技术领域Technical Field
本发明涉及一种硅烷偶联剂导向的助剂稳定的铂基分子筛催化剂，具体地说，是涉及一种软模板剂导向的助剂稳定的铂基分子筛的构建，本发明还涉及该催化剂的制备方法，以及催化丙烷脱氢制丙烯的方法。The present invention relates to a platinum-based molecular sieve catalyst stabilized by an auxiliary agent guided by a silane coupling agent, and in particular to the construction of a platinum-based molecular sieve stabilized by an auxiliary agent guided by a soft template agent. The present invention also relates to a preparation method of the catalyst and a method for catalyzing the dehydrogenation of propane to produce propylene.
背景技术Background Art
丙烯是最重要的化工基础原料之一，可以合成聚丙烯，环氧丙烷，丙二醇，聚氨酯和多元醇等。在生产丙烯的工艺中，使用铬基或铂基催化剂丙烷直接脱氢制丙烯成为一个非常有前景的手段去满足日益增长的丙烯的需求量。铂基催化剂相比铬基催化剂具有更好的碳氢键活化能力，并且对环境更加友好，铂基和铬基催化剂已经在工业生产中得到广泛的应用。Propylene is one of the most important chemical raw materials, which can be used to synthesize polypropylene, propylene oxide, propylene glycol, polyurethane and polyols. In the process of producing propylene, the direct dehydrogenation of propane to propylene using chromium-based or platinum-based catalysts has become a very promising means to meet the growing demand for propylene. Compared with chromium-based catalysts, platinum-based catalysts have better carbon-hydrogen bond activation ability and are more environmentally friendly. Platinum-based and chromium-based catalysts have been widely used in industrial production.
Ryoo等人(doi：10.1038/s41586-020-2671-4)制备了一系列Pt-La、Pt-Y、Pt-Ce等稀土铂合金，通过简单的湿润浸渍手段，然后通过煅烧和氢气还原制备沸石分子筛负载的稀土合金催化剂。介孔沸石本身的结构在催化剂合成过程中起着重要的作用，其相邻位置的硅醇基团组成的硅醇巢结构可以实现原子分散稀土元素的形成。在高温下经过煅烧-还原过程中稀土单原子与沸石骨架的配位稳定，更容易与Pt相结合。添加稀土元素(如La和Y)不仅可以改善丙烷脱氢反应的初始活性，由于金属与载体强烈的相互作用，使得活性位点铂以小纳米颗粒的形式稳定存在，催化剂的寿命得到明显的提升。值得注意的是，介孔沸石负载Pt3La金属间化合物催化剂的丙烷初始转化率达到40％，即使在纯丙烷气流下连续反应30天后，其丙烷转化率仍然保持有20％，催化剂具有极低的失活速率仅为0.0028/h，具有极好的工业应用前景。Ryoo et al. (doi: 10.1038/s41586-020-2671-4) prepared a series of rare earth platinum alloys such as Pt-La, Pt-Y, and Pt-Ce, and prepared rare earth alloy catalysts supported on zeolite molecular sieves by simple wet impregnation, followed by calcination and hydrogen reduction. The structure of the mesoporous zeolite itself plays an important role in the catalyst synthesis process. The silanol nest structure composed of silanol groups in adjacent positions can realize the formation of atomically dispersed rare earth elements. After calcination-reduction at high temperature, the coordination of rare earth single atoms with the zeolite framework is stable and easier to combine with Pt. The addition of rare earth elements (such as La and Y) can not only improve the initial activity of the propane dehydrogenation reaction, but also make the active site platinum stable in the form of small nanoparticles due to the strong interaction between the metal and the carrier, and the life of the catalyst is significantly improved. It is worth noting that the initial propane conversion rate of the mesoporous zeolite-supported Pt3 La intermetallic compound catalyst reaches 40%. Even after 30 days of continuous reaction under pure propane gas flow, its propane conversion rate still remains at 20%. The catalyst has an extremely low deactivation rate of only 0.0028/h, which has excellent industrial application prospects.
目前针对工业条件下丙烷气流下催化剂容易烧结，催化剂过度脱氢导致积碳的情况，迫切需要设计精确结构的催化剂高效稳定催化丙烷脱氢，同时引入介孔结构可以有效促进反应物和产物的扩散，缩短停留时间，一定程度下可以有效的降低积碳的形成。At present, in view of the fact that catalysts are easily sintered under propane gas flow under industrial conditions and excessive dehydrogenation of catalysts leads to carbon deposition, there is an urgent need to design catalysts with precise structures to efficiently and stably catalyze propane dehydrogenation. At the same time, the introduction of mesoporous structures can effectively promote the diffusion of reactants and products, shorten the residence time, and effectively reduce the formation of carbon deposition to a certain extent.
对于丙烷直接脱氢制丙烯反应，一直是研究人员探索的重点：The direct dehydrogenation of propane to propylene has always been the focus of researchers' exploration:
2020年，李修仪等人(CN114602495A)公开了一种丙烷脱氢Pt催化剂的制备方法。采用均匀沉淀法制备MeOx-Al2O3复合氧化物载体，获得了更加分散的金属Pt同时调控了金属Pt与氧化物载体的结合状态，改变Pt的吸附性能，抑制了氢解、积碳等副反应，有效提高了丙烯选择性。In 2020, Li Xiuyi et al. (CN114602495A) disclosed a method for preparing a propane dehydrogenation Pt catalyst. The MeOx-Al2O3composite oxide carrier was prepared by a uniform precipitation method, and a more dispersed metal Pt was obtained. At the same time, the binding state of the metal Pt and the oxide carrier was regulated, the adsorption properties of Pt were changed, and side reactions such as hydrogenolysis and carbon deposition were inhibited, effectively improving the propylene selectivity.
