A renewable hydrogen sulfide removing agent, a preparation method and application thereof

Abstract

The present application relates to a kind of renewable hydrogen sulfide removing agent and its preparation method and application, the renewable hydrogen sulfide removing agent with silica alumina gel as carrier, by loading aluminium hydroxide colloidal solution to silica alumina gel carrier, continue water vapor aging makes aluminium gel and carrier secondary combination, thereby obtains the hydrogen sulfide removing agent with more concentrated pore size distribution, active adsorption site is more abundant.The removing agent is suitable for the removal of hydrogen sulfide in hydrocarbon organic medium, the use condition range is that hydrogen sulfide concentration is less than 1000ppm, removal precision is less than 0.1ppm.When saturated with hydrogen sulfide, the scavenger can be regenerated under the purge of oxygen-free atmosphere, restore removal capacity, regeneration temperature is 250~300 ℃.Compared with prior art, the hydrogen sulfide removing agent prepared in the present application has more prominent hydrogen sulfide removal capacity, adsorption capacity is increased by 3-5 times, and regeneration cycle is prolonged by 2-5 times.

Description

Technical Field

[0001] This invention belongs to the field of adsorption material preparation technology, and relates to a renewable hydrogen sulfide remover, its preparation method and application. Background Technology

[0002] Acidic gaseous impurities are among the most prevalent impurities in industrial production processes. Hydrogen sulfide is a common example of such acidic impurities. For instance, natural gas extraction often produces water vapor and hydrogen sulfide as accompanying impurities. In the petroleum refining industry, to improve catalyst activity or passivate reactors, a certain amount of organic sulfides is often injected. These sulfides decompose into hydrogen sulfide under high temperatures and enter downstream with the material. Although the amount of injected sulfur is small and the concentration of hydrogen sulfide entering downstream is low, it still poses a significant threat to the corrosion of downstream equipment and the purity of raw materials. Particularly in processes such as alkane dehydrogenation to olefins, even trace amounts of hydrogen sulfide can affect the purity of olefin products and cause poisoning of polyolefin catalysts.

[0003] Fixed-bed adsorption is widely used in chemical plants to remove trace amounts of hydrogen sulfide from gaseous or liquid materials. For example, zinc oxide desulfurizers use active metal oxides as effective desulfurization components. CN101485954B discloses a zinc oxide desulfurizer composed of 40-90% zinc oxide, 5-50% copper oxide, and 0-20% binder, which can remove hydrogen sulfide with high precision under ambient temperature conditions. However, this type of hydrogen sulfide desulfurizer cannot be regenerated. CN103769043A discloses a gas desulfurization adsorbent, its preparation method, and its application. The adsorbent uses M41S series mesoporous materials as a carrier, zinc oxide as the active component, and adds a promoter, calcium oxyacid salts, and VB / VIB group metal oxides. This adsorbent can effectively remove sulfides at high temperatures. The M41S series mesoporous materials account for 8-40% by weight, zinc oxide for 20-80%, metal promoters for 3-22%, modified oxyacid salts for 5-38%, and VB or VIB group metal oxides for 1-20%. This type of desulfurizer is expensive to manufacture and requires oxidation and regeneration under oxygen and high-temperature conditions, making the process complex.

[0004] Developing economical, efficient, and renewable hydrogen sulfide removers is currently a major research direction in this field. US Patent US03400389 discloses a method for preparing a molecular sieve adsorbent and investigates its removal efficiency for polar impurities such as H2S. CN112295544 discloses a hydrogen sulfide adsorbent with a modified metal-organic framework, its preparation method, and its applications. The preparation method involves heat-treating a mixture containing an aluminum source, terephthalic acid, activated carbon, and water, followed by calcination to obtain the metal-organic framework adsorbent. Depending on the implementation, the breakthrough time is 150–255 min. CN112619590B obtains a renewable hydrogen sulfide adsorbent that meets industrial needs by loading aluminate onto an activated alumina support. After the adsorbent becomes saturated with hydrogen sulfide, it recovers its hydrogen sulfide adsorption capacity after regeneration in an inert or reducing atmosphere. The regeneration temperature is 180–300 °C, and the breakthrough time is 109–143 min.

