技术领域technical field
本发明涉及一种碳四烯烃制丙烯和乙烯用的催化剂及制备方法，适用于催化反应，属于工业催化技术领域的催化剂制备技术。The invention relates to a catalyst for producing propylene and ethylene from carbon tetraolefins and a preparation method, which is suitable for catalytic reactions and belongs to the catalyst preparation technology in the technical field of industrial catalysis.
背景技术Background technique
丙烯和乙烯是重要的基本有机化工原料，主要用于生产聚丙烯、聚乙烯、聚丙烯腈等化工产品。近年来，受下游丙烯和乙烯衍生物产品需求快速增长的驱动，丙烯和乙烯的消费量大幅提高。特别是丙烯，传统的乙烯联产和炼厂回收丙烯方法已难以满足需求，因此，开发增产丙烯的催化技术具有非常重要的意义。目前石化企业富产碳四烯烃，世界范围内有相当数量的碳四烯烃被用来作为液化气燃料等低附加值的产品，因此，通过碳四烯烃增产丙烯和乙烯，一方面可利用数量可观、附加值较低的碳四烯烃资源，另一方面又可以得到用途广泛、附加值高的丙烯和乙烯产品，而实现增产的技术关键是研发出生产丙烯和乙烯用的新型催化剂。目前，利用碳四烯烃催化制丙烯主要有裂解和歧化工艺，而碳四烯烃歧化制丙烯一般都要消耗一定数量的乙烯，而国内的乙烯资源较少。相反碳四烯烃裂解制丙烯工艺，则在生产丙烯的同时，还可得到一定量的乙烯，从投资费用和生产成本上具有很大的吸引力，具有较强的市场竞争力。Propylene and ethylene are important basic organic chemical raw materials, mainly used to produce chemical products such as polypropylene, polyethylene, and polyacrylonitrile. In recent years, driven by the rapid growth in demand for downstream propylene and ethylene derivative products, the consumption of propylene and ethylene has increased significantly. Especially for propylene, the traditional methods of co-production of ethylene and recovery of propylene in refineries have been difficult to meet the demand. Therefore, it is of great significance to develop catalytic technology to increase the production of propylene. At present, petrochemical enterprises are rich in C4 olefins, and a considerable amount of C4 olefins are used as low value-added products such as liquefied gas fuels in the world. Therefore, increasing the production of propylene and ethylene through C4 olefins, on the one hand, can use a considerable amount On the other hand, propylene and ethylene products with a wide range of uses and high added value can be obtained, and the technical key to increase production is to develop new catalysts for the production of propylene and ethylene. At present, there are mainly cracking and disproportionation processes for the catalytic production of propylene by C4-olefins, and a certain amount of ethylene is generally consumed for the production of propylene by the disproportionation of C4-olefins, and domestic ethylene resources are relatively small. On the contrary, the process of C4-olefin cracking to propylene can produce a certain amount of ethylene while producing propylene, which is very attractive in terms of investment cost and production cost, and has strong market competitiveness.
CN1274342A公开报道了采用以ZSM-5分子筛为载体，通过离子交换法负载碱金属、IB族金属催化剂催化混合碳四烯烃制丙烯和乙烯，其丙烯和乙烯收率分别为34％和10％；CN1712496A公开报道了由镁、钼或锆氧化物改性的超细化的硅铝磷酸盐SAPO系列分子筛催化剂催化反应物(石脑油、柴油和含碳四～碳八烯烃的烃类混合物中的至少一种)制丙烯和乙烯，其丙烯收率为27.3％，乙烯收率为40.3％；WO9929805公开用5～100％水蒸气处理的ZSM-5催化剂催化裂解碳四烯烃制丙烯，其丙烯收率为29％，没有涉及到乙烯。EP0109059专利报道了用于把碳四～碳十二烯烃转化为丙烯以及乙烯的ZSM-5或ZSM-11催化剂制备过程，其烯烃转化率为88.6％，丙烯的选择性为38.5％，乙烯的选择性为7.4％；US6307117公开了一种碳四及碳四以上烯烃制丙烯的方法，采用负载银或IB族金属的、几乎没有质子酸的ZSM-5分子筛催化剂，具备较好的抗积炭性能，其丙烯收率为27.9％，乙烯收率为12.7％，CN1317543A则公开了添加铜或银可提高乙烯的收率。US6586649公开了的催化剂为Cs-P-WO3/SiO2，用磷酸盐、硼酸盐或氧化镁等为助剂，其丙烯和乙烯收率分别可以达到35％和8％。ZSM-5分子筛作为固体酸裂解催化剂具有独特的孔道结构、良好的“择形催化”能力，可以有效地抑制产物分子在分子筛孔道中的积炭，有利于提高催化反应的选择性和稳定性，其中催化剂中的酸量、酸类型的存在对裂解反应极其重要。因此，对ZSM-5催化剂进行一系列的改性研究，适度调节催化剂表面的酸性能，可以抑制裂解催化剂表面和ZSM-5分子筛孔口的积炭。同时稀土元素金属被广泛地应用于各类催化反应中，主要基于其独特的电子结构和优异的抗积碳性能。因此，开发ZSM-5改性催化剂，添加稀土元素金属，可以得到活性、选择性、稳定性均较高和可再生的碳四烯烃制丙烯和乙烯用催化剂。目前，该类型催化剂尚处于研究阶段，未见工业化的应用报道。CN1274342A publicly reported that adopting ZSM-5 molecular sieve as a carrier, carrying alkali metals and IB group metal catalysts to catalyze mixed carbon tetraolefins to prepare propylene and ethylene by ion exchange method, the yields of propylene and ethylene were 34% and 10% respectively; CN1712496A It has been publicly reported that superfine silicoaluminophosphate SAPO series molecular sieve catalysts modified by magnesium, molybdenum or zirconium oxides catalyze reactants (naphtha, diesel oil, and at least A) Propylene and ethylene are produced, and its propylene yield is 27.3%, and its ethylene yield is 40.3%; WO9929805 discloses the ZSM-5 catalyst catalytic cracking carbon four olefins prepared propylene with 5～100% steam treatment, and its propylene yield For 29%, no ethylene is involved. EP0109059 patent reports the preparation process of ZSM-5 or ZSM-11 catalyst used to convert carbon four to carbon dodecenes into propylene and ethylene. The conversion rate of olefins is 88.6%, the selectivity of propylene is 38.5%, and the selection of ethylene The specificity is 7.4%; US6307117 discloses a method for producing propylene from olefins with four or more carbons, using a ZSM-5 molecular sieve catalyst loaded with silver or Group IB metals