2021年，宋卫余等人(CN112844445A)公开了一种MFI型Silicalite-1分子筛微孔孔道限域的ZnCo双金属催化剂的制备方法及其应用。限域在Silicalite-1分子筛微孔孔道中的ZnCo双金属催化剂能够很好的适用于丙烷无氧脱氢，具备较高的丙烷转化率和丙烯选择性，且具有良好的催化稳定性，实现了丙烷的高效转化，表现出潜在的应用前景。In 2021, Song Weiyu et al. (CN112844445A) disclosed a preparation method and application of a ZnCo bimetallic catalyst confined in the microporous channels of an MFI-type Silicalite-1 molecular sieve. The ZnCo bimetallic catalyst confined in the microporous channels of the Silicalite-1 molecular sieve is well suited for the oxygen-free dehydrogenation of propane, has a high propane conversion rate and propylene selectivity, and has good catalytic stability, achieving efficient conversion of propane, showing potential application prospects.
2022年，乔波涛等人(CN114618476A)公开了一种单原子铂基催化剂及其制备方法和在丙烷直接脱氢制丙烯反应中的应用。制备的催化剂可用于催化丙烷脱氢制备丙烯的反应，具有高效的丙烯选择性，烯烃选择性在运行期间可以维持在92％以上，同时具有非常好的稳定性和抗积碳性能，在反应条件下可持续运行70h而不发生明显失活，具备较强的发展潜力。In 2022, Qiao Botao et al. (CN114618476A) disclosed a single-atom platinum-based catalyst and its preparation method and its application in the direct dehydrogenation of propane to propylene. The prepared catalyst can be used to catalyze the reaction of propane dehydrogenation to produce propylene, with high propylene selectivity, and the olefin selectivity can be maintained at more than 92% during operation. At the same time, it has very good stability and anti-carbon deposition performance. It can operate continuously for 70 hours under reaction conditions without obvious deactivation, and has strong development potential.
由于丙烷脱氢是一个强吸热的过程，较高的反应温度和严苛的反应条件给丙烯的选择性和催化剂的稳定性带来了较大的挑战，铂基催化剂在高温下容易烧结或积碳而永久失活。与此同时，大的铂聚集体对于结构副反应很敏感，容易导致催化裂解和深度脱氢。通过将金属铂位点与助剂金属形成合金是一个非常有效的手段去增强材料的催化活性和延长催化剂寿命。常见的助剂金属有镓，锡，锌，铟，铜和锗，已经被广泛的应用去稀释大的铂聚集体，从而抑制副反应，提高丙烯的选择性。引入金属助剂导致电子从助剂向铂转移，富电子的铂有助于排斥丙烯，利于丙烯的脱附。丙烷脱氢直接制丙烯由于具有反应的高正焓(ΔH＝+124kJmol-1)，需要较高反应温度，高温低压有利于丙烷脱氢反应地进行，严苛的反应条件对于烯烃选择性和催化剂稳定性提出了巨大挑战。孤立的铂位点或团簇因为缺少强金属载体作用，在高温条件下具有较高的比表面能仍然会遭受催化剂烧结，催化剂还会因过度裂解导致积炭而失活，目前急需开发具有高效稳定的丙烷脱氢催化剂。Since propane dehydrogenation is a highly endothermic process, high reaction temperatures and harsh reaction conditions pose great challenges to the selectivity of propylene and the stability of the catalyst. Platinum-based catalysts are easily sintered or carbonized at high temperatures and permanently deactivated. At the same time, large platinum aggregates are very sensitive to structural side reactions, which can easily lead to catalytic cracking and deep dehydrogenation. Alloying metal platinum sites with promoter metals is a very effective means to enhance the catalytic activity of materials and extend the life of catalysts. Common promoter metals include gallium, tin, zinc, indium, copper and germanium, which have been widely used to dilute large platinum aggregates, thereby inhibiting side reactions and improving the selectivity of propylene. The introduction of metal promoters causes electrons to transfer from the promoter to platinum. Electron-rich platinum helps to repel propylene and facilitates the desorption of propylene. Direct production of propylene by propane dehydrogenation requires a high reaction temperature due to its high positive enthalpy of reaction (ΔH = +124 kJmol-1 ). High temperature and low pressure are conducive to the propane dehydrogenation reaction. The harsh reaction conditions pose a huge challenge to olefin selectivity and catalyst stability. Isolated platinum sites or clusters, due to the lack of strong metal support effects, will still suffer from catalyst sintering despite their high specific surface energy under high temperature conditions. The catalyst will also be deactivated due to carbon deposition caused by excessive cracking. There is an urgent need to develop efficient and stable propane dehydrogenation catalysts.
发明内容Summary of the invention
针对上述不足，本发明的第一个目的在于解决铂系催化剂在丙烷脱氢制丙烯过程中容易积炭失活和烧结的问题，该催化剂具有较好的丙烷转化率和丙烯选择性，可以及时将催化剂积碳从活性中心向载体迁移，提升催化剂的稳定性，催化剂失活速率低。In view of the above-mentioned shortcomings, the first purpose of the present invention is to solve the problem that platinum catalysts are prone to carbon deposition, deactivation and sintering in the process of propane dehydrogenation to propylene. The catalyst has good propane conversion rate and propylene selectivity, can timely migrate catalyst carbon deposits from active centers to carriers, improve the stability of the catalyst, and have a low catalyst deactivation rate.
本发明的第二个目的是提供一种硅烷偶联剂导向的助剂稳定的铂基分子筛催化剂制备方法，该制备方法原料易得，容易制备，具有很好的工业应用前景。The second object of the present invention is to provide a method for preparing a silane coupling agent-guided auxiliary-stabilized platinum-based molecular sieve catalyst, which has readily available raw materials, is easy to prepare, and has good industrial application prospects.
本发明的第三个目的是提供上述硅烷偶联剂导向的助剂稳定的铂基分子筛催化剂催化丙烷脱氢制丙烯的方法。The third object of the present invention is to provide a method for producing propylene by dehydrogenating propane using the above-mentioned silane coupling agent-guided auxiliary agent-stabilized platinum-based molecular sieve catalyst.
