WO2013075559A1 - 基于多孔材料限域的费托合成钴基纳米催化剂及其制备方法 - Google Patents

基于多孔材料限域的费托合成钴基纳米催化剂及其制备方法 Download PDF

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WO2013075559A1
WO2013075559A1 PCT/CN2012/083091 CN2012083091W WO2013075559A1 WO 2013075559 A1 WO2013075559 A1 WO 2013075559A1 CN 2012083091 W CN2012083091 W CN 2012083091W WO 2013075559 A1 WO2013075559 A1 WO 2013075559A1
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metal component
porous material
cobalt
fischer
component
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PCT/CN2012/083091
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English (en)
French (fr)
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方章建
陈义龙
张岩丰
詹晓东
薛永杰
陶磊明
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武汉凯迪工程技术研究总院有限公司
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Priority to JP2014542687A priority Critical patent/JP5947912B2/ja
Priority to SG11201402557PA priority patent/SG11201402557PA/en
Priority to AP2014007678A priority patent/AP2014007678A0/xx
Priority to MX2014006257A priority patent/MX366574B/es
Priority to AU2012343061A priority patent/AU2012343061B2/en
Priority to KR1020147014655A priority patent/KR101625987B1/ko
Priority to EP12851601.0A priority patent/EP2783750A4/en
Priority to IN970MUN2014 priority patent/IN2014MN00970A/en
Application filed by 武汉凯迪工程技术研究总院有限公司 filed Critical 武汉凯迪工程技术研究总院有限公司
Priority to CA2856748A priority patent/CA2856748A1/en
Priority to RU2014124012A priority patent/RU2624441C2/ru
Priority to BR112014012492A priority patent/BR112014012492B1/pt
Publication of WO2013075559A1 publication Critical patent/WO2013075559A1/zh
Priority to US14/285,665 priority patent/US9266097B2/en
Priority to ZA2014/04572A priority patent/ZA201404572B/en

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    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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    • B01J37/02—Impregnation, coating or precipitation
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
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    • B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
    • C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
    • C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04—Diesel oil

Definitions

  • Fischer-Tropsch synthesis cobalt-based nanocatalyst based on porous material limit region and preparation method thereof
  • the invention relates to the field of catalytic synthesis and nano material application, in particular to a Fischer-Tropsch synthesis cobalt-based nanocatalyst based on a porous material limit domain and a preparation method thereof.
  • Fischer-Tropsch synthesis refers to the reaction of syngas (CO+H 2 ) on the conversion of catalysts to hydrocarbons.
  • the synthesis products are mainly heavy hydrocarbons with higher carbon number (C 5+ ), purified and cracked by product waxes. High quality diesel and aviation kerosene are available. These products contain almost no sulfides and nitrides and are very clean motor fuels.
  • Fischer-Tropsch synthesis technology is one of the most effective ways to increase liquid fuel supply. It is expected to become one of the main channels for producing engine fuel in the near future, with important economic significance and commercial value.
  • Patent CN 101698152A provides a cobalt-based Fischer-Tropsch synthesis catalyst and a preparation method and application thereof, the catalyst comprising a carrier and a metal component, the carrier adopting spherical powder alumina; the metal component comprises a first metal component Co, second The metal component is one of Ce, La, Zr, and one of the third metal components Pt, Ru, Rh, Re, The catalyst is adapted to a bubbling slurry bed or a continuously stirred slurry bed reactor. However, this material is expensive, and the active center is easily agglomerated and inactivated.
  • Microcapsule reactor is a new concept proposed in the field of nanoassembly and catalysis in recent years. It solves the problems of difficult recycling, poor stability and poor selectivity of traditional nanocatalysts.
  • the guest molecules can selectively enter the intracavitary cavity during the reaction, but also catalytically react with the active species in the capsule, and the product will also selectively diffuse away from the microreactor. Summary of the invention
  • the object of the present invention is to draw on the advantages of the preparation of the catalyst by the microcapsule reactor, and to combine the advantages of the nanometer-catalyst limited by the porous material to provide a Fischer-Tropsch synthesis cobalt-based nanocatalyst based on the porous material limit and a preparation method thereof.
  • the catalyst preparation method is simple, the cost is low, the methane selectivity is low, the catalytic reaction activity is high, the C 5+ selectivity is good, and diesel oil and paraffin wax are the main products.
  • the porous material-based Fischer-Tropsch synthesis cobalt-based nanocatalyst of the present invention is prepared by a sol-gel method using an organogel as a template; the metal component is a core, and the porous material is a shell; wherein the metal component comprises a first metal component Co, the second metal component is one of Ce, La, Zr, and one of the third metal components Pt, Ru, Rh, Re;
  • the weight percentage of each metal component is: first metal component: 10 to 35%, second metal component: 0.5 to 10%; third component: 0.02 to 2%
  • the carrier is a porous material, the component is nano silica or alumina, and its shape is spherical; its pore diameter is 1-20 nm, the specific surface area is 300 ⁇ 500 m 2 /g, and the particle size of the active component At 0.5 ⁇ 20nm.
  • the metal component weight percentage is: first metal component: 15 to 30%, second metal component 1% to 5%; third metal component: 0.05% to 2%, the balance being a carrier.