[0005] From the perspective of existing technologies, although the regenerative adsorption of hydrogen sulfide can be achieved by loading active components with activated alumina or forming metal complexes, there is still a problem of low adsorption capacity, which leads to frequent regeneration and increased energy consumption in industrial applications. Summary of the Invention

[0006] The purpose of this invention is to provide a regenerable hydrogen sulfide removal agent, its preparation method and application, which has a more outstanding hydrogen sulfide removal capacity, an adsorption capacity increase of 3 to 5 times, and a regeneration cycle extension of 2 to 5 times.

[0007] The objective of this invention can be achieved through the following technical solutions:

[0008] One of the technical solutions of the present invention provides a renewable hydrogen sulfide removal agent, which is obtained by modifying a silica-alumina gel carrier with an aluminum hydroxide colloidal solution. The composition of the removal agent by mass ratio is: Na2O:Al2O3:SiO2=(2~10):(20~90):(10~90).

[0009] Furthermore, the composition of the renewable hydrogen sulfide removal agent is Na2O:Al2O3:SiO2 = (3-6):(25-75):(15-75); more preferably, the composition of the removal agent is Na2O:Al2O3:SiO2 = (4.5-5.5):(30-50):(40-60).

[0010] The second technical solution of the present invention provides a method for preparing a renewable hydrogen sulfide removal agent, comprising the following steps:

[0011] (1) Weigh out sodium hydroxide and dissolve it in water. Add aluminum hydroxide and wait until it is completely dissolved. Then dilute with water to obtain an aluminum hydroxide colloidal solution.

[0012] (2) Mix aluminum hydroxide colloidal solution with silica-alumina gel carrier, steam treat, dry and then calcine to obtain the removal agent product, which is the target product.

[0013] Furthermore, in step (1), the molar ratio of sodium hydroxide, aluminum hydroxide and water is (1.1-1.5):1:(3-5).

[0014] Furthermore, in step (1), the raw material for providing aluminum hydroxide is gibbsite, boehmite, diaspore, or boehmite. Preferably, it is boehmite or boehmite, and particularly preferably, it is boehmite. The alkaline aluminum hydroxide solution obtained from different aluminum hydroxide raw materials has different solution properties. Preferably, the colloidal particle size is 10-100 nm, and particularly preferably, the particle size is 15-70 nm.

[0015] Furthermore, during the dissolution process in step (1), the temperature is maintained at 70-100℃, and the dilution ratio with water is 2-5 times.

[0016] Furthermore, in step (2), the silicon dioxide and aluminum oxide contained in the silica-alumina carrier are in a mass ratio of SiO2:Al2O3 = (10-90):(20-90), and the specific surface area is 300-600 m². 2 / g, pore volume 0.55~1.35cm³ 3 / g, with a pore size of 6-15nm accounting for more than 75%. Specifically, the preparation method of the silica-alumina gel carrier applicable to this invention is not particularly limited. Commonly used silica-alumina gels prepared by methods such as sol-gel method, pH swing method, and template agent method are all applicable. Preferably, the pore size distribution is concentrated (mainly manifested in a relatively steep normal distribution curve of pores, with the pore size mainly concentrated in a certain range), especially with a pore size of 6-15nm, and more preferably with a relatively concentrated pore size distribution of 8-12nm, and silica-alumina gel with uniform distribution of silicon and aluminum elements is particularly suitable.

[0017] Furthermore, in step (2), the mass ratio of aluminum hydroxide colloidal solution to silica-alumina gel carrier is (60-80):100, wherein the pH of aluminum hydroxide colloidal solution is 9-14 and its solid content is 3-15%wt.

[0018] Furthermore, in step (2), the steam treatment temperature is 120–150°C, and the time is 12–15 h. The purpose of steam treatment is to provide a reaction environment and motive force to promote the combination of aluminum elements and the silica-alumina gel carrier. On the one hand, it further optimizes the pore structure of the silica-alumina gel carrier, giving it a more regular pore size, and on the other hand, it provides abundant active adsorption sites.

[0019] Furthermore, in step (2), the drying temperature is 100-150℃, preferably 120-130℃, and the time is 2-3 hours.