为此，本发明提供的第一个技术方案如下：To this end, the first technical solution provided by the present invention is as follows:
一种硅烷偶联剂导向的助剂稳定的铂基分子筛催化剂的制备方法，依次包括下述步骤：A method for preparing a silane coupling agent-guided additive-stabilized platinum-based molecular sieve catalyst comprises the following steps in sequence:
1)0.1-0.5重量份铂盐加入到配位体水溶液中，搅拌至澄清，得到铂基络合物；1) 0.1-0.5 parts by weight of platinum salt is added to the ligand aqueous solution and stirred until it is clear to obtain a platinum-based complex;
2)将5-8重量份质量浓度25％四丙基氢氧化铵溶液加入水中，加入步骤1)制备的铂络合物和碱金属盐，搅拌20-40min；2) adding 5-8 parts by weight of 25% tetrapropylammonium hydroxide solution into water, adding the platinum complex and alkali metal salt prepared in step 1), and stirring for 20-40 minutes;
3)向步骤2)中加入金属助剂，然后加入0.1-2重量份软模板剂溶液，最后加入0.5-5重量份正硅酸乙酯，在室温下搅拌10-14h；再在150-180℃下晶化2-4天，经过离心分离下，洗涤干燥；3) adding a metal additive to step 2), then adding 0.1-2 parts by weight of a soft template solution, and finally adding 0.5-5 parts by weight of tetraethyl orthosilicate, stirring at room temperature for 10-14 hours; then crystallizing at 150-180° C. for 2-4 days, centrifugally separating, washing, and drying;
4)在空气气氛中，温度500-560℃，煅烧时间4-8h；4) In air atmosphere, temperature 500-560°C, calcination time 4-8h;
5)将上述催化剂压片制备成大小为20-40目的颗粒状催化剂。5) The catalyst is pressed into pellets to prepare a granular catalyst with a size of 20-40 mesh.
进一步的，上述的一种硅烷偶联剂导向的助剂稳定的铂基分子筛催化剂的制备方法，依次包括下述步骤：Furthermore, the preparation method of the above-mentioned silane coupling agent-guided additive-stabilized platinum-based molecular sieve catalyst comprises the following steps in sequence:
1)0.1-0.5g铂盐加入到10mL配位体水溶液中，搅拌至澄清，得到铂基络合物；1) 0.1-0.5 g of platinum salt is added to 10 mL of ligand aqueous solution and stirred until clear to obtain a platinum-based complex;
2)将5-8g质量浓度25％四丙基氢氧化铵溶液加入5-10mL水中，加入步骤1)制备的铂络合物和碱金属盐，在400-600rpm下搅拌20-40min；2) adding 5-8 g of 25% tetrapropylammonium hydroxide solution into 5-10 mL of water, adding the platinum complex and alkali metal salt prepared in step 1), and stirring at 400-600 rpm for 20-40 min;
3)向步骤2)中加入金属助剂，然后加入0.1-2g软模板剂溶液，最后加入0.5-5g正硅酸乙酯，在室温下搅拌10-14h；再在150-180℃下晶化2-4天，经过离心分离下，洗涤干燥；3) adding a metal additive to step 2), then adding 0.1-2 g of a soft template solution, and finally adding 0.5-5 g of tetraethyl orthosilicate, stirring at room temperature for 10-14 h; then crystallizing at 150-180° C. for 2-4 days, centrifugally separating, washing, and drying;
4)在空气气氛中，温度500-560℃，煅烧时间4-8h；4) In air atmosphere, temperature 500-560°C, calcination time 4-8h;
5)将上述催化剂压片制备成大小为20-40目的颗粒状催化剂。5) The catalyst is pressed into pellets to prepare a granular catalyst with a size of 20-40 mesh.
进一步的，上述的一种硅烷偶联剂导向的助剂稳定的铂基分子筛催化剂的制备方法，步骤1)所述的铂盐为二氯化铂、氯铂酸、四氨和硝酸铂的其中一种。Furthermore, in the above-mentioned method for preparing a silane coupling agent-guided additive-stabilized platinum-based molecular sieve catalyst, the platinum salt in step 1) is one of platinum dichloride, chloroplatinic acid, tetraammine and platinum nitrate.
进一步的，上述的一种硅烷偶联剂导向的助剂稳定的铂基分子筛催化剂的制备方法，步骤1)所述的配位体水溶液为体积浓度5-15％。Furthermore, in the above-mentioned method for preparing a silane coupling agent-guided additive-stabilized platinum-based molecular sieve catalyst, the ligand aqueous solution in step 1) has a volume concentration of 5-15%.
进一步的，上述的一种硅烷偶联剂导向的助剂稳定的铂基分子筛催化剂的制备方法，所述的配位体为氨水、二乙烯三胺、乙二胺四乙酸钠盐、四乙烯五胺、乙二胺、草酸、乳酸，水杨酸酒石酸的其中之一。Furthermore, in the preparation method of the above-mentioned silane coupling agent-guided auxiliary agent-stabilized platinum-based molecular sieve catalyst, the ligand is one of ammonia water, diethylenetriamine, sodium salt of ethylenediaminetetraacetic acid, tetraethylenepentamine, ethylenediamine, oxalic acid, lactic acid, and salicylic acid tartaric acid.
进一步的，上述的一种硅烷偶联剂导向的助剂稳定的铂基分子筛催化剂的制备方法，步骤3)所述的软模板剂为聚乙二醇、十六烷基三甲基溴化铵、二甲基十八烷基[3-(三甲氧基硅基)丙基]氯化铵、聚二烯丙基二甲基氯化铵中的其中之一。Furthermore, in the above-mentioned method for preparing a silane coupling agent-guided additive-stabilized platinum-based molecular sieve catalyst, the soft template agent described in step 3) is one of polyethylene glycol, hexadecyltrimethylammonium bromide, dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride, and polydiallyldimethylammonium chloride.
进一步的，上述的一种硅烷偶联剂导向的助剂稳定的铂基分子筛催化剂的制备方法，步骤3)所述的金属助剂为铜盐、锌盐、锡盐、镓盐、铟盐、锰盐、钴盐、锗盐、铁盐的其中之一。Furthermore, in the above-mentioned method for preparing a silane coupling agent-guided additive-stabilized platinum-based molecular sieve catalyst, the metal additive described in step 3) is one of copper salt, zinc salt, tin salt, gallium salt, indium salt, manganese salt, cobalt salt, germanium salt, and iron salt.
