技术领域Technical Field
本发明涉及一种催化剂及其制备方法，具体涉及一种灵活焦化气羰基硫水解催化剂及其制备方法。The invention relates to a catalyst and a preparation method thereof, and in particular to a flexible coking gas carbonyl sulfide hydrolysis catalyst and a preparation method thereof.
背景技术Background Art
羰基硫是焦化气等工业气体中的一种有害成分，其脱除对于环境保护和后续工艺至关重要。在众多脱除方法中，水解法因其高效、环保的特点而备受关注。水解法脱除羰基硫的过程中，催化剂的选择和使用是关键。催化剂的载体不仅需要能够有效地支撑活性组分，还需要提供良好的传质性能，以确保催化反应的顺利进行。Carbonyl sulfide is a harmful component in industrial gases such as coking gas, and its removal is crucial for environmental protection and subsequent processes. Among the many removal methods, the hydrolysis method has attracted much attention due to its high efficiency and environmental protection. In the process of removing carbonyl sulfide by hydrolysis, the selection and use of catalysts are key. The catalyst carrier not only needs to be able to effectively support the active components, but also needs to provide good mass transfer performance to ensure the smooth progress of the catalytic reaction.
在羰基硫水解催化剂的载体选择中，活性炭因其良好的吸附性能和稳定性而常被用作传统载体。然而，随着对催化剂性能要求的不断提高，活性炭的局限性逐渐显现。为此，碳分子筛作为一种新型的多孔材料开始受到关注，并尝试作为羰基硫水解催化剂的载体。In the selection of carriers for carbonyl sulfide hydrolysis catalysts, activated carbon is often used as a traditional carrier due to its good adsorption performance and stability. However, with the continuous improvement of catalyst performance requirements, the limitations of activated carbon are gradually emerging. For this reason, carbon molecular sieves as a new type of porous material have begun to attract attention and have been tried as carriers for carbonyl sulfide hydrolysis catalysts.
但是申请人在采用微孔碳分子筛作为羰基硫水解催化剂载体并负载过渡金属氧化物作为活性成分时发现，上述催化剂的高反应活性仅能维持较短的时间（1-2h）。为此，申请人经过研究发现，上述技术方案存在以下两个问题：However, when the applicant used microporous carbon molecular sieve as a carbonyl sulfide hydrolysis catalyst carrier and loaded transition metal oxide as an active ingredient, it was found that the high reaction activity of the above catalyst can only be maintained for a short time (1-2 hours). Therefore, the applicant found through research that the above technical solution has the following two problems:
首先，微孔碳分子筛的孔道较小，反应过程中生成的硫容易堵塞孔道，导致催化剂的反应活性迅速下降。其次，负载在碳分子筛上的活性组分（如金属氧化物）在高温、高压或长时间反应条件下容易发生脱落，这进一步影响了催化剂的稳定性和性能。上述两个因素导致了微孔碳分子筛作为羰基硫水解催化剂的局限性。因此，如何克服上述问题是一个亟待解决的技术问题。First, the microporous carbon molecular sieve has small pores, and the sulfur generated during the reaction easily blocks the pores, causing the reaction activity of the catalyst to drop rapidly. Secondly, the active components (such as metal oxides) loaded on the carbon molecular sieve are prone to fall off under high temperature, high pressure or long reaction conditions, which further affects the stability and performance of the catalyst. The above two factors lead to the limitations of microporous carbon molecular sieves as carbonyl sulfide hydrolysis catalysts. Therefore, how to overcome the above problems is a technical problem that needs to be solved urgently.
发明内容Summary of the invention
针对上述问题，本发明制备了氧化铝掺杂的介孔碳分子筛作为催化剂载体，并采用溶胶凝胶法负载金属氧化物作为活性成分，从而制备出了具有高稳定性的羰基硫水解催化剂。In view of the above problems, the present invention prepares an alumina-doped mesoporous carbon molecular sieve as a catalyst carrier, and uses a sol-gel method to load metal oxides as active ingredients, thereby preparing a carbonyl sulfide hydrolysis catalyst with high stability.
