技术领域technical field
本发明涉及一种催化剂、制备方法及其应用；尤其是涉及一种活性组分纳米颗粒嵌入分子筛结晶的催化剂、方法及应用。The invention relates to a catalyst, a preparation method and its application; in particular, it relates to a catalyst, a method and an application in which active component nanoparticles are embedded in molecular sieve crystals.
背景技术Background technique
在世界石油资源逐渐匮乏和能源危机日益凸显的背景下，碳一化学（C1化学）得到了广泛研究和快速发展。以仅有一个碳原子的化合物（如CO、甲烷、甲醇、氢氰酸等）为原料，合成制备含有两个或两个以上碳原子有机化合物的碳链增长的过程叫做碳一化学。碳一化学原料来源广泛，可减少对石油资源的过分依赖，是替代石油合成路线制备基本有机化工原料、燃料和其他重要化学品的最重要和最有发展前景的途径，包括费托合成，合成气经甲醇一步法制备二甲醚、低碳烯烃、芳烃，甲烷制芳烃，氢甲酰化反应等重要反应过程。Under the background of the world's oil resource shortage and energy crisis becoming increasingly prominent, carbon-one chemistry (C1 chemistry) has been extensively studied and developed rapidly. The carbon chain growth process of synthesizing and preparing organic compounds containing two or more carbon atoms from compounds with only one carbon atom (such as CO, methane, methanol, hydrocyanic acid, etc.) is called carbon-one chemistry. Carbon-chemical raw materials have a wide range of sources, which can reduce the excessive dependence on petroleum resources. It is the most important and promising way to replace petroleum synthesis routes to prepare basic organic chemical raw materials, fuels and other important chemicals, including Fischer-Tropsch synthesis, synthetic One-step process of gas passing through methanol to prepare dimethyl ether, light olefins, aromatics, methane to aromatics, hydroformylation and other important reaction processes.
1923年，德国科学家Frans Fischer和Hans Tropsch发明了费托合成方法（Fischer-Tropsch Synthesis，简称F-T合成或费托合成）。费托合成是将煤炭、天然气、生物质等非石油基化石燃料转化为清洁、优质的液体燃料和高附加值化学品的重要途径。费托产物相比于传统石油衍生物具有无硫、无氮、不含芳烃等众多优点，可满足日益苛刻的环保要求。随着石油资源的逐渐耗竭以及世界范围内对新能源和资源需求的不断攀升，通过费托合成反应制备液体燃料或高附加值化学品的途径已获得广泛认可。In 1923, German scientists Frans Fischer and Hans Tropsch invented the Fischer-Tropsch Synthesis method (Fischer-Tropsch Synthesis, referred to as F-T synthesis or Fischer-Tropsch synthesis). Fischer-Tropsch synthesis is an important way to convert non-petroleum-based fossil fuels such as coal, natural gas, and biomass into clean, high-quality liquid fuels and high value-added chemicals. Compared with traditional petroleum derivatives, Fischer-Tropsch products have many advantages such as no sulfur, no nitrogen, no aromatics, etc., and can meet the increasingly stringent environmental protection requirements. With the gradual depletion of petroleum resources and the increasing demand for new energy and resources worldwide, the way to prepare liquid fuels or high value-added chemicals through Fischer-Tropsch synthesis has been widely recognized.
费托合成是一个极为复杂的反应体系，虽然反应过程以简单的合成气（CO和H2）为原料，但合成后的产物服从Anderson-Schulz-Flory分布规律，即只有甲烷和高分子蜡具有较高的选择性，其余馏分都有选择性限制。减少甲烷生成，选择性地合成目标烃类（液体燃料、重质烃或烯烃等）以及研究开发可控产物选择性的催化剂始终是费托合成的研究方向。分子筛由于其高度有序的孔道结构和优异的酸催化功能，在费托合成中得到了广泛应用。Fischer-Tropsch synthesis is an extremely complex reaction system. Although the reaction process uses simple synthesis gas (CO and H2 ) as raw materials, the synthesized products obey the Anderson-Schulz-Flory distribution law, that is, only methane and polymer waxes have Higher selectivity, the remaining fractions have selectivity limitations. Reducing methane generation, selectively synthesizing target hydrocarbons (liquid fuels, heavy hydrocarbons or olefins, etc.), and researching and developing catalysts with controllable product selectivity are always the research directions of Fischer-Tropsch synthesis. Molecular sieves have been widely used in Fischer-Tropsch synthesis due to their highly ordered pore structure and excellent acid catalytic function.
在费托合成中，分子筛可与费托合成活性组分有效结合，以达到调控费托合成产物的目的。其中，最常用的是普通浸渍法，即以分子筛为载体，浸渍费托活性金属（Fe、Co、Ru等）和助剂（如Mn、Cu、Zr、Mg、Zn、Ce、K等），由费托合成制备的长链碳氢化合物可在分子筛上进行裂解和异构化反应而分解为轻质碳氢化合物，调控费托合成产物分布。但是此类负载型催化剂具有如下缺陷：1)大部分活性金属位于分子筛外表面；2)颗粒尺寸大；3）金属活性中心和酸中心不能有效匹配，重组分产物不能有效裂解；4）由于金属和分子筛间强烈的相互作用，导致催化活性低、金属还原度差、甲烷选择性高。另外一种研究较多的是物理混合法，即将费托合成催化剂和分子筛进行机械混合，制成物理混合催化剂，合成气在活性金属的费托产物可在其附近的分子筛上进行裂解和异构化反应，其中蜡质产物的裂解可有效抑制催化剂的失活。但是在物理混合催化剂上进行的裂解和异构化反应是随机的，部分碳氢化合物直接脱附而不能与分子筛酸性位有效接触，分子筛的酸催化功能未能得到有效利用。In Fischer-Tropsch synthesis, molecular sieves can be effectively combined with active components of Fischer-Tropsch synthesis to achieve the purpose of regulating Fischer-Tropsch synthesis products. Among them, the most commonly used is the common impregnation method, that is, molecular sieves are used as carriers to impregnate Fischer-Tropsch active metals (Fe, Co, Ru, etc.) and additives (such as Mn, Cu, Zr, Mg, Zn, Ce, K, etc.). Long-chain hydrocarbons prepared by Fischer-Tropsch synthesis can be decomposed into light hydrocarbons by cracking and isomerization reactions on molecular sieves, and the distribution of Fischer-Tropsch synthesis products can be regulated. However, this type of supported catalyst has the following defects: 1) most of the active metals are located on the outer surface of the molecular sieve; 2) the particle size is large; 3) the metal active center and the acid center cannot be effectively matched, and the heavy component product cannot be effectively cracked; 4) due to the metal Strong interaction with molecular sieves leads to low catalytic activity, poor metal reduction degree and high methane selectivity. Another method that has been studied more is the physical mixing method, which is to mechanically mix the Fischer-Tropsch synthesis catalyst and molecular sieve to make a physical mixed catalyst. The Fischer-Tropsch product of the active metal in the synthesis gas can be cracked and isomerized on the nearby molecular sieve. Catalyst reaction, in which the cracking of waxy product can effectively inhibit the deactivation of the catalyst. However, the cracking and isomerization reactions on physically mixed catalysts are random, some hydrocarbons are directly desorbed and cannot effectively contact with the acid sites of molecular sieves, and the acid catalytic function of molecular sieves has not been effectively utilized.
日本Noritatsu Tsubaki研究组将分子筛膜包覆型催化剂用于费托合成，在传统负载型费托催化剂（如Co/SiO2、Co/Al2O3）等表面构筑分子筛膜（如HZSM-5、H-β），以实现费托催化过程和膜基分离过程的耦合（Angew.Chem.，2008,120:359-362,Energy&Fuels,2008,22,1463-1468）。此类分子筛膜包覆型催化剂中，合成气通过分子筛膜与费托催化剂反应，其中生成的长链碳氢化合物进入分子筛膜进行裂解和异构化反应，分子筛孔道的限域效应可抑制已脱附产物的再吸附。此外，由于裂解反应为吸热反应，可吸收费托反应放出的热量，避免催化剂床层过热，减缓催化剂失活速率。但是此类分子筛膜催化剂具有如下缺陷：1）一般均在毫米级的核催化剂表面直接构筑，分子筛膜的存在会增大CO和H2的扩散阻力，降低费托反应活性；2）分子筛膜的制备过程复杂，往往需要各种预处理过程，分子筛膜的生成要求催化剂和分子筛膜有较好的相容性，成膜性质不易控制，往往会形成裂缝、针孔等缺陷；3）分子筛膜通过焙烧除去模板剂的过程中，分子筛膜可能因为与费托催化剂因为热胀系数的差异而破裂，强碱性分子筛膜前驱体合成液的侵蚀也会造成催化剂的机械强度下降。因此，设计可将分子筛酸性中心与费托金属活性中心有效耦合的新型结构催化剂，对于充分发挥分子筛的酸催化功能，提高费托合成中目标产物的选择性有重要意义。The Japanese Noritatsu Tsubaki research group used molecular sieve membrane-coated catalysts for Fischer-Tropsch synthesis, and constructed molecular sieve membranes (such as HZSM-5 , H-β) to realize the coupling of Fischer-Tropsch catalytic process and membrane-based separation process (Angew. Chem., 2008, 120:359-362, Energy & Fuels, 2008, 22, 1463-1468). In this type of molecular sieve membrane-coated catalyst, the synthesis gas passes through the molecular sieve membrane and reacts with the Fischer-Tropsch catalyst, and the long-chain hydrocarbons generated enter the molecular sieve membrane for cracking and isomerization reactions. Resorption of by-products. In addition, since the cracking reaction is an endothermic reaction, it can absorb the heat released by the Fischer-Tropsch reaction, avoid overheating of the catalyst bed, and slow down the catalyst deactivation rate. However, this type of molecular sieve membrane catalyst has the following defects: 1) Generally, it is directly constructed on the surface of the millimeter-scale nuclear catalyst, and the existence of the molecular sieve membrane will increase the diffusion resistance of CO and H2 and reduce the Fischer-Tropsch reaction activity; The preparation process is complex and often requires various pretreatment processes. The formation of molecular sieve membranes requires good compatibility between catalysts and molecular sieve membranes, and the film-forming properties are not easy to control, and defects such as cracks and pinholes often form; 3) Molecular sieve membranes pass through During the process of calcination to remove the template agent, the molecular sieve membrane may be broken due to the difference in thermal expansion coefficient with the Fischer-Tropsch catalyst, and the erosion of the strong basic molecular sieve membrane precursor synthesis liquid will also cause the mechanical strength of the catalyst to decrease. Therefore, it is of great significance to design a new structural catalyst that can effectively couple the acidic center of the molecular sieve to the active center of the Fischer-Tropsch metal to give full play to the acid catalytic function of the molecular sieve and improve the selectivity of the target product in the Fischer-Tropsch synthesis.