进一步的，上述的一种硅烷偶联剂导向的助剂稳定的铂基分子筛催化剂的制备方法，步骤3)所述的所述的碱金属为氯化钾、氯化钠、氯化锂、氯化铷的其中之一。Furthermore, in the above-mentioned method for preparing a silane coupling agent-guided additive-stabilized platinum-based molecular sieve catalyst, the alkali metal described in step 3) is one of potassium chloride, sodium chloride, lithium chloride, and rubidium chloride.
本发明提供的第二个技术方案是上述一种硅烷偶联剂导向的助剂稳定的铂基分子筛催化剂，采用第一个技术方案所述的方法制备得到的。The second technical solution provided by the present invention is the above-mentioned silane coupling agent-guided auxiliary agent-stabilized platinum-based molecular sieve catalyst, which is prepared by the method described in the first technical solution.
本发明提供的第三个技术方案是上述的硅烷偶联剂导向的助剂稳定的铂基分子筛催化剂催化丙烷脱氢制丙烯的方法，将第二个技术方案所述的硅烷偶联剂导向的助剂稳定的铂基分子筛催化剂装入内径为7mm的石英玻璃反应管中，通入体积比1∶4的氢气和氮气，然后升温至500-600℃进行还原处理0.5-1.5h，然后通入纯丙烷进行反应。The third technical solution provided by the present invention is a method for catalyzing the dehydrogenation of propane to propylene using the above-mentioned silane coupling agent-guided auxiliary-stabilized platinum-based molecular sieve catalyst, wherein the silane coupling agent-guided auxiliary-stabilized platinum-based molecular sieve catalyst described in the second technical solution is loaded into a quartz glass reaction tube with an inner diameter of 7 mm, hydrogen and nitrogen are introduced in a volume ratio of 1:4, and then the temperature is raised to 500-600°C for reduction treatment for 0.5-1.5h, and then pure propane is introduced for reaction.
与现有技术相比，本发明提供的技术方案具有如下技术优点：Compared with the prior art, the technical solution provided by the present invention has the following technical advantages:
1、本申请提供的催化剂具有较低的铂载量，有效地降低了催化剂地制备成本，加入软模板剂和碱金属钾提高材料稳定性，催化剂原料易得，容易制备，具有很好的工业应用前景；1. The catalyst provided in this application has a low platinum loading, which effectively reduces the preparation cost of the catalyst. The addition of a soft template and alkali metal potassium improves the material stability. The catalyst raw materials are easily available and easy to prepare, and have good industrial application prospects.
2、本申请提供的催化剂金属助剂很好的促进了助剂金属与铂物种之间的电子转移，优化了铂物种电子和几何结构；另一方面，软模板剂的引入提升了材料的稳定性和丙烯的选择性。催化剂可以及时将反应积碳从活性中心向载体迁移大大延长了催化剂的寿命。2. The catalyst metal promoter provided in this application promotes the electron transfer between the promoter metal and the platinum species, and optimizes the electronic and geometric structure of the platinum species; on the other hand, the introduction of the soft template improves the stability of the material and the selectivity of propylene. The catalyst can timely migrate the reaction carbon deposits from the active center to the carrier, which greatly prolongs the life of the catalyst.
3、本申请提供的催化剂，直接纯丙烷进料进行丙烷脱氢，不需要加入氢气，该催化剂具有较高的丙烷转化率和丙烯选择性，催化剂稳定性好，催化剂失活速率极低；可以高效稳定催化丙烷脱氢制丙烯，丙烯生成速率较高，催化剂还具有良好的循环再生能力。3. The catalyst provided in the present application directly feeds pure propane for propane dehydrogenation without the need to add hydrogen. The catalyst has a high propane conversion rate and propylene selectivity, good catalyst stability, and an extremely low catalyst deactivation rate. It can efficiently and stably catalyze the dehydrogenation of propane to produce propylene, with a high propylene production rate, and the catalyst also has good recycling and regeneration capabilities.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1为实施例1的长时间稳定性性能测试图；FIG1 is a long-term stability performance test diagram of Example 1;
图2为实施例1的in situ CO-FTIR谱图；FIG2 is an in situ CO-FTIR spectrum of Example 1;
图3为实施例1在不同温度下的丙烷原位红外谱图；FIG3 is an in-situ infrared spectrum of propane at different temperatures in Example 1;
图4为实施例1反应后的透射电镜图。FIG4 is a transmission electron microscope image of Example 1 after the reaction.
具体实施方式DETAILED DESCRIPTION
以下是本发明的具体实施例说明，对本发明的技术方案作进一步的描述，但不发明不限于这些实施例。The following are specific embodiments of the present invention, which further describe the technical solutions of the present invention, but the invention is not limited to these embodiments.
实施例与对比例中试剂均属市售分析纯试剂。The reagents in the examples and comparative examples are all commercially available analytically pure reagents.
实施例1Example 1
本实施例提供的一种硅烷偶联剂导向的助剂稳定的铂基分子筛催化剂的制备方法，包括下述步骤：This embodiment provides a method for preparing a silane coupling agent-guided additive-stabilized platinum-based molecular sieve catalyst, comprising the following steps:
(1)铂基络合物构建：0.24g PtCl2加入到含有1mL乙二胺的10mL水溶液中，搅拌至澄清得到铂络合物；(1) Construction of platinum-based complex: 0.24 g PtCl2 was added to 10 mL aqueous solution containing 1 mL ethylenediamine and stirred until clear to obtain a platinum complex;
(2)将6.5g四丙基氢氧化铵(25wt％水溶液)加入7.5mL水中，加入0.375mL步骤1)制备的铂络合物，加入30mg氯化钾，在500rpm下搅拌半小时；(3)加入72μL金属助剂化合物乙氧基锗，然后加入0.85mL二甲基十八烷基[3-(三甲氧基硅基)丙基]氯化铵(25wt％甲醇溶液)，最后加入4.16g正硅酸乙酯，在室温下搅拌12h；(2) Add 6.5 g of tetrapropylammonium hydroxide (25 wt % aqueous solution) to 7.5 mL of water, add 0.375 mL of the platinum complex prepared in step 1), add 30 mg of potassium chloride, and stir at 500 rpm for half an hour; (3) Add 72 μL of the metal auxiliary compound ethoxygermanium, then add 0.85 mL of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride (25 wt % methanol solution), and finally add 4.16 g of ethyl orthosilicate, and stir at room temperature for 12 h;
(4)反应釜在170℃下晶化3天，经过去离子水离心洗涤，70℃下干燥12小时。(4) The reactor was crystallized at 170°C for 3 days, washed by centrifugation with deionized water, and dried at 70°C for 12 hours.