具体的，本发明提供了一种灵活焦化气羰基硫水解催化剂的制备方法，包括以下步骤：Specifically, the present invention provides a method for preparing a flexible coking gas carbonyl sulfide hydrolysis catalyst, comprising the following steps:
(a) 将碳前驱体、氧化铝前驱体以及模板剂混合，形成均匀的混合溶液，所述模板剂为介孔硅模板；(a) mixing a carbon precursor, an aluminum oxide precursor and a template to form a uniform mixed solution, wherein the template is a mesoporous silicon template;
(b) 对混合溶液进行干燥与固化处理；(b) drying and solidifying the mixed solution;
(c) 对固化后的样品进行碳化处理，形成碳分子筛；(c) performing carbonization treatment on the solidified sample to form a carbon molecular sieve;
(d) 对碳化后的样品进行活化处理，去除模板剂，形成介孔结构；(d) Activating the carbonized sample to remove the template and form a mesoporous structure;
(e) 采用溶胶凝胶法将金属氧化物负载在介孔碳分子筛上，所述金属氧化物为过渡金属氧化物；(e) loading a metal oxide on the mesoporous carbon molecular sieve by a sol-gel method, wherein the metal oxide is a transition metal oxide;
(f) 对负载后的样品进行干燥和碳化处理，得到催化剂。(f) The loaded sample is dried and carbonized to obtain the catalyst.
优选地，碳前驱体选自酚醛树脂或蔗糖，氧化铝前驱体选自氧化铝溶胶或纳米颗粒，氧化铝溶胶和纳米颗粒的粒径范围为5-30nm。Preferably, the carbon precursor is selected from phenolic resin or sucrose, the alumina precursor is selected from alumina sol or nanoparticles, and the particle size of the alumina sol and the nanoparticles ranges from 5 to 30 nm.
优选地，步骤(a)中的混合溶液中，碳前驱体与氧化铝前驱体的质量比为5:1至20:1，模板剂的质量占混合溶液总质量的1%至10%。Preferably, in the mixed solution in step (a), the mass ratio of the carbon precursor to the aluminum oxide precursor is 5:1 to 20:1, and the mass of the template accounts for 1% to 10% of the total mass of the mixed solution.
优选地，步骤(b)中的干燥与固化处理包括在室温下干燥12至48小时，然后在50至150°C下进一步干燥2至8小时。Preferably, the drying and curing treatment in step (b) comprises drying at room temperature for 12 to 48 hours, and then further drying at 50 to 150° C. for 2 to 8 hours.
优选地，步骤(c)中的碳化处理包括在氮气保护下，以2至10°C/min的升温速率升至400至600°C，保温1至4小时，再以1至5°C/min的升温速率升至600至900°C，保温2至6小时。Preferably, the carbonization treatment in step (c) comprises heating the temperature to 400 to 600°C at a heating rate of 2 to 10°C/min under nitrogen protection, keeping the temperature for 1 to 4 hours, and then heating the temperature to 600 to 900°C at a heating rate of 1 to 5°C/min, and keeping the temperature for 2 to 6 hours.
优选地，步骤(d)中的活化处理包括使用氢氟酸（HF）溶液或氢氧化钠（NaOH）溶液浸泡2至12小时，然后用去离子水洗涤至洗涤液呈中性。Preferably, the activation treatment in step (d) comprises soaking in a hydrofluoric acid (HF) solution or a sodium hydroxide (NaOH) solution for 2 to 12 hours, and then washing with deionized water until the washing solution is neutral.
优选地，步骤(e)中的溶胶凝胶法包括将碳化后的样品浸入含有金属盐和溶胶凝胶化试剂的溶液中，浸泡时间为6至24小时，所述的金属盐为Fe3+、Co2+、Ni2+、Cu2+、 Zn2+的硝酸盐，所述溶胶凝胶化试剂为柠檬酸或乙二醇。Preferably, the sol-gel method in step (e) includes immersing the carbonized sample in a solution containing a metal salt and a sol-gelling agent for 6 to 24 hours, wherein the metal salt is a nitrate of Fe3+, Co2+, Ni2+, Cu2+, or Zn2+, and the sol-gelling agent is citric acid or ethylene glycol.
优选地，金属盐溶液的浓度为0.01至0.5mol/L，溶胶凝胶化试剂的质量占溶液总质量的5%至30%。Preferably, the concentration of the metal salt solution is 0.01 to 0.5 mol/L, and the mass of the sol-gelling agent accounts for 5% to 30% of the total mass of the solution.
