WO2015161700A1 - 一种用于合成气生产α-烯烃的结构化铁基催化剂及制备方法和应用 - Google Patents

一种用于合成气生产α-烯烃的结构化铁基催化剂及制备方法和应用 Download PDF

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WO2015161700A1
WO2015161700A1 PCT/CN2015/072400 CN2015072400W WO2015161700A1 WO 2015161700 A1 WO2015161700 A1 WO 2015161700A1 CN 2015072400 W CN2015072400 W CN 2015072400W WO 2015161700 A1 WO2015161700 A1 WO 2015161700A1
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Prior art keywords
iron
based catalyst
auxiliary agent
auxiliary
structured
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English (en)
French (fr)
Inventor
陈义龙
张岩丰
陈建刚
宋德臣
张娟
孙桃梅
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Wuhan Kaidi Engineering Technology Research Institute Co Ltd
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Wuhan Kaidi Engineering Technology Research Institute Co Ltd
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Priority to AU2015251402A priority Critical patent/AU2015251402B2/en
Priority to RU2016145065A priority patent/RU2659067C2/ru
Priority to CA2946450A priority patent/CA2946450A1/en
Priority to JP2016563184A priority patent/JP6403797B2/ja
Priority to KR1020167032466A priority patent/KR102000821B1/ko
Priority to EP15782614.0A priority patent/EP3135371A4/en
Publication of WO2015161700A1 publication Critical patent/WO2015161700A1/zh
Priority to US15/299,441 priority patent/US10266776B2/en
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    • C10G2400/20—C2-C4 olefins

Definitions

  • the invention belongs to the field of catalysts and their preparation and application, and in particular relates to a structured iron-based catalyst for syngas production of ⁇ -olefins, a preparation method and application thereof.
  • the long-chain ⁇ -olefin refers to a monoolefin or a mixed olefin having an unsaturated bond at a carbon terminal position of a chain hydrocarbon terminal or more and a carbon number of 16 or less. Since the molecule contains an active site (ethylenic bond), the ⁇ -olefin is easily incorporated into various functional groups and derivatized into alcohol, acid, ester and other compounds, and is widely used in the production of fine chemicals such as surfactants and plasticizers. At present, ⁇ -olefins are mainly used as comonomers for the production of polyethylene, accounting for 44.1% of the total consumption.
  • comonomers The most widely used varieties for comonomers are C 4 (1-butene), C 6 (1-hexene) and C 8 (1-octene) in the production of high density polyethylene and linear low density polyethylene.
  • the use of these comonomers in (HDPE/LLDPE) improves PE density and increases tear and tensile strength.
  • ⁇ -olefins are also used to produce high-carbon alcohols.
  • the final products are plasticizers and detergents, accounting for 19.6% of the total consumption.
  • High-carbon alcohol is the basic raw material for surfactants and plasticizers, and the annual consumption in the world has reached about 10 million tons.
  • Octanol is mainly used in the preparation of various esters, with annual sales of more than $1 billion worldwide.
  • Heptanol can be used to prepare perfumes and flavors with high value.
  • ⁇ -olefins are also used to produce polyalphaolefins (PAO), which accounts for 16.6% of the total consumption.
  • PAO is a raw material for high-end lubricant base oils. The viscosity index is high and the price is 2-3 times that of mineral oil.
  • ⁇ -olefins are also used as raw materials for emulsifiers, leather treatment agents, lubricating oil additives, rust inhibitors, fabric finishing agents, and papers for chemicals and the like.
  • the total production capacity of foreign alpha-olefins is about 2.12 million tons, and the domestic production capacity is 260,000 tons. Moreover, domestic lack of ability to produce long-chain alpha-olefins, 1-octene and 1-hexene are almost completely dependent on imports.
  • paraffin cracking or ethylene oligomerization.
  • the paraffin cracking method is generally used as a raw material for deoiling and refining wax.
  • the raw material wax is preheated and mixed with steam, and the reaction is carried out in a tubular cracking furnace at about 550 °C.
