as 15min, 20min, 25min, 30min, etc.; the pH value can be any point value or any two points within the range of 8-10, such as 8, 8.5, 9, 9.5, 10, etc.

[0047] The present invention has found that selecting the temperature, time, and pH value within the above-mentioned range in the co-precipitation reaction can effectively increase the specific surface area of ​​the prepared room-temperature gas-phase fine desulfurizing agent and enhance its desulfurization activity.

[0048] In some embodiments, the volume ratio of mixed solution A to sodium carbonate aqueous solution is 1:(0.5-1.5).

[0049] In some embodiments, the mixed solution A and the sodium carbonate aqueous solution are added in parallel at rates of 15-20 mL / min, each independently.

[0050] In some implementations, the amount of mixed solution B is not particularly required, as long as it can be stirred as a base liquid; for example, mixed solution B can be 80-120 mL.

[0051] In some embodiments, the drying temperature is 100-120°C and the drying time is 2-4 hours.

[0052] In some embodiments, the drying temperature is 100-120°C and the drying time is 4-6 hours.

[0053] In some embodiments, the calcination temperature is 250-350°C, and the calcination time is 4-6 hours.

[0054] The present invention has found that by using the co-precipitation method described in the early stage of the present invention for reaction, and combining the calcination temperature and time range, metal oxides and metal carbonates can be effectively retained in the room temperature gas phase fine desulfurizing agent at the same time. This improves the adsorption effect of the room temperature gas phase fine desulfurizing agent on hydrogen sulfide and mercaptan sulfides in gases such as natural gas and syngas, thereby achieving excellent desulfurization effect.

[0055] In some embodiments, the alkali includes at least one of sodium carbonate and potassium carbonate.

[0056] In some embodiments, the adjuvant includes a nitric acid solution.

[0057] In some embodiments, the nitric acid solution contains 1%-4% by mass of nitric acid.

[0058] In some embodiments, the manganese salt includes at least one of manganese nitrate and its hydrate, and manganese acetate and its hydrate.

[0059] In some embodiments, the copper salt includes at least one of copper nitrate and its hydrate, and copper acetate and its hydrate.

[0060] In some embodiments, the zinc salt includes at least one of zinc nitrate and its hydrate, and zinc acetate and its hydrate.

[0061] In some embodiments, the nickel salt includes at least one of nickel nitrate and its hydrate, and nickel acetate and its hydrate.

[0062] In some embodiments, the dispersant includes at least one of polyethylene glycol and sodium polyacrylate.

[0063] In a second aspect, the present invention provides a method for preparing a room-temperature gas-phase fine desulfurizing agent, the preparation method comprising the following steps:

[0064] (1) Add manganese salt and at least one of copper salt, zinc salt and nickel salt to water and mix to obtain a mixed salt solution;

[0065] (2) Add the dispersant aqueous solution to the mixed salt solution to obtain mixed solution A;

[0066] (3) Add the carrier to the alkaline aqueous solution to obtain mixed solution B;

[0067] (4) Mixed solution A and sodium carbonate aqueous solution are added to mixed solution B in parallel to carry out coprecipitation reaction. After the reaction is completed, the mixture is filtered, the filter residue is collected, washed and dried to obtain filter cake.

[0068] (5) After the filter cake and carrier are mixed evenly, the additives are added and extruded into shape. Then, the mixture is dried and calcined to obtain a room temperature gas phase fine desulfurizing agent.

[0069] In some embodiments, the amount of manganese salt and at least one of copper salt, zinc salt and nickel salt is 70-90 parts, and the amount of carrier is 10-30 parts.

[0070] The active component includes manganese salt, and also includes at least one of copper salt, zinc salt, and nickel salt; the carrier includes at least one of boehmite powder, sepiolite, and montmorillonite.

[0071] In some embodiments, the molar ratio of manganese to the total molar ratio of copper, zinc and nickel is (0.5-3.5):1.