  • the carrier porous material preferably has a pore diameter of from 1 to 10 nm and a specific surface area of from 300 to 400 m 2 /g, wherein the active component has a particle diameter of from 0.5 to 5 nm.
  • the carrier porous material preferably has a pore diameter of 10 to 15 nm and a specific surface area of 400 to 500 m 2 /g, wherein the active component has a particle diameter of 6 nm to 15 nm.
  • the carrier porous material preferably has a pore diameter of 10 to 20 nm and a specific surface area of 400 to 500 m 2 /g, wherein the active component has a particle diameter of 16 to 20 nm.
  • the organic gel template method includes the following steps:
  • Raw material selection Select orthosilicate or aluminum nitrate, water-soluble salt of the first metal cobalt, second metal component and nitrate or sub-component of the third metal component according to the weight percentage of each component Nitrosyl nitrate and gel template reagents;
  • the spray-dried powder is placed in a muffle furnace and calcined at 300 to 750 ° C for 3 h to 12 h to obtain a finished catalyst.
  • step 4) the gel prepared by the sol gel template method is spray-dried at 110 to 150 ° C to obtain an organic-inorganic hybrid material.
  • step 5 the spray dried powder is placed in a muffle furnace and fired at 350 to 700 ° C for 51! ⁇ 10h, the finished catalyst is obtained.
  • the gel templating agent used is an amphiphilic linear polymer containing an amine group.
  • the salt of the first active metal component cobalt used is cobalt nitrate, cobalt acetate or cobalt carbonate;
  • the salt of the second metal component is a metal nitrate;
  • the third metal component The salt is a metal nitrate.
  • the active metal which is mainly catalyzed by the Fischer-Tropsch synthesis catalyst according to the present invention is Co.
  • the specific surface area, pore size and pore properties limit the maximum loading of Co.
  • the loading of Co is too large, it is easy to aggregate, which will reduce the activity of the catalyst. Therefore, those skilled in the art have been attempting to add an auxiliary agent to improve the dispersion of Co on the catalyst carrier, thereby exerting the catalytic action of Co as much as possible.
  • a porous nanocatalyst having a shape, a particle diameter and a controlled pore diameter can be obtained, which is suppressed due to uniform dispersion of the active component in the porous material.
  • the mutual agglomeration of the active components helps to increase the catalytic activity of the catalyst and the selectivity of the reaction product.
  • the reactivity and selectivity of the catalyst can be further improved by the addition of an auxiliary agent. By this method, the content of the metal active component can be lowered, and the cost of the catalyst can be reduced.
  • the catalyst is suitable for use in a bubbling slurry bed or a continuously stirred slurry bed reactor. 2.
  • the Fischer-Tropsch synthesis product is too broadly distributed, and the synthesized product ranges from methane to paraffin wax with a large molecular weight.
  • the poor selectivity is a disadvantage of the reaction.
  • the size of the cobalt particles in the catalytic material not only significantly alters the activity of the Fischer-Tropsch reaction but also changes the product selectivity.
  • the present invention can adjust the product distribution of the Fischer-Tropsch synthesis by using a porous material having a specific pore size and specific surface area as a carrier, and the selectivity of the diesel and paraffin components in the resulting product is high.
  • the core of the core-shell nanocatalyst has catalytic activity
  • the shell has a stabilizing effect on the core layer, and due to the existence of the shell structure, the closed inner cavity will form a micro-environment during the catalytic reaction.
  • the cavity often forms a local high concentration by accumulating the reactants, promoting the reaction to perform more efficiently, increasing the overall activity of the catalyst, and also significantly improving the selectivity of the product, as well as improving the catalyst against carbon deposition, sintering, and water heat.
  • Stability and other properties when the catalyst active component particle diameter is 0.5 ⁇ 20nm, and the specific surface area is 300 ⁇ 500m 2 /g, it is more favorable to generate diesel and paraffin components.
  • the porous material-limited cobalt-based nanocatalyst according to the present invention is formed in situ by a sol-gel method, so that the active component of the catalyst and the porous material as a carrier can be synthesized simultaneously, the preparation process is simple, the operation is convenient, and the industrialization is more suitable. produce.
  • the invention draws on the advantages of the preparation of the catalyst by the microcapsule reactor, and combines the advantages of the nanometer catalyst with the limitation of the porous material to invent a new catalyst.
  • the catalyst of the invention adopts the organogel as a template, and the active component grows on the surface of the template, and is designed and prepared.
  • the core-shell structured cobalt-based porous catalyst has high reactivity and low methane selectivity, with diesel and paraffin as the main products.
  • the active components of the catalyst are more readily dispersed uniformly in the porous support, resulting in higher activity of the material, higher CO conversion and lower methane selectivity.
  • the addition of less precious metal auxiliaries in the present invention enables high catalytic performance and thus lower cost.