  • the ethylene oligomerization reaction is carried out under the action of a triethylaluminum catalyst, and ethylene undergoes a controlled chain growth reaction to polymerize into a chain length olefin. Specifically, it can be divided into a two-step method, a one-step method, and a SHOP process.
  • the Chinese Patent of Publication No. 101265151 discloses a process for producing light olefins from methanol or dimethyl ether.
  • the methanol or dimethyl ether feed is fed to the reaction zone of the reactor through a feed distributor and contacted with the molecular sieve catalyst to form a mixture comprising light olefins, diolefins, oxygenates, and carbon tetrahydrocarbons.
  • the Chinese invention patent represented by Publication Nos. 101265149 and 1537674 discloses an iron/activated carbon catalyst which directly reacts ethylene, propylene and butene from synthesis gas, and is characterized by the specific chemical composition of the self-made catalyst.
  • the Chinese invention patent represented by Publication No. 1284898A, 1515359A discloses a method of producing self-supporting precipitated iron-based catalyst particles for use in a Fischer-Tropsch slurry bed process.
  • a structured iron-based catalyst for syngas production of ⁇ -olefins of the present invention comprises an active component, an auxiliary agent and a carrier, the active component of which is iron; and the auxiliary agent includes the first auxiliary VIB , Group VIIB or Group VIII transition metal ruthenium, platinum, copper, cobalt, zinc, second auxiliary metal oxide: ruthenium oxide, ruthenium oxide, magnesium oxide, aluminum oxide, silicon oxide, potassium oxide, manganese oxide, zirconia
  • the weight percentage of the catalyst is: active component iron: 50.0 to 99.8%, first auxiliary transition metal or transition metal oxide content: 0 to 5.0%; second auxiliary metal oxide: 0 to 10%, balance
  • the carrier silica; the active component iron, the first auxiliary agent, and the carrier silica are formed into monodisperse particles by a heat dispersion method, and then impregnated with a second auxiliary solution.
  • the content of the first auxiliary agent is selected from 0 to 2%; the content of the second auxiliary metal oxide is selected from 2 to 6%, and the content of the active component is selected from 60 to 97%.
  • the carrier has a silica content of 1 to 40%, a first auxiliary agent content of 1 to 2%, a second auxiliary metal oxide content of 2 to 6%, and a balance of the active component of iron.
  • a method for preparing a structured iron-based catalyst the steps are as follows:
  • the iron nitrate of the decrystallization water and the nitrate of the first auxiliary agent and the amorphous silica are added to n-octanol according to the weight ratio thereof, and the total weight of each substance accounts for 3-20% of the mixed solution, and the mixture is stirred.
  • the salt is dissolved, heated to 140-180 ° C, and kept at a constant temperature for 4 h. After cooling, it is filtered and dried to obtain a black solid. After grinding for 20 to 40 minutes by planetary grinding, it is placed in a muffle furnace at 400-600 ° C for 5 h to obtain a catalyst.
  • Precursor A
  • the weight percentage of each component of the structured iron-based catalyst is: carrier silica content: 1 to 40%, first additive content is selected from 1 to 2%; second additive metal oxide content is selected from 2 to 6%.
  • the balance is that the active component is iron.
  • the method for preparing the structured iron-based catalyst the step 1) mixing the ferric nitrate of the decrystallized water and the nitrate of the first auxiliary agent and the amorphous silica into the n-octanol according to the weight ratio thereof, respectively
  • the total weight of the substance is 5 to 15% of the mixed liquid.
  • the catalyst precursor A has a particle size of 50 to 60 nm and is spherical and has a monodisperse distribution.
  • the invention has the following advantages:
  • the catalyst of the invention uses the thermal decomposition method to prepare the main active component of the catalyst, and the powder obtained by the invention has the characteristics of regular shape and uniform pore size, and the catalytic material finally prepared has a unique shape. Appearance and microstructure.