优选地，步骤(f)中的干燥和碳化处理包括在室温下干燥6至24小时，然后在氮气保护下以2至10°C/min的升温速率升至400至700°C，保温1至5小时。Preferably, the drying and carbonization treatment in step (f) comprises drying at room temperature for 6 to 24 hours, then heating to 400 to 700° C. at a heating rate of 2 to 10° C./min under nitrogen protection, and keeping the temperature for 1 to 5 hours.
本发明还提供了一种灵活焦化气羰基硫水解催化剂，所述催化剂包括载体和负载于载体上的活性成分，所述活性成分为过渡金属氧化物，所述载体为氧化铝掺杂的介孔碳分子筛。The present invention also provides a flexible coking gas carbonyl sulfide hydrolysis catalyst, which includes a carrier and an active component loaded on the carrier, wherein the active component is a transition metal oxide, and the carrier is an alumina-doped mesoporous carbon molecular sieve.
相对于现有技术，本发明具有以下优势：Compared with the prior art, the present invention has the following advantages:
首先，通过设计氧化铝掺杂的介孔碳分子筛，有效解决了现有技术中微孔碳分子筛孔道易堵塞的问题。氧化铝的掺杂不仅提升了碳分子筛与活性组分的结合力，还增强了催化剂的强度，使得催化剂在高温、高压或长时间反应条件下更加稳定。First, by designing alumina-doped mesoporous carbon molecular sieves, the problem of easy clogging of microporous carbon molecular sieve channels in the prior art was effectively solved. The doping of alumina not only improves the binding force between the carbon molecular sieve and the active components, but also enhances the strength of the catalyst, making the catalyst more stable under high temperature, high pressure or long-term reaction conditions.
其次，氧化铝的加入促进了介孔结构的形成，相比微孔结构，介孔结构更不容易堵塞，从而延长了催化剂的反应活性时间，提高了催化剂的使用寿命。Secondly, the addition of alumina promotes the formation of mesoporous structure, which is less prone to clogging than microporous structure, thereby extending the reaction activity time of the catalyst and increasing the service life of the catalyst.
另外，采用溶胶凝胶法负载金属氧化物的活性成分，使得金属氧化物与碳分子筛之间可能发生化学键合或物理吸附，这种相互作用进一步增强了负载强度，提高了催化剂的稳定性和性能，使得催化剂能够在更恶劣的反应条件下保持高效的催化活性。In addition, the sol-gel method is used to load the active components of metal oxides, so that chemical bonding or physical adsorption may occur between the metal oxides and the carbon molecular sieve. This interaction further enhances the loading strength, improves the stability and performance of the catalyst, and enables the catalyst to maintain efficient catalytic activity under more severe reaction conditions.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1 为本申请实施例2制备的催化剂SEM表征图；FIG1 is a SEM characterization image of the catalyst prepared in Example 2 of the present application;
图2为本申请实施例和对比例制备的催化剂样品的活性测试结果。FIG. 2 is the activity test results of the catalyst samples prepared in the examples and comparative examples of the present application.
具体实施方式DETAILED DESCRIPTION
实施例1：原料选择：Example 1: Raw material selection:
碳前驱体：酚醛树脂Carbon Precursor: Phenolic Resin
氧化铝前驱体：粒径为10nm的氧化铝溶胶Alumina precursor: Alumina sol with a particle size of 10nm
模板剂：MCM-41型介孔硅模板Template: MCM-41 mesoporous silica template
金属盐：硝酸铁Metal salt: ferric nitrate
溶胶凝胶化试剂：柠檬酸。Sol-gelling reagent: citric acid.
制备步骤：Preparation steps:
(a) 混合溶液制备：(a) Preparation of mixed solution:
- 将酚醛树脂、氧化铝溶胶以及MCM-41型介孔硅模板按照质量比10:2:1混合，通过搅拌形成均匀的混合溶液。- Phenolic resin, alumina sol and MCM-41 mesoporous silica template were mixed in a mass ratio of 10:2:1 and stirred to form a uniform mixed solution.