  • FIG. 1 is a process flow diagram of a method for preparing a Fischer-Tropsch synthesis cobalt-based nanocatalyst based on a porous material limit in the present invention. detailed description
  • the porous material-based Fischer-Tropsch synthesis cobalt-based nanocatalyst of the invention is prepared by a sol-gel method using an organogel as a template; the metal component is a core, and the porous material is a shell; wherein the metal component Including a first metal component Co, the second metal component is one of Ce, La, Zr, and one of the third metal components Pt, Ru, Rh, Re;
  • the weight percentage of the metal component is: The first metal component: 10 to 35%, a second metal component: 0.5 to 10%; a third component: 0.02 to 2%, the balance being a carrier;
  • the carrier is a porous material, the component of which is nano silica or alumina, and its shape is spherical;
  • the pore diameter is from 1 to 20 nm, and the specific surface area is from 300 to 500 m 2 /g, wherein the active component has a particle diameter of from 0.5 to 20 nm.
  • the weight percentage of the metal component is: the first metal component: 15 to 30%, the second metal component 1% to 5%; the third metal component: 0.05% to 2%, the balance is Carrier.
  • the catalyst carrier is a porous material having a pore diameter of from 1 to 10 nm and a specific surface area of from 300 to 400 m 2 /g, wherein the active component has a particle diameter of from 0.5 to 5 nm.
  • the catalyst carrier is a porous material having a pore diameter of 10 to 15 nm and a specific surface area of 400 to 500 m 2 /g, wherein the active component is granules.
  • the diameter is between 6 nm and 15 nm.
  • the catalyst carrier is a porous material having a pore diameter of 10 to 20 nm and a specific surface area of 400 to 500 m 2 /g, wherein the active component has a particle diameter of 16 ⁇ 20nm.
  • the preparation method of the Fischer-Tropsch synthesis cobalt-based nanocatalyst based on the porous material limit is prepared by the organic gel template method, and comprises the following steps:
  • Raw material selection selecting orthosilicate or aluminum nitrate, the first metal cobalt salt, the second metal component and the third metal component nitrate or nitrosyl group according to the weight percentage of each component Nitrate or gel template agent for use;
  • the spray-dried powder is placed in a muffle furnace and calcined at 300 to 750 ° C for 3 h to 12 h to obtain a finished catalyst.
  • step 4) the gel prepared by the sol gel template method is spray-dried at 110 to 150 ° C to obtain an organic-inorganic hybrid material.
  • step 5 the spray dried powder is placed in a muffle furnace and fired at 350 to 700 ° C for 51! ⁇ 10h, the finished catalyst is obtained.
  • the gel templating agent used is an amphiphilic linear polymer containing an amine group.
  • the salt of the first active metal component cobalt used is cobalt nitrate, cobalt acetate or cobalt carbonate;
  • the salt of the second metal component is a metal nitrate;
  • the third metal component The salt is a metal nitrate.
  • Nanocatalyst activation was carried out on a pressurized fixed bed reactor: 100 g of the prepared nanocatalyst was taken into a reactor, and pure 3 ⁇ 4 (purity >99.9 %) was a reducing gas, and the volumetric space velocity was 1000 h -1 .
  • the activation temperature was 350 °C
  • the activation pressure was 0.5 MPa
  • the activation time was 4 h.
  • the catalytic reaction is carried out on a slurry bed reactor: 50 g of the activated catalyst is transferred to a slurry bed reactor under anhydrous and oxygen-free conditions, and a polyolefin is used as a reaction medium, and a synthesis gas is introduced into the synthesis gas.
  • CO 1.5, adjust the flow rate so that the space velocity is 1000O - adjust the pressure inside the reactor to 3.0 MPa.
  • the temperature rise procedure was set such that the reaction temperature was raised from room temperature to 150 ° C at a rate of 3 ° C /min, and then the temperature was raised to 220 ° C at a rate of 2 ° C /min, and the reaction was carried out at 220 ° C.
  • the product selectivity (wt%) results were as follows: , 6.1; C 2 _ 4 , 7.3; C 5 _u, 32.2; C 12 _ 18 , 29.5; C 18+ , 24.9.
  • the CO conversion reached 81.5.
  • Catalyst activation was carried out on a pressurized fluidized bed reactor: 100 g of the prepared catalyst was taken into the reactor, pure 3 ⁇ 4 (purity >99.9) was a reducing gas, the volumetric space velocity was 1000 h- 1 , and the heating rate was 2 °C /min, activation temperature is 350 °C, activation pressure is 1.5MPa, activation time is 4h.
  • the catalytic reaction is carried out on a slurry bed reactor: 50 g of the activated catalyst is transferred to a slurry bed reactor under anhydrous and oxygen-free conditions, and a polyolefin is used as a reaction medium, and a synthesis gas is introduced into the synthesis gas.
  • Catalyst activation was carried out on a pressurized fluidized bed reactor: 100 g of the prepared catalyst was taken into the reactor, pure 3 ⁇ 4 (purity >99.9) was a reducing gas, the volumetric space velocity was 1000 h- 1 , and the heating rate was 2 °C /min, activation temperature is 350 °C, activation pressure is 1.5MPa, activation time is 4h.
  • the temperature raising procedure was set such that the reaction temperature was raised from room temperature to 150 ° C at a rate of 3 ° C / min, and then the temperature was raised to 220 ° C at a rate of 2 ° C / min, and the reaction was carried out at 220 ° C.
  • the product selectivity (wt%) was obtained as follows: C 1 5.6; C 2 _ 4 , 7.1; C 5 _ u , 23.9; C 12 _ 18 , 29.8; C 18+ , 33.6.