(5)最后通过空气煅烧除去模板剂二甲基十八烷基[3-(三甲氧基硅基)丙基]氯化铵，煅烧温度550℃，煅烧时间6h。(5) Finally, the template agent dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride was removed by air calcination at a temperature of 550° C. for 6 h.
(6)将上述催化剂压片制备成大小为20-40目的颗粒状催化剂。(6) The above catalyst is pressed into pellets to prepare a granular catalyst with a size of 20-40 mesh.
将上述制备的将颗粒状催化剂装入内径为7mm的石英玻璃反应管中，通入20vol％氢气氮气混合气(氢气氮气体积比为1∶4)，然后升温至550℃进行还原处理1h，然后升温至580℃，通入纯丙烷气体或25％丙烷氮气混合气进行反应，丙烷的质量空速为10.8/h。The prepared granular catalyst is loaded into a quartz glass reaction tube with an inner diameter of 7 mm, and a 20 vol% hydrogen-nitrogen mixture (hydrogen-nitrogen volume ratio of 1:4) is introduced. The temperature is then raised to 550°C for reduction treatment for 1 h, and then the temperature is raised to 580°C, and pure propane gas or a 25% propane-nitrogen mixture is introduced for reaction, with a mass space velocity of propane of 10.8/h.
催化剂活性以丙烷转化率，丙烯选择性和失活速率表示，丙烷转化率，丙烯选择性和失活速率以下方式计算：(实施例2-6均采用该计算公式计算丙烷转化率，丙烯选择性和失活速率)The catalyst activity is expressed as propane conversion, propylene selectivity and deactivation rate, which are calculated as follows: (Examples 2-6 all use this calculation formula to calculate propane conversion, propylene selectivity and deactivation rate)
Ai代表出口处物质i的相对含量；[Fi]out代表物质i在出口的流量；代表物质C3H8在入口处的流量；Ai represents the relative content of substance i at the outlet; [Fi ]out represents the flow rate of substance i at the outlet; represents the flow rate of substance C3 H8 at the inlet;
反应产物采用气相色谱仪在线分析，在550℃、25％丙烷进料条件下，催化剂的丙烷初始转化率达42.4％，丙烯选择性为98.9％，经过20h的连续反应，催化剂的丙烷转化率仍然有42.5％，丙烯选择性为99.4％，催化剂具有较高的稳定性和丙烯选择性。在580℃、纯丙烷进料条件下，催化剂的丙烷初始转化率达35.4％，丙烯选择性为95.9％，经过20h的连续反应，催化剂的丙烷转化率仍然有36.6％，丙烯选择性为97.7％，最终经过50小时的连续反应，催化剂的丙烷转化率仍然高达36.8％，丙烯选择性为98.2％。即使在纯丙烷进料的严苛条件下，催化剂仍然具有较高的稳定性和丙烯选择性。不同温度下，催化剂对于丙烷脱氢均有较好的表现，550℃下，催化剂的初始转化率为25.4％，丙烯选择性为98.2％；600℃下，催化剂的初始转化率为43.6％，丙烯选择性为95.5％；其丙烷脱氢长时间催化性能测试图(参阅图1)，CO原位红外图(参阅图2)，丙烷原位红外谱图(参阅图3)；反应后的透射电镜图(参阅图4)。硅烷偶联剂导向的助剂稳定的铂基分子筛催化剂具有极好的催化活性和稳定性，催化剂具有较好的抗积碳性能。通过表征测试证实金属助剂与助剂之间的电子转移，介孔的引入调控了分子筛的酸性，很好的延长了催化剂的寿命，丙烷的原位红外测试，证实了脱氢过程中，丙烷的活化是从断裂亚甲基的碳氢键开始的。The reaction products were analyzed online by gas chromatography. Under the conditions of 550°C and 25% propane feed, the initial propane conversion rate of the catalyst reached 42.4%, and the propylene selectivity was 98.9%. After 20 hours of continuous reaction, the propane conversion rate of the catalyst was still 42.5%, and the propylene selectivity was 99.4%. The catalyst has high stability and propylene selectivity. Under the conditions of 580°C and pure propane feed, the initial propane conversion rate of the catalyst reached 35.4%, and the propylene selectivity was 95.9%. After 20 hours of continuous reaction, the propane conversion rate of the catalyst was still 36.6%, and the propylene selectivity was 97.7%. Finally, after 50 hours of continuous reaction, the propane conversion rate of the catalyst was still as high as 36.8%, and the propylene selectivity was 98.2%. Even under the harsh conditions of pure propane feed, the catalyst still has high stability and propylene selectivity. At different temperatures, the catalyst has good performance for propane dehydrogenation. At 550°C, the initial conversion rate of the catalyst is 25.4%, and the propylene selectivity is 98.2%; at 600°C, the initial conversion rate of the catalyst is 43.6%, and the propylene selectivity is 95.5%; its propane dehydrogenation long-term catalytic performance test diagram (see Figure 1), CO in-situ infrared diagram (see Figure 2), propane in-situ infrared spectrum (see Figure 3); transmission electron microscope diagram after the reaction (see Figure 4). The platinum-based molecular sieve catalyst stabilized by the silane coupling agent has excellent catalytic activity and stability, and the catalyst has good anti-carbon deposition performance. Characterization tests confirmed the electron transfer between metal additives and additives, and the introduction of mesopores regulated the acidity of the molecular sieve, which greatly extended the life of the catalyst. The in-situ infrared test of propane confirmed that during the dehydrogenation process, the activation of propane started from breaking the carbon-hydrogen bond of the methylene group.