(b) 干燥与固化处理：(b) Drying and curing:
- 将混合溶液在室温下干燥24小时，然后在80°C下进一步干燥4小时，使溶液固化。- Dry the mixed solution at room temperature for 24 hours and then further dry at 80°C for 4 hours to solidify the solution.
(c) 碳化处理：(c) Carbonization treatment:
- 在氮气保护下，以5°C/min的升温速率将固化后的样品升至500°C，保温2小时，再以3°C/min的升温速率升至800°C，保温4小时，形成碳分子筛。- Under nitrogen protection, the cured sample was heated to 500°C at a heating rate of 5°C/min and kept at this temperature for 2 hours, and then heated to 800°C at a heating rate of 3°C/min and kept at this temperature for 4 hours to form a carbon molecular sieve.
(d) 活化处理：(d) Activation treatment:
- 使用氢氟酸（HF）溶液浸泡碳化后的样品6小时，然后用去离子水洗涤至洗涤液呈中性，去除MCM-41型介孔硅模板，形成介孔结构。经测试，该碳分子筛的比表面积为1340m2/g，平均孔径为5.0nm，孔容为1.95cm3/g，抗压强度为102N/pc。- Soak the carbonized sample in hydrofluoric acid (HF) solution for 6 hours, then wash with deionized water until the washing liquid is neutral, remove the MCM-41 mesoporous silicon template, and form a mesoporous structure. According to the test, the specific surface area of the carbon molecular sieve is1340m2 /g, the average pore size is 5.0nm, the pore volume is1.95cm3 /g, and the compressive strength is 102N/pc.
(e) 金属氧化物负载：(e) Metal oxide loading:
- 采用溶胶凝胶法，将碳化后的样品浸入含有0.1mol/L硝酸铁和15%质量分数的柠檬酸溶液中，浸泡时间为12小时，使金属氧化物负载在介孔碳分子筛上。- Using the sol-gel method, the carbonized sample was immersed in a solution containing 0.1 mol/L ferric nitrate and 15% mass fraction of citric acid for 12 hours to load the metal oxide on the mesoporous carbon molecular sieve.
(f) 干燥和碳化处理：(f) Drying and carbonization:
- 在室温下干燥负载后的样品12小时，然后在氮气保护下以5°C/min的升温速率升至600°C，保温3小时，得到催化剂。- The loaded sample was dried at room temperature for 12 hours, and then heated to 600°C at a rate of 5°C/min under nitrogen protection and kept at this temperature for 3 hours to obtain the catalyst.
实施例2：原料选择：Embodiment 2: Raw material selection:
碳前驱体：酚醛树脂Carbon Precursor: Phenolic Resin
氧化铝前驱体：粒径为10nm的氧化铝溶胶Alumina precursor: Alumina sol with a particle size of 10nm
模板剂：MCM-41型介孔硅模板Template: MCM-41 mesoporous silica template
金属盐：硝酸铜Metal salt: copper nitrate
溶胶凝胶化试剂：柠檬酸。Sol-gelling reagent: citric acid.
制备步骤：Preparation steps:
(a) 混合溶液制备：(a) Preparation of mixed solution:
- 将酚醛树脂、氧化铝溶胶以及MCM-41型介孔硅模板按照质量比10:2:1混合，通过搅拌形成均匀的混合溶液。- Phenolic resin, alumina sol and MCM-41 mesoporous silica template were mixed in a mass ratio of 10:2:1 and stirred to form a uniform mixed solution.
(b) 干燥与固化处理：(b) Drying and curing:
- 将混合溶液在室温下干燥24小时，然后在80°C下进一步干燥4小时，使溶液固化。- Dry the mixed solution at room temperature for 24 hours and then further dry at 80°C for 4 hours to solidify the solution.
(c) 碳化处理：(c) Carbonization treatment:
- 在氮气保护下，以5°C/min的升温速率将固化后的样品升至500°C，保温2小时，再以3°C/min的升温速率升至800°C，保温4小时，形成碳分子筛。- Under nitrogen protection, the cured sample was heated to 500°C at a heating rate of 5°C/min and kept at this temperature for 2 hours, and then heated to 800°C at a heating rate of 3°C/min and kept at this temperature for 4 hours to form a carbon molecular sieve.