  • the CO conversion reached 76.3.
  • a cobalt-based Fischer-Tropsch synthesis catalyst was prepared according to the method of the patent CN 101698152A.
  • A1 2 0 3 carrier was weighed and calcined at 550 ° C for 4 h in a muffle furnace before taking 100 g of the solution. 53.6 g of cobalt nitrate hexahydrate, 1.7 g of cerium nitrate hexahydrate, 5.9 g of nitrosoyl cerium nitrate were weighed, dissolved in deionized water, stirred sufficiently to dissolve and uniformly mixed, and the solution volume was diluted to 110 mL. The solution was impregnated onto a calculated amount of A1 2 0 3 support using a full pore impregnation method.
  • the impregnated catalyst was vacuum dried in a water bath at 80 ° C, and then placed in Aging at room temperature for 24 h. After aging, it was placed in a muffle furnace and slowly heated to 120 ° C for 6 h, then heated to 500 ° C and calcined for 8 h.
  • Catalyst activation was carried out on a pressurized fluidized bed reactor: 100 g of the prepared catalyst was taken into the reactor, pure 3 ⁇ 4 (purity >99.9) was a reducing gas, the volumetric space velocity was 1000 h- 1 , and the heating rate was 2 °C /min, activation temperature is 350 °C, activation pressure is 1.5MPa, activation time is 4h.
  • the catalytic reaction is carried out on a slurry bed reactor: 50 g of the activated catalyst is transferred to a slurry bed reactor under anhydrous and oxygen-free conditions, and a polyolefin is used as a reaction medium, and a synthesis gas is introduced into the synthesis gas.
  • 2: CO 1.5, adjust the flow rate to make the space velocity 1000h - adjust the pressure inside the reactor to 3.0MPa.
  • the temperature rise procedure was set such that the reaction temperature was raised from room temperature to 150 ° C at a rate of 3 ° C / min, and then the temperature was raised to 220 ° C at a rate of 2 ° C / min, and the reaction was carried out at 220 ° C.
  • the product selectivity (wt) was obtained as follows: Ci, 9.3; C 2 -4, 9.1; C5-11, 27.8; C12-18, 21.2; Ci 8+ , 32.6.
  • the CO conversion was 71.3.
  • the catalyst of the present invention has high activity, and the CO conversion rate can reach 80% or more even if the Co content is only 10% under the condition that the synthesis gas space velocity is 1000 h -1 .