实施例2Example 2
本实施例提供的一种硅烷偶联剂导向的助剂稳定的铂基分子筛催化剂的制备方法，包括下述步骤：This embodiment provides a method for preparing a silane coupling agent-guided additive-stabilized platinum-based molecular sieve catalyst, comprising the following steps:
(1)铂基络合物构建：0.24g PtCl2加入到含有1mL 乙二胺的10mL水溶液中，搅拌至澄清得到铂络合物；(1) Construction of platinum-based complex: 0.24 g PtCl2 was added to 10 mL aqueous solution containing 1 mL ethylenediamine and stirred until the solution was clear to obtain a platinum complex;
(2)将6.5g四丙基氢氧化铵(25wt％水溶液)加入7.5mL水中，加入0.375mL步骤1)制备的铂络合物，加入30mg氯化钾，在500rpm下搅拌半小时；(2) Add 6.5 g of tetrapropylammonium hydroxide (25 wt % aqueous solution) to 7.5 mL of water, add 0.375 mL of the platinum complex prepared in step 1), add 30 mg of potassium chloride, and stir at 500 rpm for half an hour;
(3)加入18μL金属助剂化合物乙氧基锗，然后加入0.85mL二甲基十八烷基[3-(三甲氧基硅基)丙基]氯化铵(25wt％甲醇溶液)，最后加入4.16g正硅酸乙酯，在室温下搅拌12h；(3) Add 18 μL of the metal auxiliary compound ethoxygermanium, then add 0.85 mL of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride (25 wt% methanol solution), and finally add 4.16 g of ethyl orthosilicate, and stir at room temperature for 12 h;
(4)反应釜在170℃下晶化3天，经过去离子水离心洗涤，70℃下干燥12小时。(4) The reactor was crystallized at 170°C for 3 days, washed by centrifugation with deionized water, and dried at 70°C for 12 hours.
(5)最后通过空气煅烧除去模板剂和二甲基十八烷基[3-(三甲氧基硅基)丙基]氯化铵，煅烧温度550℃，煅烧时间6h。(5) Finally, the template and dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride were removed by air calcination at a temperature of 550° C. for 6 h.
(6)将上述催化剂压片制备成大小为20-40目的颗粒状催化剂。(6) The above catalyst is pressed into pellets to prepare a granular catalyst with a size of 20-40 mesh.
将上述制备的将颗粒状催化剂装入内径为7mm的石英玻璃反应管中，通入20vol％氢气氮气混合气(氢气氮气体积比为1∶4)，然后升温至550℃进行还原处理1h，通入25％丙烷氮气混合气进行反应，丙烷的质量空速为5.4/h。反应产物采用气相色谱仪在线分析，催化剂刚开始的丙烷转化率高达40.0％，丙烯选择性只有98.6％，经过20h的连续反应，催化剂的丙烷转化率为41.9％，丙烯选择性为99.3％；催化剂的稳定性较好，催化剂活性与初始活性基本一致。The prepared granular catalyst was placed in a quartz glass reaction tube with an inner diameter of 7 mm, and a 20 vol% hydrogen-nitrogen mixed gas (hydrogen-nitrogen volume ratio of 1:4) was introduced, and then the temperature was raised to 550°C for reduction treatment for 1 hour, and a 25% propane-nitrogen mixed gas was introduced for reaction, and the mass space velocity of propane was 5.4/h. The reaction product was analyzed online by gas chromatograph. The initial propane conversion rate of the catalyst was as high as 40.0%, and the propylene selectivity was only 98.6%. After 20 hours of continuous reaction, the propane conversion rate of the catalyst was 41.9%, and the propylene selectivity was 99.3%. The catalyst had good stability, and the catalyst activity was basically consistent with the initial activity.
实施例3Example 3
本实施例提供的一种硅烷偶联剂导向的助剂稳定的铂基分子筛催化剂的制备方法，包括下述步骤：This embodiment provides a method for preparing a silane coupling agent-guided additive-stabilized platinum-based molecular sieve catalyst, comprising the following steps:
(1)铂基络合物构建：0.24g PtCl2加入到含有1mL乙二胺的10mL水溶液中，搅拌至澄清得到铂络合物；(1) Construction of platinum-based complex: 0.24 g PtCl2 was added to 10 mL aqueous solution containing 1 mL ethylenediamine and stirred until clear to obtain a platinum complex;
(2)将6.5g四丙基氢氧化铵(25wt％水溶液)加入7.5mL水中，加入0.375mL步骤1)制备的铂络合物，加入30mg氯化钾，在500rpm下搅拌半小时；(2) Add 6.5 g of tetrapropylammonium hydroxide (25 wt % aqueous solution) to 7.5 mL of water, add 0.375 mL of the platinum complex prepared in step 1), add 30 mg of potassium chloride, and stir at 500 rpm for half an hour;
(3)加入36μL金属助剂化合物乙氧基锗，然后加入0.85mL二甲基十八烷基[3-(三甲氧基硅基)丙基]氯化铵(25wt％甲醇溶液)，最后加入4.16g正硅酸乙酯，在室温下搅拌12h；(3) Add 36 μL of the metal auxiliary compound ethoxygermanium, then add 0.85 mL of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride (25 wt% methanol solution), and finally add 4.16 g of ethyl orthosilicate, and stir at room temperature for 12 h;
(4)反应釜在170℃下晶化3天，经过去离子水离心洗涤，70℃下干燥12小时。(4) The reactor was crystallized at 170°C for 3 days, washed by centrifugation with deionized water, and dried at 70°C for 12 hours.
(5)最后通过空气煅烧除去模板剂和二甲基十八烷基[3-(三甲氧基硅基)丙基]氯化铵，煅烧温度550℃，煅烧时间6h。(5) Finally, the template and dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride were removed by air calcination at a temperature of 550° C. for 6 h.
(6)将上述催化剂压片制备成大小为20-40目的颗粒状催化剂。(6) The above catalyst is pressed into pellets to prepare a granular catalyst with a size of 20-40 mesh.