合成气经甲醇一步法制备二甲醚、低碳烯烃、芳烃等过程是指合成气先催化合成甲醇，甲醇再在分子筛等催化剂上生成二甲醚、低碳烯烃、芳烃等的反应过程，随着石油价格的上涨和甲醇生产技术的日趋成熟，开发甲醇下游产品有极大的工业前景和现实意义。传统的两步法过程中，合成路线长，设备投资大，一步法可将合成甲醇及分子筛催化两个过程耦合，省去中间过程，减少设备投资和操作费用，提高经济效益，直接得到所需目标产品。The one-step process of preparing dimethyl ether, low-carbon olefins, aromatics, etc. from syngas through methanol refers to the reaction process in which syngas is first catalyzed to synthesize methanol, and methanol is then generated on molecular sieves and other catalysts to generate dimethyl ether, low-carbon olefins, aromatics, etc., followed by With the rise of oil prices and the maturity of methanol production technology, the development of methanol downstream products has great industrial prospects and practical significance. In the traditional two-step process, the synthesis route is long and the equipment investment is large. The one-step method can couple the two processes of methanol synthesis and molecular sieve catalysis, eliminating the need for intermediate processes, reducing equipment investment and operating costs, improving economic benefits, and directly obtaining the required target product.
此外，对于二甲醚的生产，工业上主要采用甲醇气相脱水，即传统的两步法，合成气先在铜基催化剂上加氢制备甲醇，甲醇再在固体酸催化剂上脱水生成二甲醚，该合成路线长，设备投资大。合成气一步法制二甲醚是指将上述两步反应集中在一个反应器中进行，生成的甲醇可直接脱水得到二甲醚。目前，合成气一步法制备二甲醚主要是将甲醇催化剂和固体酸催化剂物理混合。In addition, for the production of dimethyl ether, methanol gas-phase dehydration is mainly used in industry, that is, the traditional two-step method. The synthesis gas is first hydrogenated on a copper-based catalyst to produce methanol, and then methanol is dehydrated on a solid acid catalyst to form dimethyl ether. The synthesis route is long and the equipment investment is large. The one-step method of producing dimethyl ether from synthesis gas means that the above two-step reactions are concentrated in one reactor, and the generated methanol can be directly dehydrated to obtain dimethyl ether. At present, the one-step method for preparing DME from syngas mainly involves physical mixing of methanol catalyst and solid acid catalyst.
甲烷在烃类化合物中分子量最小且最稳定，其碳氢键的键能很高，反应能力低，不易液化，与其他分子量较高的烃相比，难以作为化工原料直接利用，甲烷的转化利用具有重大意义。甲烷芳构化是伴随着甲烷氧化偶联发展起来的甲烷直接综合利用的重要途径，包括甲烷氧化芳构化和无氧芳构化两个方向，甲烷氧化芳构化的选择性往往不高，苯的选择性很低，而甲烷无氧芳构化反应过程中由于不使用氧气，避免了甲烷的燃烧和深度氧化，并且其产物芳烃易于同其它产物分离，是甲烷催化转化的一个有前途的方向。甲烷无氧芳构化所用催化剂主要为分子筛负载的Mo基催化剂，如Mo/HZSM-5等。Methane has the smallest and most stable molecular weight among hydrocarbon compounds. Its carbon-hydrogen bond has high bond energy, low reactivity, and is not easy to liquefy. Compared with other hydrocarbons with higher molecular weight, it is difficult to be directly used as a chemical raw material. The conversion and utilization of methane has great significance. Methane aromatization is an important way for the direct comprehensive utilization of methane developed along with methane oxidative coupling, including two directions of methane oxidative aromatization and oxygen-free aromatization. The selectivity of methane oxidative aromatization is often not high. The selectivity of benzene is very low, and the combustion and deep oxidation of methane are avoided due to the absence of oxygen in the oxygen-free aromatization reaction of methane, and the product aromatics are easy to separate from other products, which is a promising method for the catalytic conversion of methane. direction. The catalysts used in the oxygen-free aromatization of methane are mainly Mo-based catalysts supported by molecular sieves, such as Mo/HZSM-5, etc.
氢甲酰化反应是烯烃与合成气（CO和H2）在过渡金属络合催化剂作用下反应生成比原烯烃多一分子的醛或醇的反应过程。传统工业所用催化剂为铑膦配合物，如[Rh(CO)(TPPTS)3][TPPTS=P(m-C6H4SO3Na)3]等，此类催化剂难以从液相中分离和回收。为解决这一问题，近年来发展了活性组分固载化催化剂，但此类催化剂难以获得高的正构醛选择性，而正构醛具有更高的工业应用价值。The hydroformylation reaction is a reaction process in which olefins react with synthesis gas (CO and H2 ) under the action of transition metal complex catalysts to produce aldehydes or alcohols with one molecule more than the original olefins. The catalysts used in traditional industries are rhodium-phosphine complexes, such as [Rh(CO)(TPPTS)3 ][TPPTS=P(mC6 H4 SO3 Na)3 ], etc., which are difficult to separate and recover from the liquid phase. To solve this problem, catalysts with active components immobilized have been developed in recent years, but it is difficult for such catalysts to obtain high selectivity for n-aldehydes, which have higher industrial application value.
发明内容Contents of the invention
本发明要解决的第一个技术问题是提供一种活性组分纳米颗粒嵌入分子筛结晶的催化剂。该催化剂活性金属颗粒嵌入分散到分子筛中；颗粒尺寸小，达纳米级；金属活性中心和酸中心能有效匹配，重组分产物能有效裂解；催化活性高、金属还原度高、甲烷选择性低；不降低费托反应活性；制备过程简单，成本降低，适宜大规模工业应用；分子筛不会因热胀系数的差异而破裂，机械强度高。The first technical problem to be solved by the present invention is to provide a catalyst in which nano particles of active components are embedded in molecular sieve crystals. The catalytically active metal particles are embedded and dispersed in molecular sieves; the particle size is small, up to nanoscale; the metal active center and acid center can be effectively matched, and the heavy component product can be effectively cracked; high catalytic activity, high metal reduction degree, and low methane selectivity; The Fischer-Tropsch reaction activity is not reduced; the preparation process is simple, the cost is reduced, and it is suitable for large-scale industrial applications; the molecular sieve will not be broken due to the difference in thermal expansion coefficient, and the mechanical strength is high.
本发明要解决的第二个技术问题是提供一种活性组分纳米颗粒嵌入分子筛结晶的催化剂的制备方法。The second technical problem to be solved by the present invention is to provide a preparation method of a catalyst in which nano particles of active components are embedded in molecular sieve crystals.
本发明要解决的第三个技术问题是提供一种活性组分纳米颗粒嵌入分子筛结晶的催化剂的应用。The third technical problem to be solved by the present invention is to provide the application of a catalyst in which the active component nanoparticles are embedded in molecular sieve crystals.
为解决上述第一个技术问题，本发明采用如下技术手段：In order to solve the above-mentioned first technical problem, the present invention adopts the following technical means:
一种活性组分纳米颗粒嵌入分子筛结晶的催化剂，包括金属活性组分纳米颗粒和分子筛，所述金属活性组分纳米颗粒嵌入分散在分子筛中，所述金属活性组分纳米颗粒在催化剂中含量为2～70wt%，活性金属纳米颗粒粒径为4～200nm，分子筛晶粒大小为1～10μm。A catalyst in which active component nanoparticles are embedded in molecular sieve crystals, including metal active component nanoparticles and molecular sieves, the metal active component nanoparticles are embedded and dispersed in the molecular sieve, and the content of the metal active component nanoparticles in the catalyst is 2-70wt%, the particle size of active metal nanoparticles is 4-200nm, and the molecular sieve grain size is 1-10μm.
优选地，活性金属纳米颗粒粒径为4～100nm；更优选地，活性金属纳米颗粒粒径为4～50nm；最优选地，活性金属纳米颗粒粒径为5～30nm；Preferably, the particle size of the active metal nanoparticles is 4-100 nm; more preferably, the particle size of the active metal nanoparticles is 4-50 nm; most preferably, the particle size of the active metal nanoparticles is 5-30 nm;
优选地，所述金属活性组分纳米颗粒在催化剂中含量为9～60wt%；更优选地，所述金属活性组分纳米颗粒在催化剂中含量为9～40wt%；最优选地，所述金属活性组分纳米颗粒在催化剂中含量为17～21wt%。Preferably, the content of the metal active component nanoparticles in the catalyst is 9-60wt%; more preferably, the content of the metal active component nanoparticles in the catalyst is 9-40wt%; most preferably, the metal The content of the active component nanoparticles in the catalyst is 17-21wt%.
优选地，所述金属活性组分纳米颗粒是如下活性组分纳米颗粒中的一种或多种：Fe、Co、Ru、Cu、Pd、Ni、Rh、Pt、Mo。Preferably, the metal active component nanoparticles are one or more of the following active component nanoparticles: Fe, Co, Ru, Cu, Pd, Ni, Rh, Pt, Mo.
优选地，所述分子筛是如下分子筛中一种或多种：HZSM-5分子筛、Hβ分子筛、Silicate-1分子筛、MCM-41分子筛、HMS分子筛、SBA-15分子筛、HY分子筛、SAPO-34分子筛、TS-1分子筛。Preferably, the molecular sieve is one or more of the following molecular sieves: HZSM-5 molecular sieve, Hβ molecular sieve, Silicate-1 molecular sieve, MCM-41 molecular sieve, HMS molecular sieve, SBA-15 molecular sieve, HY molecular sieve, SAPO-34 molecular sieve, TS-1 molecular sieve.
优选地，催化剂中还包括助剂。更优选地，所述助剂是如下元素的氧化物、还原态颗粒或金属合金中的一种或多种：Mn、Cu、Zr、Mg、Cr、Zn、Ce、K、Al、Ag、Pd、Pt、Ru、Rh。Preferably, an auxiliary agent is also included in the catalyst. More preferably, the additive is one or more of the oxides, reduced particles or metal alloys of the following elements: Mn, Cu, Zr, Mg, Cr, Zn, Ce, K, Al, Ag, Pd , Pt, Ru, Rh.
为解决上述第二个技术问题，本发明一种活性组分纳米颗粒嵌入分子筛结晶的催化剂的制备方法，包括如下步骤：In order to solve the above-mentioned second technical problem, a method for preparing a catalyst in which active component nanoparticles are embedded in molecular sieve crystals of the present invention comprises the following steps:
1）取含有硅、铝、钛或磷的负载型或共沉淀催化剂作为前驱体催化剂，将前驱体催化剂粉碎，过≥20目筛，得前驱体催化剂粉末；所述前驱体中含有金属活性组分纳米颗粒；1) Take a supported or co-precipitated catalyst containing silicon, aluminum, titanium or phosphorus as a precursor catalyst, pulverize the precursor catalyst, and pass through a ≥20 mesh sieve to obtain a precursor catalyst powder; the precursor contains metal active groups sub-nanoparticles;
2）取硅源、铝源、钛源或磷源，用水和乙醇的混合溶液进行溶解，再加入模板剂和前驱体催化剂粉末，搅拌均匀，得合成液；本领域技术人员都了解，在取硅源、铝源、钛源或磷源时，要和前驱体催化剂相匹配；通常来说前驱体催化剂的元素和后面取的硅源、铝源、钛源或磷源要匹配，即不相同，例如，前驱体催化剂中含硅，则后面则不选硅源以免重复；2) Take silicon source, aluminum source, titanium source or phosphorus source, dissolve it in a mixed solution of water and ethanol, then add template agent and precursor catalyst powder, stir evenly, and obtain a synthetic solution; When the silicon source, aluminum source, titanium source or phosphorus source is used, it must match the precursor catalyst; generally speaking, the elements of the precursor catalyst must match the silicon source, aluminum source, titanium source or phosphorus source taken later, that is, they are not the same , for example, if the precursor catalyst contains silicon, then the silicon source will not be selected later to avoid repetition;
3）在pH值大于8的条件下，步骤2）得到的合成液在密封的反应釜内进行水热合成反应；反应后过滤得固体中间催化剂，用去离子水或乙醇洗涤固体中间催化剂至洗液pH值小于8；所述水热合成反应是指温度为100～1000℃、压力为1MPa～1GPa条件下利用水溶液中物质化学反应所进行的合成；3) Under the condition that the pH value is greater than 8, the synthesis solution obtained in step 2) is subjected to hydrothermal synthesis reaction in a sealed reactor; after the reaction, the solid intermediate catalyst is filtered, and the solid intermediate catalyst is washed with deionized water or ethanol until washed. The pH value of the liquid is less than 8; the hydrothermal synthesis reaction refers to the synthesis carried out by using the chemical reaction of substances in the aqueous solution at a temperature of 100-1000°C and a pressure of 1MPa-1GPa;
4）将固体中间催化剂在80～150℃下干燥，加入到350～600℃焙烧，以脱除模板剂，得到产品。4) Dry the solid intermediate catalyst at 80-150°C, add it to 350-600°C and roast to remove the template and obtain the product.