  • the method of the present invention can obtain an iron phase in which the particles are uniform and spherical, having a particle size of about 70 nm and a monodisperse structure. This structure makes the iron catalytically active center more consistent and facilitates the construction of the active center. At the same time, the powder with uniform morphology is more likely to form an ideal pore structure.
  • the catalyst of the invention has a high degree of reduction and degree of carbonization due to the reasonable blending of the strength between the iron and the auxiliary agent.
  • the adjustment of the amount and the use of the auxiliary agent the interaction between the active component of the catalyst and the carrier is reasonable, that is, the sintering of the iron component is prevented, and the occurrence of the difficult-reducing component is avoided, and the catalyst is Has excellent chemical properties.
  • the synergistic effect of both structural and chemical factors allows the catalyst to have higher long-chain alpha-olefin selectivity and activity.
  • the catalyst can be formed from powder tableting or spray drying, and has good mechanical properties.
  • the present invention provides a novel process for the production of alpha-olefins which utilizes syngas as a feedstock to directly synthesize alpha-olefins under the action of the catalyst of the present invention.
  • the present invention is different in raw materials, target products, technical routes, catalyst manufacturing methods, and the like, thereby forming a new technology which is distinct from the prior art and has outstanding innovation in producing ⁇ -olefins.
  • the monodisperse structure of the present invention and suitable metal-support chemistry allow the catalyst to produce an active center suitable for alpha-olefin formation and thus have excellent selectivity.
  • Figure 1 is a TEM photograph of the structure of an iron catalyst prepared by thermal decomposition.
  • Example 1 53%Fe 1% La 2 O 3
  • Example 2 75% Fe 2% K 2 O 1% MnO
  • Example 3 60% Fe 10%Co 2% CuO
  • Example 4 54%Fe 5% Co 4% ZrO 2
  • Example 5 90%Fe 6% Al 2 O 3
  • Example 6 80%Fe 3%Cr 2 O 3 0.5%
  • K 2 O Example 7
  • Example 8 70% Fe 2% CeO 2 0.3% CuO

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Abstract

一种用于合成气生产α-烯烃的结构化铁基催化剂及制备方法和应用，该催化剂包括活性组分铁、助剂和载体，活性组分铁：50.0～99.8％，助剂包括第一助剂过渡金属或过渡金属氧化物：0～5.0％；第二助剂金属氧化物：0～10％，余量为载体二氧化硅；将活性组分铁的前体、第一助剂的前体、载体二氧化硅用热分散法制成单分散颗粒后，用第二助剂的前体溶液浸渍为结构化铁基催化剂。上述结构化铁基催化剂应用于合成气生产α-烯烃，由于单分散的结构化铁基催化剂能够产生适合α-烯烃生成的活性中心，因而具有优良的选择性。

Description

一种用于合成气生产α-烯烃的结构化铁基催化剂及制备方法和应用 技术领域
本发明属于催化剂及其制备和应用于领域，具体地说涉及一种用于合成气生产α-烯烃的结构化铁基催化剂及制备方法和应用。
背景技术
长链α-烯烃是指不饱和键位于链烃端位的碳四以上、碳十六以下的单烯烃或混合烯烃。由于分子中含有活性位(烯键)，α-烯烃容易接入各种官能团，衍化成醇、酸、酯等化合物，广泛应用于表面活性剂、增塑剂等精细化学品生产。目前α-烯烃主要作为共聚单体用于生产聚乙烯，占总消费量的44.1％。用于共聚单体的最为广泛的品种是C4(1-丁烯)、C6(1-己烯)和C8(1-辛烯)，在生产高密度聚乙烯和线性低密度聚乙烯(HDPE/LLDPE)中使用于这些共聚单体可改善PE密度，提高其抗撕裂和拉伸强度。其次，α-烯烃也用于生产高碳醇，最终产品为增塑剂和洗涤剂，占总消费量的19.6％。高碳醇是表面活性剂和增塑剂的基础原料，世界每年消费量已达千万吨左右。辛醇主要用于制备各种酯类，每年在全世界销售额约十多亿美元。庚醇可用于制备香料和香精，价值很高；再有，α-烯烃还用于生产聚α-烯烃(PAO)，占总消费量的16.6％，PAO是高端润滑油基础油的原料，其黏度指数高，价格是矿物油的2-3倍。此外，α-烯烃也作为乳化剂、皮革处理剂、润滑油添加剂、防锈剂、织物整理剂、纸张用于化学品等产品的原料。
国外α-烯烃总生产能力约为212万吨，国内生产能力26万吨。并且，国内缺乏生产长链α-烯烃的能力，1-辛烯和1-己烯几乎完全依赖进口。
传统的α-烯烃生产工艺有石蜡裂解法或乙烯齐聚法。石蜡裂解法一般采用于脱油精制蜡为原料。原料蜡预热后与蒸汽混合，于约550℃下在管式裂解炉中进行反应。对于乙烯齐聚法生产α-烯烃，乙烯齐聚反应是在三乙基铝催化剂作用于下，乙烯发生受控链增长反应，聚合成一定链长的烯烃。具体又可分成两步法、一步法及SHOP工艺等。
传统的α-烯烃生产工艺基于蜡或乙烯，原料来源于石油。伴随着世界范围内油气资源的萎缩，国内外正在进行着能源原材料的多样化变革。煤、生物质或天然气通过合成气间接转化为清洁液体燃料和化学品的非石油路线日益受到重视。
在已公开的中国国家发明专利中，涉及到制取烯烃的有多项，按照核心技术路线的差异，可大致分为以下类型。