and almost free of protonic acids, which has good anti-coking properties , its propylene yield is 27.9%, and the ethylene yield is 12.7%, and CN1317543A discloses that adding copper or silver can improve the yield of ethylene. The catalyst disclosed in US6586649 is Cs-P-WO3 /SiO2 , with phosphate, borate or magnesium oxide as additives, and the yields of propylene and ethylene can reach 35% and 8% respectively. As a solid acid cracking catalyst, ZSM-5 molecular sieve has a unique pore structure and good "shape-selective catalysis" ability, which can effectively inhibit the carbon deposition of product molecules in the pores of the molecular sieve, which is conducive to improving the selectivity and stability of the catalytic reaction. Among them, the amount and type of acid in the catalyst are extremely important to the cracking reaction. Therefore, a series of researches on the modification of ZSM-5 catalyst, moderately adjusting the acidity of the catalyst surface, can inhibit the carbon deposition on the surface of cracking catalyst and the pores of ZSM-5 molecular sieve. At the same time, rare earth element metals are widely used in various catalytic reactions, mainly based on their unique electronic structure and excellent anti-carbon deposition performance. Therefore, by developing ZSM-5 modified catalyst and adding rare earth element metals, a catalyst for the production of propylene and ethylene from carbon tetraolefins with high activity, selectivity and stability can be obtained. At present, this type of catalyst is still in the research stage, and there are no industrial application reports.
发明内容Contents of the invention
技术问题：本发明的目的是提供一种碳四烯烃制丙烯和乙烯用的催化剂及制备方法，该催化剂在高温、低压的条件下，可以将碳四烯烃催化转化为丙烯和乙烯，具有较高的碳四烯烃转化率、丙烯收率和乙烯收率。Technical problem: the purpose of this invention is to provide a kind of catalyst and preparation method that carbon four olefins are used for producing propylene and ethylene, this catalyst can convert carbon four olefins into propylene and ethylene under the condition of high temperature and low pressure. The carbon four olefin conversion, propylene yield and ethylene yield.
技术方案：本发明的碳四烯烃制丙烯和乙烯用的催化剂包括以分子筛为主活性组份，以过渡元素金属为助剂，以碱土金属或非金属磷、稀土元素金属为改性剂，以耐高温的无机氧化物为粘结剂成型；以分子筛的重量计算，过渡元素金属的添加量为0.1～15wt％，碱土金属的添加量为0.01～10wt％，非金属磷的添加量为0.01～10wt％，稀土元素金属的添加量为0.01～10wt％，无机氧化物粘结剂的添加量为2～60wt％，其余为分子筛。Technical solution: The catalyst for producing propylene and ethylene from carbon tetraolefins of the present invention includes molecular sieve as the main active component, transition element metals as additives, alkaline earth metals or non-metallic phosphorus, and rare earth element metals as modifiers. The high temperature-resistant inorganic oxide is formed as a binder; calculated by the weight of molecular sieve, the addition amount of transition element metal is 0.1-15wt%, the addition amount of alkaline earth metal is 0.01-10wt%, and the addition amount of non-metallic phosphorus is 0.01-10wt%. 10wt%, the addition amount of rare earth element metal is 0.01-10wt%, the addition amount of inorganic oxide binder is 2-60wt%, and the rest is molecular sieve.
所述的分子筛是A型、或X型、或Y型、或者ZSM型系列或者MCM型系列中的一种或多种混合物。The molecular sieve is A type, or X type, or Y type, or one or more mixtures in ZSM type series or MCM type series.
所述的过渡元素金属为钼、钨、铼中的一种或者几种金属的组合。The transition element metal is one of molybdenum, tungsten and rhenium or a combination of several metals.
所述的碱土金属为钙、镁、锶、钡中的一种或几种金属的组合。The alkaline earth metal is one or a combination of calcium, magnesium, strontium and barium.
所述的稀土元素金属选自镧、铈、镨、钕、钷、钐、铕中的一种或几种金属的组合。The rare earth element metal is selected from one or a combination of several metals selected from lanthanum, cerium, praseodymium, neodymium, promethium, samarium and europium.
所述的无机氧化物粘结剂是固体或是溶胶，其中固体为氧化铝、二氧化硅、蒙脱土、高岭土中的一种或几种的复合物；溶胶为硅溶胶、铝溶胶中的一种或两种的复合物。The inorganic oxide binder is solid or sol, wherein the solid is one or more composites of alumina, silicon dioxide, montmorillonite, and kaolin; the sol is silica sol, aluminum sol A compound of one or two.
碳四烯烃制丙烯和乙烯用的催化剂的制备方法为：The preparation method of the catalyst used for carbon tetraolefins to produce propylene and ethylene is as follows:
步骤1)、将分子筛与含非金属磷的水溶液或含碱土金属的水溶液在60～100℃下浸渍2～10h，60～100℃下蒸发至干涸，60～180℃干燥2～12h，400～700℃焙烧3～10h，冷却后得一次改性催化剂，Step 1), impregnating the molecular sieve with the aqueous solution containing non-metallic phosphorus or the aqueous solution containing alkaline earth metal at 60-100°C for 2-10h, evaporating to dryness at 60-100°C, drying at 60-180°C for 2-12h, 400-100°C Calcined at 700°C for 3 to 10 hours, and cooled to obtain a primary modified catalyst.