[0020] Furthermore, in step (2), the roasting temperature is 350-550℃ and the time is 1-5h.

[0021] Furthermore, after the aforementioned steam, drying, and calcination treatments, the regenerable hydrogen sulfide remover exhibits a more concentrated pore structure, with pore sizes ranging from 8 to 12 nm accounting for more than 80%, and a specific surface area of ​​400 to 500 m². 2 / g, pore volume 0.5~0.9cm 3 / g.

[0022] The third technical solution of the present invention provides an application of a renewable hydrogen sulfide removal agent, which is used to deeply remove trace amounts of hydrogen sulfide impurities from hydrocarbon organic compounds.

[0023] Specifically, in application, the hydrogen sulfide content at the inlet is 100-1000 ppm, and the removal accuracy at the outlet is less than 0.1 ppm.

[0024] Furthermore, the renewable hydrogen sulfide removal agent proposed in this invention is not only suitable for removing hydrogen sulfide impurities from saturated alkanes, but also for removing hydrogen sulfide from unsaturated hydrocarbons.

[0025] Furthermore, the renewable hydrogen sulfide removal agent proposed in this invention is particularly suitable for the removal of trace amounts of hydrogen sulfide from product gas in propane dehydrogenation processes, with an olefin concentration molar concentration greater than 30%.

[0026] Furthermore, the regenerable hydrogen sulfide remover of the present invention can regenerate and restore its adsorption activity under certain conditions after being saturated with adsorbed hydrogen sulfide. The regeneration temperature is 250–300°C, the purging gas is an oxygen-free inert gas, including nitrogen, hydrogen, and methane hydrogen, and the regeneration time is 8–12 hours. For industrial plants that produce hydrogen as a byproduct, such as reforming units and alkane dehydrogenation units, using hydrogen as the regeneration medium is more economical and efficient. Typically, during regeneration, the flow direction of the purging medium is opposite to that of the raw material to ensure thorough regeneration. For example, if the material flows from top to bottom through the adsorbent bed, the regeneration medium flows from bottom to top through the bed. The preferred regeneration temperature is 250–280°C. The temperature rise of the bed during regeneration should not be too rapid, generally not exceeding 5°C / min.

[0027] Compared with the prior art, the present invention has at least one of the following advantages:

[0028] (1) The adsorption capacity of hydrogen sulfide is significantly improved. The adsorption capacity of the remover for hydrogen sulfide is increased by 2 to 5 times, which can greatly extend the regeneration time, reduce the switching frequency, and reduce the regeneration energy consumption.

[0029] (2) It has lower olefin self-polymerization side reaction activity, which significantly inhibits olefin polymerization initiated during adsorption;

[0030] (3) Use water vapor treatment to obtain a macroporous channel structure with more concentrated pore size, thereby improving adsorption performance and stability. Detailed Implementation

[0031] The present invention will now be described in detail with reference to specific embodiments. These embodiments are based on the technical solution of the present invention and provide detailed implementation methods and specific operating procedures. However, the scope of protection of the present invention is not limited to the following embodiments.

[0032] In the following embodiments, the commercially available aluminum hydroxide powder used was purchased from China Aluminum Corporation; and the hydrogen sulfide standard gas was customized from Shanghai Shenkai Gas Co., Ltd.

[0033] The silicone-aluminum adhesive samples were purchased from Qingdao Ocean Chemical Group and Grace China Co., Ltd., as well as prepared in-house. The in-house preparation process was based on CN104549540B.

[0034] In the following embodiments, the prepared catalyst samples were subjected to desulfurization performance evaluation tests and butadiene side reaction evaluation tests, as detailed below:

[0035] Table 1. Evaluation conditions for adsorbents

[0036]

[0037]