  • the metal component of the cobalt-based Fischer-Tropsch synthesis catalyst prepared by the method has obvious effects.
  • the selectivity to methane was low and the selectivity above C 5+ was good.
  • the catalyst prepared by the method has lower cost, lower methane selectivity, better selectivity than C 5+, and more selective selectivity than C 12+ .

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Abstract

本发明提供一种基于多孔材料限域的费托合成钴基纳米催化剂及其制备方法，本发明的催化剂是以有机凝胶为模板，通过溶胶凝胶法制备得到；以金属组分为核，多孔材料为壳；其中金属组分包括第一种金属组分Co，第二种金属组分为Ce、La、Zr中的一种，第三种金属组分Pt、Ru、Rh、Re中的一种；在成品催化剂中，各金属组分的重量百分比为：第一种金属组分：10～35%，第二种金属组分：0.5～10%；第三种组分：0.02～2%，余量为载体；载体为多孔材料，其组分是纳米二氧化硅或氧化铝，形状为球形；其孔径在1～20nm，比表面积为300～500m2/g，其中活性组分的粒径在0.5～20nm。本发明的核壳结构钴基多孔催化剂具有甲烷选择性低，催化反应活性高，C5+选择性好，以柴油和石蜡为主要产物。

Description

基于多孔材料限域的费托合成钴基纳米催化剂及其制备方法 技术领域
本发明涉及催化合成、 纳米材料应用领域， 具体地指一种基于多孔材料限域的费托 合成钴基纳米催化剂及其制备方法。 背景技术
近年来， 随着世界石油资源的萎縮和石油价格的上涨， 寻求使用替代品的相关研究 和技术进步方兴未艾。 以煤、石油气和生物质气化获得合成气（CO+H2)， 然后通过费托 合成将合成气转变成碳氢化合物受到广泛的关注。 费托合成是指合成气 （CO+H2) 在催 化剂上转化生成烃类的反应， 其合成产物主要是具有较高碳数的重质烃 (C5+)， 通过产物 蜡的精制和裂解可以获得高品质的柴油和航空煤油， 这些产物中几乎不含硫化物和氮化 物，是非常洁净的马达燃料。它是 1923年德国化学家 Frans Fischer和 Hans Tropsch发明的。 费托合成技术是增加液体燃料供给最有效的途径之一， 有望在不久的将来成为生产发动 机燃料的主要渠道之一， 具有重要的经济意义和商业价值。
活性金属粒子的类型、 尺寸、 分散度、 可还原性对反应性能的影响， 载体的孔道效 应 （限域效应、 择形效应等） 和助剂的促进作用等都与费托反应机理的问题相关， 这些 因素对反应机理中的具体步骤产生影响， 并从而影响反应活性以及产物的类型和分布。 众多的研究结果表明， 催化材料的构筑， 包括活性组分的分散程度、 活性中心结构、 微 环境、 落位、 载体的孔道结构等， 极大地影响其在合成气转化反应中的活性和选择性。 孙予罕等制备了具有核壳结构的易于还原， 活性相稳定的催化剂 Co304@MCM-41。 他们 首先利用热分解法制备了 Co304粒子， 采用 PVP作为两亲试剂， 设计制备了介孔硅包裹 Co304粒子核壳结构的钴基催化剂， 该催化剂可抑制钴活性中心的相互团聚。 但其制备 工艺复杂， 催化材料的金属组分单一， CO转化率较低， 产物主要是轻质烃， 甲烷选择性 高。 （孙予罕， 化工进展， 2010, 380)
专利 CN 101698152A提供一种钴基费托合成催化剂及其制备方法和应用，该催化剂 包括载体和金属组分， 载体采用球形粉体氧化铝； 金属组分包括第一种金属组分 Co, 第 二种金属组分为 Ce、 La、 Zr中的一种， 第三种金属组分 Pt、 Ru、 Rh、 Re中的一种， 该 催化剂适应于鼓泡浆态床或连续搅拌浆态床反应器。 但这种材料价格昂贵， 活性中心易 团聚， 失活。
微囊反应器是近年来在纳米组装和催化领域中提出的一个新概念， 它解决了传统纳 米催化剂存在的难回收、 稳定性差、 选择性差等问题。 对于该反应器而言， 在反应过程 中不仅客体分子可以选择性的进入囊内空腔， 并与囊内活性物种发生催化反应， 而且其 产物也将选择性地扩散离开微反应器。 发明内容
本发明的目的就是借鉴了微囊反应器制备催化剂的优点， 结合多孔材料限域的纳米 催化剂的优点提供一种基于多孔材料限域的费托合成钴基纳米催化剂及其制备方法。 使 催化剂的制备方法简单， 成本低， 甲烷选择性低， 催化反应活性高， C5+选择性好， 以柴 油和石蜡为主要产物。
本发明的技术方案： 本发明的基于多孔材料限域的费托合成钴基纳米催化剂是以一 种有机凝胶为模板， 通过溶胶凝胶法制备得到； 以金属组分为核， 多孔材料为壳； 其中 金属组分包括第一种金属组分 Co, 第二种金属组分为 Ce、 La、 Zr中的一种， 第三种金属 组分 Pt、 Ru、 Rh、 Re中的一种； 在成品催化剂中， 各金属组分的重量百分比为： 第一种 金属组分： 10〜35%， 第二种金属组分： 0.5〜10%； 第三种组分： 0.02〜2%， 余量为载 体； 载体为多孔材料， 其组分是纳米二氧化硅或氧化铝， 其形状为球形； 其孔径在 1〜 20nm， 比表面积为 300〜500m2/g， 其中活性组分的粒径在 0.5〜20nm。