步骤2)、将一次改性催化剂与含稀土元素金属的水溶液，在60～100℃下浸渍2～10h，60～100℃下蒸发至干涸，60～180℃下干燥2～12h，400～700℃焙烧3～10h，冷却后得二次改性催化剂，Step 2), impregnating the primary modification catalyst and the aqueous solution containing rare earth metals at 60-100°C for 2-10 hours, evaporating to dryness at 60-100°C, drying at 60-180°C for 2-12 hours, 400-700 ℃ roasting for 3 to 10 hours, and after cooling, the secondary modification catalyst is obtained.
步骤3)、将二次改性催化剂与一定量的助挤剂混合均匀，再加无机氧化物粘结剂调成糊状物，混匀后滚球或挤条成型；60～180℃干燥2～12h，400～700℃下焙烧3～10h，冷却后得到成型催化剂，Step 3), mix the secondary modification catalyst with a certain amount of extrusion aid evenly, add an inorganic oxide binder to make a paste, roll the ball or extrude after mixing; dry at 60-180°C for 2 ～12h, calcined at 400～700℃ for 3～10h, and obtained molded catalyst after cooling,
步骤4)、将成型催化剂在600～900℃下，按水蒸气与氮气的体积比为1∶5～1∶30计，用水蒸气处理成型催化剂2～40h，以每克催化剂的重量计算，每小时通入水蒸气的量为1～10mL；冷却后，按每毫升有机酸水溶液处理成型催化剂3～6克计，用0.1～5mol/L的有机酸水溶液在60～100℃温度下处理成型催化剂1～5h；冷却后抽滤，然后60～180℃干燥2～12h，400～700℃焙烧3～10h，冷却后得到水蒸气处理催化剂，Step 4), the molded catalyst is treated with water vapor at 600-900°C for 2-40 hours according to the volume ratio of water vapor to nitrogen of 1:5-1:30, calculated by the weight of each gram of catalyst, each The amount of water vapor introduced per hour is 1-10mL; after cooling, treat the shaped catalyst with 0.1-5mol/L organic acid aqueous solution at a temperature of 60-100°C for 3-6 grams per milliliter of organic acid aqueous solution. ~5h; suction filtration after cooling, then drying at 60~180°C for 2~12h, calcining at 400~700°C for 3~10h, and cooling to obtain a steam treatment catalyst.
步骤5)、将水蒸气处理催化剂加到含过渡元素金属的水溶液中，并用1～10wt％的无机酸调pH为1.0～5.0，在60～100℃下浸渍2～10h，60～100℃下蒸发至干涸，60～180℃干燥2～12h，400～700℃焙烧3～10h，冷却后得到反应催化剂，Step 5), add the steam treatment catalyst to the aqueous solution containing transition element metals, adjust the pH to 1.0-5.0 with 1-10 wt% inorganic acid, soak at 60-100°C for 2-10h, and then immerse at 60-100°C Evaporate to dryness, dry at 60-180°C for 2-12 hours, roast at 400-700°C for 3-10 hours, and obtain a reaction catalyst after cooling.
步骤6)、将反应催化剂在400～600℃，通氮气或氦气，活化处理1～5h，冷却后得到活化催化剂；活化催化剂可直接用于碳四烯烃裂解制丙烯和乙烯的催化反应。Step 6), the reaction catalyst is heated at 400-600° C. with nitrogen or helium, activated for 1-5 hours, and cooled to obtain an activated catalyst; the activated catalyst can be directly used in the catalytic reaction of C4-olefin cracking to produce propylene and ethylene.
在步骤3)中，助挤剂是田菁粉、多元羧酸或二者的复合物，其中多元羧酸可以是柠檬酸、草酸和酒石酸中的一种或几种酸的混合物，以分子筛的重量计，助挤剂的添加量为1～15wt％；步骤4)中的有机酸为甲酸、乙酸、丙二酸、丁酸中的一种或几种酸的混合物；步骤5)中的无机酸为硝酸、硫酸、盐酸中的一种或几种酸的混合物。In step 3), the extruding aid is squash powder, polycarboxylic acid or the compound of the two, wherein polycarboxylic acid can be the mixture of one or more acids in citric acid, oxalic acid and tartaric acid, and the molecular sieve On a weight basis, the amount of extrusion aid added is 1 to 15% by weight; the organic acid in step 4) is one or more acid mixtures in formic acid, acetic acid, malonic acid, butyric acid; the inorganic acid in step 5) The acid is one or a mixture of nitric acid, sulfuric acid, and hydrochloric acid.
有益效果：本发明提供一种碳四烯烃制丙烯和乙烯用的催化剂及制备方法，该催化剂在高温、低压的条件下具有较高的碳四烯烃转化率、丙烯收率和乙烯收率，反应稳定性好，可反复再生，且再生后的催化剂反应性能较好。Beneficial effects: the present invention provides a catalyst for producing propylene and ethylene from carbon tetraolefins and a preparation method thereof. The catalyst has a relatively high conversion rate of carbon tetraolefins, propylene yield and ethylene yield under conditions of high temperature and low pressure. It has good stability and can be regenerated repeatedly, and the regenerated catalyst has better reaction performance.
本发明的特点为：The features of the present invention are:
(1)以分子筛为主活性组份，利用分子筛具有大比表面积的特点，使非金属磷或碱土金属、稀土元素金属和过渡元素金属在分子筛催化剂表面得到充分的分散，提高了催化反应活性，同时利用分子筛良好的容炭能力，提高了催化反应的稳定性。(1) Molecular sieves are used as the main active component, and the characteristics of large specific surface area of molecular sieves are used to fully disperse non-metallic phosphorus or alkaline earth metals, rare earth element metals and transition element metals on the surface of molecular sieve catalysts, which improves the catalytic activity. At the same time, the good carbon capacity of the molecular sieve is used to improve the stability of the catalytic reaction.