优选地，步骤1）中，所述金属活性组分纳米颗粒是如下活性组分纳米颗粒中的一种或多种：Fe、Co、Ru、Cu、Pd、Ni、Rh、Pt、Mo。Preferably, in step 1), the metal active component nanoparticles are one or more of the following active component nanoparticles: Fe, Co, Ru, Cu, Pd, Ni, Rh, Pt, Mo.
优选地，步骤1）中，所述前驱体催化剂的载体为含有Si、Al、Ti、P一种或两种以上的氧化物载体;前驱体催化剂包括金属活性组分纳米颗粒和载体；Preferably, in step 1), the carrier of the precursor catalyst is an oxide carrier containing one or more of Si, Al, Ti, P; the precursor catalyst includes metal active component nanoparticles and a carrier;
优选地，所述前驱体催化剂中还含有助剂颗粒，助剂在前驱体催化剂中的含量为2～50wt%；优选地，助剂在前驱体催化剂中的含量为2～20wt%；优选地，助剂在前驱体催化剂中的含量为4～14wt%；更优选地，所述助剂是如下元素的氧化物、还原态颗粒或金属合金中的一种或多种：Mn、Cu、Zr、Mg、Cr、Zn、Ce、K、Al、Ag、Pd、Pt、Ru、Rh。Preferably, the precursor catalyst also contains auxiliary agent particles, and the content of the auxiliary agent in the precursor catalyst is 2 to 50wt%; preferably, the content of the auxiliary agent in the precursor catalyst is 2 to 20wt%; preferably , the content of the auxiliary agent in the precursor catalyst is 4 to 14wt%; more preferably, the auxiliary agent is one or more of the oxides, reduced particles or metal alloys of the following elements: Mn, Cu, Zr , Mg, Cr, Zn, Ce, K, Al, Ag, Pd, Pt, Ru, Rh.
优选地，步骤2）中，所述硅源选自下列物质中的一种或多种：正硅酸乙酯（TEOS）、硅溶胶（Silica Gel）、正硅酸甲酯（TMeOS）、硅酸钠（Na2SiO3）；所述铝源选自下列物质中的一种或多种：硝酸铝（Al(NO3)3）、硫酸铝（Al2(SO4)3）、氯化铝（AlCl3）、异丙醇铝（[(CH3)2CHO]3Al）;所述钛源选自下列物质中的一种或多种：钛酸四丁酯（Ti(OC4H9)4）、四氯化钛（TiCl4）、硫酸氧钛（TiOSO4）；所述磷源选自下列物质中的一种或多种：磷酸三丁酯（OP(OCH2CH2CH2CH3)3）、磷酸（H3PO4）、偏磷酸（HPO3）。Preferably, in step 2), the silicon source is selected from one or more of the following substances: tetraethyl orthosilicate (TEOS), silica sol (Silica Gel), methyl orthosilicate (TMeOS), silicon sodium nitrate (Na2 SiO3 ); the aluminum source is selected from one or more of the following substances: aluminum nitrate (Al(NO3 )3 ), aluminum sulfate (Al2 (SO4 )3 ), chloride Aluminum (AlCl3 ), aluminum isopropoxide ([(CH3 )2 CHO]3 Al); the titanium source is selected from one or more of the following substances: tetrabutyl titanate (Ti(OC4 H9 )4 ), titanium tetrachloride (TiCl4 ), titanium oxysulfate (TiOSO4 ); the phosphorus source is selected from one or more of the following substances: tributyl phosphate (OP(OCH2 CH2 CH2 CH3 )3 ), phosphoric acid (H3 PO4 ), metaphosphoric acid (HPO3 ).
优选地，步骤2）中，所述模板剂为四丙基氢氧化铵（简称：TPAOH）、四乙基氢氧化铵（简称：TEAOH）、四甲基氢氧化铵（简称：TMAOH）、十六烷基三甲基溴化铵（简称：CTAB）、聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物（简称：P123）或十八胺(简称：ODA)。Preferably, in step 2), the template agent is tetrapropylammonium hydroxide (abbreviation: TPAOH), tetraethylammonium hydroxide (abbreviation: TEAOH), tetramethylammonium hydroxide (abbreviation: TMAOH), ten Hexaalkyltrimethylammonium bromide (abbreviation: CTAB), polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (abbreviation: P123) or octadecylamine (abbreviation: ODA) .
优选地，步骤2）中，所述合成液中各组分的摩尔比为：硅、铝、钛和/或磷:模板剂:乙醇:水=5～100:8～90:50～1000:100～3000。优选地，所述硅、铝、钛和/或磷:模板剂:乙醇:水=40～60:10～20:400～600:500～1000。Preferably, in step 2), the molar ratio of each component in the synthesis liquid is: silicon, aluminum, titanium and/or phosphorus:template agent:ethanol:water=5～100:8～90:50～1000: 100~3000. Preferably, the silicon, aluminum, titanium and/or phosphorus:template agent:ethanol:water=40-60:10-20:400-600:500-1000.
优选地，模板剂的加入为逐滴加入。Preferably, the templating agent is added dropwise.
优选地，步骤3）中，反应温度为140～260℃，反应时间为20～750小时，反应压力为1～30MPa。Preferably, in step 3), the reaction temperature is 140-260° C., the reaction time is 20-750 hours, and the reaction pressure is 1-30 MPa.
优选地，步骤3）中，所述反应釜为带有聚四氟乙烯内衬的不锈钢水热合成釜。Preferably, in step 3), the reaction kettle is a stainless steel hydrothermal synthesis kettle with polytetrafluoroethylene lining.
优选地，步骤4）中，干燥时间为2～12小时;焙烧时间为2～12小时。Preferably, in step 4), the drying time is 2-12 hours; the roasting time is 2-12 hours.
为解决上述第三个技术问题，一种活性组分纳米颗粒嵌入分子筛结晶的催化剂在碳一化学的相关反应过程中应用。In order to solve the third technical problem above, a catalyst in which the active component nanoparticles are embedded in molecular sieve crystals is applied in the relevant reaction process of carbon-chemistry.
优选地，所述碳一化学相关反应过程包括费托合成，合成气经甲醇一步法制备二甲醚、低碳烯烃、芳烃，甲烷制芳烃或氢甲酰化反应。Preferably, the carbon-chemical related reaction process includes Fischer-Tropsch synthesis, a one-step method of preparing dimethyl ether, light olefins, aromatics from syngas via methanol, methane to aromatics or hydroformylation.
优选地，所述碳一化学相关反应过程中，采用固定床反应器、流化床反应器或浆态床反应器。Preferably, in the carbon-chemical related reaction process, a fixed bed reactor, a fluidized bed reactor or a slurry bed reactor is used.
本发明具有如下有益效果：The present invention has following beneficial effects:
1）本发明的新型结构催化剂包括活性组分纳米颗粒和分子筛两部分，合成过程简单，采用水热合成法制备，合成过程以传统的含硅、铝、钛、磷的负载型或共沉淀催化剂为前驱体，其溶出的硅、铝、钛、磷作为合成分子筛的硅源、铝源、钛源、磷源的全部或一部分，通过控制合成过程中的溶出速率和分子筛的晶化速率（如改变前驱体催化剂粉末粒度，调节合成液pH值，调整水热反应温度、压力和时间等），可将活性组分纳米颗粒嵌入分子筛结晶，结构性能优异；1) The novel structure catalyst of the present invention includes two parts of active component nanoparticles and molecular sieve, the synthesis process is simple, and it is prepared by hydrothermal synthesis method. It is a precursor, and the dissolved silicon, aluminum, titanium, and phosphorus are used as all or part of the silicon source, aluminum source, titanium source, and phosphorus source for the synthesis of molecular sieves. By controlling the dissolution rate during the synthesis process and the crystallization rate of the molecular sieve (such as Change the particle size of the precursor catalyst powder, adjust the pH value of the synthesis liquid, adjust the hydrothermal reaction temperature, pressure and time, etc.), and the active component nanoparticles can be embedded in molecular sieve crystals, with excellent structural properties;
2）本发明的新型结构催化剂可将分子筛的酸催化功能与活性组分的酸催化功能有效耦合，在活性组分上生成的产物可通过分子筛优异的酸催化性质及高度有序的孔道结构进一步反应和分离，该协同作用可将多步反应过程耦合，一步合成符合纯度和收率要求的目标产物，有效调控产物分布，防止催化剂活性组分流失，减缓催化剂失活速率；2) The novel structural catalyst of the present invention can effectively couple the acid catalytic function of the molecular sieve with the acid catalytic function of the active component. Reaction and separation, the synergistic effect can couple the multi-step reaction process, synthesize the target product that meets the purity and yield requirements in one step, effectively control the product distribution, prevent the loss of catalyst active components, and slow down the catalyst deactivation rate;
3）本发明的新型结构催化剂，催化剂寿命长，机械稳定性能好，可在碳一化学相关过程中获得重要应用。3) The novel structure catalyst of the present invention has long catalyst life and good mechanical stability, and can be used in important applications in carbon-chemical related processes.
附图说明Description of drawings
图1为本发明的催化剂结构示意图；Fig. 1 is the catalyst structural representation of the present invention;
图2为实施例1制得的新型结构催化剂的透射电镜（TEM）图；Fig. 2 is the transmission electron microscope (TEM) picture of the novel structure catalyst that embodiment 1 makes;
图3为本发明的催化剂截面结构示意图。Fig. 3 is a schematic cross-sectional structure diagram of the catalyst of the present invention.