技术路线1：公开号101265151的中国发明专利公开了从甲醇或二甲醚制备轻烯烃的方法。将甲醇或二甲醚原料通过进料分布器送入反应器的反应区中，与分子筛催化剂接触，生成包含轻烯烃、二烯烃、含氧化合物、碳四烃的混合物。
技术路线2：公开号101265149、1537674代表的中国发明专利公开了从合成气直接制取乙烯、丙烯、丁烯反应的铁/活性炭催化剂，其特征在于自制催化剂的特定化学组成。
技术路线3：公开号1444551、1545520、1443149、1440311代表的中国发明专利公开了从乙烯低聚生产直链α-烯烃用于配位体及其催化剂体系、工艺。
技术路线4：公开号1403425、1421424代表的中国发明专利公开了蜡裂解制α-烯烃或从高碳烷基铝制备高碳α-烯烃的方法及设备。
技术路线5：公开号1284898A、1515359A代表的中国发明专利公开了一种生产用于于费托浆态床工艺的自支撑型沉淀法铁基催化剂颗粒的方法。
发明内容
本发明的目的在于提供一种用于合成气生产α-烯烃的结构化铁基催化剂及制备方法和应用。
本发明的技术方案：本发明的一种用于合成气生产α-烯烃的结构化铁基催化剂包括活性组分、助剂和载体，其活性组分为铁；助剂包括第一助剂VIB、VIIB族或VIII族的过渡金属钌、铂、铜、钴、锌，第二助剂金属氧化物：氧化镧、氧化铈、氧化镁、氧化铝、氧化硅、氧化钾、氧化锰、氧化锆；催化剂的重量百分比为：活性组分铁：50.0～99.8％，第一助剂过渡金属或过渡金属氧化物含量：0～5.0％；第二助剂金属氧化物：0～10％，余量为载体二氧化硅；将活性组分铁、第一助剂、载体二氧化硅用热分散法制成单分散颗粒后，用第二助剂溶液浸渍。
所述的第一助剂含量选0～2％；第二助剂金属氧化物含量选2～6％，活性组分铁含量选60～97％。
所述的载体二氧化硅含量：1～40％、第一助剂含量选1～2％；第二助剂金属氧化物含量选2～6％，余量为活性组分为铁。
一种结构化铁基催化剂的制备方法，步骤如下：
1)用热分散法制备单分散颗粒催化剂前驱体A：
将去结晶水的硝酸铁和第一助剂的硝酸盐以及无定形二氧化硅按其重量比要求加入到正辛醇中混合，各物质总重量占混合液的3～20％，搅拌，硝酸盐溶解，升温到140～180℃度后，恒温4h，冷却后抽滤烘干，得到黑色固体，经行星磨研磨20～40分钟后置于马弗炉中400-600℃焙烧5h，得到催化剂前驱体A；
2)将第二助剂按重量比溶于水或乙醇，用配制好的第二助剂的溶液干法浸渍上述催化剂前驱体A，老化12～24小时，然后于100～130℃干燥，于300～1200℃焙烧4～10小时，压片，筛分，制得结构化铁基催化剂。
所述的结构化铁基催化剂的各成分重量百分比为：载体二氧化硅含量：1～40％、第一助剂含量选1～2％；第二助剂金属氧化物含量选2～6％，余量为活性组分为铁。
所述的结构化铁基催化剂的制备方法，步骤1)将去结晶水的硝酸铁和第一助剂的硝酸盐以及无定形二氧化硅按其重量比要求加入到正辛醇中混合，各物质总重量占混合液的5～15％。
所述的催化剂前驱体A的粒度为50～60nm，且为球形，呈单分散分布。
一种结构化铁基催化剂的应用，用于合成气生产α-烯烃在固定床进行费托合成反应的作条件为：还原条件为：300～500℃，0.2～1.2MPa，400～1500h-1(V/V)，6～18h，纯氢气氛；合成气反应条件为：190～360℃，0.5～5.0MPa，400～20000h-1(V/V)，H2/CO＝1/1～3/1。
第二种结构化铁基催化剂的应用，用于合成气生产α-烯烃在浆态床中进行费托合成反应的作条件为：还原条件为：300～500℃，0.2～1.2MPa，400～1400rpm，400～1500h-1(V/V)，6～18h，纯氢气氛；合成气反应条件为：190～360℃，0.5～5.0MPa，400～20000h-1(V/V)，400～1400rpm，H2/CO＝1/1～3/1。
本发明与已有技术相比具有如下优点：
1.本发明的催化剂使用了热分解法制备催化剂主活性组分，与传统方法相比，本发明所得粉体具有形貌规整，孔径均匀等特点，使最终制备的催化材料拥有了独特的形貌和微观结构。由图1可见，本发明的所述方法可得到颗粒均匀，且呈球形，粒度约70nm，单分散结构的铁物相。该结构使铁催化活性中心更为一致，有利于活性中心的构建。同时，形貌均匀的粉体更易形成理想的孔道结构。这些独特的结构使本发明催化剂具有较高的α-烯烃选择性。