(2)催化剂的制备采用浸渍法，尤其采用分步浸渍法，有利于非金属磷或碱土金属、稀土元素金属和过渡元素金属在分子筛表面得到充分的分散。非金属磷或碱土金属作为催化剂改性剂，可有效调节主活性组份分子筛的结构和酸性能，提高其水热稳定性；稀土元素金属的加入，可进一步增强催化剂的抗积炭能力，提高催化反应的稳定性；过渡元素金属的添加，可进一步提高乙烯的收率。(2) The preparation of the catalyst adopts an impregnation method, especially a step-by-step impregnation method, which is conducive to the sufficient dispersion of non-metallic phosphorus or alkaline earth metals, rare earth element metals and transition element metals on the surface of the molecular sieve. Non-metallic phosphorus or alkaline earth metal as catalyst modifier can effectively adjust the structure and acid properties of the main active component molecular sieve and improve its hydrothermal stability; the addition of rare earth metals can further enhance the anti-coking ability of the catalyst and improve The stability of the catalytic reaction; the addition of transition element metals can further increase the yield of ethylene.
(3)催化剂的制备采用先成型后进行水蒸气处理，再用有机酸进行处理工艺，采用催化剂成型前浸渍改性和成型后再次浸渍改性的二次浸渍工艺，提高了催化剂的水热稳定性，使催化剂具有较高的活性、选择性、稳定性和再生性能。(3) The preparation of the catalyst adopts the process of steam treatment after molding first, and then the treatment process with organic acid, and the secondary impregnation process of impregnation modification before catalyst molding and impregnation modification again after molding, which improves the hydrothermal stability of the catalyst properties, so that the catalyst has higher activity, selectivity, stability and regeneration performance.
(4)本发明所述的催化剂成型过程中加入了无机氧化物粘结剂，明显提高了催化剂的机械强度，本发明制得的催化剂机械强度高，完全满足工业化生产、使用的条件，且催化剂制备工艺操作性强，重复性好。(4) Inorganic oxide binding agent is added in the catalyst forming process of the present invention, obviously improved the mechanical strength of catalyst, the catalyst mechanical strength that the present invention makes is high, satisfies the condition of suitability for industrialized production, use fully, and catalyst The preparation process has strong operability and good repeatability.
(5)本发明所述的碳四烯烃制丙烯和乙烯的催化反应采用流化床或固定床反应器，优选固定床反应器。其反应装置是由一个预热器和一个裂解反应器组成。其中，预热器反应器的使用温度为100～500℃，优选200～350℃。裂解反应器中装填的是碳四烯烃裂解活化催化剂，反应温度为400～700℃，优选500～600℃。反应压力为0.1MPa，碳四烯烃的质量空速为1.0～5.0h-1，优选1.0～3.0h-1。反应过程中稀释气(氮气或氦气)与碳四烯烃的体积比为1∶1～8∶1。(5) The catalytic reaction of carbon tetraolefins to propylene and ethylene according to the present invention adopts a fluidized bed or fixed bed reactor, preferably a fixed bed reactor. The reaction device is composed of a preheater and a cracking reactor. Wherein, the operating temperature of the preheater reactor is 100-500°C, preferably 200-350°C. The cracking reactor is filled with a carbon tetraolefin cracking activated catalyst, and the reaction temperature is 400-700°C, preferably 500-600°C. The reaction pressure is 0.1 MPa, and the mass space velocity of carbon tetraolefins is 1.0-5.0 h-1 , preferably 1.0-3.0 h-1 . During the reaction, the volume ratio of diluent gas (nitrogen or helium) to carbon tetraolefin is 1:1-8:1.
具体实施方式Detailed ways
所述的碳四烯烃制丙烯和乙烯用的催化剂是以分子筛为主活性组份，以过渡元素金属为助剂，以碱土金属或非金属磷(P)、稀土元素金属为改性剂，以耐高温的无机氧化物为粘结剂成型。以分子筛的重量计算，各组份的添加量为：过渡元素金属的添加量为0.1～15wt％，优选1～10wt％；碱土金属的添加量为0.01～10wt％，优选0.1～3wt％；非金属磷的添加量为0.01～10wt％，优选0.5～5wt％；稀土元素金属的添加量为0.01～10wt％，优选0.1～5wt％；无机氧化物粘结剂的添加量为2～60wt％，优选10～50wt％；其余为分子筛。The catalyst for the preparation of propylene and ethylene from carbon tetraolefins is based on molecular sieve as the main active component, with transition element metals as additives, alkaline earth metals or non-metallic phosphorus (P), and rare earth element metals as modifiers. High temperature resistant inorganic oxides are used for binder molding. Calculated by the weight of the molecular sieve, the addition amount of each component is: the addition amount of transition element metal is 0.1-15wt%, preferably 1-10wt%; the addition amount of alkaline earth metal is 0.01-10wt%, preferably 0.1-3wt%; The addition amount of metal phosphorus is 0.01～10wt%, preferably 0.5～5wt%; the addition amount of rare earth element metal is 0.01～10wt%, preferably 0.1～5wt%; the addition amount of inorganic oxide binder is 2～60wt%, Preferably 10-50wt%; the rest is molecular sieves.
所述的催化剂中的分子筛是A型、或X型、或Y型、或者ZSM型系列或者MCM型系列中的一种或多种混合物，以ZSM-5型分子筛为最佳。The molecular sieve in the catalyst is A type, or X type, or Y type, or one or more mixtures in ZSM type series or MCM type series, and ZSM-5 type molecular sieve is the best.