具体实施方式Detailed ways
实施例1Example 1
一种活性组分纳米颗粒嵌入分子筛结晶的催化剂的制备方法，包括如下步骤：A method for preparing a catalyst in which active component nanoparticles are embedded in molecular sieve crystals, comprising the following steps:
1）Co/SiO2前驱体催化剂的现有等体积浸渍法制备：1) Preparation of Co/SiO2 Precursor Catalyst by Existing Isometric Impregnation Method:
将SiO2于空气中200℃处理2h，然后以Co(NO3)2·6H2O为Co源对其等体积浸渍，活性金属Co负载量20wt%，真空处理1h，120℃干燥12h，400℃焙烧2h，得前驱体颗粒催化剂;将前驱体颗粒催化剂破碎筛分为过80目的粉末；SiO2 was treated in air at 200°C for 2h, then impregnated with an equal volume of Co(NO3 )2 ·6H2 O as the Co source, the active metal Co loading was 20wt%, vacuum treated for 1h, dried at 120°C for 12h, 400 ℃ roasting for 2 hours to obtain the precursor particle catalyst; crush and sieve the precursor particle catalyst into powder of 80 mesh;
2）以TPAOH为模板剂，以Al(NO3)3·9H2O为Al源，以Co/SiO2在合成过程中溶出的Si作为Si源；2) TPAOH was used as the template, Al(NO3 )3 9H2 O was used as the Al source, and Si dissolved during the synthesis of Co/SiO2 was used as the Si source;
将Al(NO 3)3·9H 2O以去离子水和乙醇（简称：Et OH）溶解，搅拌均匀后，加入步骤1）得到的前驱体催化剂粉末，逐滴加入模板剂TPAOH，搅拌混合均匀，得合成液；合成液中摩尔比为1.0Al:50S i:15TPAOH:500Et OH:880H 2O；Dissolve Al(NO3 )3 9H2 O in deionized water and ethanol (abbreviation: Et OH), stir evenly, add the precursor catalyst powder obtained in step 1), add the template agent TPAOH drop by drop, stir and mix evenly , to obtain the synthetic liquid; the molar ratio in the synthetic liquid is 1.0Al:50S i:15TPAOH:500Et OH:880H2 O;
3）将合成液密封在带有聚四氟乙烯内筒的不锈钢水热合成釜内进行水热合成反应，水热合成温度为180℃，合成时间为100h；反应结束后，将催化剂从溶液中过滤，得固体中间催化剂，以去离子水或乙醇洗涤至洗液pH值小于8；3) Seal the synthesis solution in a stainless steel hydrothermal synthesis kettle with a polytetrafluoroethylene inner cylinder for hydrothermal synthesis reaction. The hydrothermal synthesis temperature is 180°C, and the synthesis time is 100 hours. After the reaction, remove the catalyst from the solution Filtrate to obtain a solid intermediate catalyst, wash with deionized water or ethanol until the pH value of the washing solution is less than 8;
4）将固体中间催化剂在120℃下干燥12h，加热到500℃焙烧5h，以脱除模板剂，制得新型结构Co·HZSM-5分子筛催化剂。4) The solid intermediate catalyst was dried at 120°C for 12h, heated to 500°C and calcined for 5h to remove the templating agent and obtain a new structure Co·HZSM-5 molecular sieve catalyst.
经检测，Co·HZSM-5催化剂的结构参见图1所示，经透射电镜（TEM）检测参见图2。Co·HZSM-5催化剂包括Co活性组分纳米颗粒和HZSM-5分子筛，所述Co活性组分纳米颗粒嵌入分散在HZSM-5分子筛中，所述Co活性组分纳米颗粒在催化剂中含量为19.8wt%，活性金属纳米颗粒粒径为10nm，分子筛晶粒大小为5μm；After testing, the structure of the Co·HZSM-5 catalyst is shown in Figure 1, and it is shown in Figure 2 through transmission electron microscopy (TEM). The Co HZSM-5 catalyst includes Co active component nanoparticles and HZSM-5 molecular sieves, the Co active component nanoparticles are embedded and dispersed in the HZSM-5 molecular sieve, and the Co active component nanoparticles have a content of 19.8% in the catalyst. wt%, the particle size of active metal nanoparticles is 10nm, and the molecular sieve grain size is 5μm;
将上述所得Co·HZSM-5分子筛催化剂于10MPa下压片，粉碎后取20～40目的颗粒用于固定床费托合成反应性能测试。催化剂的活化条件为：在常压下以80ml/min的H2在400℃还原10h。催化剂的反应条件为：260℃，1.0MPa，H2/CO摩尔比为2.0，Wcat/F=5gh mol-1，反应结果如下表所示。The Co·HZSM-5 molecular sieve catalyst obtained above was pressed into tablets under 10 MPa, and after crushing, 20-40 mesh particles were taken for the performance test of the fixed-bed Fischer-Tropsch synthesis reaction. The activation condition of the catalyst is: reduction with 80ml/minH2 at 400°C for 10h under normal pressure. The catalyst reaction conditions are: 260°C, 1.0MPa, H2 /CO molar ratio 2.0, Wcat /F=5gh mol-1 , and the reaction results are shown in the table below.
αi so-C5-C12为C5-C12中支链烷烃的选择性。根据上表可知，实施例1制得的催化剂对C5-C12有良好的选择性。α iso-C5 -C12 is the selectivity of branched alkanes in C5 -C12 . According to the above table, it can be seen that the catalyst prepared in Example 1 has good selectivity to C5 -C12 .
实施例2Example 2
一种活性组分纳米颗粒嵌入分子筛结晶的催化剂的制备方法，包括如下步骤：A method for preparing a catalyst in which active component nanoparticles are embedded in molecular sieve crystals, comprising the following steps:
1）Co/Al2O3前驱体催化剂的现有等体积浸渍法制备1) Preparation of Co/Al2 O3 Precursor Catalyst by Existing Isometric Impregnation Method
将载体γ-Al2O3于空气中200℃处理2h，然后以Co(NO3)2·6H2O为Co源对其等体积浸渍，活性金属Co负载量20wt%，真空处理1h，120℃干燥12h，400℃焙烧2h，得到前驱体催化剂；将所得前驱体催化剂破碎筛分为过20目的粉末；The carrier γ-Al2 O3 was treated in the air at 200°C for 2 hours, then impregnated with an equal volume of Co(NO3 )2 ·6H2 O as the Co source, the active metal Co loading was 20wt%, vacuum treatment for 1 hour, 120 Drying at ℃ for 12 hours, calcining at 400 ℃ for 2 hours to obtain a precursor catalyst; crushing and sieving the obtained precursor catalyst into 20-mesh powder;
2）以TPAOH为模板剂，以TEOS为Si源，以Co/Al2O3在合成过程中溶出的Al作为Al源；2) TPAOH was used as template, TEOS was used as Si source, and Al dissolved in Co/Al2 O3 during the synthesis process was used as Al source;
将TEOS与去离子水和乙醇混合，搅拌均匀后，加入步骤1）得到的前驱体催化剂粉末，之后逐滴加入模板剂，搅拌混合均匀，得合成液；合成液中摩尔比为1.0Al:50Si:15TPAOH:500EtOH:880H2O；Mix TEOS with deionized water and ethanol, stir evenly, add the precursor catalyst powder obtained in step 1), and then add template agent drop by drop, stir and mix evenly to obtain a synthetic solution; the molar ratio in the synthetic solution is 1.0Al:50Si :15TPAOH:500EtOH:880H2 O;
3）将合成液密封在带有聚四氟乙烯内筒的不锈钢水热合成釜内进行水热合成反应，水热合成温度为240℃，合成时间为20h；反应结束后，将催化剂从溶液中过滤，得固体中间催化剂，以去离子水、乙醇洗涤至洗液pH值小于8；3) Seal the synthesis liquid in a stainless steel hydrothermal synthesis kettle with a polytetrafluoroethylene inner cylinder for hydrothermal synthesis reaction. The hydrothermal synthesis temperature is 240°C, and the synthesis time is 20h; after the reaction, remove the catalyst from the solution Filtrate to obtain a solid intermediate catalyst, wash with deionized water and ethanol until the pH value of the washing solution is less than 8;
4）将固体中间催化剂在120℃下干燥10h，加热到500℃焙烧10h，以脱除模板剂，制得新型结构Co·HZSM-5分子筛催化剂。4) The solid intermediate catalyst was dried at 120 °C for 10 h, and then heated to 500 °C for 10 h to remove the template agent and obtain a new structure Co·HZSM-5 molecular sieve catalyst.
Co·HZSM-5催化剂包括Co活性组分纳米颗粒和HZSM-5分子筛，所述Co活性组分纳米颗粒嵌入分散在HZSM-5分子筛中，所述Co活性组分纳米颗粒在催化剂中含量经检测为19.2wt%，活性金属纳米颗粒粒径为12nm，分子筛晶粒大小为5μm；The Co HZSM-5 catalyst includes Co active component nanoparticles and HZSM-5 molecular sieves, the Co active component nanoparticles are embedded and dispersed in the HZSM-5 molecular sieve, and the content of the Co active component nanoparticles in the catalyst is detected is 19.2wt%, the particle size of the active metal nanoparticles is 12nm, and the molecular sieve grain size is 5μm;
将所得Co·HZSM-5分子筛催化剂于10MPa下压片，粉碎后取20-40目的颗粒用于固定床费托合成反应性能测试。The obtained Co·HZSM-5 molecular sieve catalyst was pressed into tablets under 10 MPa, and after being pulverized, 20-40 mesh particles were taken for the performance test of the fixed-bed Fischer-Tropsch synthesis reaction.
催化剂的费托反应活性评价同实施例1，反应结果如下表所示。The evaluation of the Fischer-Tropsch reaction activity of the catalyst is the same as in Example 1, and the reaction results are shown in the table below.
αiso-C5-C12为C5-C12中支链烷烃的选择性。α iso-C5 -C12 is the selectivity of branched alkanes in C5 -C12 .
实施例3Example 3
一种活性组分纳米颗粒嵌入分子筛结晶的催化剂的制备方法，包括如下步骤：A method for preparing a catalyst in which active component nanoparticles are embedded in molecular sieve crystals, comprising the following steps:
采用传统的等体积浸渍法制备Co-Zr/SiO2催化剂：Preparation of Co-Zr/SiO2 catalyst by traditional equal volume impregnation method:
将SiO2于空气中200℃处理2h，然后以Co(NO3)2·6H2O和Zr(NO3)4·5H2O的水溶液对其等体积浸渍，活性金属Co负载量为20wt%，助剂Zr负载量为6wt%，真空处理1h，120℃干燥12h，400℃焙烧2h，得到Co-Zr/SiO2前驱体催化剂；将所得前驱体催化剂破碎筛分为过60目的粉末；SiO2 was treated in air at 200°C for 2h, and then impregnated with an equal volume of Co(NO3 )2 6H2 O and Zr(NO3 )4 5H2 O aqueous solutions, the active metal Co loading was 20wt% , the additive Zr loading is 6wt%, vacuum treatment for 1h, drying at 120°C for 12h, and roasting at 400°C for 2h to obtain a Co-Zr/SiO2 precursor catalyst; crush and sieve the obtained precursor catalyst into a 60-mesh powder;
其余操作步骤同实施例1，制备得到新型结构Co-Zr·HZSM-5分子筛催化剂。Co-Zr·HZSM-5催化剂包括Co活性组分纳米颗粒、Zr助剂颗粒和HZSM-5分子筛，所述Co活性组分纳米颗粒嵌入分散在HZSM-5分子筛中，所述Co活性组分纳米颗粒在催化剂中含量经检测为19.0wt%，活性金属纳米颗粒粒径为9nm，分子筛晶粒大小为5μm；The rest of the operation steps are the same as in Example 1, and a novel structure Co-Zr·HZSM-5 molecular sieve catalyst is prepared. The Co-Zr·HZSM-5 catalyst includes Co active component nanoparticles, Zr additive particles and HZSM-5 molecular sieve, the Co active component nanoparticles are embedded and dispersed in the HZSM-5 molecular sieve, and the Co active component nano The content of the particles in the catalyst was detected to be 19.0wt%, the particle size of the active metal nanoparticles was 9nm, and the grain size of the molecular sieve was 5μm;
将所得Co-Zr·HZSM-5分子筛催化剂于10MPa下压片，粉碎后取20～40目的颗粒用于费托合成反应性能测试。催化剂的费托反应活性评价同实施例1，反应结果如下表所示。The obtained Co-Zr·HZSM-5 molecular sieve catalyst was pressed into tablets under 10 MPa, and after crushing, 20-40 mesh particles were taken for the performance test of Fischer-Tropsch synthesis reaction. The evaluation of the Fischer-Tropsch reaction activity of the catalyst is the same as in Example 1, and the reaction results are shown in the table below.