优选金属组分重量百分比为：第一种金属组分： 15〜30%，第二种金属组分 1%〜5%； 第三种金属组分： 0.05%〜2%， 余量为载体。
为了获得主要产物为轻质烃， 所述的载体多孔材料优选孔径在 l〜10nm， 比表面积 为 300〜400m2/g， 其中活性组分的粒径在 0.5〜5nm。
为了获得主要产物为中间馏分 （C5-C18 )， 所述的载体多孔材料优选孔径在 10〜 15nm， 比表面积为 400〜500m2/g， 其中活性组分的粒径在 6nm〜15nm。
为了使产物中 C18+产物含量较高， 所述的载体多孔材料优选孔径在 10〜20nm， 比表 面积为 400〜500m2/g， 其中活性组分的粒径在 16〜20nm。
所述的基于多孔材料限域的费托合成钴基纳米催化剂的制备方法， 其制备方法采用 有机凝胶模板法， 包括如下步骤：
1 )原料选取： 按各组份重量百分比选取正硅酸乙酯或硝酸铝、第一种金属钴的水溶 性盐类、 第二种金属组分和第三种金属组分的硝酸盐或亚硝酰基硝酸盐及凝胶模板剂备 用；
2)将模板剂溶解在极性溶剂中，然后在恒温下向上述溶液中加入含有各种金属盐的 水溶液， 加入适量氨水调节 pH值到 8〜10， 恒温搅拌 0.1〜3小时；
3) 向上述溶液中加入计算量的正硅酸乙酯或硝酸铝， 并继续恒温搅拌 3-24小时；
4) 对上述反应物在 90〜150°C下进行喷雾干燥， 得到有机一无机杂化材料；
5) 将喷雾干燥后的粉末放入马弗炉中， 在 300〜750°C焙烧 3h-12h， 制得成品催化 剂。
优选地， 步骤 4) 利用溶胶凝胶模板法制备得到的凝胶在 110〜150°C喷雾干燥得到 有机 _无机杂化材料。
优选地， 步骤 5)将喷雾干燥后的粉末放入马弗炉中， 在 350〜700°C焙烧 51！〜 10h， 制得成品催化剂。
优选地， 所用的凝胶模板剂是含有胺基的两亲性线形高分子。
优选地， 配置溶液时， 所用的第一种活性金属组分钴的盐为硝酸钴、 乙酸钴或碳酸 钴； 第二种金属组分的盐为金属的硝酸盐； 第三种金属组分的盐为金属的硝酸盐。
本发明所涉及的催化剂具有以下优点：
1. 本发明涉及的费托合成催化剂起主要催化作用的活性金属是 Co, 理论上来说， 在分散度相同的情况下， Co的含量越高， 催化剂的活性就越高， 但实际上载体的比表面 积， 孔径和孔道等性质限制了 Co的最大负载量； 同时如果 Co的负载量过大， 则很容易 聚集成团， 反而会降低催化剂活性。 所以， 本领域技术人员一直在尝试添加助剂以改善 Co在催化剂载体上的分散， 从而尽可能的发挥 Co的催化作用。 本发明中， 通过选择合 适的有机凝胶模板剂、 反应时间及反应物的量， 可以得到形状、 粒径和孔径可控的多孔 纳米催化剂， 由于活性组分在多孔材料中均匀分散， 抑制了活性组分的相互团聚， 有助 于提高催化剂的催化活性、 反应产物的选择性。 同时， 通过添加助剂可进一步改善催化 剂的反应活性和选择性。 利用这种方法可以降低金属活性组分的含量， 降低催化剂的成 本。 该催化剂适用于鼓泡浆态床或连续搅拌浆态床反应器。 2. 费托合成产物分布过宽， 合成的产物从甲烷一直到分子量很大的石蜡， 选择性差 是该反应的一个缺点。 催化材料中钴颗粒的大小不仅明显改变费托反应的活性而且改变 产物选择性。 本发明通过选用特定孔径和比表面积的多孔材料为载体， 可调节费托合成 的产物分布， 生成的产物中柴油和石蜡组分的选择性高。 我们通过研究发现， 核壳结构 纳米催化剂的核具有催化活性， 壳对核层有稳定作用， 而且由于壳层结构的存在， 其封 闭的内腔将形成一个微环境， 在催化反应过程中， 内腔往往通过对反应物的积累而形成 局部的高浓度， 促进反应更高效地迸行， 提高催化剂的整体活性， 也可明显改善产物的 选择性， 以及提高催化剂抗积碳、 抗烧结、 水热稳定性等性能， 当催化剂活性组分粒径 在 0.5〜20nm， 比表面积在 300〜500m2/g时， 更有利于生成柴油和石蜡组分。
3. 本发明涉及的多孔材料限域的钴基纳米催化剂是通过溶胶凝胶法原位生成， 因 而催化剂活性组分和作为载体的多孔材料可同步合成， 制备流程简单， 便于操作， 更适 合工业化生产。
本发明借鉴了微囊反应器制备催化剂的优点， 结合多孔材料限域的纳米催化剂的优 点发明了新的催化剂， 本发明的催化剂以有机凝胶为模板， 活性组分在模板表面生长， 设计制备的核壳结构钴基多孔催化剂具有高反应活性， 甲烷选择性较低， 以柴油和石蜡 为主要产物。与专利 CN 101698152A相比该催化剂中各活性组分更易于在多孔载体中均 匀分散， 从而导致材料的活性更高， CO转化率高， 甲烷选择性更低。 同时， 本发明中 加入较少的贵金属助剂便可实现高的催化性能， 因而成本更低。 附图说明
图 1为本发明中基于多孔材料限域的费托合成钴基纳米催化剂制备方法的工艺流程 图。 具体实施方式