[0038] The specific evaluation method is as follows: First, add 40.0g of fresh adsorbent to the fixed-bed reactor, purge the system with hydrogen, and then adjust the back pressure valve to stabilize the system pressure at 1.5MPa before proceeding to the evaluation step. Switch the gas path and introduce hydrogen sulfide standard gas into the system, setting the mass flow meter parameter to 2000mL / min to begin the evaluation. Introduce the tail gas into a gas chromatograph, collecting data every 3 minutes. When the hydrogen sulfide outlet concentration exceeds 0.1ppm, adsorption is considered saturated, and the regeneration step begins. First, switch the gas path to hydrogen, purge the system for 10 minutes, and adjust the pressure to 0.5MPa. Then, begin heating at a bed temperature of 4℃ / min. When the bed temperature reaches 250℃, maintain this temperature for 3.0 hours to complete regeneration. Afterward, cool the system to room temperature, switch the gas path to hydrogen sulfide standard gas, adjust the flow rate, and begin the second adsorption cycle. Adsorption performance is calculated based on adsorption time. When the adsorption time decreases, it indicates that the adsorbent lifetime begins to decline. When the adsorption time decreases to 75% of the initial adsorption time, the bed is considered to be deactivated.

[0039] The butadiene side reaction evaluation experiment was conducted using an McBain apparatus. The test conditions were 30°C. After evacuating the system, butadiene was introduced to raise the system pressure to approximately 100 torr, and this pressure was maintained at the test temperature for 48 hours. The degree of butadiene polymerization in the sample was evaluated by the change in sample mass. A smaller increase in sample mass indicated a lower degree of polymerization.

[0040] Unless otherwise specified, all other raw materials or processing techniques are commercially available materials or conventional processing techniques in the field.

[0041] Example 1

[0042] The parameters of the silica-alumina adhesive used in this embodiment are as follows: SiO2:Al2O3 = 85.8:13.6 by mass, and a specific surface area of ​​547.2 m². 2 / g, pore volume 1.13cm 3 / g, of which 77% have a pore size in the range of 6-15nm, and were purchased from Qingdao Marine Chemical Group.

[0043] (1) Prepare an aluminum hydroxide colloidal solution. Dissolve sodium hydroxide in water according to the molar ratio of sodium hydroxide: gibbsite: water = 1.5: 1: 3.0, and then add aluminum hydroxide powder. During this process, keep the temperature of the sodium hydroxide solution at 90-100℃. After it is completely dissolved, dilute the concentrated solution with hot water by 2 times to obtain an aluminum hydroxide colloidal solution.

[0044] (2) Mix the aluminum hydroxide colloidal solution and the silica-alumina gel carrier. The mass ratio of the aluminum hydroxide colloidal solution to the silica-alumina gel particles is 60:100.

[0045] (3) Maintain the steam temperature at 120℃ and the steam pressure at 0.2~0.3MPa for 6 hours;

[0046] (4) The sample after steam treatment was dried at 100℃ and calcined at 350℃ for 2 hours to obtain the final product of the removal agent. The sample was tableted and crushed to obtain particles with a particle size of 2mm, and this sample was marked as S-1. The butadiene side reaction test showed that the sample weight gain was <0.15%wt.

[0047] Example 2

[0048] The parameters of the silica-alumina adhesive used in this embodiment are as follows: SiO2:Al2O3 = 85.8:13.6 by mass, and a specific surface area of ​​547.2 m². 2 / g, pore volume 1.13cm 3 / g, of which 77% have a pore size in the range of 6-15nm, and were purchased from Qingdao Marine Chemical Group.

[0049] (1) Prepare an aluminum hydroxide colloidal solution. Dissolve sodium hydroxide in water according to the molar ratio of sodium hydroxide: gibbsite: water = 1.1:1:4.8, and then add aluminum hydroxide powder. During this process, keep the temperature of the sodium hydroxide solution at 90-100℃. After it is completely dissolved, dilute the concentrated solution with hot water 5 times to obtain an aluminum hydroxide colloidal solution.

[0050] (2) Mix the aluminum hydroxide colloidal solution and the silica-alumina gel carrier. The mass ratio of the aluminum hydroxide colloidal solution to the silica-alumina gel particles is 60:100.

[0051] (3) Maintain the steam temperature at 150℃ and the steam pressure at 0.4~0.5MPa for 16 hours;

[0052] (4) The sample after steam treatment was dried at 100℃ and calcined at 450℃ for 2 hours to obtain the final product of the removal agent. The sample was tableted and crushed to obtain particles with a particle size of 2mm, and this sample was labeled as S-2. Butadiene side reaction test showed that the sample weight gain was <0.15%wt.