αiso-C5-C12为C5-C12中支链烷烃的选择性。α iso-C5 -C12 is the selectivity of branched alkanes in C5 -C12 .
实施例4Example 4
一种活性组分纳米颗粒嵌入分子筛结晶的催化剂的制备方法，包括如下步骤：A method for preparing a catalyst in which active component nanoparticles are embedded in molecular sieve crystals, comprising the following steps:
采用传统的等体积浸渍法制备Co-Ru/Al2O3前驱体催化剂；载体γ-Al2O3于空气中200℃处理2h，之后以Co(NO3)2·6H 2O和RuCl3的水溶液对其等体积浸渍，活性金属Co负载量为20wt%，助剂Ru负载量为2wt%，真空处理1h，120℃干燥12h，400℃焙烧2h，得到前驱体催化剂；将所得前驱体催化剂破碎筛分为过80目的粉末；The Co-Ru/Al2 O3 precursor catalyst was prepared by the traditional equal-volume impregnation method; the carrier γ-Al2 O3 was treated in air at 200°C for 2 h, and then coated with Co(NO3 )2 ·6H2 O and RuCl3 The aqueous solution is impregnated with an equal volume, the active metal Co loading is 20wt%, the additive Ru loading is 2wt%, vacuum treatment for 1h, drying at 120°C for 12h, and roasting at 400°C for 2h to obtain a precursor catalyst; the obtained precursor catalyst Crushed and sieved into 80-mesh powder;
其余操作步骤同实施例2，制备得到新型结构Co-Ru·HZSM-5分子筛催化剂。Co-Ru·HZSM-5催化剂包括Co活性组分纳米颗粒、Ru助剂颗粒和HZSM-5分子筛，所述Co活性组分纳米颗粒嵌入分散在HZSM-5分子筛中，所述Co活性组分纳米颗粒在催化剂中含量经检测为19.4wt%，活性金属纳米颗粒粒径为8nm，分子筛晶粒大小为5μm；The rest of the operation steps are the same as in Example 2, and a novel structure Co-Ru·HZSM-5 molecular sieve catalyst is prepared. The Co-Ru·HZSM-5 catalyst includes Co active component nanoparticles, Ru additive particles and HZSM-5 molecular sieve, the Co active component nanoparticles are embedded and dispersed in the HZSM-5 molecular sieve, and the Co active component nano The content of the particles in the catalyst was detected to be 19.4wt%, the particle size of the active metal nanoparticles was 8nm, and the grain size of the molecular sieve was 5μm;
将所得Co-Ru·HZSM-5分子筛催化剂于10MPa下压片，粉碎后取20～40目的颗粒用于费托合成反应性能测试。催化剂的费托反应活性评价同实施例1，反应结果如下表所示。The obtained Co-Ru·HZSM-5 molecular sieve catalyst was pressed into tablets under 10 MPa, and after crushing, 20-40 mesh particles were taken for the performance test of Fischer-Tropsch synthesis reaction. The evaluation of the Fischer-Tropsch reaction activity of the catalyst is the same as in Example 1, and the reaction results are shown in the table below.
αiso-C5-C12为C5-C12中支链烷烃的选择性。α iso-C5 -C12 is the selectivity of branched alkanes in C5 -C12 .
实施例5Example 5
一种活性组分纳米颗粒嵌入分子筛结晶的催化剂的制备方法，包括如下步骤：A method for preparing a catalyst in which active component nanoparticles are embedded in molecular sieve crystals, comprising the following steps:
采用传统的过量浸渍法制备Fe-Mn-K/SiO2前驱体催化剂，将SiO2于空气中200℃处理2h，之后将其加入一定量Fe(NO3)3·9H2O、Mn(NO3)2·4H2O、KNO3的混合溶液中（活性金属Fe负载量20wt%，助剂Mn、K的负载量分别为6wt%、4wt%），70℃连续搅拌至水大部分蒸发，之后放入干燥箱120℃干燥12h，400℃焙烧2h，得到前驱体催化剂；将所得前驱体催化剂破碎筛分为过120目的粉末；The Fe-Mn-K/SiO2 precursor catalyst was prepared by the traditional excessive impregnation method, and the SiO2 was treated in the air at 200°C for 2 hours, and then a certain amount of Fe(NO3 )3 ·9H2 O, Mn(NO3 ) In the mixed solution of2 4H2 O and KNO3 (the loading of active metal Fe is 20wt%, and the loading of additives Mn and K are 6wt% and 4wt%, respectively), stirring continuously at 70°C until most of the water evaporates, Then put it into a drying oven for 12 hours at 120°C, and then bake it at 400°C for 2 hours to obtain a precursor catalyst; crush and sieve the obtained precursor catalyst into a 120-mesh powder;
其余操作步骤同实施例1，制备得到新型结构Fe-Mn-K·HZSM-5分子筛催化剂。The rest of the operation steps are the same as in Example 1, and a novel structure Fe-Mn-K·HZSM-5 molecular sieve catalyst is prepared.
Fe-Mn-K·HZSM-5催化剂包括Fe活性组分纳米颗粒、Mn和K助剂颗粒和HZSM-5分子筛，所述Fe活性组分纳米颗粒嵌入分散在HZSM-5分子筛中，所述Fe活性组分纳米颗粒在催化剂中含量经检测为18.8wt%，活性Fe纳米颗粒粒径为12nm，分子筛晶粒大小为5μm；The Fe-Mn-K HZSM-5 catalyst includes Fe active component nanoparticles, Mn and K additive particles and HZSM-5 molecular sieve, the Fe active component nanoparticles are embedded and dispersed in the HZSM-5 molecular sieve, the Fe The content of active component nanoparticles in the catalyst was detected to be 18.8wt%, the particle size of active Fe nanoparticles was 12nm, and the molecular sieve grain size was 5μm;
将所得Fe-Mn-K·HZSM-5分子筛催化剂于10MPa下压片，粉碎后取20～40目的颗粒用于费托合成反应性能测试；催化剂的活化条件为：在常压下以38ml/mi n的合成气（H2/CO摩尔比为1.0）在300℃还原10h。催化剂的反应条件为：280℃，1.0MPa，H2/CO摩尔比为1.0，Wcat/F=5ghmol-1，反应结果如下表所示。The obtained Fe-Mn-K·HZSM-5 molecular sieve catalyst was pressed into tablets under 10 MPa, and after crushing, 20-40 mesh particles were taken for the performance test of Fischer-Tropsch synthesis reaction; the activation conditions of the catalyst were: 38ml/min under normal pressure The synthesis gas of n (H2 /CO molar ratio 1.0) was reduced at 300°C for 10 h. The reaction conditions of the catalyst are: 280°C, 1.0MPa, H2 /CO molar ratio 1.0, Wcat /F=5ghmol-1 , and the reaction results are shown in the table below.
αC2=-C4=为C2-C4中烯烃的选择性α C2= -C4= is the selectivity of alkenes in C2 -C4
实施例6Example 6
一种活性组分纳米颗粒嵌入分子筛结晶的催化剂的制备方法，包括如下步骤：A method for preparing a catalyst in which active component nanoparticles are embedded in molecular sieve crystals, comprising the following steps:
采用传统的共沉淀法制备Co-Zr-Al前驱体催化剂；按照比例配制Co(NO3)2·6H2O、Zr(NO3)4·5H2O和Al(NO3)3·9H2O的混合溶液（溶液中Co、Zr、Al2O3的质量比为20：6：100），以(NH4)2·CO3为沉淀剂，在60℃的恒温水浴中连续均匀共沉淀，剧烈搅拌，同时调节加料速度以控制沉淀液的pH值为7±0.2，沉淀结束后，继续搅拌1h，静置陈化过夜，之后过滤并以去离子水和乙醇洗涤至洗液pH值小于8，之后120℃干燥12h，400℃焙烧2h，得到前驱体催化剂；将所得前驱体催化剂破碎筛分为过180目的粉末；The Co-Zr-Al precursor catalyst was prepared by the traditional co-precipitation method; Co(NO3 )2 ·6H2 O, Zr(NO3 )4 ·5H2 O and Al(NO3 )3 ·9H2 were prepared in proportion A mixed solution of O (the mass ratio of Co, Zr, and Al2 O3 in the solution is 20:6:100), with (NH4 )2 CO3 as the precipitant, continuous and uniform co-precipitation in a constant temperature water bath at 60°C , stirring vigorously, while adjusting the feeding speed to control the pH value of the precipitation solution to 7±0.2, after the precipitation, continue to stir for 1h, let it stand and age overnight, then filter and wash with deionized water and ethanol until the pH value of the washing solution is less than 8. Afterwards, dry at 120°C for 12 hours, and roast at 400°C for 2 hours to obtain a precursor catalyst; crush and sieve the obtained precursor catalyst into a 180-mesh powder;
其余操作步骤同实施例2，制备得到新型结构Co-Zr·HZSM-5分子筛催化剂。The rest of the operation steps are the same as in Example 2, and a novel structure Co-Zr·HZSM-5 molecular sieve catalyst is prepared.
Co-Zr·HZSM-5催化剂包括Co活性组分纳米颗粒、Zr助剂颗粒和HZSM-5分子筛，所述Co活性组分纳米颗粒嵌入分散在HZSM-5分子筛中，所述Co活性组分纳米颗粒在催化剂中含量经检测为19.7wt%，活性Co纳米颗粒粒径为15nm，分子筛晶粒大小为5μm；The Co-Zr·HZSM-5 catalyst includes Co active component nanoparticles, Zr additive particles and HZSM-5 molecular sieve, the Co active component nanoparticles are embedded and dispersed in the HZSM-5 molecular sieve, and the Co active component nano The content of the particles in the catalyst was detected to be 19.7wt%, the particle size of the active Co nanoparticles was 15nm, and the molecular sieve grain size was 5μm;
将所得Co-Zr·HZSM-5分子筛催化剂于10MPa下压片，粉碎后取20～40目的颗粒用于费托合成反应性能测试。催化剂的费托反应活性评价同实施例1，反应结果如下表所示。The obtained Co-Zr·HZSM-5 molecular sieve catalyst was pressed into tablets under 10 MPa, and after crushing, 20-40 mesh particles were taken for the performance test of Fischer-Tropsch synthesis reaction. The evaluation of the Fischer-Tropsch reaction activity of the catalyst is the same as in Example 1, and the reaction results are shown in the table below.
αiso-C5-C12为C5-C12中支链烷烃的选择性。α iso-C5 -C12 is the selectivity of branched alkanes in C5 -C12 .