[0072] In some embodiments, the carrier is boehmite powder, and the specific surface area of ​​the boehmite powder is 350-400 m². 2 / g, pore volume 0.8-1.2m 3 / g.

[0073] In some embodiments, the molar concentration of the solute in the mixed salt solution is 0.4-1 mol / L.

[0074] In some embodiments, the dispersant comprises 5-10% by mass of the active component.

[0075] In some embodiments, the mass-volume concentration of the dispersant in the dispersant solution is (60-100) g / L.

[0076] In some embodiments, the pH value of the alkaline aqueous solution is 8-10.

[0077] In some embodiments, the sodium carbonate aqueous solution has a sodium carbonate mass concentration of 5-10%.

[0078] In some embodiments, the coprecipitation reaction is carried out at a temperature of 30-60°C for 15-30 minutes and at a pH of 8-10.

[0079] In some embodiments, the drying temperature is 100-120°C and the drying time is 2-4 hours.

[0080] In some embodiments, the drying temperature is 100-120°C and the drying time is 4-6 hours.

[0081] In some embodiments, the calcination temperature is 250-350°C, and the calcination time is 4-6 hours.

[0082] In some embodiments, the alkali includes at least one of sodium carbonate and potassium carbonate.

[0083] In some embodiments, the adjuvant includes a nitric acid solution.

[0084] In some embodiments, the nitric acid solution contains 1%-4% by mass of nitric acid.

[0085] In some embodiments, the manganese salt includes at least one of manganese nitrate and its hydrate, and manganese acetate and its hydrate.

[0086] In some embodiments, the copper salt includes at least one of copper nitrate and its hydrate, and copper acetate and its hydrate.

[0087] In some embodiments, the zinc salt includes at least one of zinc nitrate and its hydrate, and zinc acetate and its hydrate.

[0088] In some embodiments, the nickel salt includes at least one of nickel nitrate and its hydrate, and nickel acetate and its hydrate.

[0089] In some embodiments, the dispersant includes at least one of polyethylene glycol and sodium polyacrylate.

[0090] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0091] The ambient temperature gas-phase fine desulfurizer provided by this invention has a high specific surface area and a high sulfur penetration capacity. It can deeply adsorb hydrogen sulfide, mercaptans, and carbonyl sulfide in gaseous materials such as natural gas and syngas at ambient temperature, reducing the sulfide content in the feed gas to below 5 ppb, thus achieving excellent desulfurization effect. Furthermore, the preparation method of the ambient temperature gas-phase fine desulfurizer provided by this invention is simple to operate and beneficial to actual production.

[0092] Example 1

[0093] This invention provides a room-temperature gas-phase fine desulfurizing agent, the preparation method of which includes the following steps:

[0094] (1) Manganese nitrate tetrahydrate (25g, 0.18mol), copper nitrate trihydrate (12g, 0.083mol), and nickel nitrate hexahydrate (15g, 0.052mol) were mixed and dissolved in 350mL of deionized water to obtain a mixed salt solution;

[0095] The ratio of the molar amount of manganese to the total molar amount of copper and nickel is 1.33:1; the molar concentration of the solute in the mixed salt solution is 0.90 mol / L.

[0096] (2) Dissolve 4g of PEG-20000 polyethylene glycol in 50mL of deionized water to obtain a dispersant aqueous solution. Add the dispersant aqueous solution to the mixed salt solution and keep it at 40℃ to obtain mixed solution A.

[0097] The dispersant has a mass percentage of 7.70% based on the mass of the active component, and the mass volume concentration of the dispersant in the aqueous solution is 80 g / L.

[0098] (3) Add sodium carbonate to 100 mL of deionized water and adjust the pH to 9.0, then keep it at 40 °C to obtain an alkaline aqueous solution; subsequently add 2 g of pseudoboehmite powder (specific surface area of ​​380 m²). 2 / g, pore volume 1m 3 Mix the mixtures (g) thoroughly to obtain a mixed solution B, which is then added to the reaction vessel as the base solution.