[0053] Example 3

[0054] The parameters of the silica-alumina adhesive used in this embodiment are as follows: SiO2:Al2O3 = 85.8:13.6 by mass, and a specific surface area of ​​547.2 m². 2 / g, pore volume 1.13cm 3 / g, of which 77% have a pore size in the range of 6-15nm, and were purchased from Qingdao Marine Chemical Group.

[0055] (1) Prepare an aluminum hydroxide colloidal solution. Dissolve sodium hydroxide in water according to the molar ratio of sodium hydroxide: diaspore monohydrate: water = 1.3:1:4.0, and then add aluminum hydroxide powder. During this process, keep the temperature of the sodium hydroxide solution at 90-100℃. After it is completely dissolved, dilute the concentrated solution with hot water 3.5 times to obtain the aluminum hydroxide colloidal solution.

[0056] (2) Mix the aluminum hydroxide colloidal solution and the silica-alumina gel carrier. The mass ratio of the aluminum hydroxide colloidal solution to the silica-alumina gel particles is 60:100.

[0057] (3) Maintain the steam temperature at 150℃ and the steam pressure at 0.4~0.5MPa for 16 hours;

[0058] (4) The sample after steam treatment was dried at 100℃ and calcined at 450℃ for 2 hours to obtain the final product of the removal agent. The sample was tableted and crushed to obtain particles with a particle size of 2mm, and this sample was marked as S-3. Butadiene side reaction test showed that the sample weight gain was <0.15%wt.

[0059] Example 4

[0060] The parameters of the silica-alumina adhesive used in this embodiment are as follows: SiO2:Al2O3 = 67.2:32.5 by mass, and a specific surface area of ​​481.9 m². 2 / g, pore volume is 0.78cm 3 / g, of which 83% have a pore size in the range of 6–15 nm, purchased from Grace Company.

[0061] (1) Prepare an aluminum hydroxide colloidal solution. Dissolve sodium hydroxide in water according to the molar ratio of sodium hydroxide: gibbsite: water = 1.5: 1: 3.1, and then add aluminum hydroxide powder. During this process, keep the temperature of the sodium hydroxide solution at 90-100℃. After it is completely dissolved, dilute the concentrated solution with hot water 3 times to obtain the aluminum hydroxide colloidal solution.

[0062] (2) Mix the aluminum hydroxide colloidal solution and the silica-alumina gel carrier. The mass ratio of the aluminum hydroxide colloidal solution to the silica-alumina gel particles is 75:100.

[0063] (3) Maintain the steam temperature at 130℃ and the steam pressure at 0.2~0.3MPa for 12 hours;

[0064] (4) The sample after steam treatment was dried at 100℃ and calcined at 500℃ for 2 hours to obtain the final product of the removal agent. The sample was tableted and crushed to obtain particles with a particle size of 2mm, and this sample was marked as S-4. Butadiene side reaction test showed that the sample weight gain was <0.15%wt.

[0065] Example 5

[0066] The parameters of the silica-alumina adhesive used in this embodiment are as follows: SiO2:Al2O3 = 67.2:32.5 by mass, and a specific surface area of ​​481.9 m². 2 / g, pore volume is 0.78cm 3 / g, of which 83% have a pore size in the range of 6-15nm, was prepared according to Example 4 in CN104549540B.

[0067] (1) Prepare an aluminum hydroxide colloidal solution. Dissolve sodium hydroxide in water according to the molar ratio of sodium hydroxide: boehmite: water = 1.2:1:5, and then add aluminum hydroxide powder. During this process, keep the temperature of the sodium hydroxide solution at 90-100℃. After it is completely dissolved, dilute the concentrated solution with hot water 4.5 times to obtain the aluminum hydroxide colloidal solution.

[0068] (2) Mix the aluminum hydroxide colloidal solution and the silica-alumina gel carrier. The mass ratio of the aluminum hydroxide colloidal solution to the silica-alumina gel particles is 75:100.