本发明的基于多孔材料限域的费托合成钴基纳米催化剂是以一种有机凝胶为模板， 通过溶胶凝胶法制备得到； 以金属组分为核， 多孔材料为壳； 其中金属组分包括第一种 金属组分 Co, 第二种金属组分为 Ce、 La、 Zr中的一种， 第三种金属组分 Pt、 Ru、 Rh、 Re 中的一种； 在成品催化剂中， 各金属组分的重量百分比为： 第一种金属组分： 10〜35%， 第二种金属组分： 0.5〜10%； 第三种组分： 0.02〜2%， 余量为载体； 载体为多孔材料， 其组分是纳米二氧化硅或氧化铝，其形状为球形；其孔径在 l〜20nm， 比表面积为 300〜 500m2/g， 其中活性组分的粒径在 0.5〜20nm。
优选地，金属组分重量百分比为：第一种金属组分： 15〜30%，第二种金属组分 1%〜 5%； 第三种金属组分： 0.05%〜2%， 余量为载体。
优选地，为了获得主要产物为轻质烃，所述的催化剂载体为多孔材料，其孔径在 1〜 10nm, 比表面积为 300〜400m2/g， 其中活性组分的粒径在 0.5〜5nm。
优选地， 为了获得主要产物为中间馏分 （c5-c18)， 所述的催化剂载体为多孔材料， 其孔径在 10〜15nm， 比表面积为 400〜500m2/g， 其中活性组分的粒径在 6nm〜15nm。
优选地， 为了使产物中 C18+产物含量较高， 所述的催化剂载体为多孔材料， 其孔径 在 10〜20nm， 比表面积为 400〜500m2/g， 其中活性组分的粒径在 16〜20nm。
所述的基于多孔材料限域的费托合成钴基纳米催化剂的制备方法， 其制备方法采用 有机凝胶模板法， 包括如下步骤：
1 )原料选取：按各组份重量百分比选取正硅酸乙酯或硝酸铝、第一种金属钴的盐类、 第二种金属组分和第三种金属组分的硝酸盐或亚硝酰基硝酸盐或及凝胶模板剂备用；
2)将模板剂溶解在极性溶剂中，然后在恒温下向上述溶液中加入含有各种金属盐的 水溶液， 加入适量氨水调节 pH值到 8〜10， 恒温搅拌 0.1〜3小时；
3 ) 向上述溶液中加入计算量的正硅酸乙酯或硝酸铝， 并继续恒温搅拌 3-24小时；
4) 对上述反应物在 90〜150°C下进行喷雾干燥， 得到有机一无机杂化材料；
5 ) 将喷雾干燥后的粉末放入马弗炉中， 在 300〜750°C焙烧 3h-12h， 制得成品催化 剂。
优选地， 步骤 4) 利用溶胶凝胶模板法制备得到的凝胶在 110〜150°C喷雾干燥得到 有机 _无机杂化材料。
优选地， 步骤 5 )将喷雾干燥后的粉末放入马弗炉中， 在 350〜700°C焙烧 51！〜 10h， 制得成品催化剂。
优选地， 所用的凝胶模板剂是含有胺基的两亲性线形高分子。
优选地， 配置溶液时， 所用的第一种活性金属组分钴的盐为硝酸钴、 乙酸钴或碳酸 钴； 第二种金属组分的盐为金属的硝酸盐； 第三种金属组分的盐为金属的硝酸盐。 为了更好地解释本发明，以下结合图 1和具体实施例进一步阐明本发明的主要内容， 但本发明的内容不仅仅局限于以下实施例。
实施例 1:
称取 20g的聚乙烯亚胺， 在 80°C温度下将其溶解在 lOOmL乙醇中。 称取 93.8g六水 合硝酸钴， 39.1g六水合硝酸镧， 2.32g硝酸铂， 溶解在 lOOmL去离于水中， 搅拌使之充 分溶解并与溶剂 1混合均匀， 加入 5mL氨水， 恒温温搅拌 2h后将计算量的正硅酸乙酯加 入反应液中， 最后将室温搅拌过夜后用喷雾干燥的方法得到的粉末放置在马弗炉中缓慢 升温至 400 °C干燥 6h， 获得多孔材料限域的用于费托合成的钴基纳米催化剂。 制得的 纳米催化剂组成为： Co: La: Pt: Si02=15: 10:0.5: 74.5。
纳米催化剂活化在加压固定床反应器上进行： 取制备好的纳米催化剂 100g， 装入反 应器中，纯 ¾ (纯度 >99.9 % )为还原气体，体积空速为 1000 h-1，升温速率为 2 °C /min， 活化温度为 350 °C， 活化压力为 0.5MPa， 活化时间为 4h。
催化反应在浆态床反应器上进行： 取活化好的催化剂 50g在无水无氧的条件下转移 入浆态床反应器中， 以聚烯烃为反应介质， 通入合成气， 合成气中 H2: CO=1.5， 调节流 量使空速为 lOOOh- 调节反应器内压力为 3.0MPa。设定升温程序，使反应温度以 3 °C /min 的速率从室温升至 150 °C， 然后以 2°C /min的速率升温至 220 °C， 在 220 °C进行反应。 得到产物选择性（wt%)结果如下： , 6.1; C2_4, 7.3; C5_u, 32.2; C12_18, 29.5; C18+, 24.9. CO 转化率达到 81.5。
实施例 2:
称取 20g的聚乙烯亚胺， 在 80°C温度下将其溶解在 lOOmL乙醇中。 称取 53.6g六水 合硝酸钴， 1.7g六水合硝酸铈， 5.9g亚硝酰基硝酸钌， 溶解在 lOOmL去离于水中， 搅拌 使之充分溶解并与溶剂 1混合均匀。恒温搅拌 2h后将计算量的硝酸铝加入反应液中， 最 后将室温搅拌过夜后用喷雾干燥的方法得到的粉末放置在马弗炉中缓慢升温至 550 °C 干燥 3h，获得多孔材料限域的用于费托合成的钴基催化剂。制得的催化剂组成为： Co: Ce: Ru: Α12Ο3=10: 0.5:1.5: 88。