[0099] (4) Add sodium carbonate to 400 mL of water to prepare a sodium carbonate aqueous solution with a sodium carbonate mass concentration of 6.5%;

[0100] (5) Mixed solution A and sodium carbonate aqueous solution were added to a constant temperature reactor at a certain rate (20 mL / min) and co-precipitated at 40 °C for 20 min. The pH of the reaction system was controlled to be 9.0-9.5. After the co-precipitation reaction was completed, the mixture was filtered, the filter residue was collected and washed, and then dried at 100 °C for 2 h to obtain filter cake.

[0101] (6) Mix 18g of filter cake and 3g of pseudo-boehmite powder evenly, add 2% nitric acid solution for wet mixing and extrusion molding, then dry at 120℃ for 5h, and calcine at 350℃ for 5h to obtain room temperature gas phase fine desulfurizing agent.

[0102] Example 2

[0103] This invention provides a room-temperature gas-phase fine desulfurizing agent, the preparation method of which includes the following steps:

[0104] (1) Manganese nitrate tetrahydrate (42g, 0.30mol), copper nitrate trihydrate (8g, 0.055mol), and zinc nitrate hexahydrate (12g, 0.040mol) were mixed and dissolved in 450mL of deionized water to obtain a mixed salt solution;

[0105] The ratio of the molar amount of manganese to the total molar amount of copper and zinc is 3.16:1; the molar concentration of the solute in the mixed salt solution is 0.88 mol / L.

[0106] (2) Dissolve 5g of PEG-20000 polyethylene glycol in 50mL of deionized water to obtain a dispersant aqueous solution. Add the dispersant aqueous solution to the mixed salt solution and keep it at 40℃ to obtain mixed solution A.

[0107] The mass percentage of the dispersant, based on the mass of the active component, is 8.06%, and the mass-volume concentration of the dispersant in the aqueous solution is 100 g / L.

[0108] (3) Add sodium carbonate to 100 mL of deionized water and adjust the pH to 8.5, then keep it at 40 °C to obtain an alkaline aqueous solution; subsequently add 2 g of pseudoboehmite powder (specific surface area of ​​380 m²). 2 / g, pore volume 1m 3 Mix the mixtures (g) thoroughly to obtain a mixed solution B, which is then added to the reaction vessel as the base solution.

[0109] (4) Add sodium carbonate to 500 mL of water to prepare a sodium carbonate aqueous solution with a sodium carbonate mass concentration of 6%;

[0110] (5) Mixed solution A and sodium carbonate aqueous solution were added to a constant temperature reactor at a certain rate (16.5 mL / min) and co-precipitated at 40°C for 30 min. The pH of the reaction system was controlled to be 8.5-8.7. After the co-precipitation reaction was completed, the mixture was filtered, the filter residue was collected and washed, and then dried at 100°C for 2 h to obtain filter cake.

[0111] (6) Mix 18g of filter cake and 3g of pseudo-boehmite powder evenly, add 2% nitric acid solution for wet mixing and extrusion molding, then dry at 120℃ for 5h, and calcine at 350℃ for 5h to obtain room temperature gas phase fine desulfurizing agent.

[0112] Example 3

[0113] This invention provides a room-temperature gas-phase fine desulfurizing agent, the preparation method of which includes the following steps:

[0114] (1) Manganese nitrate tetrahydrate (27g, 0.19mol), copper acetate monohydrate (15g, 0.075mol), and zinc acetate dihydrate (12g, 0.055mol) were mixed and dissolved in 500mL of deionized water to obtain a mixed salt solution.

[0115] The ratio of the molar amount of manganese to the total molar amount of copper and zinc is 1.46:1; the molar concentration of the solute in the mixed salt solution is 0.64 mol / L.