将上述制备的将颗粒状催化剂装入内径为7mm的石英玻璃反应管中，通入20vol％氢气氮气混合气(氢气氮气体积比为1∶4)，然后升温至550℃进行还原处理1h，通入25％丙烷氮气混合气进行反应，丙烷的质量空速为5.4/h。催化剂的丙烷初始转化率高达40.3％，丙烯选择性只有98.8％，经过20h的连续反应，催化剂的丙烷转化率为38.9％，丙烯选择性为99.4％；催化剂的稳定性一般，催化剂的催化活性还有待提高。The prepared granular catalyst was placed in a quartz glass reaction tube with an inner diameter of 7 mm, and a 20 vol% hydrogen-nitrogen mixed gas (hydrogen-nitrogen volume ratio of 1:4) was introduced, and then the temperature was raised to 550°C for reduction treatment for 1 hour, and a 25% propane-nitrogen mixed gas was introduced for reaction, and the mass space velocity of propane was 5.4/h. The initial propane conversion rate of the catalyst was as high as 40.3%, and the propylene selectivity was only 98.8%. After 20 hours of continuous reaction, the propane conversion rate of the catalyst was 38.9%, and the propylene selectivity was 99.4%; the stability of the catalyst was general, and the catalytic activity of the catalyst needed to be improved.
实施例4Example 4
本实施例提供的一种硅烷偶联剂导向的助剂稳定的铂基分子筛催化剂的制备方法，包括下述步骤：This embodiment provides a method for preparing a silane coupling agent-guided additive-stabilized platinum-based molecular sieve catalyst, comprising the following steps:
(1)铂基络合物构建：0.24g PtCl2加入到含有1mL乙二胺的10mL水溶液中，搅拌至澄清得到铂络合物；(1) Construction of platinum-based complex: 0.24 g PtCl2 was added to 10 mL aqueous solution containing 1 mL ethylenediamine and stirred until clear to obtain a platinum complex;
(2)将6.5g四丙基氢氧化铵(25wt％水溶液)加入7.5mL水中，加入0.375mL步骤1)制备的铂络合物，加入30mg氯化钾，在500rpm下搅拌半小时；(2) Add 6.5 g of tetrapropylammonium hydroxide (25 wt % aqueous solution) to 7.5 mL of water, add 0.375 mL of the platinum complex prepared in step 1), add 30 mg of potassium chloride, and stir at 500 rpm for half an hour;
(3)加入108μL金属助剂化合物乙氧基锗，然后加入0.85mL二甲基十八烷基[3-(三甲氧基硅基)丙基]氯化铵(25wt％甲醇溶液)，最后加入4.16g正硅酸乙酯，在室温下搅拌12h；(3) Add 108 μL of the metal auxiliary compound ethoxygermanium, then add 0.85 mL of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride (25 wt % methanol solution), and finally add 4.16 g of ethyl orthosilicate, and stir at room temperature for 12 h;
(4)反应釜在170℃下晶化3天，经过去离子水离心洗涤，70℃下干燥12小时。(4) The reactor was crystallized at 170°C for 3 days, washed by centrifugation with deionized water, and dried at 70°C for 12 hours.
(5)最后通过空气煅烧除去模板剂和二甲基十八烷基[3-(三甲氧基硅基)丙基]氯化铵，煅烧温度550℃，煅烧时间6h。(5) Finally, the template and dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride were removed by air calcination at a temperature of 550° C. for 6 h.
(6)将上述催化剂压片制备成大小为20-40目的颗粒状催化剂。(6) The above catalyst is pressed into pellets to prepare a granular catalyst with a size of 20-40 mesh.
将上述制备的将颗粒状催化剂装入内径为7mm的石英玻璃反应管中，通入20vol％氢气氮气混合气(氢气氮气体积比为1∶4)，然后升温至550℃进行还原处理1h，通入25％丙烷氮气混合气进行反应，丙烷的质量空速为5.4/h。催化剂的丙烷初始转化率高达42.0％，丙烯选择性只有98.9％，经过20h的连续反应，催化剂的丙烷转化率为42.9％，丙烯选择性为99.3％；催化剂具有较好的稳定性，催化活性与初始的活性基本一致。The prepared granular catalyst was placed in a quartz glass reaction tube with an inner diameter of 7 mm, and a 20 vol% hydrogen-nitrogen mixed gas (hydrogen-nitrogen volume ratio of 1:4) was introduced, and then the temperature was raised to 550°C for reduction treatment for 1 hour, and a 25% propane-nitrogen mixed gas was introduced for reaction, and the mass space velocity of propane was 5.4/h. The initial propane conversion rate of the catalyst was as high as 42.0%, and the propylene selectivity was only 98.9%. After 20 hours of continuous reaction, the propane conversion rate of the catalyst was 42.9%, and the propylene selectivity was 99.3%; the catalyst had good stability, and the catalytic activity was basically consistent with the initial activity.
实施例5Example 5
本实施例提供的一种硅烷偶联剂导向的助剂稳定的铂基分子筛催化剂的制备方法，包括下述步骤：This embodiment provides a method for preparing a silane coupling agent-guided additive-stabilized platinum-based molecular sieve catalyst, comprising the following steps:
(1)铂基络合物构建：0.24g PtCl2加入到含有1mL乙二胺的10mL水溶液中，搅拌至澄清得到铂络合物；(1) Construction of platinum-based complex: 0.24 g PtCl2 was added to 10 mL aqueous solution containing 1 mL ethylenediamine and stirred until clear to obtain a platinum complex;
(2)将6.5g四丙基氢氧化铵(25wt％水溶液)加入7.5mL水中，加入0.225mL步骤1)制备的铂络合物，加入30mg氯化钾，在500rpm下搅拌半小时；(2) Add 6.5 g of tetrapropylammonium hydroxide (25 wt % aqueous solution) to 7.5 mL of water, add 0.225 mL of the platinum complex prepared in step 1), add 30 mg of potassium chloride, and stir at 500 rpm for half an hour;
(3)加入72μL金属助剂化合物乙氧基锗，然后加入0.85mL二甲基十八烷基[3-(三甲氧基硅基)丙基]氯化铵(25wt％甲醇溶液)，最后加入4.16g正硅酸乙酯，在室温下搅拌12h；(3) Add 72 μL of the metal auxiliary compound ethoxygermanium, then add 0.85 mL of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride (25 wt % methanol solution), and finally add 4.16 g of ethyl orthosilicate, and stir at room temperature for 12 h;
(4)反应釜在170℃下晶化3天，经过去离子水离心洗涤，70℃下干燥12小时。(4) The reactor was crystallized at 170°C for 3 days, washed by centrifugation with deionized water, and dried at 70°C for 12 hours.