(d) 活化处理：(d) Activation treatment:
- 使用氢氟酸（HF）溶液浸泡碳化后的样品6小时，然后用去离子水洗涤至洗涤液呈中性，去除MCM-41型介孔硅模板，形成介孔结构。- The carbonized sample was immersed in hydrofluoric acid (HF) solution for 6 hours and then washed with deionized water until the washing solution was neutral to remove the MCM-41 mesoporous silica template and form a mesoporous structure.
(e) 金属氧化物负载：(e) Metal oxide loading:
- 采用溶胶凝胶法，将碳化后的样品浸入含有0.1mol/L硝酸铜和15%质量分数的柠檬酸溶液中，浸泡时间为12小时，使金属氧化物负载在介孔碳分子筛上。- Using the sol-gel method, the carbonized sample was immersed in a solution containing 0.1 mol/L copper nitrate and 15% mass fraction of citric acid for 12 hours to load the metal oxide on the mesoporous carbon molecular sieve.
(f) 干燥和碳化处理：(f) Drying and carbonization:
- 在室温下干燥负载后的样品12小时，然后在氮气保护下以5°C/min的升温速率升至600°C，保温3小时，得到催化剂（其SEM表征见图1）。- The loaded sample was dried at room temperature for 12 hours, and then heated to 600°C at a rate of 5°C/min under nitrogen protection and kept at this temperature for 3 hours to obtain the catalyst (see Figure 1 for its SEM characterization).
对比例1：原料选择：Comparative Example 1: Raw material selection:
碳前驱体：酚醛树脂Carbon Precursor: Phenolic Resin
氧化铝前驱体：粒径为10nm的氧化铝溶胶Alumina precursor: Alumina sol with a particle size of 10nm
模板剂：活性炭（作为微孔模板替代MCM-41型介孔硅模板）Template: Activated carbon (as a microporous template to replace the MCM-41 mesoporous silica template)
金属盐：硝酸铜Metal salt: copper nitrate
溶胶凝胶化试剂：柠檬酸。Sol-gelling reagent: citric acid.
制备步骤：Preparation steps:
(a) 混合溶液制备：(a) Preparation of mixed solution:
- 将酚醛树脂、氧化铝溶胶以及活性炭模板按照质量比10:2:2混合，通过搅拌形成均匀的混合溶液。- Mix phenolic resin, alumina sol and activated carbon template in a mass ratio of 10:2:2 and stir to form a uniform mixed solution.
(b) 干燥与固化处理：(b) Drying and curing:
- 将混合溶液在室温下干燥24小时，然后在80°C下进一步干燥4小时，使溶液固化。- Dry the mixed solution at room temperature for 24 hours and then further dry at 80°C for 4 hours to solidify the solution.
(c) 碳化处理：(c) Carbonization treatment:
- 在氮气保护下，以5°C/min的升温速率将固化后的样品升至500°C，保温2小时，再以3°C/min的升温速率升至700°C（相对较低温度以保留微孔结构），保温4小时，形成微孔碳分子筛。- Under nitrogen protection, the cured sample was heated to 500°C at a heating rate of 5°C/min, kept at this temperature for 2 hours, and then heated to 700°C at a heating rate of 3°C/min (relatively low temperature to retain the microporous structure), kept at this temperature for 4 hours to form a microporous carbon molecular sieve.
(d) 活化处理：(d) Activation treatment:
- 使用氧气流在400°C下活化处理碳化后的样品2小时，以去除活性炭模板并进一步增强微孔结构。经测试，该碳分子筛的比表面积为1510m2/g，平均孔径为1.1nm，孔容为1.45cm3/g。- Use oxygen The carbonized sample was activated at 400°C for 2 hours to remove the activated carbon template and further enhance the microporous structure. The carbon molecular sieve was tested to have a specific surface area of 1510 m2 /g, an average pore diameter of 1.1 nm, and a pore volume of 1.45 cm3 /g.
(e) 金属氧化物负载：(e) Metal oxide loading:
- 采用溶胶凝胶法，将活化后的样品浸入含有0.1mol/L硝酸铜和15%质量分数的柠檬酸溶液中，浸泡时间为12小时，使金属氧化物负载在微孔碳分子筛上。- Using the sol-gel method, the activated sample was immersed in a solution containing 0.1 mol/L copper nitrate and 15% mass fraction of citric acid for 12 hours to load the metal oxide on the microporous carbon molecular sieve.