[0116] (2) Dissolve 5g of PEG-20000 polyethylene glycol in 50mL of deionized water to obtain a dispersant aqueous solution. Add the dispersant aqueous solution to the mixed salt solution and keep it at 40℃ to obtain mixed solution A.

[0117] The mass percentage of the dispersant, based on the mass of the active component, is 9.26%, and the mass-volume concentration of the dispersant in the aqueous solution is 100 g / L.

[0118] (3) Add sodium carbonate to 100 mL of deionized water and adjust the pH to 9.5, then keep it at 40 °C to obtain an alkaline aqueous solution; subsequently add 2 g of pseudoboehmite powder (specific surface area of ​​380 m²). 2 / g, pore volume 1m 3 Mix the mixtures (g) thoroughly to obtain a mixed solution B, which is then added to the reaction vessel as the base solution.

[0119] (4) Add sodium carbonate to 550 mL of water to prepare a sodium carbonate aqueous solution with a sodium carbonate mass concentration of 6%;

[0120] (5) Mixed solution A and sodium carbonate aqueous solution were added to a constant temperature reactor at a certain rate (18 mL / min) and co-precipitated at 40°C for 30 min. The pH of the reaction system was controlled to be 9.0-9.5. After the co-precipitation reaction was completed, the mixture was filtered, the filter residue was collected and washed, and then dried at 100°C for 2 h to obtain filter cake.

[0121] (6) Mix 18g of filter cake and 5g of pseudo-boehmite powder evenly, add 2% nitric acid solution for wet mixing and extrusion molding, then dry at 120℃ for 5h, and calcine at 350℃ for 5h to obtain room temperature gas phase fine desulfurizing agent.

[0122] Example 4

[0123] This invention provides a room-temperature gas-phase fine desulfurizing agent, the preparation method of which includes the following steps:

[0124] (1) Manganese acetate tetrahydrate (25g, 0.10mol) and zinc acetate dihydrate (30g, 0.14mol) were mixed and dissolved in 500mL of deionized water to obtain a mixed salt solution;

[0125] The molar ratio of manganese to zinc is 0.71:1; the molar concentration of the solute in the mixed salt solution is 0.48 mol / L.

[0126] (2) Dissolve 3g of PEG-20000 polyethylene glycol in 50mL of deionized water to obtain a dispersant aqueous solution. Add the dispersant aqueous solution to the mixed salt solution and keep it at 40℃ to obtain mixed solution A.

[0127] The mass percentage of the dispersant, based on the mass of the active component, is 5.45%, and the mass-volume concentration of the dispersant in the aqueous solution is 60 g / L.

[0128] (3) Add sodium carbonate to 100 mL of deionized water and adjust the pH to 10, then keep it at 40 °C to obtain an alkaline aqueous solution; subsequently add 2 g of pseudoboehmite powder (specific surface area of ​​380 m²) 2 / g, pore volume 1m 3 Mix the mixtures (g) thoroughly to obtain a mixed solution B, which is then added to the reaction vessel as the base solution.

[0129] (4) Add sodium carbonate to 550 mL of water to prepare a sodium carbonate aqueous solution with a sodium carbonate mass concentration of 10%;

[0130] (5) Mixed solution A and sodium carbonate aqueous solution were added to a constant temperature reactor at a certain rate (18 mL / min) and co-precipitated at 40°C for 30 min. The pH of the reaction system was controlled to be 9.5-10. After the co-precipitation reaction was completed, the mixture was filtered, the filter residue was collected and washed, and then dried at 100°C for 2 h to obtain filter cake.

[0131] (6) Mix 18g of filter cake and 5g of pseudo-boehmite powder evenly, add 2% nitric acid solution for wet mixing and extrusion molding, then dry at 120℃ for 5h, and calcine at 350℃ for 5h to obtain room temperature gas phase fine desulfurizing agent.

[0132] Example 5

[0133] This invention provides a room temperature gas phase fine desulfurizing agent. The only difference between the preparation method of the room temperature gas phase fine desulfurizing agent and that of Example 1 is that the calcination temperature in step (6) is 250°C.