[0069] (3) Maintain the steam temperature at 120℃ and the steam pressure at 0.2~0.3MPa for 10 hours;

[0070] (4) The steam-treated sample was dried at 100℃ and calcined at 400℃ for 2 hours to obtain the final product of the removal agent. The sample was tableted and crushed to obtain particles with a diameter of 2mm, and this sample was labeled S-5. Butadiene side reaction test showed a sample weight gain of <0.15% wt.

[0071] Example 6

[0072] The parameters of the silica-alumina adhesive used in this embodiment are as follows: SiO2:Al2O3 = 67.2:32.5 by mass, and a specific surface area of ​​481.9 m². 2 / g, pore volume is 0.78cm 3 / g, of which 83% have a pore size in the range of 6-15nm, was prepared according to Example 4 in CN104549540B.

[0073] (1) Prepare an aluminum hydroxide colloidal solution. Dissolve sodium hydroxide in water according to the molar ratio of sodium hydroxide: diaspore monohydrate: water = 1.35: 1: 4, and then add aluminum hydroxide powder. During this process, keep the temperature of the sodium hydroxide solution at 90-100℃. After it is completely dissolved, dilute the concentrated solution with hot water 3.5 times to obtain the aluminum hydroxide colloidal solution.

[0074] (2) Mix the aluminum hydroxide colloidal solution and the silica-alumina gel carrier. The mass ratio of the aluminum hydroxide colloidal solution to the silica-alumina gel particles is 75:100.

[0075] (3) Maintain the steam temperature at 120℃ and the steam pressure at 0.2~0.3MPa for 10 hours;

[0076] (4) The sample after steam treatment was dried at 100℃ and calcined at 450℃ for 2 hours to obtain the final product of the removal agent. The sample was tableted and crushed to obtain particles with a particle size of 2mm, and this sample was marked as S-6. Butadiene side reaction test showed that the sample weight gain was <0.15%wt.

[0077] Example 7

[0078] The parameters of the silica-alumina adhesive used in this embodiment are as follows: SiO2:Al2O3 = 46.8:53.0 by mass, and a specific surface area of ​​508.2 m². 2 / g, pore volume 0.96cm 3 / g, of which 91% have a pore size in the range of 6-15nm, was prepared according to Example 3 in CN104549540B.

[0079] (1) Prepare an aluminum hydroxide colloidal solution. Dissolve sodium hydroxide in water according to the molar ratio of sodium hydroxide: gibbsite water = 1.5: 1: 3, and then add aluminum hydroxide powder. During this process, keep the temperature of the sodium hydroxide solution at 90-100℃. After it is completely dissolved, dilute the concentrated solution with hot water 4 times to obtain an aluminum hydroxide colloidal solution.

[0080] (2) Mix the aluminum hydroxide colloidal solution and the silica-alumina gel carrier. The mass ratio of the aluminum hydroxide colloidal solution to the silica-alumina gel particles is 83:100.

[0081] (3) Maintain the steam temperature at 120℃ and the steam pressure at 0.2~0.3MPa for 12 hours;

[0082] (4) The steam-treated sample was dried at 125°C and calcined at 480°C for 3 hours to obtain the final product of the removal agent. The sample was tableted and crushed to obtain particles with a particle size of 2 mm, and this sample was labeled S-7. Butadiene side reaction testing showed a sample weight gain of <0.15% wt.

[0083] Example 8

[0084] The parameters of the silica-alumina adhesive used in this embodiment are as follows: SiO2:Al2O3 = 46.8:53.0 by mass, and a specific surface area of ​​508.2 m². 2 / g, pore volume 0.96cm 3 / g, of which 91% have a pore size in the range of 6-15nm, was prepared according to Example 3 in CN104549540B.

[0085] (1) Prepare an aluminum hydroxide colloidal solution. Dissolve sodium hydroxide in water according to the molar ratio of sodium hydroxide: diaspore monohydrate: water = 1.1:1:5, and then add aluminum hydroxide powder. During this process, keep the temperature of the sodium hydroxide solution at 90-100℃. After it is completely dissolved, dilute the concentrated solution with hot water 3.5 times to obtain the aluminum hydroxide colloidal solution.

[0086] (2) Mix the aluminum hydroxide colloidal solution and the silica-alumina gel carrier. The mass ratio of the aluminum hydroxide colloidal solution to the silica-alumina gel particles is 83:100.