(f) 干燥和碳化处理：(f) Drying and carbonization:
- 在室温下干燥负载后的样品12小时，然后在氮气保护下以5°C/min的升温速率升至500°C，保温3小时，得到催化剂。- The loaded sample was dried at room temperature for 12 hours, and then heated to 500°C at a rate of 5°C/min under nitrogen protection and kept at this temperature for 3 hours to obtain the catalyst.
对比例2：原料选择：Comparative Example 2: Raw material selection:
碳前驱体：酚醛树脂Carbon Precursor: Phenolic Resin
模板剂：MCM-41型介孔硅模板Template: MCM-41 mesoporous silica template
金属盐：硝酸铜Metal salt: copper nitrate
溶胶凝胶化试剂：柠檬酸。Sol-gelling reagent: citric acid.
制备步骤：Preparation steps:
(a) 混合溶液制备：(a) Preparation of mixed solution:
将酚醛树脂和MCM-41型介孔硅模板按照质量比10:1混合，通过搅拌形成均匀的混合溶液。注意，此步骤中未添加氧化铝溶胶。The phenolic resin and the MCM-41 mesoporous silica template were mixed at a mass ratio of 10:1 and stirred to form a uniform mixed solution. Note that no alumina sol was added in this step.
(b) 干燥与固化处理：(b) Drying and curing:
将混合溶液在室温下干燥24小时，然后在80°C下进一步干燥4小时，使溶液固化。The mixed solution was dried at room temperature for 24 h and then further dried at 80 °C for 4 h to solidify the solution.
(c) 碳化处理：(c) Carbonization treatment:
在氮气保护下，以5°C/min的升温速率将固化后的样品升至500°C，保温2小时，再以3°C/min的升温速率升至800°C，保温4小时，形成碳分子筛。Under nitrogen protection, the cured sample was heated to 500°C at a heating rate of 5°C/min and kept at that temperature for 2 hours, and then heated to 800°C at a heating rate of 3°C/min and kept at that temperature for 4 hours to form a carbon molecular sieve.
(d) 活化处理：(d) Activation treatment:
使用氢氟酸（HF）溶液浸泡碳化后的样品6小时，然后用去离子水洗涤至洗涤液呈中性，去除MCM-41型介孔硅模板，形成介孔结构。经测试，该碳分子筛的比表面积为1320m2/g，平均孔径为3.9nm，孔容为1.67cm3/g。The carbonized sample was soaked in hydrofluoric acid (HF) solution for 6 hours, then washed with deionized water until the washing solution was neutral, and the MCM-41 mesoporous silicon template was removed to form a mesoporous structure. The carbon molecular sieve was tested to have a specific surface area of1320m2 /g, an average pore size of 3.9nm, and a pore volume of1.67cm3 /g.
(e) 金属氧化物负载：(e) Metal oxide loading:
采用溶胶凝胶法，将碳化后的样品浸入含有0.1mol/L硝酸铜和15%质量分数的柠檬酸溶液中，浸泡时间为12小时，使金属氧化物负载在介孔碳分子筛上。The carbonized sample was immersed in a solution containing 0.1 mol/L copper nitrate and 15% mass fraction of citric acid by the sol-gel method for 12 hours to load the metal oxide on the mesoporous carbon molecular sieve.
(f) 干燥和碳化处理：(f) Drying and carbonization:
在室温下干燥负载后的样品12小时，然后在氮气保护下以5°C/min的升温速率升至600°C，保温3小时，得到催化剂。The loaded sample was dried at room temperature for 12 hours, and then heated to 600°C at a heating rate of 5°C/min under nitrogen protection and kept at this temperature for 3 hours to obtain a catalyst.
对比例3：原料选择：Comparative Example 3: Raw material selection:
碳前驱体：酚醛树脂Carbon Precursor: Phenolic Resin
氧化铝前驱体：粒径为10nm的氧化铝溶胶Alumina precursor: Alumina sol with a particle size of 10nm
模板剂：MCM-41型介孔硅模板Template: MCM-41 mesoporous silica template
金属盐：硝酸铜。Metal salt: copper nitrate .