2.本发明的催化剂由于铁与助剂之间作用强度合理调配，具有很高的还原程度和炭化程度。通过载体类型的选择和用量的调整、助剂的使用，使催化剂活性组分与载体之间的作用强弱合理，即防止了铁组分的烧结，也避免了难还原成份的出现，使催化剂具有优良的化学性能。结构和化学两方面因素的协同效应下，使催化剂具有较高的长链α-烯烃选择性和活性。
3.催化剂可以从粉末压片成型，也可通过喷雾干燥成型，具有良好的机械性能。
本发明提供了一种生产α-烯烃的新的工艺路线，它以合成气为原料，在本发明的催化剂的作用下，直接合成α-烯烃。与现有技术相比，本发明在原料、目标产品、技术路线、催化剂制造方法等方面均不相同，从而形成一个与已有技术截然不同，具有突出创新性的生产α-烯烃的新技术。本发明的单分散的结构和适宜的金属-载体化学作用，使催化剂产生适合α-烯烃生成的活性中心，因而具有优良的选择性。
附图说明
图1热分解法制备的铁催化剂结构的TEM照片。
具体实施方式
实施例1
称取60g去结晶水的硝酸铁和10g无定形二氧化硅加入到800mL正辛醇中，搅拌，硝酸盐溶解，升温到140℃后，恒温4h，冷却后抽滤烘干，得到黑褐色固体，经行星磨研磨后置于马弗炉中400℃焙烧5h。称取0.55g La(NO3)3配成水溶液18ml，浸渍上述所得的氧化物粉末，老化12小时，100℃干燥，于800℃焙烧10小时。压片，筛分制得含Fe为53(wt％)、La2O3为1(wt％)、其余为SiO2的铁基催化剂，标记为53％Fe1％La2O3/SiO2。
在加压固定床反应器中(Φ10×500mm)装填1.5ml 60～80目的上述催化剂，在纯氢气中程序升温还原，还原条件为400℃，0.2MPa，400h-1(V/V)，18h。还原后，降温切换合成气进行反应，反应条件为230℃，2.5MPa，2000h-1(V/V)，H2/CO＝2/1。反应结果见表2。
取140目以上的上述催化剂15ml放入1L的浆态搅拌釜中，然后加入500ml液体石蜡，在纯氢气中程序升温还原，还原条件为，300℃，0.2MPa，400h-1(V/V)，400rpm，18h。还原后，降温切换成合成气进行反应，反应条件为240℃，0.5MPa，3000h-1 (V/V)，400rpm，H2/CO＝2/1。反应结果见表2。
实施例2
称取80g去结晶水的硝酸铁和5g无定形二氧化硅加入到800mL正辛醇中，搅拌，硝酸盐溶解，升温到140℃后，恒温4h，冷却后抽滤烘干，得到黑色固体，经行星磨研磨后置于马弗炉中400℃焙烧5h。称取0.55g K2CO3配成水溶液18ml，浸渍上述所得的氧化物粉末，老化12小时，100℃干燥，于400℃焙烧10小时。压片，筛分制得含Fe为75(wt％)、K2O为2(wt％)、MnO为1％，其余为SiO2的铁基催化剂75％Fe2％K2O 1％MnO/SiO2。
在加压固定床反应器中(Φ10×500mm)装填1.5ml 60～80目的上述催化剂，在纯氢气中程序升温还原，还原条件为400℃，0.4MPa，800h-1(V/V)，12h。还原后，降温切换合成气进行反应，反应条件为200℃，1.0MPa，1500h-1(V/V)，H2/CO＝3/1。反应结果见表2。
取140目以上的上述催化剂15ml放入1L的浆态搅拌釜中，然后加入500ml液体石蜡，在纯氢气中程序升温还原，还原条件为，400℃，0.4MPa，600h-1(V/V)，600rpm，12h。还原后，降温切换成合成气进行反应，反应条件为200℃，1.0MPa，2000h-1(V/V)，600rpm，H2/CO＝3/1。反应结果见表2。
实施例3
称取60g去结晶水的硝酸铁、10g硝酸钴和5g无定形二氧化硅加入到800mL正辛醇中，搅拌，硝酸盐溶解，升温到140℃后，恒温4h，冷却后抽滤烘干，得到黑色固体，经行星磨研磨后置于马弗炉中400℃焙烧5h。称取1.5g Cu(NO3)2配成水溶液18ml，浸渍上述所得的氧化物粉末，老化12小时，100℃干燥，于400℃焙烧10小时。压片，筛分制得含Fe为60(wt％)、Co为10(wt％)、CuO为2(wt％)的，其余为SiO2的铁基催化剂60％Fe 10％Co 2％CuO/SiO2。