实施例7Example 7
一种活性组分纳米颗粒嵌入分子筛结晶的催化剂的制备方法，包括如下步骤：A method for preparing a catalyst in which active component nanoparticles are embedded in molecular sieve crystals, comprising the following steps:
采用传统的共沉淀法制备Fe-Mn-Cu-K-Al前驱体催化剂。按照比例配制Fe(NO3)3·9H2O、Mn(NO3)2·4H2O、Cu(NO3)2·3H2O、KNO3和Al(NO 3)3·9H2O的混合溶液（催化剂中Fe、Mn、Cu、K、Al2O3的质量比为20：6：6：2：100），以K2CO3为沉淀剂，在60℃的恒温水浴中连续均匀共沉淀，剧烈搅拌，同时调节加料速度以控制沉淀液的pH值为7±0.2，沉淀结束后，继续搅拌1h，静置陈化过夜，之后过滤并以去离子水和乙醇洗涤至洗液pH值小于8，之后120℃干燥12h，400℃焙烧2h；将所得颗粒催化剂破碎筛分为80目的粉末；The Fe-Mn-Cu-K-Al precursor catalyst was prepared by the traditional co-precipitation method. Prepare Fe(NO3 )3 ·9H2 O, Mn(NO3 )2 ·4H2 O, Cu(NO3 )2 ·3H2 O, KNO3 and Al(NO3 )3 ·9H2 O in proportion The mixed solution (the mass ratio of Fe, Mn, Cu, K, and Al2 O3 in the catalyst is 20:6:6:2:100), with K2 CO3 as the precipitant, is continuously and uniformly placed in a constant temperature water bath at 60°C Co-precipitate, stir vigorously, and adjust the feeding speed at the same time to control the pH value of the precipitation solution to 7±0.2. After the precipitation is completed, continue to stir for 1 hour, let stand and age overnight, then filter and wash with deionized water and ethanol to the pH of the washing solution The value is less than 8, then dried at 120°C for 12 hours, and calcined at 400°C for 2 hours; the obtained granular catalyst was crushed and sieved into 80-mesh powder;
其余操作步骤同实施例2，制备得到新型结构Fe-Mn-Cu-K·HZSM-5分子筛催化剂。Fe-Mn-Cu-K·HZSM-5催化剂包括Fe活性组分纳米颗粒、助剂Mn和助剂Cu和助剂K颗粒和HZSM-5分子筛，所述Fe活性组分纳米颗粒嵌入分散在HZSM-5分子筛中，所述Fe活性组分纳米颗粒在催化剂中含量为17.9wt%，活性Fe纳米颗粒粒径为19nm，分子筛晶粒大小为5μm；The rest of the operation steps are the same as in Example 2, and a molecular sieve catalyst with a new structure Fe-Mn-Cu-K·HZSM-5 is prepared. The Fe-Mn-Cu-K HZSM-5 catalyst includes Fe active component nanoparticles, auxiliary agent Mn and auxiliary agent Cu and auxiliary agent K particles and HZSM-5 molecular sieve, and the Fe active component nanoparticle is embedded and dispersed in HZSM In -5 molecular sieves, the content of the Fe active component nanoparticles in the catalyst is 17.9wt%, the particle size of the active Fe nanoparticles is 19nm, and the molecular sieve grain size is 5 μm;
将所得Fe-Mn-Cu-K·HZSM-5分子筛催化剂于10MPa下压片，粉碎后取20-40目的颗粒用于费托合成反应性能测试。催化剂的费托反应活性评价同实施例5，反应结果如下表所示。The obtained Fe-Mn-Cu-K·HZSM-5 molecular sieve catalyst was pressed into tablets under 10 MPa, and after crushing, 20-40 mesh particles were taken for the performance test of Fischer-Tropsch synthesis reaction. The evaluation of the Fischer-Tropsch reaction activity of the catalyst is the same as in Example 5, and the reaction results are shown in the table below.
αC2=-C4=为C2-C4中烯烃的选择性。α C2= -C4= is the selectivity of olefins in C2 -C4 .
实施例8：Embodiment 8:
一种活性组分纳米颗粒嵌入分子筛结晶的催化剂的制备方法，包括如下步骤：A method for preparing a catalyst in which active component nanoparticles are embedded in molecular sieve crystals, comprising the following steps:
Co/SiO2前驱体催化剂的制备同实施例1，采用水热合成法制备Co·Hβ催化剂，以四乙基氢氧化铵（TEAOH）为模板剂，以Al(NO 3)3·9H2O为Al源，以Co/SiO2在合成过程中溶出的Si作为Si源；合成液摩尔比为1.0Al:70Si:80TEAOH:900EtOH:2000H 2O；The preparation of the Co/SiO2 precursor catalyst is the same as in Example 1. The Co Hβ catalyst is prepared by the hydrothermal synthesis method, using tetraethylammonium hydroxide (TEAOH) as the template agent, and Al(NO3 )3 9H2 O As the Al source, the Si dissolved out of Co/SiO2 during the synthesis process is used as the Si source; the molar ratio of the synthesis solution is 1.0Al:70Si:80TEAOH:900EtOH:2000H2 O;
将Al(NO3)3·9H2O以去离子水和乙醇溶解，搅拌均匀后，加入催化剂前驱体粉末，之后逐滴加入模板剂TEAOH，搅拌混合均匀，之后将合成液密封在带有聚四氟乙烯内筒的不锈钢水热合成釜内，水热合成温度为155℃，合成时间为80h。反应结束后，将催化剂从溶液中过滤，以去离子水、乙醇洗涤至洗液pH值小于8，之后120℃干燥12h，500℃焙烧5h脱除模板剂，即制备得到新型结构Co·Hβ分子筛催化剂。Dissolve Al(NO3 )3 ·9H2 O in deionized water and ethanol, stir evenly, add catalyst precursor powder, then add template agent TEAOH drop by drop, stir and mix evenly, and then seal the synthesis liquid in a poly In the stainless steel hydrothermal synthesis kettle with tetrafluoroethylene inner cylinder, the hydrothermal synthesis temperature is 155° C., and the synthesis time is 80 h. After the reaction, the catalyst was filtered from the solution, washed with deionized water and ethanol until the pH value of the washing solution was less than 8, then dried at 120°C for 12 hours, and calcined at 500°C for 5 hours to remove the template agent, and the new structure Co Hβ molecular sieve was prepared catalyst.
Co·Hβ催化剂包括Co活性组分纳米颗粒和Hβ分子筛，所述Co活性组分纳米颗粒嵌入分散在Hβ分子筛中，所述Co活性组分纳米颗粒在催化剂中含量经检测为19.5wt%，活性Co纳米颗粒粒径为12nm，分子筛晶粒大小为2μm；The Co Hβ catalyst includes Co active component nanoparticles and Hβ molecular sieves, the Co active component nanoparticles are embedded and dispersed in the Hβ molecular sieve, and the content of the Co active component nanoparticles in the catalyst is detected to be 19.5wt%. The particle size of Co nanoparticles is 12nm, and the molecular sieve grain size is 2μm;
将所得Co·Hβ分子筛催化剂于10MPa下压片，粉碎后取20～40目的颗粒用于固定床费托合成反应性能测试。催化剂的费托反应活性评价同实施例1，反应结果如下表所示。The obtained Co·Hβ molecular sieve catalyst was pressed into tablets under 10 MPa, and after crushing, 20-40 mesh particles were taken for the performance test of the fixed-bed Fischer-Tropsch synthesis reaction. The evaluation of the Fischer-Tropsch reaction activity of the catalyst is the same as in Example 1, and the reaction results are shown in the table below.
αiso-C5-C12为C5-C12中支链烷烃的选择性。α iso-C5 -C12 is the selectivity of branched alkanes in C5 -C12 .
实施例9：Embodiment 9:
一种活性组分纳米颗粒嵌入分子筛结晶的催化剂的制备方法，包括如下步骤：A method for preparing a catalyst in which active component nanoparticles are embedded in molecular sieve crystals, comprising the following steps:
Co/Al2O3前驱体催化剂的制备同实施例2，采用水热合成法制备Co·Hβ催化剂，以四乙基氢氧化铵（TEAOH）为模板剂，以Al(NO 3)3·9H2O为Al源，以Co/SiO2在合成过程中溶出的Si作为Si源；合成溶液摩尔比为2.0Al:50Si:50TEAOH:500EtOH:880H2O；The preparation of the Co/Al2 O3 precursor catalyst is the same as in Example 2. The Co Hβ catalyst is prepared by the hydrothermal synthesis method, using tetraethylammonium hydroxide (TEAOH) as the template agent, and Al(NO3 )3 9H2 O is the Al source, and the Si dissolved out of Co/SiO2 during the synthesis process is used as the Si source; the molar ratio of the synthesis solution is 2.0Al:50Si:50TEAOH:500EtOH:880H2 O;
将TEOS与去离子水和乙醇混合，搅拌均匀后，加入催化剂前驱体粉末，之后逐滴加入模板剂，搅拌混合均匀，之后将合成液密封在带有聚四氟乙烯内筒的不锈钢水热合成釜内，水热合成温度为155℃，合成时间为500h；反应结束后，将催化剂从溶液中过滤，以去离子水、乙醇洗涤至洗液pH值小于8，之后120℃干燥2h，500℃焙烧5h脱除模板剂，即制备得到新型结构Co·HMix TEOS with deionized water and ethanol, stir evenly, add catalyst precursor powder, then add template agent drop by drop, stir and mix evenly, and then seal the synthesis solution in a stainless steel hydrothermal synthesis chamber with a PTFE inner cylinder In the kettle, the hydrothermal synthesis temperature is 155°C, and the synthesis time is 500h; after the reaction, the catalyst is filtered from the solution, washed with deionized water and ethanol until the pH of the washing solution is less than 8, then dried at 120°C for 2h, and then dried at 500°C Calcined for 5 hours to remove the template agent, the new structure Co·H
β分子筛催化剂。Beta molecular sieve catalyst.
Co·Hβ催化剂包括Co活性组分纳米颗粒和Hβ分子筛，所述Co活性组分纳米颗粒嵌入分散在Hβ分子筛中，所述Co活性组分纳米颗粒在催化剂中含量为19.5wt%，活性Co纳米颗粒粒径为14nm，分子筛晶粒大小为2μm；The Co Hβ catalyst includes Co active component nanoparticles and Hβ molecular sieves, the Co active component nanoparticles are embedded and dispersed in the Hβ molecular sieve, the Co active component nanoparticles are contained in the catalyst at 19.5wt%, and the active Co nano The particle size is 14nm, and the molecular sieve grain size is 2μm;
将所得Co·Hβ分子筛催化剂于10MPa下压片，粉碎后取20～40目的颗粒用于固定床费托合成反应性能测试。催化剂的费托反应活性评价同实施例1，反应结果如下表所示。The obtained Co·Hβ molecular sieve catalyst was pressed into tablets under 10 MPa, and after crushing, 20-40 mesh particles were taken for the performance test of the fixed-bed Fischer-Tropsch synthesis reaction. The evaluation of the Fischer-Tropsch reaction activity of the catalyst is the same as in Example 1, and the reaction results are shown in the table below.
αiso-C5-C12为C5-C12中支链烷烃的选择性。α iso-C5 -C12 is the selectivity of branched alkanes in C5 -C12 .