[0087] (3) Maintain the steam temperature at 120℃ and the steam pressure at 0.2~0.3MPa for 12 hours;

[0088] (4) The steam-treated sample was dried at 125°C and calcined at 400°C for 3 hours to obtain the final product of the removal agent. The sample was tableted and crushed to obtain particles with a particle size of 2 mm, and this sample was labeled S-8. Butadiene side reaction testing showed a sample weight gain of <0.15% wt.

[0089] Example 9

[0090] The parameters of the silica-alumina adhesive used in this embodiment are as follows: SiO2:Al2O3 = 46.8:53.0 by mass, and a specific surface area of ​​508.2 m². 2 / g, pore volume 0.96cm 3 / g, of which 91% have a pore size in the range of 6-15nm, was prepared according to Example 3 in CN104549540B.

[0091] (1) Prepare an aluminum hydroxide colloidal solution. Dissolve sodium hydroxide in water according to the molar ratio of sodium hydroxide: boehmite: water = 1.25: 1: 4, and then add aluminum hydroxide powder. During this process, keep the temperature of the sodium hydroxide solution at 90-100℃. After it is completely dissolved, dilute the concentrated solution with hot water 3.5 times to obtain the aluminum hydroxide colloidal solution.

[0092] (2) Mix the aluminum hydroxide colloidal solution and the silica-alumina gel carrier. The mass ratio of the aluminum hydroxide colloidal solution to the silica-alumina gel particles is 83:100.

[0093] (3) Maintain the steam temperature at 120℃ and the steam pressure at 0.2~0.3MPa for 12 hours;

[0094] (4) The steam-treated sample was dried at 125°C and calcined at 450°C for 3 hours to obtain the final product of the removal agent. The sample was tableted and crushed to obtain particles with a particle size of 2 mm, and this sample was labeled S-9. Butadiene side reaction test showed a sample weight gain of <0.15% wt.

[0095] Comparative Example 1

[0096] According to Example 4 of CN 112619590 B, spherical particles with a diameter of 2 mm were obtained by mixing activated alumina powder and sodium aluminate solid and molding, denoted as D-1. Butadiene side reaction test showed a sample weight gain of 2.25 wt%.

[0097] Comparative Example 2

[0098] Using existing aluminosilicate granules as a sample, with a particle size of 2.0 mm, the parameters of the aluminosilicate granules were: SiO2:Al2O3 = 46.8:53.0 by mass ratio, and a specific surface area of ​​508.2 m². 2 / g, pore volume 0.96cm3 / g, of which 91% have a pore size in the range of 6–15 nm, prepared according to Example 3 in CN104549540B, denoted as D-2. Butadiene side reaction test showed a sample weight gain of 1.02 wt%.

[0099] Comparative Example 3

[0100] The sample was prepared according to Example 9, except that the third step of steam treatment was omitted, and the sample was directly dried and calcined; this was designated D-3. Butadiene side reaction testing showed a sample weight gain of 2.22 wt%.

[0101] Comparative Example 4

[0102] The sample was prepared according to Example 9, except that steps one and two were omitted. Only the silica-alumina gel sample was steam-treated and then dried and calcined. The steam treatment conditions were the same as in Example 9, denoted as D-4. Butadiene side reaction testing showed a sample weight gain of 0.27 wt%.

[0103] Comparative Example 5

[0104] A sodium aluminate solution was prepared and loaded onto the silica-alumina colloid particle sample (with parameters consistent with Comparative Example 2). After loading, the sodium oxide content was 9.45% wt. The sample was then dried at 120℃ and calcined at 400℃ to obtain the control sample, designated D-5. Butadiene side reaction testing showed a sample weight gain of 2.47 wt%.

[0105] Comparative Example 6

[0106] Comparative Example 6 is similar to Comparative Example 5, except that the sample was steam-treated according to step three of the examples. The steam temperature was 120°C, and the steam pressure was maintained at 0.2–0.3 MPa for 12 hours to obtain the sample, which was denoted as D-6. The butadiene side reaction test showed a sample weight gain of 3.14 wt%.