取140目以上的上述催化剂15ml放入1L的浆态搅拌釜中，然后加入500ml液体石蜡，在纯氢气中程序升温还原，还原条件为，400℃，0.8MPa，600h-1(V/V)，1000rpm，10h。还原后，降温切换成合成气进行反应，反应条件为220℃，2.0MPa，2000h-1(V/V)，1000rpm，H2/CO＝1/1。反应结果见表2。
实施例4
称取60g去结晶水的硝酸铁、4g硝酸钴和5g无定形二氧化硅加入到800mL正辛醇中，搅拌，硝酸盐溶解，升温到140℃后，恒温4h，冷却后抽滤烘干，得到黑色固 体，经行星磨研磨后置于马弗炉中400℃焙烧5h。称取3g Zr(NO3)4配成水溶液18ml，浸渍上述所得的氧化物粉末，老化12小时，100℃干燥，于600℃焙烧10小时。压片，筛分制得含Fe为54(wt％)、Co为5(wt％)、ZrO2为4(wt％)的铁基催化剂54％Fe 5％Co 4％ZrO2/SiO2。
在加压固定床反应器中(Φ10×500mm)装填1.5ml 60～80目的上述催化剂，在纯氢气中程序升温还原，还原条件为400℃，1.2MPa，1000h-1(V/V)，10h。还原后，降温切换合成气进行反应，反应条件为240℃，3.0MPa，800h-1(V/V)，H2/CO＝2/1。反应结果见表2。
取140目以上的上述催化剂15ml放入1L的浆态搅拌釜中，然后加入500ml液体石蜡，在纯氢气中程序升温还原，还原条件为，400℃，0.4MPa，600h-1(V/V)，600rpm，12h。还原后，降温切换成合成气进行反应，反应条件为200℃，1.0MPa，2000h-1(V/V)，600rpm，H2/CO＝3/1。反应结果见表2。
实施例5
称取80g去结晶水的硝酸铁和1g无定形二氧化硅加入到800mL正辛醇中，搅拌，硝酸盐溶解，升温到140℃后，恒温4h，冷却后抽滤烘干，得到黑色固体，经行星磨研磨后置于马弗炉中400℃焙烧5h。称取5g Al(NO3)3配成水溶液18ml，浸渍上述所得的氧化物粉末，老化12小时，100℃干燥，于800℃焙烧10小时。压片，筛分制得含Fe为90(wt％)Al2O3为4(wt％)的，其余为SiO2的铁基催化剂90％Fe 4％Al2O3/SiO2。
在加压固定床反应器中(Φ10×500mm)装填1.5ml 60～80目的上述催化剂，在纯氢气中程序升温还原，还原条件为500℃，1.2MPa，1500h-1(V/V)，6h。还原后，降温切换合成气进行反应，反应条件为260℃，5.0MPa，400h-1(V/V)，H2/CO＝2/1。反应结果见表2。
取140目以上的上述催化剂15ml放入1L的浆态搅拌釜中，然后加入500ml液体石蜡，在纯氢气中程序升温还原，还原条件为，500℃，1.2MPa，1500h-1(V/V)，1400rpm，6h。还原后，降温切换成合成气进行反应，反应条件为260℃，4.0MPa，700h-1(V/V)，1400rpm，H2/CO＝2/1。反应结果见表2。
实施例6-10
与实施例5方法相同，唯有含量和助剂的种类不同，各实施例的组分含量如表1所示。除所列三组分外，其余组分是氧化硅。
表1各实施例的组分含量
编号 Fe含量 助剂1含量 助剂2含量
实施例1 53％Fe 1％La2O3  
实施例2 75％Fe 2％K2O 1％MnO
实施例3 60％Fe 10％Co 2％CuO
实施例4 54％Fe 5％Co 4％ZrO2
实施例5 90％Fe 6％Al2O3  
实施例6 80％Fe 3％Cr2O3 0.5％K2O
实施例7 95％Fe 1％ZnO 0.2％K2O
实施例8 70％Fe 2％CeO2 0.3％CuO
实施例9 68％Fe 2％TiO2 0.1％Ru
实施例10 98％Fe 1％Al2O3 0.2％K2O
表2 结构型铁基催化剂的烯烃合成反应性能
Figure PCTCN2015072400-appb-000001
Figure PCTCN2015072400-appb-000002