所述的催化剂中的过渡元素金属为钼(Mo)、钨(W)、铼(Re)中的一种或者几种金属的组合，其中以金属钨(W)为最佳。碱土金属为镁(Mg)、钙(Ca)、锶(Sr)钡(Ba)中的一种或几种金属的组合，以金属钡(Ba)为佳。稀土元素金属为镧(La)、铈(Ce)、镨(Pr)、钕(Nd)、钷(Pm)、钐(Sm)、铕(Eu)中的一种或几种金属的组合，以金属镧(La)、铈(Ce)为佳。The transition element metal in the catalyst is one of molybdenum (Mo), tungsten (W) and rhenium (Re) or a combination of several metals, among which metal tungsten (W) is the best. The alkaline earth metal is one or a combination of several metals in magnesium (Mg), calcium (Ca), strontium (Sr) and barium (Ba), preferably metal barium (Ba). The rare earth element metal is one or a combination of several metals in lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), and Metal lanthanum (La) and cerium (Ce) are preferred.
上述催化剂的制备方法可以采用共浸渍法或分步浸渍法，以分步浸渍法为佳，浸渍时可采用常规浸渍、微波浸渍和超声浸渍等方法，以常规浸渍法为佳。共浸渍法是将主活性组份分子筛共浸含非金属磷(或碱土金属)和稀土元素金属的可溶性溶液后，加无机氧化物粘结剂和助挤剂成型，水蒸汽处理后，用有机酸水溶液处理，再浸渍含过渡元素金属的可溶性溶液；分步浸渍法即先将主活性组份分子筛浸渍含非金属磷或碱土金属的可溶性溶液，，然后再浸渍含稀土元素金属的可溶性溶液后，加无机氧化物粘结剂和助挤剂成型，水蒸汽处理后，用有机酸水溶液处理，最后再浸渍含过渡元素金属的可溶性溶液。The preparation method of the above-mentioned catalyst can adopt co-impregnation method or step-by-step impregnation method, preferably step-by-step impregnation method, conventional impregnation, microwave impregnation and ultrasonic impregnation can be used during impregnation, and conventional impregnation method is preferred. The co-impregnation method is to co-impregnate the main active component molecular sieve with a soluble solution containing non-metallic phosphorus (or alkaline earth metal) and rare earth element metal, then add inorganic oxide binder and extrusion aid to form, after steam treatment, use organic Acid aqueous solution treatment, and then impregnated with a soluble solution containing transition element metals; the step-by-step impregnation method is to impregnate the main active component molecular sieve with a soluble solution containing non-metallic phosphorus or alkaline earth metals, and then impregnated with a soluble solution containing rare earth element metals , adding inorganic oxide binders and extrusion aids to shape, steam treatment, organic acid aqueous solution, and finally impregnated with a soluble solution containing transition element metals.
所述的无机氧化物粘结剂是固体或是溶胶，其中固体为氧化铝、二氧化硅、蒙脱土、高岭土中的一种或几种的复合物，以二氧化硅为佳；溶胶为硅溶胶、铝溶胶中的一种或两种的复合物。The inorganic oxide binder is a solid or a sol, wherein the solid is a compound of one or more of alumina, silicon dioxide, montmorillonite, and kaolin, preferably silicon dioxide; the sol is One or both of silica sol and aluminum sol.
所述的助挤剂可以是田菁粉、多元羧酸或二者的复合物，以田菁粉为佳；其中多元羧酸可以是柠檬酸、草酸和酒石酸中的一种或几种酸的混合物，以分子筛的重量计算，助挤剂的添加量为1～15wt％，优选2～10wt％。Said extruding aid can be kale powder, polycarboxylic acid or a compound of the two, preferably kale powder; wherein the polybasic carboxylic acid can be one or more of citric acid, oxalic acid and tartaric acid The mixture is calculated by the weight of the molecular sieve, and the amount of the extrusion aid added is 1-15 wt%, preferably 2-10 wt%.
所述的有机酸为甲酸、乙酸、丙二酸、丁酸中的一种或几种酸的混合物，以乙酸为佳。The organic acid is one or a mixture of formic acid, acetic acid, malonic acid, butyric acid, preferably acetic acid.
本发明碳四烯烃制丙烯和乙烯用的催化剂的制备方法为：The preparation method of the catalyst used for carbon four olefins of the present invention to produce propylene and ethylene is:
步骤1)、将分子筛与含非金属磷的水溶液或含碱土金属的水溶液在60～100℃下浸渍2～10h，60～100℃下蒸发至干涸，60～180℃干燥2～12h，400～700℃焙烧3～10h，冷却后得一次改性催化剂，Step 1), impregnating the molecular sieve with the aqueous solution containing non-metallic phosphorus or the aqueous solution containing alkaline earth metal at 60-100°C for 2-10h, evaporating to dryness at 60-100°C, drying at 60-180°C for 2-12h, 400-100°C Calcined at 700°C for 3 to 10 hours, and cooled to obtain a primary modified catalyst.
步骤2)、将一次改性催化剂与含稀土元素金属的水溶液，在60～100℃下浸渍2～10h，60～100℃下蒸发至干涸，60～180℃下干燥2～12h，400～700℃焙烧3～10h，冷却后得二次改性催化剂，Step 2), impregnating the primary modification catalyst and the aqueous solution containing rare earth metals at 60-100°C for 2-10 hours, evaporating to dryness at 60-100°C, drying at 60-180°C for 2-12 hours, 400-700 ℃ roasting for 3 to 10 hours, and after cooling, the secondary modification catalyst is obtained.
步骤3)、将二次改性催化剂与一定量的助挤剂混合均匀，再加无机氧化物粘结剂调成糊状物，混匀后滚球或挤条成型。60～180℃干燥2～12h，400～700℃下焙烧3～10h，冷却后得到成型催化剂，Step 3), mix the secondary modified catalyst and a certain amount of extrusion aid evenly, add an inorganic oxide binder to make a paste, and roll the ball or extrude after mixing. Dry at 60-180°C for 2-12 hours, calcinate at 400-700°C for 3-10 hours, and obtain a molded catalyst after cooling.