实施例10：Example 10:
一种活性组分纳米颗粒嵌入分子筛结晶的催化剂的制备方法，包括如下步骤：A method for preparing a catalyst in which active component nanoparticles are embedded in molecular sieve crystals, comprising the following steps:
1）Cu-Zn-Al前驱体催化剂的制备1) Preparation of Cu-Zn-Al precursor catalyst
采用传统的共沉淀法制备Cu-Zn-Al前驱体催化剂：按照一定比例配制Cu(NO3)2·3H2O、Zn(NO3)2·6H2O、和Al(NO3)3·9H2O的混合溶液（催化剂中Cu、Zn、Al的摩尔比为6：3：1），以(NH4)2CO3为沉淀剂，在60℃的恒温水浴中连续均匀共沉淀，剧烈搅拌，同时调节加料速度以控制沉淀液的pH值为7±0.2，沉淀结束后，继续搅拌1h，静置陈化过夜，之后过滤并以去离子水和乙醇洗涤至洗液pH值小于8，之后120℃干燥5h，350℃焙烧3h。将所得颗粒催化剂破碎筛分为80目的粉末；Prepare Cu-Zn-Al precursor catalyst by traditional co-precipitation method: prepare Cu(NO3 )2 ·3H2 O, Zn(NO3 )2 ·6H2 O, and Al(NO3 )3 · A mixed solution of 9H2 O (the molar ratio of Cu, Zn, and Al in the catalyst is 6:3:1), using (NH4 )2 CO3 as the precipitating agent, continuously and uniformly co-precipitates in a constant temperature water bath at 60°C, violently Stir while adjusting the feeding speed to control the pH of the precipitation solution to be 7±0.2. After the precipitation is complete, continue to stir for 1 hour, let stand and age overnight, then filter and wash with deionized water and ethanol until the pH of the washing solution is less than 8. Afterwards, dry at 120°C for 5 hours, and bake at 350°C for 3 hours. Gained granular catalyst is crushed and sieved into 80 mesh powder;
2）新型结构Cu-Zn·Hβ催化剂的制备2) Preparation of new structure Cu-Zn·Hβ catalyst
采用水热合成法制备Cu-Zn·Hβ催化剂，以四乙基氢氧化铵（TEAOH）为模板剂，以Al(NO3)3·9H2O为Al源，以Co/SiO2在合成过程中溶出的Si作为Si源。合成溶液摩尔比为10Al:20Si:15TEAOH:300EtOH:500H2O；Cu-Zn·Hβ catalyst was prepared by hydrothermal synthesis method, using tetraethylammonium hydroxide (TEAOH) as template, Al(NO3 )3 9H2 O as Al source, Co/SiO2 in the synthesis process The Si dissolved out of the solution was used as the Si source. The molar ratio of the synthesis solution is 10Al:20Si:15TEAOH:300EtOH:500H2 O;
将Al(NO 3)3·9H2O以去离子水和乙醇溶解，搅拌均匀后，加入步骤1）中的催化剂粉末，之后逐滴加入模板剂TEAOH，搅拌混合均匀，之后将合成液密封在带有聚四氟乙烯内筒的不锈钢水热合成釜内，水热合成温度为155℃，合成时间为80h。反应结束后，将催化剂从溶液中过滤，以去离子水、乙醇洗涤至洗液pH值小于8，之后140℃干燥12h，600℃焙烧2h脱除模板剂；得到新型结构Cu-Zn·Hβ分子筛催化剂。Dissolve Al(NO3 )3 ·9H2 O in deionized water and ethanol, stir evenly, add the catalyst powder in step 1), then add the template agent TEAOH drop by drop, stir and mix evenly, and then seal the synthesis solution in In a stainless steel hydrothermal synthesis kettle with a polytetrafluoroethylene inner cylinder, the hydrothermal synthesis temperature is 155° C., and the synthesis time is 80 h. After the reaction, the catalyst was filtered from the solution, washed with deionized water and ethanol until the pH value of the washing solution was less than 8, then dried at 140°C for 12 hours, and calcined at 600°C for 2 hours to remove the template agent; a new structure Cu-Zn·Hβ molecular sieve was obtained catalyst.
Cu-Zn·Hβ催化剂包括Cu活性组分纳米颗粒、助剂Zn颗粒和Hβ分子筛，所述Cu活性组分纳米颗粒嵌入分散在Hβ分子筛中，所述Cu活性组分纳米颗粒在催化剂中含量为60.4wt%，活性Cu纳米颗粒粒径为20nm，分子筛晶粒大小为2μm；The Cu-Zn·Hβ catalyst includes Cu active component nanoparticles, additive Zn particles and Hβ molecular sieves, the Cu active component nanoparticles are embedded and dispersed in the Hβ molecular sieve, and the content of the Cu active component nanoparticles in the catalyst is 60.4wt%, the particle size of active Cu nanoparticles is 20nm, and the molecular sieve grain size is 2μm;
将所得Cu-Zn·Hβ催化剂于10MPa下压片，粉碎后取20～40目的颗粒用于合成气一步法制二甲醚反应性能测试；催化剂的活化条件为：在常压下以60ml/min的H2在220℃还原10h。催化剂的反应条件为：250℃，3.0MPa，H2/CO摩尔比为1.5，Wcat/F=5ghmol-1，反应结果如下表所示：The obtained Cu-Zn·Hβ catalyst was pressed into tablets under 10 MPa, and after crushing, 20-40 mesh particles were taken to test the reaction performance of the one-step synthesis gas to dimethyl ether; the activation conditions of the catalyst were:H2 was reduced at 220 °C for 10 h. The reaction conditions of the catalyst are: 250°C, 3.0MPa, H2 /CO molar ratio 1.5, Wcat /F=5ghmol-1 , the reaction results are shown in the following table:
本实施例催化剂对二甲醚生产有良好的选择性。The catalyst of this example has good selectivity to the production of dimethyl ether.
实施例11：Example 11:
一种活性组分纳米颗粒嵌入分子筛结晶的催化剂的制备方法，包括如下步骤：A method for preparing a catalyst in which active component nanoparticles are embedded in molecular sieve crystals, comprising the following steps:
1）Pd/Al2O3前驱体催化剂的制备1) Preparation of Pd/Al2 O3 precursor catalyst
采用传统的等体积浸渍法，将载体γ-Al2O3于空气中200℃处理2h，之后以Pd(NO3)2·2H2O为Pd源对其等体积浸渍，活性金属Pd负载量10wt%，真空处理1h，120℃干燥12h，400℃焙烧2h，将所得Pd/Al2O3前驱体催化剂破碎筛分为70目的粉末；Using the traditional equal-volume impregnation method, the carrier γ-Al2 O3 was treated in the air at 200°C for 2 hours, and then impregnated with equal volume with Pd(NO3 )2 ·2H2 O as the Pd source. The active metal Pd loading 10wt%, vacuum treatment for 1h, drying at 120°C for 12h, calcination at 400°C for 2h, crushing and sieving the obtained Pd/Al2 O3 precursor catalyst into 70-mesh powder;
2）新型结构Pd·HZSM-5催化剂的制备2) Preparation of new structure Pd·HZSM-5 catalyst
采用水热合成法制备Pd·HZSM-5催化剂：以四丙基氢氧化铵（TPAOH）为模板剂，以正硅酸乙酯（TEOS）为Si源，以Co/Al2O3在合成过程中溶出的Al作为Al源；The Pd·HZSM-5 catalyst was prepared by hydrothermal synthesis method: Tetrapropylammonium hydroxide (TPAOH) was used as the template, tetraethyl orthosilicate (TEOS) was used as the Si source, and Co/Al2 O3 was used in the synthesis process The Al dissolved in the medium is used as the Al source;
将TEOS与去离子水和乙醇混合，搅拌均匀后，加入步骤1）得到的前躯体催化剂粉末，之后逐滴加入模板剂，搅拌混合均匀，得合成液，合成液中摩尔比为1.0Al:5S i:8TPAOH:50EtOH:100H2O；之后将合成液密封在带有聚四氟乙烯内筒的不锈钢水热合成釜内，水热合成温度为165℃，合成时间为100h。反应结束后，将催化剂从溶液中过滤，以去离子水、乙醇洗涤至洗液pH值小于8，之后130℃干燥10h，500℃焙烧12h脱除模板剂，得到新型结构Pd·HZSM-5分子筛催化剂。Mix TEOS with deionized water and ethanol, stir evenly, add the precursor catalyst powder obtained in step 1), then add the template agent drop by drop, stir and mix evenly to obtain a synthetic solution, the molar ratio of which is 1.0Al:5S i: 8TPAOH: 50EtOH: 100H2 O; then the synthesis solution was sealed in a stainless steel hydrothermal synthesis kettle with a polytetrafluoroethylene inner cylinder, the hydrothermal synthesis temperature was 165°C, and the synthesis time was 100h. After the reaction, the catalyst was filtered from the solution, washed with deionized water and ethanol until the pH value of the washing liquid was less than 8, then dried at 130°C for 10h, and calcined at 500°C for 12h to remove the template agent to obtain a new structure Pd·HZSM-5 molecular sieve catalyst.
Pd·HZSM-5催化剂包括Pd活性组分纳米颗粒颗粒和HZSM-5分子筛，所述Pd活性组分纳米颗粒嵌入分散在HZSM-5分子筛中，所述Pd活性组分纳米颗粒在催化剂中含量经检测为9.8wt%，活性Pd纳米颗粒粒径为7nm，分子筛晶粒大小为4μm；The Pd·HZSM-5 catalyst includes Pd active component nanoparticle particles and HZSM-5 molecular sieve, the Pd active component nanoparticle is embedded and dispersed in the HZSM-5 molecular sieve, and the content of the Pd active component nanoparticle in the catalyst is determined by The detection rate is 9.8wt%, the particle size of active Pd nanoparticles is 7nm, and the molecular sieve grain size is 4μm;
将所得Pd·HZSM-5分子筛催化剂于10MPa下压片，粉碎后取20-40目的颗粒用于合成气直接制芳烃反应性能测试。The obtained Pd·HZSM-5 molecular sieve catalyst was pressed into tablets under 10 MPa, and after being pulverized, 20-40 mesh particles were taken to test the reaction performance of the direct production of aromatics from synthesis gas.
催化剂的活化条件为：在常压下以80ml/min的H2在400℃还原10h。催化剂的反应条件为：500℃，5.0MPa，H2/CO摩尔比为2.0，Wcat/F=5ghmol-1，反应结果如下表所示。The activation condition of the catalyst is: reduction with 80ml/minH2 at 400°C for 10h under normal pressure. The catalyst reaction conditions are: 500°C, 5.0MPa, H2 /CO molar ratio 2.0, Wcat /F=5ghmol-1 , and the reaction results are shown in the table below.
本实施例催化剂对芳烃生产有良好的选择性。The catalyst in this example has good selectivity for the production of aromatics.
实施例12Example 12
一种活性组分纳米颗粒嵌入分子筛结晶的催化剂的制备方法，重复实施例1，其不同之处仅在于：活性金属选用Cu，Cu负载量为2wt%，制得新型结构Cu·HZSM-5分子筛催化剂。A method for preparing a catalyst in which active component nanoparticles are embedded in molecular sieve crystals, repeating Example 1, the only difference is that: the active metal is Cu, and the Cu loading is 2wt%, and a new structure Cu HZSM-5 molecular sieve is obtained catalyst.