[0134] Example 6

[0135] This invention provides a room temperature gas phase fine desulfurizing agent. The preparation method of the room temperature gas phase fine desulfurizing agent differs from that of Example 1 in that it is kept at 60°C in step (2), kept at 60°C in step (3), and co-precipitated at 60°C for 15 min in step (5).

[0136] Example 7

[0137] This invention provides a room temperature gas phase fine desulfurizing agent. The preparation method of the room temperature gas phase fine desulfurizing agent differs from that of Example 1 in that it is kept at 30°C in step (2), kept at 30°C in step (3), and co-precipitated at 30°C for 30 min in step (5).

[0138] Example 8

[0139] This invention provides a room-temperature gas-phase fine desulfurizing agent. The difference between the preparation method of the room-temperature gas-phase fine desulfurizing agent and that of Example 1 is the use of montmorillonite (with a specific surface area of ​​40 m²). 2 / g, pore volume 0.25m 3 / g) to replace pseudoboehmite powder.

[0140] Example 9

[0141] This invention provides a room-temperature gas-phase fine desulfurizing agent. The difference between the preparation method of the room-temperature gas-phase fine desulfurizing agent and that of Example 1 is that the specific surface area of ​​the pseudoboehmite powder is 400 m². 2 / g, pore volume 0.8m 3 / g.

[0142] Comparative Example 1

[0143] The present invention provides a room temperature gas phase fine desulfurizing agent in a comparative example. The difference between the preparation method of the room temperature gas phase fine desulfurizing agent and that in Example 1 is that manganese nitrate tetrahydrate is not added, but copper nitrate trihydrate is used instead in equimolar amounts.

[0144] Comparative Example 2

[0145] The present invention provides a room temperature gas phase fine desulfurizing agent in a comparative example. The difference between the preparation method of the room temperature gas phase fine desulfurizing agent and that in Example 1 is that copper nitrate trihydrate and nickel nitrate hexahydrate are not added, but are replaced with an equal amount of manganese nitrate tetrahydrate.

[0146] Comparative Example 3

[0147] This invention provides a room-temperature gas-phase fine desulfurizing agent in a comparative example. The preparation method of the room-temperature gas-phase fine desulfurizing agent includes the following steps:

[0148] (1) Manganese nitrate tetrahydrate (25g, 0.18mol), copper nitrate trihydrate (12g, 0.083mol), nickel nitrate hexahydrate (15g, 0.052mol), and 5.5g of pseudoboehmite powder (specific surface area 380m²) were added. 2 / g, pore volume 1m 3 Add / g) to a grinder and grind for 15 minutes until well mixed;

[0149] The ratio of the molar amount of manganese to the total molar amount of copper and nickel is 1.33:1.

[0150] (2) Add 2% nitric acid solution and wet mix for 30 minutes, then extrude and mold.

[0151] (3) The molded sample was dried at 105℃ for 3 hours and then calcined at 350℃ for 3 hours to obtain a room temperature gas phase desulfurizing agent.

[0152] Example of effect

[0153] Examples of the present invention test the specific surface area and desulfurization performance of the room-temperature gas-phase fine desulfurizing agents prepared in Examples 1-9 and Comparative Examples 1-3:

[0154] 1. Specific surface area: The specific surface area of ​​the desulfurizing agent sample was obtained from the BET standard data of the sample, and the instrument used was a Micron Tristar-II plus, 3030. First, the sample was pretreated by vacuuming at 160℃, and then nitrogen adsorption was performed at liquid nitrogen temperature. The specific surface area of ​​the sample was then determined by desorption.

[0155] 2. Desulfurization performance: The prepared room-temperature gas-phase fine desulfurizing agent is loaded into... Figure 1The fixed-bed reactor 5 of the evaluation device shown is tested under the following conditions: the raw gas is metered by the raw gas cylinder 1 through the regulating valve 2, the pressure stabilizing valve 3 and the mass flow meter 4 and then enters the fixed-bed 5 for adsorption desulfurization reaction under normal temperature and pressure conditions. The outlet gas is detected online by the Agilent 8890 chromatograph and the rest is vented.