步骤4)、将成型催化剂在600～900℃下，用水蒸气(按水蒸气与氮气的体积比为1∶5～1∶30)处理2～40h，以每克成型催化剂的重量计算，每小时通入水蒸气的量为1～10mL；按每毫升有机酸溶液处理成型催化剂3～6克计，用0.1～5mol/L的有机酸水溶液在60～100℃温度下处理成型催化剂1～5h，冷却后抽滤，然后60～180℃干燥2～12h，400～700℃焙烧3～10h，冷却后得到水蒸气处理催化剂，Step 4), the molded catalyst is treated with water vapor (1:5-1:30 according to the volume ratio of water vapor and nitrogen) at 600-900°C for 2-40 hours, calculated by the weight of each gram of molded catalyst, per hour The amount of water vapor introduced is 1-10mL; according to 3-6 grams per milliliter of organic acid solution to treat the shaped catalyst, treat the shaped catalyst with 0.1-5mol/L organic acid aqueous solution at 60-100°C for 1-5 hours, and cool Suction filtration, then drying at 60-180°C for 2-12 hours, calcining at 400-700°C for 3-10 hours, and cooling to obtain a steam-treated catalyst.
步骤5)、将水蒸气处理催化剂加到含过渡元素金属的水溶液中，并用1～10wt％的无机酸调pH为1.0～5.0，在60～100℃下浸渍2～10h，60～100℃下蒸发至干涸，60～180℃干燥2～12h，400～700℃焙烧3～10h，冷却后得到反应催化剂，Step 5), add the steam treatment catalyst to the aqueous solution containing transition element metals, adjust the pH to 1.0-5.0 with 1-10 wt% inorganic acid, soak at 60-100°C for 2-10h, and then immerse at 60-100°C Evaporate to dryness, dry at 60-180°C for 2-12 hours, roast at 400-700°C for 3-10 hours, and obtain a reaction catalyst after cooling.
步骤6)、将反应催化剂在400～600℃，通氮气或氦气，活化处理1～5h，冷却后得到活化催化剂。活化催化剂可直接用于碳四烯烃裂解制丙烯和乙烯的催化反应。Step 6), the reaction catalyst is activated at 400-600° C. with nitrogen or helium for 1-5 hours, and the activated catalyst is obtained after cooling. The activated catalyst can be directly used in the catalytic reaction of C4-olefin cracking to produce propylene and ethylene.
其中，in,
步骤1)中，含非金属磷的水溶液优选(NH4)2HPO4水溶液，碱土金属水溶液优选Ba(NO3)2水溶液；以分子筛的重量计算，控制非金属磷的添加量为0.01～10wt％，优选0.5～5wt％；碱土金属的添加量为0.01～5wt％，优选0.1～3wt％。In step 1), the aqueous solution containing non-metallic phosphorus is preferably (NH4 )2 HPO4 aqueous solution, and the aqueous solution of alkaline earth metal is preferably Ba(NO3 )2 aqueous solution; calculated by the weight of molecular sieves, the amount of non-metallic phosphorus added is controlled to be 0.01-10wt %, preferably 0.5-5wt%; the amount of alkaline earth metal added is 0.01-5wt%, preferably 0.1-3wt%.
步骤2)中，含稀土元素金属的水溶液优选La(NO3)3或Ce(NO3)3水溶液，浸渍过程中，缓慢升高温度，快速搅拌溶液，以保证浸渍过程充分进行。以分子筛的重量计算，控制稀土元素金属的添加量为0.01～10wt％，优选0.1～5wt％。In step 2), the aqueous solution containing rare earth element metal is preferably La(NO3 )3 or Ce(NO3 )3 aqueous solution. During the impregnation process, the temperature is raised slowly and the solution is stirred rapidly to ensure that the impregnation process is fully carried out. Calculated by the weight of the molecular sieve, the addition amount of the rare earth element metal is controlled to be 0.01-10 wt%, preferably 0.1-5 wt%.
步骤3)中，以分子筛的重量计算，控制无机氧化物粘结剂的添加量为2～60wt％，优选10～50wt％；助挤剂的添加量为1～15wt％，优选2～10wt％。In step 3), based on the weight of the molecular sieve, the added amount of the inorganic oxide binder is controlled to be 2-60wt%, preferably 10-50wt%; the added amount of the extrusion aid is 1-15wt%, preferably 2-10wt% .
步骤5)中，含过渡元素金属的水溶液优选(NH4)2WO4，以分子筛的重量计算，控制过渡元素金属的添加量为0.1～15wt％，优选1～10wt％。无机酸为硝酸、硫酸、盐酸中的一种或多种混合酸，以硝酸为佳。In step 5), the aqueous solution containing transition element metal is preferably (NH4 )2 WO4 , and the addition amount of transition element metal is controlled to be 0.1-15wt%, preferably 1-10wt%, calculated by molecular sieve weight. The inorganic acid is one or more mixed acids in nitric acid, sulfuric acid, hydrochloric acid, preferably nitric acid.