催化剂的活化条件为：在常压下以80ml/min的H2在400℃还原10h。催化剂的反应条件为：400℃，10.0MPa，H2/CO摩尔比为2.0，Wcat/F=5ghmo -l，反应结果如下表所示。The activation condition of the catalyst is: reduction with 80ml/minH2 at 400°C for 10h under normal pressure. The catalyst reaction conditions are: 400°C, 10.0MPa, H2 /CO molar ratio 2.0, Wcat /F=5ghmo-l , and the reaction results are shown in the table below.
实施例13Example 13
一种活性组分纳米颗粒嵌入分子筛结晶的催化剂的制备方法，重复实施例1，其不同之处仅在于：活性金属选用Ni，Ni负载量为40wt%，制得新型结构Ni·HZSM-5分子筛催化剂。A method for preparing a catalyst in which active component nanoparticles are embedded in molecular sieve crystallization, repeating Example 1, the difference is only that: the active metal is selected from Ni, and the Ni load is 40wt%, and a new structure Ni HZSM-5 molecular sieve is obtained catalyst.
反应结果如下表所示。The reaction results are shown in the table below.
αiso-C5-C12为C5-C12中支链烷烃的选择性。α iso-C5 -C12 is the selectivity of branched alkanes in C5 -C12 .
实施例14Example 14
重复实施例1，其不同之处仅在于：活性金属选用Co和Pt，Co 68wt%，Pt 2wt%。其选择性效果和实施例13分子筛催化剂接近。Repeat embodiment 1, its difference is only: active metal selects Co and Pt for use, Co 68wt%, Pt 2wt%. Its selectivity effect is close to that of the molecular sieve catalyst in Example 13.
实施例15Example 15
重复实施例1，其不同之处仅在于：活性金属选用Ru和Rh，Ru 50wt%和Rh 7wt%，其选择性效果和实施例1分子筛催化剂接近。Repeat embodiment 1, its difference is only: active metal selects Ru and Rh for use, Ru 50wt% and Rh 7wt%, its selectivity effect and embodiment 1 molecular sieve catalyst are close.
实施例16Example 16
重复实施例1，其不同之处仅在于：以十六烷基三甲基溴化铵为模板剂，制得制得新型结构Co·MCM-41分子筛催化剂。其选择性效果和实施例1分子筛催化剂接近。Repeat Example 1, the only difference is that cetyltrimethylammonium bromide is used as a template to prepare a novel structure Co·MCM-41 molecular sieve catalyst. Its selectivity effect is close to that of the molecular sieve catalyst in Example 1.
实施例17Example 17
重复实施例1，其不同之处仅在于：以十八胺为模板剂，制得制得新型结构Co·HMS分子筛催化剂。其选择性效果和实施例1分子筛催化剂接近。Repeat Example 1, the only difference is that octadecylamine is used as a template to prepare a Co·HMS molecular sieve catalyst with a new structure. Its selectivity effect is close to that of the molecular sieve catalyst in Example 1.
实施例18Example 18
重复实施例1，其不同之处仅在于：以聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物为模板剂，制得制得新型结构Co·SBA-15分子筛催化剂。其选择性效果和实施例1分子筛催化剂接近。Repeat Example 1, its difference is only: take polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer as template agent, make Co SBA-15 molecular sieve of novel structure catalyst. Its selectivity effect is close to that of the molecular sieve catalyst in Example 1.
实施例19Example 19
重复实施例1，其不同之处仅在于：以四甲基氢氧化铵为模板剂，制得制得新型结构Co·HY分子筛催化剂。其选择性效果和实施例1分子筛催化剂接近。Repeat Example 1, the only difference is that tetramethylammonium hydroxide is used as a template to prepare a Co·HY molecular sieve catalyst with a new structure. Its selectivity effect is close to that of the molecular sieve catalyst in Example 1.
实施例20Example 20
重复实施例1，其不同之处仅在于：分子筛合成液中不添加其他物质(即只添加模板剂制得纯硅分子筛silicate-1)，制得制得新型结构Co·Silicate-1分子筛催化剂。其选择性效果和实施例1分子筛催化剂接近。Repeat Example 1, the only difference is that no other substances are added to the molecular sieve synthesis liquid (that is, only a template agent is added to obtain pure silicon molecular sieve silicate-1), and a novel structure Co·Silicate-1 molecular sieve catalyst is obtained. Its selectivity effect is close to that of the molecular sieve catalyst in Example 1.
实施例21Example 21
重复实施例1，其不同之处仅在于：分子筛合成液中不是添加Al源，而是添加钛源：钛酸四丁酯（Ti(OC4H 9)4），制得制得新型结构Co·TS-1分子筛催化剂。其选择性效果和实施例1分子筛催化剂接近。Repeat Example 1, the only difference is that instead of adding an Al source to the molecular sieve synthesis solution, a titanium source: tetrabutyl titanate (Ti(OC4 H9 )4 ) is added to obtain a new structure Co ·TS-1 molecular sieve catalyst. Its selectivity effect is close to that of the molecular sieve catalyst in Example 1.
实施例22Example 22
重复实施例2，其不同之处仅在于：分子筛合成液中添加了磷源：磷酸三丁酯（OP(OCH2CH2CH2CH 3)3），，制得制得新型结构Co·SAPO-34分子筛催化剂。其选择性效果和实施例2分子筛催化剂接近。Repeat Example 2, the only difference is that a phosphorus source: tributyl phosphate (OP(OCH2 CH2 CH2 CH3 )3 ) is added to the molecular sieve synthesis liquid, and a new structure Co·SAPO is obtained. -34 molecular sieve catalyst. Its selectivity effect is close to that of the molecular sieve catalyst in Example 2.
实施例23Example 23
重复实施例1，其不同之处仅在于：所述的铝源是硫酸铝（Al2(SO4)3），制得新型结构Co·HZSM-5分子筛催化剂，其选择性效果和实施例1分子筛催化剂接近。Repeat Example 1, the difference is only: the aluminum source is aluminum sulfate (Al2 (SO4 )3 ), and a novel structure Co HZSM-5 molecular sieve catalyst is prepared, and its selectivity effect is the same as that of Example 1 Molecular sieve catalysts approach.
实施例24Example 24
重复实施例1，其不同之处仅在于：所述的铝源是氯化铝（AlCl3），制得新型结构Co·HZSM-5分子筛催化剂，其选择性效果和实施例1分子筛催化剂接近。Repeat Example 1, the only difference is that the aluminum source is aluminum chloride (AlCl3 ), and a new structure Co·HZSM-5 molecular sieve catalyst is prepared, and its selectivity effect is close to that of the molecular sieve catalyst in Example 1.
实施例25Example 25
重复实施例1，其不同之处仅在于：所述的铝源是异丙醇铝（[(CH3)2CHO]3Al），制得新型结构Co·HZSM-5分子筛催化剂，其选择性效果和实施例1分子筛催化剂接近。Repeat Example 1, the difference is only: the aluminum source is aluminum isopropoxide ([(CH3 )2 CHO]3 Al), and a novel structure Co·HZSM-5 molecular sieve catalyst is prepared, and its selectivity The effect is close to that of the molecular sieve catalyst in Example 1.
实施例26Example 26
重复实施例2，其不同之处仅在于：所述的硅源是硅溶胶（SilicaGel），制得Co·HZSM-5分子筛催化剂，其选择性效果和实施例2分子筛催化剂接近。Repeat Example 2, the only difference is that the silicon source is silica sol (SilicaGel), and the Co·HZSM-5 molecular sieve catalyst is prepared, and its selectivity effect is close to that of the molecular sieve catalyst in Example 2.
实施例27Example 27
重复实施例2，其不同之处仅在于：所述的硅源是正硅酸甲酯（TMeOS），制得Co·HZSM-5分子筛催化剂，其选择性效果和实施例2分子筛催化剂接近。Repeat Example 2, the only difference is that the silicon source is methyl orthosilicate (TMeOS), and the Co·HZSM-5 molecular sieve catalyst is prepared, and its selectivity effect is close to that of the molecular sieve catalyst in Example 2.
实施例28Example 28
重复实施例2，其不同之处仅在于：所述的硅源是硅酸钠（Na2SiO3），制得Co·HZSM-5分子筛催化剂，其选择性效果和实施例2分子筛催化剂接近。Repeat Example 2, the only difference is that the silicon source is sodium silicate (Na2 SiO3 ), and the Co·HZSM-5 molecular sieve catalyst is prepared, and its selectivity effect is close to that of the molecular sieve catalyst in Example 2.
实施例29Example 29
重复实施例1，其不同之处仅在于：所述的钛源是四氯化钛（TiCl4），制得Co·TS-1分子筛催化剂，其选择性效果和实施例1分子筛催化剂接近。Repeat Example 1, the only difference is that the titanium source is titanium tetrachloride (TiCl4 ), and the Co·TS-1 molecular sieve catalyst is prepared, and its selectivity effect is close to that of the molecular sieve catalyst in Example 1.
实施例30Example 30
重复实施例1，其不同之处仅在于：所述的钛源是硫酸氧钛（TiOSO4），制得Co·TS-1分子筛催化剂，其选择性效果和实施例1分子筛催化剂接近。Repeat Example 1, the only difference is that: the titanium source is titanyl sulfate (TiOSO4 ), and the Co·TS-1 molecular sieve catalyst is prepared, and its selectivity effect is close to that of the molecular sieve catalyst in Example 1.
实施例31Example 31
重复实施例1，其不同之处仅在于：所述的钛源是硫酸氧钛（TiOSO4），制得Co·TS-1分子筛催化剂，其选择性效果和实施例1分子筛催化剂接近。Repeat Example 1, the only difference is that: the titanium source is titanyl sulfate (TiOSO4 ), and the Co·TS-1 molecular sieve catalyst is prepared, and its selectivity effect is close to that of the molecular sieve catalyst in Example 1.
实施例32Example 32
重复实施例2，其不同之处仅在于：所述的磷源是磷酸（H3PO4），制得Co·SAPO-34分子筛催化剂，其选择性效果和实施例2分子筛催化剂接近。Repeat Example 2, the only difference is that the phosphorus source is phosphoric acid (H3 PO4 ), and the Co·SAPO-34 molecular sieve catalyst is prepared, and its selectivity effect is close to that of the molecular sieve catalyst in Example 2.
实施例33Example 33
重复实施例2，其不同之处仅在于：所述的磷源是偏磷酸（HPO3），制得Co·SAPO-34分子筛催化剂，其选择性效果和实施例2分子筛催化剂接近。Example 2 was repeated, the only difference being that the phosphorus source was metaphosphoric acid (HPO3 ), and the Co·SAPO-34 molecular sieve catalyst was prepared, and its selectivity effect was close to that of the molecular sieve catalyst in Example 2.
显然，本发明的上述实施例仅仅是为清楚地说明本发明所作的举例，而并非是对本发明的实施方式的限定。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。这里无法对所有的实施方式予以穷举。凡是属于本发明的技术方案所引伸出的显而易见的变化或变动仍处于本发明的保护范围之列。Apparently, the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, rather than limiting the implementation of the present invention. For those of ordinary skill in the art, other changes or changes in different forms can be made on the basis of the above description. All the implementation manners cannot be exhaustively listed here. All obvious changes or variations derived from the technical solutions of the present invention are still within the protection scope of the present invention.
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