[0156] The filling conditions for the ambient temperature gas-phase fine desulfurization agent are as follows: reactor inner diameter: 8 mm, particle size: 40-60 mesh, height-to-diameter ratio: 4:1; space velocity: 3000 h⁻¹ -1 The composition of the raw gas is shown in Table 1.

[0157] The evaluation conditions were normal temperature and pressure.

[0158] Table 1

[0159] Components hydrogen sulfide Ethyl mercaptan <![CDATA[CO2]]> <![CDATA[CH4]]> V％ 320ppm 320ppm 2％ Balanced gas

[0160] The results are shown in Table 2;

[0161] Table 2

[0162] <![CDATA[Specific surface area / m 2 / g]]> Export hydrogen sulfide Export of ethanethiol Sulfur penetration capacity / % Example 1 187 <2ppb <2ppb 23.2 Example 2 185 <2ppb <2ppb 25.6 Example 3 198 <2ppb <2ppb 25.8 Example 4 201 <2ppb <2ppb 27.6 Example 5 189 <2ppb <2ppb 23.1 Example 6 180 <2ppb <2ppb 21.6 Example 7 190 <2ppb <2ppb 23.5 Example 8 168 <2ppb <2ppb 20.6 Example 9 198 <2ppb <2ppb 25.8 Comparative Example 1 189 <2ppb <2ppb 17.8 Comparative Example 2 180 <2ppb <2ppb 16.5 Comparative Example 3 110 <10ppb <10ppb 7.2

[0163] As can be seen from Table 2, when the technical solution provided by this invention is adopted, the obtained room-temperature gas-phase fine desulfurizer has a large surface area and a high sulfur penetration capacity, while also exhibiting excellent desulfurization performance; specifically, the specific surface area of ​​the obtained room-temperature gas-phase fine desulfurizer is ≥168 m². 2 / g, with a sulfur penetration capacity ≥20.6%, and both outlet hydrogen sulfide and outlet ethanethiol <2ppb; that is, it has excellent desulfurization precision;

[0164] In addition, the XRD pattern of the room-temperature gas-phase fine desulfurizer prepared in Example 1 is as follows: Figure 2 As shown, the SEM image is as follows: Figure 3 As shown, from Figure 2 As can be seen from the spectrum, the prepared room-temperature gas-phase fine desulfurizing agent exhibits amorphous diffuse peaks; from Figure 3 It can be seen that the prepared room temperature gas-phase fine desulfurizing agent has good particle size distribution uniformity;

[0165] As can be seen from Example 1 and Comparative Examples 1-2, when the active component does not include manganese or only contains manganese, the sulfur capacity of the obtained product decreases. As can be seen from Example 1 and Comparative Example 3, when the co-precipitation method of the present invention is not used, the desulfurization accuracy and sulfur capacity of the obtained product are significantly reduced.

[0166] Finally, it should be noted that the above embodiments are used to illustrate the technical solutions of the present invention and not to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A room-temperature gas-phase fine desulfurizing agent, characterized in that, The specific surface area of ​​the ambient temperature gas-phase desulfurizing agent is ≥168m². 2 / g, breakthrough sulfur capacity ≥20.6%.

2. The ambient temperature gas-phase fine desulfurizing agent according to claim 1, characterized in that, The raw materials for preparing the ambient temperature gas phase fine desulfurizing agent include the following components in parts by weight: 70-90 parts of active component and 10-30 parts of carrier. The active component includes manganese salt, and also includes at least one of copper salt, zinc salt, and nickel salt; the carrier includes at least one of boehmite powder, sepiolite, and montmorillonite.