实施例1Example 1
将HY分子筛和(NH4)2HPO4水溶液在80℃下浸渍2h，80℃下加热至干，120℃干燥12h，580℃焙烧6h。得到的磷改性的P-Y催化剂和Ce(NO3)3的水溶液在80℃浸渍2h，80℃下加热至干涸，120℃干燥12h，580℃焙烧6h，得到P-Ce-Y催化剂。在P-Ce-Y催化剂中加入45wt％的硅溶胶粘结剂和10wt％的田菁粉，混合均匀，挤条成型，120℃干燥12h，580℃、空气中焙烧6h。将成型后的P-Ce-Y催化剂在800℃，用水蒸气(按水蒸气与氮气的体积比为1∶10)处理12h，以每克P-Ce-Y催化剂的重量计算，每小时通入水蒸气的量为5mL，然后用1mol/L的乙酸水溶液在90℃搅拌2h(每毫升有机酸溶液中含催化剂固体3克)，抽滤，120℃干燥12h，580℃焙烧6h；将得到的P-Ce-Y催化剂加入到(NH4)2WO4水溶液中，并用2wt％的稀硫酸调节pH为2.0，80℃下浸渍2h，80℃下加热至干，120℃干燥12h，580℃焙烧6h后，冷却后得P-Ce-W-Y催化剂，并于500℃的氮气中活化2h得到活化催化剂。催化剂中各组分的添加量为：P：1.0wt％，Ce：1.0wt％，W：1.0wt％。The HY molecular sieve and (NH4 )2 HPO4 aqueous solution were impregnated at 80°C for 2h, heated to dryness at 80°C, dried at 120°C for 12h, and calcined at 580°C for 6h. The obtained phosphorus-modified PY catalyst and Ce(NO3 )3 aqueous solution were impregnated at 80°C for 2h, heated to dryness at 80°C, dried at 120°C for 12h, and calcined at 580°C for 6h to obtain P-Ce-Y catalyst. Add 45wt% silica sol binder and 10wt% squash powder to the P-Ce-Y catalyst, mix well, extrude, dry at 120°C for 12h, and roast at 580°C for 6h in air. Treat the formed P-Ce-Y catalyst at 800°C with water vapor (the volume ratio of water vapor to nitrogen is 1:10) for 12 hours, and pass water per hour based on the weight of each gram of P-Ce-Y catalyst The amount of steam was 5 mL, then stirred with 1 mol/L acetic acid aqueous solution at 90°C for 2h (each ml of organic acid solution contained 3 grams of catalyst solids), suction filtered, dried at 120°C for 12h, and roasted at 580°C for 6h; -Ce-Y catalyst was added to (NH4 )2 WO4 aqueous solution, and the pH was adjusted to 2.0 with 2wt% dilute sulfuric acid, impregnated at 80°C for 2h, heated to dryness at 80°C, dried at 120°C for 12h, and calcined at 580°C for 6h Finally, P-Ce-WY catalyst was obtained after cooling, and activated in nitrogen at 500°C for 2 hours to obtain an activated catalyst. The addition amount of each component in the catalyst is: P: 1.0wt%, Ce: 1.0wt%, W: 1.0wt%.
评价条件：催化剂质量1.0g，碳四烯烃的质量空速1.5h-1，反应温度为550℃，氮气与碳四烯烃的体积比为6∶1，反应压力为0.1MPa。Evaluation conditions: catalyst mass 1.0 g, mass space velocity of carbon tetraolefins 1.5 h-1 , reaction temperature 550°C, volume ratio of nitrogen to carbon tetraolefins 6:1, reaction pressure 0.1 MPa.
结果显示，该催化剂的碳四烯烃转化率为80.2％，丙烯收率为35.2％，乙烯收率为29.1％。The results showed that the conversion rate of carbon tetraolefins of the catalyst was 80.2%, the yield of propylene was 35.2%, and the yield of ethylene was 29.1%.
实施例2Example 2
将HZSM-5分子筛和Ba(NO3)2水溶液在80℃下浸渍2h，80℃下加热至干，120℃干燥12h，580℃焙烧6h，得Ba-ZSM-5催化剂，将Ba-ZSM-5和Ce(NO3)3的水溶液在80℃浸渍2h，80℃下加热至干，120℃干燥12h，580℃焙烧6h，得Ba-Ce-ZSM-5催化剂。在Ba-Ce-ZSM-5催化剂中加入45wt％的硅溶胶粘结剂和10wt％的田菁粉，混合均匀，挤条成型，120℃干燥12h，580℃空气中焙烧6h。将成型后的Ba-Ce-ZSM-5催化剂在850℃，用水蒸气(按水蒸气与氮气的体积比为1∶8)处理10h，以每克Ba-Ce-ZSM-5催化剂的重量计算，每小时通入水蒸气的量为6mL，然后用1.5mol/L的乙酸水溶液在80℃搅拌2h(每毫升有机酸溶液中含催化剂固体5克)，冷却后抽滤，120℃干燥12h，580℃焙烧6h；将得到的Ba-Ce-ZSM-5催化剂加入到(NH4)2MoO4水溶液中，并用质量分数为5％的稀硫酸调节pH为3.0，90℃下浸渍3h，90℃下加热至干，120℃干燥12h，580℃焙烧6h后，得到Ba-Ce-Mo-ZSM-5催化剂，于500℃的氮气中活化2h得活化催化剂。催化剂中各组分的添加量为：Ba：1.0wt％，Ce：1.0wt％，Mo：2.5wt％。HZSM-5 molecular sieve and Ba(NO3 )2 aqueous solution were impregnated at 80°C for 2h, heated to dryness at 80°C, dried at 120°C for 12h, and calcined at 580°C for 6h to obtain Ba-ZSM-5 catalyst. Ba-ZSM- The aqueous solution of 5 and Ce(NO3 )3 was impregnated at 80°C for 2h, heated to dryness at 80°C, dried at 120°C for 12h, and calcined at 580°C for 6h to obtain Ba-Ce-ZSM-5 catalyst. Add 45wt% silica sol binder and 10wt% scallop powder to the Ba-Ce-ZSM-5 catalyst, mix well, extrude, dry at 120°C for 12h, and roast in air at 580°C for 6h. Treat the shaped Ba-Ce-ZSM-5 catalyst at 850° C. with water vapor (the volume ratio of water vapor to nitrogen is 1:8) for 10 h, calculated by weight per gram of Ba-Ce-ZSM-5 catalyst, The amount of water vapor introduced per hour is 6mL, then stirred with 1.5mol/L acetic acid aqueous solution at 80°C for 2h (5 grams of catalyst solids are contained in each ml of organic acid solution), cooled and filtered, dried at 120°C for 12h, 580°C Roast for 6 hours; add the obtained Ba-Ce-ZSM-5 catalyst into (NH4 )2 MoO4 aqueous solution, adjust the pH to 3.0 with dilute sulfuric acid with a mass fraction of 5%, immerse at 90°C for 3h, and heat at 90°C To dryness, dry at 120°C for 12h, calcined at 580°C for 6h to obtain a Ba-Ce-Mo-ZSM-5 catalyst, and activate it in nitrogen at 500°C for 2h to obtain an activated catalyst. The addition amount of each component in the catalyst is: Ba: 1.0wt%, Ce: 1.0wt%, Mo: 2.5wt%.