在满足发明组成和采用所述制备方法的前提下，可得到粒径均匀，约70nm的单分散粒子，见附图。由实施例可知，在不满足发明的组成情况下，例如例3和例5烯烃的含量较低；在满足发明要求的组成情况下，催化剂表现出高的烯烃含量。在优选组成范围内，催化剂的α-烯烃选择性更高。

Claims (10)

  1. 一种用于合成气生产α-烯烃的结构化铁基催化剂，包括活性组分、助剂和载体，其特征在于：活性组分为铁；助剂包括第一助剂VIB、VIIB族或VIII族的过渡金属钌、铂、铜、钴、锌，第二助剂金属氧化物：氧化镧、氧化铈、氧化镁、氧化铝、氧化硅、氧化钾、氧化锰、氧化锆；催化剂的重量百分比为：活性组分铁：50.0～99.8％，第一助剂过渡金属或过渡金属氧化物含量：0～5.0％；第二助剂金属氧化物：0～10％，余量为载体二氧化硅；将活性组分铁、第一助剂、载体二氧化硅用热分散法制成单分散颗粒后，用第二助剂溶液浸渍。
  2. 根据权利要求1所述的用于合成气生产α-烯烃的结构化铁基催化剂，其特征在于：第一助剂含量选0～2％；第二助剂金属氧化物含量选2～6％，活性组分铁含量选60～97％。
  3. 根据权利要求1所述的用于合成气生产α-烯烃的结构化铁基催化剂，其特征在于：载体二氧化硅含量：1～40％、第一助剂含量选1～2％；第二助剂金属氧化物含量选2～6％，余量为活性组分为铁。
  4. 一种权利要求1～3之一的结构化铁基催化剂的制备方法，步骤如下：
    1)用热分散法制备单分散颗粒催化剂前驱体A：
    将去结晶水的硝酸铁和第一助剂的硝酸盐以及无定形二氧化硅按其重量比要求加入到正辛醇中混合，各物质总重量占混合液的3～20％，搅拌，硝酸盐溶解，升温到140～180℃度后，恒温4h，冷却后抽滤烘干，得到黑色固体，经行星磨研磨20～40分钟后置于马弗炉中400-600℃焙烧5h，得到催化剂前驱体A；
    2)将第二助剂按重量比溶于水或乙醇，用配制好的第二助剂的溶液干法浸渍上述催化剂前驱体A，老化12～24小时，然后于100～130℃干燥，于300～1200℃焙烧4～10小时，压片，筛分，制得结构化铁基催化剂。
  5. 根据权利要求4所述的结构化铁基催化剂的制备方法，其特征在于：各成分重量百分比为：载体二氧化硅含量：1～40％、第一助剂含量选1～2％；第二助剂金属氧化物含量选2～6％，余量为活性组分为铁。
  6. 根据权利要求4或5所述的结构化铁基催化剂的制备方法，其特征在于：步骤1)将去结晶水的硝酸铁和第一助剂的硝酸盐以及无定形二氧化硅按其重量比要求加入到正辛醇中混合，各物质总重量占混合液的5～15％。
  7. 根据权利要求4或5所述的结构化铁基催化剂的制备方法，其特征在于：催化剂前驱体A的粒度为50～60nm，且为球形，呈单分散分布。
  8. 根据权利要求6所述的结构化铁基催化剂的制备方法，其特征在于：催化剂前驱体A的粒度为50～60nm，且为球形，呈单分散分布。
  9. 一种权利要求4～8之一方法制备的结构化铁基催化剂的应用，用于合成气生产α-烯烃在固定床进行费托合成反应的作条件为：还原条件为：300～500℃，0.2～1.2MPa，400～1500h-1(V/V)，6～18h，纯氢气氛；合成气反应条件为：190～360℃，0.5～5.0MPa，400～20000h-1(V/V)，H2/CO＝1/1～3/1。
  10. 一种权利要求4～8之一方法制备的结构化铁基催化剂的应用，用于合成气生产α-烯烃在浆态床中进行费托合成反应的作条件为：还原条件为：300～500℃，0.2～1.2MPa，400～1400rpm，400～1500h-1(V/V)，6～18h，纯氢气氛；合成气反应条件为：190～360℃，0.5～5.0MPa，400～20000h-1(V/V)，400～1400rpm，H2/CO＝1/1～3/1。
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EP3135371A4 (en) 2018-01-17
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