3. The ambient temperature gas-phase fine desulfurizing agent according to claim 2, characterized in that, The ratio of the molar amount of manganese to the total molar amount of copper, zinc and nickel is (0.5-3.5):

1.

4. The ambient temperature gas-phase fine desulfurizing agent according to claim 2, characterized in that, The carrier is boehmite powder, and the specific surface area of ​​the boehmite powder is 350-400 m². 2 / g, pore volume 0.8-1.2m 3 / g.

5. The ambient temperature gas-phase fine desulfurizing agent according to claim 2, characterized in that, The preparation method of the ambient temperature gas-phase fine desulfurizing agent includes the following steps: (1) Add manganese salt and at least one of copper salt, zinc salt and nickel salt to water and mix to obtain a mixed salt solution; (2) Add the dispersant aqueous solution to the mixed salt solution to obtain mixed solution A; (3) Add the carrier to the alkaline aqueous solution to obtain mixed solution B; (4) Mixed solution A and sodium carbonate aqueous solution are added to mixed solution B in parallel to carry out coprecipitation reaction. After the reaction is completed, the mixture is filtered, the filter residue is collected, washed and dried to obtain filter cake. (5) After the filter cake and carrier are mixed evenly, the additives are added and extruded into shape. Then, the mixture is dried and calcined to obtain a room temperature gas phase fine desulfurizing agent.

6. The ambient temperature gas-phase fine desulfurizing agent according to claim 5, characterized in that, In the mixed salt solution, the molar concentration of the solute is 0.4-1 mol / L; And / or, based on the mass of the active component, the dispersant is 5-10% by mass; And / or, in the aqueous solution of the dispersant, the mass-volume concentration of the dispersant is (60-100) g / L; And / or, the pH value of the alkaline aqueous solution is 8-10; And / or, the sodium carbonate aqueous solution has a sodium carbonate mass concentration of 5-10%.

7. The ambient temperature gas-phase fine desulfurizing agent according to claim 5, characterized in that, The coprecipitation reaction is carried out at a temperature of 30-60℃ for 15-30 minutes, with a pH value of 8-10. And / or, the drying temperature is 100-120℃, and the drying time is 2-4 hours; And / or, the drying temperature is 100-120℃, and the drying time is 4-6 hours; And / or, the calcination temperature is 250-350℃. The calcination time is 4-6 hours.

8. The ambient temperature gas-phase fine desulfurizing agent according to claim 5, characterized in that, The alkali includes at least one of sodium carbonate and potassium carbonate; And / or, the adjuvant includes a nitric acid solution.

9. The ambient temperature gas-phase fine desulfurizing agent according to claim 5, characterized in that, The manganese salt includes at least one of manganese nitrate and its hydrate, and manganese acetate and its hydrate; And / or, the copper salt includes at least one of copper nitrate and its hydrate, copper acetate and its hydrate; And / or, the zinc salt includes at least one of zinc nitrate and its hydrate, zinc acetate and its hydrate; And / or, the nickel salt includes at least one of nickel nitrate and its hydrate, nickel acetate and its hydrate; And / or, the dispersant includes at least one of polyethylene glycol and sodium polyacrylate.

10. A method for preparing a room-temperature gas-phase fine desulfurizing agent, the preparation method comprising the following steps: (1) Add manganese salt and at least one of copper salt, zinc salt and nickel salt to water and mix to obtain a mixed salt solution; (2) Add the dispersant aqueous solution to the mixed salt solution to obtain mixed solution A; (3) Add the carrier to the alkaline aqueous solution to obtain mixed solution B; (4) Mixed solution A and sodium carbonate aqueous solution are added to mixed solution B in parallel to carry out coprecipitation reaction. After the reaction is completed, the mixture is filtered, the filter residue is collected, washed and dried to obtain filter cake. (5) After the filter cake and carrier are mixed evenly, the additives are added and extruded into shape. Then, the mixture is dried and calcined to obtain a room temperature gas phase fine desulfurizing agent.

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