评价条件：催化剂质量1.0g，碳四烯烃的质量空速1.5h-1，反应温度为550℃，反应压力：0.1MPa，氮气与碳四烯烃的体积比为6∶1。Evaluation conditions: catalyst mass 1.0 g, mass space velocity of carbon tetraolefins 1.5 h-1 , reaction temperature 550°C, reaction pressure 0.1 MPa, volume ratio of nitrogen to carbon tetraolefins 6:1.
结果显示，该催化剂的碳四烯烃转化率为83.0％，丙烯收率为36.4％，乙烯收率为32.0％。The results showed that the conversion rate of carbon tetraolefins of the catalyst was 83.0%, the yield of propylene was 36.4%, and the yield of ethylene was 32.0%.
实施例3：Example 3:
将HZSM-5分子筛和(NH4)2HPO4水溶液在80℃下浸渍2h，80℃下加热至干，120℃干燥12h，580℃焙烧6h，得P-ZSM-5催化剂，P-ZSM-5催化剂和La(NO3)3的水溶液在80℃浸渍2h，80℃下加热至干，120℃干燥12h，580℃焙烧6h，得P-La-ZSM-5催化剂。在P-La-ZSM-5催化剂中加入45wt％的硅溶胶粘结剂和10wt％的田菁粉，混合均匀，挤条成型，120℃干燥12h，580℃、空气中焙烧6h。将成型后的P-La-ZSM-5催化剂在800℃，用水蒸气(按水蒸气与氮气的体积比为1∶8)处理12h，以每克催化剂的重量计算，每小时通入水蒸气的量为5mL，然后用1mol/L的乙酸水溶液在90℃搅拌2h(每毫升有机酸溶液中含催化剂固体5克)，冷却后抽滤，120℃干燥12h，580℃焙烧6h；将成型的P-La-ZSM-5催化剂加入到(NH4)2WO4水溶液中，并用质量分数为2％的稀硝酸调节pH为3.0，80℃下浸渍2h，80℃下加热至干，120℃干燥12h，580℃焙烧6h后，得到P-La-W-ZSM-5催化剂，并于500℃的氮气中活化2h得到活化催化剂。催化剂中各组分的添加量为：P：1.8wt％，La：0.5wt％，W：3.2wt％。Immerse HZSM-5 molecular sieve and (NH4 )2 HPO4 aqueous solution at 80°C for 2h, heat to dryness at 80°C, dry at 120°C for 12h, and roast at 580°C for 6h to obtain P-ZSM-5 catalyst, P-ZSM- 5 Catalyst and La(NO3 )3 aqueous solution were impregnated at 80°C for 2h, heated to dryness at 80°C, dried at 120°C for 12h, and calcined at 580°C for 6h to obtain P-La-ZSM-5 catalyst. Add 45wt% silica sol binder and 10wt% squid powder to the P-La-ZSM-5 catalyst, mix well, extrude, dry at 120°C for 12h, and roast at 580°C for 6h in air. Treat the formed P-La-ZSM-5 catalyst at 800°C with water vapor (the volume ratio of water vapor to nitrogen is 1:8) for 12 hours, and the amount of water vapor introduced per hour is calculated by the weight of each gram of catalyst to 5 mL, then stirred with 1 mol/L aqueous acetic acid solution at 90°C for 2 hours (5 grams of catalyst solids per mL of organic acid solution), cooled and filtered, dried at 120°C for 12 hours, and calcined at 580°C for 6 hours; the formed P- The La-ZSM-5 catalyst was added to (NH4 )2 WO4 aqueous solution, and the pH was adjusted to 3.0 with dilute nitric acid with a mass fraction of 2%, impregnated at 80°C for 2h, heated to dryness at 80°C, and dried at 120°C for 12h. After calcining at 580°C for 6h, the P-La-W-ZSM-5 catalyst was obtained, and activated in nitrogen at 500°C for 2h to obtain an activated catalyst. The addition amount of each component in the catalyst is: P: 1.8wt%, La: 0.5wt%, W: 3.2wt%.
评价条件：催化剂质量1.0g，碳四烯烃的质量空速1.5h-1，反应温度为550℃，反应压力为0.1MPa，氮气与碳四烯烃的体积比为6∶1。Evaluation conditions: catalyst mass 1.0 g, mass space velocity of carbon tetraolefins 1.5 h-1 , reaction temperature 550°C, reaction pressure 0.1 MPa, volume ratio of nitrogen to carbon tetraolefins 6:1.
结果显示，该催化剂的碳四烯烃转化率为87.4％，丙烯收率为38.5％，乙烯收率为42.1％。The results showed that the conversion rate of carbon tetraolefins of the catalyst was 87.4%, the yield of propylene was 38.5%, and the yield of ethylene was 42.1%.
| Application Number | Priority Date | Filing Date | Title |
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| CN2007101346990ACN101147874B (en) | 2007-11-06 | 2007-11-06 | Catalyst for preparing propylene and ethylene by C4 olefins and preparation method |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101346990ACN101147874B (en) | 2007-11-06 | 2007-11-06 | Catalyst for preparing propylene and ethylene by C4 olefins and preparation method |
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