(5)最后通过空气煅烧除去模板剂和二甲基十八烷基[3-(三甲氧基硅基)丙基]氯化铵，煅烧温度550℃，煅烧时间6h。(5) Finally, the template and dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride were removed by air calcination at a temperature of 550° C. for 6 h.
(6)将上述催化剂压片制备成大小为20-40目的颗粒状催化剂。(6) The above catalyst is pressed into pellets to prepare a granular catalyst with a size of 20-40 mesh.
将上述制备的将颗粒状催化剂装入内径为7mm的石英玻璃反应管中，通入20vol％氢气氮气混合气(氢气氮气体积比为1∶4)，然后升温至550℃进行还原处理1h，通入25％丙烷氮气混合气进行反应，丙烷的质量空速为10.8/h。催化剂刚开始的丙烷转化率高达40.5％，丙烯选择性只有99.0％，经过20h的连续反应，催化剂的丙烷转化率为39.3％，丙烯选择性为99.5％；催化剂稳定性和活性都较差，催化剂失活速率高达0.0025/h。The prepared granular catalyst was placed in a quartz glass reaction tube with an inner diameter of 7 mm, and a 20 vol% hydrogen-nitrogen mixed gas (hydrogen-nitrogen volume ratio of 1:4) was introduced, and then the temperature was raised to 550°C for reduction treatment for 1 hour, and a 25% propane-nitrogen mixed gas was introduced for reaction, and the mass space velocity of propane was 10.8/h. The initial propane conversion rate of the catalyst was as high as 40.5%, and the propylene selectivity was only 99.0%. After 20 hours of continuous reaction, the propane conversion rate of the catalyst was 39.3%, and the propylene selectivity was 99.5%; the catalyst stability and activity were poor, and the catalyst deactivation rate was as high as 0.0025/h.
对比例1Comparative Example 1
本对比例提供的一种硅烷偶联剂导向的助剂稳定的铂基分子筛催化剂的制备方法，包括下述步骤：The present comparative example provides a method for preparing a silane coupling agent-guided additive-stabilized platinum-based molecular sieve catalyst, comprising the following steps:
(1)铂基络合物构建：0.24g PtCl2加入到含有1mL乙二胺的10mL水溶液中，搅拌至澄清得到铂络合物；(1) Construction of platinum-based complex: 0.24 g PtCl2 was added to 10 mL aqueous solution containing 1 mL ethylenediamine and stirred until clear to obtain a platinum complex;
(2)将6.5g四丙基氢氧化铵(25wt％水溶液)加入7.5mL水中，加入0.375mL步骤1)制备的铂络合物，加入30mg氯化钾，在500rpm下搅拌半小时；(2) Add 6.5 g of tetrapropylammonium hydroxide (25 wt % aqueous solution) to 7.5 mL of water, add 0.375 mL of the platinum complex prepared in step 1), add 30 mg of potassium chloride, and stir at 500 rpm for half an hour;
(3)加入72μL金属助剂化合物乙氧基锗，最后加入4.16g正硅酸乙酯，在室温下搅拌12h；(3) Add 72 μL of the metal additive compound ethoxygermanium, and finally add 4.16 g of ethyl orthosilicate, and stir at room temperature for 12 h;
(4)反应釜在170℃下晶化3天，经过去离子水离心洗涤，70℃下干燥12小时。(4) The reactor was crystallized at 170°C for 3 days, washed by centrifugation with deionized water, and dried at 70°C for 12 hours.
(5)最后通过空气煅烧除去模板剂，煅烧温度550℃，煅烧时间6h。(5) Finally, the template is removed by air calcination at a temperature of 550°C for 6 hours.
(6)将上述催化剂压片制备成大小为20-40目的颗粒状催化剂。(6) The above catalyst is pressed into pellets to prepare a granular catalyst with a size of 20-40 mesh.
将上述制备的将颗粒状催化剂装入内径为7mm的石英玻璃反应管中，通入20vol％氢气氮气混合气(氢气氮气体积比为1∶4)，然后升温至550℃进行还原处理1h，通入25％丙烷氮气混合气进行反应，丙烷的质量空速为5.4/h。催化剂的丙烷初始转化率高达44.83％，丙烯选择为87.9％，经过20h的连续反应，催化剂的丙烷转化率为39.7％，丙烯选择性为98.5％；催化剂的稳定性一般，催化剂的失活常数仅为0.012/h。在580℃、纯丙烷条件下反应，丙烷质量空速为10.8/h。催化剂的丙烷初始转化率高达37.2％，丙烯选择为82.5％，经过20h的连续反应，催化剂的丙烷转化率为25.6％，丙烯选择性为95.8％，催化剂稳定性较差，失活速率常数高达0.016/h，催化剂的稳定性有待提高。The prepared granular catalyst was placed in a quartz glass reaction tube with an inner diameter of 7 mm, and a 20 vol% hydrogen-nitrogen mixed gas (hydrogen-nitrogen volume ratio of 1:4) was introduced, and then the temperature was raised to 550°C for reduction treatment for 1 hour, and a 25% propane-nitrogen mixed gas was introduced for reaction, and the mass space velocity of propane was 5.4/h. The initial propane conversion rate of the catalyst was as high as 44.83%, and the propylene selectivity was 87.9%. After 20 hours of continuous reaction, the propane conversion rate of the catalyst was 39.7%, and the propylene selectivity was 98.5%; the stability of the catalyst was general, and the deactivation constant of the catalyst was only 0.012/h. The reaction was carried out at 580°C and pure propane, and the mass space velocity of propane was 10.8/h. The initial propane conversion rate of the catalyst was as high as 37.2%, and the propylene selectivity was 82.5%. After 20 hours of continuous reaction, the propane conversion rate of the catalyst was 25.6%, and the propylene selectivity was 95.8%. The catalyst stability was poor, and the deactivation rate constant was as high as 0.016/h. The stability of the catalyst needs to be improved.
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| CN202410140072.XACN118527169A (en) | 2024-01-31 | 2024-01-31 | Auxiliary stable platinum-based molecular sieve catalyst guided by silane coupling agent and preparation method and application thereof |
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