制备步骤：Preparation steps:
(a) 混合溶液制备：(a) Preparation of mixed solution:
将酚醛树脂、氧化铝溶胶以及MCM-41型介孔硅模板按照质量比10:2:1混合，通过搅拌形成均匀的混合溶液。Phenolic resin, alumina sol and MCM-41 mesoporous silica template were mixed in a mass ratio of 10:2:1 and stirred to form a uniform mixed solution.
(b) 干燥与固化处理：(b) Drying and curing:
将混合溶液在室温下干燥24小时，然后在80°C下进一步干燥4小时，使溶液固化。The mixed solution was dried at room temperature for 24 h and then further dried at 80 °C for 4 h to solidify the solution.
(c) 碳化处理：(c) Carbonization treatment:
在氮气保护下，以5°C/min的升温速率将固化后的样品升至500°C，保温2小时，再以3°C/min的升温速率升至800°C，保温4小时，形成碳分子筛。Under nitrogen protection, the cured sample was heated to 500°C at a heating rate of 5°C/min and kept at that temperature for 2 hours, and then heated to 800°C at a heating rate of 3°C/min and kept at that temperature for 4 hours to form a carbon molecular sieve.
(d) 活化处理：(d) Activation treatment:
使用氢氟酸（HF）溶液浸泡碳化后的样品6小时，然后用去离子水洗涤至洗涤液呈中性，去除MCM-41型介孔硅模板，形成介孔结构。The carbonized sample was immersed in a hydrofluoric acid (HF) solution for 6 hours and then washed with deionized water until the washing solution was neutral to remove the MCM-41 mesoporous silicon template and form a mesoporous structure.
(e) 金属氧化物负载：(e) Metal oxide loading:
将碳化并活化后的样品浸入0.1mol/L的硝酸铜溶液中，浸泡时间为12小时，使金属氧化物负载在介孔碳分子筛上。The carbonized and activated sample was immersed in a 0.1 mol/L copper nitrate solution for 12 hours to load the metal oxide on the mesoporous carbon molecular sieve.
(f) 干燥和碳化处理：(f) Drying and carbonization:
在室温下干燥负载后的样品12小时，然后在氮气保护下以5°C/min的升温速率升至600°C，保温3小时，得到催化剂。The loaded sample was dried at room temperature for 12 hours, and then heated to 600°C at a heating rate of 5°C/min under nitrogen protection and kept at this temperature for 3 hours to obtain a catalyst.
催化剂活性测试：以羰基硫浓度为500×10-6为反应气，空速为1200h-1,反应温度为80℃下测试催化剂性能，结果如图1所示。由图2可见，本申请实施例1-2制备的羰基硫水解催化剂具有较高的稳定性。Catalyst activity test: The catalyst performance was tested with a carbonyl sulfide concentration of 500×10-6 as the reaction gas, a space velocity of 1200h-1, and a reaction temperature of 80°C, and the results are shown in Figure 1. As can be seen from Figure 2, the carbonyl sulfide hydrolysis catalyst prepared in Examples 1-2 of the present application has high stability.
显然，上述实施例仅仅是为清楚地说明所作的举例，而并非对实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引伸出的显而易见的变化或变动仍处于本发明创造的保护范围之中。Obviously, the above embodiments are merely examples for the purpose of clear explanation, and are not intended to limit the implementation methods. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the implementation methods here. The obvious changes or modifications derived therefrom are still within the scope of protection of the invention.
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| CN202411072827.3ACN118594598B (en) | 2024-08-06 | 2024-08-06 | A flexible coking gas carbonyl sulfide hydrolysis catalyst and preparation method thereof |
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| CN202411072827.3ACN118594598B (en) | 2024-08-06 | 2024-08-06 | A flexible coking gas carbonyl sulfide hydrolysis catalyst and preparation method thereof |
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| BE769800A (en)* | 1971-04-23 | 1972-01-10 | Bergwerksverband Gmbh | MOLECULAR SIEVE CONTAINING CARBON AND SUITABLE TO SEPARATE SMALL MOLECULATED GASES FROM THE MIXTURES CONTAINING THEM |
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| CN118594598A (en) | 2024-09-06 |
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