[0107] The performance indicators of the samples from the above embodiments and comparative examples are shown in Table 2 below.

[0108] Table 2 Comparison of Sample Performance

[0109]

[0110]

[0111] *XRF Test Results

[0112] The above description of the embodiments is provided to enable those skilled in the art to understand and use the invention. It will be apparent to those skilled in the art that various modifications can be made to these embodiments, and the general principles described herein can be applied to other embodiments without inventive effort. Therefore, the present invention is not limited to the above embodiments, and any improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the invention should be within the protection scope of the present invention.

Claims

1. A renewable hydrogen sulfide removal agent, characterized in that, It is obtained by modifying the silica-alumina gel carrier with aluminum hydroxide colloidal solution. The composition of the remover by mass ratio is: Na2O : Al2O3 : SiO2 = (2~10) : (20~90) : (10~90); This renewable hydrogen sulfide removal agent is prepared through the following steps: (1) Weigh out sodium hydroxide and dissolve it in water. Add aluminum hydroxide and wait until it is completely dissolved. Then dilute with water to obtain an aluminum hydroxide colloidal solution. (2) The aluminum hydroxide colloidal solution is mixed with the silica-alumina gel carrier, steam-treated, dried and then calcined to obtain the removal agent product, which is the target product; In step (2), the silica and alumina contained in the silica-alumina carrier have a mass ratio of SiO2 : Al2O3 = (10~90 : (20~90), and a specific surface area of ​​300~600 m². 2 / g, pore volume 0.55~1.35 cm³ 3 / g, with pore sizes ranging from 6 to 15 nm accounting for more than 75%; In step (2), the mass ratio of aluminum hydroxide colloidal solution to aluminosilicate carrier is (60~80):100, wherein the pH of the aluminum hydroxide colloidal solution is 9~14, and its solid content is 3~15wt%. In step (2), the temperature of steam treatment is 120~150℃ and the time is 12~15h.

2. The method for preparing a renewable hydrogen sulfide removal agent as described in claim 1, characterized in that, Includes the following steps: (1) Weigh out sodium hydroxide and dissolve it in water. Add aluminum hydroxide and wait until it is completely dissolved. Then dilute with water to obtain an aluminum hydroxide colloidal solution. (2) The aluminum hydroxide colloidal solution is mixed with the silica-alumina gel carrier, steam-treated, dried and then calcined to obtain the removal agent product, which is the target product; In step (2), the silica and alumina contained in the silica-alumina carrier have a mass ratio of SiO2 : Al2O3 = (10~90 : (20~90), and a specific surface area of ​​300~600 m². 2 / g, pore volume 0.55~1.35 cm³ 3 / g, with pore sizes ranging from 6 to 15 nm accounting for more than 75%; In step (2), the mass ratio of aluminum hydroxide colloidal solution to silica-alumina gel carrier is (60 ~ 80): 100, wherein the pH of aluminum hydroxide colloidal solution is 9 ~ 14 and its solid content is 3 ~ 15% wt. In step (2), the temperature of steam treatment is 120~150℃ and the time is 12~15h.

3. The method for preparing a renewable hydrogen sulfide removal agent according to claim 2, characterized in that, In step (1), the molar ratio of sodium hydroxide, aluminum hydroxide and water is (1.1~1.5):1:(3~5).

4. The method for preparing a renewable hydrogen sulfide removal agent according to claim 2, characterized in that, In step (1), the raw materials for providing aluminum hydroxide are gibbsite, boehmite, diaspore or boehmite.

5. The method for preparing a renewable hydrogen sulfide removal agent according to claim 2, characterized in that, During the dissolution process in step (1), the temperature is maintained at 70 ~ 100℃, and the dilution ratio with water is 2-5 times.

6. The method for preparing a renewable hydrogen sulfide removal agent according to claim 2, characterized in that, In step (2), the drying temperature is 100~150℃ and the time is 2~3h; The roasting temperature is 350~550℃, and the time is 1~5h.

7. The application of the renewable hydrogen sulfide removal agent as described in claim 1, characterized in that, It is used to remove trace amounts of hydrogen sulfide impurities from hydrocarbon organic compounds.

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