催化剂活化在加压流化床反应器上进行： 取制备好的催化剂 100g， 装入反应器中， 纯 ¾ (纯度 >99.9 ) 为还原气体， 体积空速为 1000 h-1, 升温速率为 2 °C /min， 活化 温度为 350 °C， 活化压力为 1.5MPa， 活化时间为 4h。 催化反应在浆态床反应器上进行： 取活化好的催化剂 50g在无水无氧的条件下转移 入浆态床反应器中， 以聚烯烃为反应介质， 通入合成气， 合成气中 H2: CO=1.5， 调节流 量使空速为 1000h- 调节反应器内压力为 3.0MPa。设定升温程序，使反应温度以 3 °C /min 的速率从室温升至 150°C， 然后以 2°C / min的速率升温至 220 °C， 在 220 °C进行反应。 得到产物选择性（wt%)结果如下： , 6.8; C2— 4, 7.9; C5— u, 27.2; C12— 18, 28.6; C18+, 29.5. CO 转化率达到 85.3。
实施例 3:
称取 20g的聚乙烯亚胺， 在 80°C温度下将其溶解在 lOOmL乙醇中。 称取 53.6g六水 合硝酸钴， 1.7g六水合硝酸铈， 5.9g亚硝酰基硝酸钌， 溶解在 lOOmL去离于水中， 搅拌 使之充分溶解并与溶剂 1混合均匀。恒温搅拌 2h后将计算量的正硅酸乙酯加入反应液中， 最后将室温搅拌过夜后用喷雾干燥的方法得到的粉末放置在马弗炉中缓慢升温至 450 °C干燥 3h，获得多孔材料限域的用于费托合成的钴基催化剂。制得的催化剂组成为： Co: Ce: Ru: SiO2=10: 0.5:1.5: 88。
催化剂活化在加压流化床反应器上进行： 取制备好的催化剂 100g， 装入反应器中， 纯 ¾ (纯度 >99.9 ) 为还原气体， 体积空速为 1000 h-1, 升温速率为 2 °C /min， 活化 温度为 350 °C， 活化压力为 1.5MPa， 活化时间为 4h。
催化反应在浆态床反应器上进行： 取活化好的催化剂 50g在无水无氧的条件下转移 入浆态床反应器中， 以聚烯烃为反应介质， 通入合成气， 合成气中 H2: CO=1.5， 调节流 量使空速为 1000h- 调节反应器内压力为 3.0MPa。设定升温程序，使反应温度以 3 °C /min 的速率从室温升至 150°C， 然后以 2°C/min的速率升温至 220 °C， 在 220 °C进行反应。得 到产物选择性 （wt% ) 结果如下： C1 5.6; C2_4, 7.1; C5_u, 23.9; C12_18, 29.8; C18+, 33.6. CO 转化率达到 76.3。
实施例 4:
作为对比， 根据专利 CN 101698152A的方法制备了钴基费托合成催化剂
称取适量的 A1203载体， 预先在马弗炉中于 550°C焙烧 4h后取其中 100g备用。 称取 53.6g六水合硝酸钴， 1.7g六水合硝酸铈， 5.9g亚硝基酰基硝酸钌， 溶解在去离子水中， 搅拌使之充分溶解并混合均匀， 将溶液体积稀释至 110mL。 采用满孔浸渍法， 将溶液浸 渍到计算量的 A1203载体上。 将浸渍好的催化剂在 80°C下水浴抽真空干燥， 然后放置在 室温下老化 24h。老化后放置在马弗炉中缓慢升温至 120°C下干燥 6h，然后升温至 500°C 焙烧 8h。 制得的催化剂组成为： Co: Ce: Ru: Α12Ο3=10: 0.5:1.5: 88。
催化剂活化在加压流化床反应器上进行： 取制备好的催化剂 100g， 装入反应器中， 纯 ¾ (纯度 >99.9 ) 为还原气体， 体积空速为 1000 h-1 , 升温速率为 2 °C /min， 活化 温度为 350 °C， 活化压力为 1.5MPa， 活化时间为 4h。
催化反应在浆态床反应器上进行： 取活化好的催化剂 50g在无水无氧的条件下转移 入浆态床反应器中， 以聚烯烃为反应介质， 通入合成气， 合成气中 H2 : CO=1.5， 调节流 量使空速为 1000h- 调节反应器内压力为 3.0MPa。设定升温程序，使反应温度以 3 °C /min 的速率从室温升至 150°C， 然后以 2 °C / min的速率升温至 220 °C， 在 220 °C进行反应。 得到产物选择性 (wt )结果如下： Ci, 9.3; C2-4, 9.1; C5-11, 27.8; C12-18, 21.2; Ci8+, 32.6. CO 转化率达到 71.3。
从以上实施例 1〜3可以看出：本发明的催化剂活性较高，在合成气空速为 1000h- 1的 条件下， 即使 Co含量只有 10%， CO转化率仍能达到 80%以上， 说明本方法制备的钴基 费托合成催化剂各金属组分的作用明显。在所有实施例中， 甲烷选择性较低， C5+以上选 择性好。 实施例 2与实施例 4相比， 本方法制备得到的催化剂成本较低， 甲烷选择性较 低， C5+以上选择性更好， 特别是 C12+以上选择性优势更大。
实施例 5-12:
根据本发明的具体实施方法，制备了系列多孔材料限域的费托合成钴基纳米催化剂， 其催化性能如表 1所示。
表 1 : 钴基纳米催化剂在费托合成中的催化性能
Figure imgf000011_0001
T60C80/Zl0ZN3/X3d 6SSS.0/CT0Z OAV

Claims

权利要求书
1. 一种基于多孔材料限域的费托合成钴基纳米催化剂，其特征在于：它以一种有机 凝胶为模板， 通过溶胶凝胶法制备得到； 以金属组分为核， 多孔材料为壳； 其中金属组 分包括第一种金属组分 Co, 第二种金属组分为 Ce、 La、 Zr中的一种， 第三种金属组分 Pt、 Ru、 Rh、 Re中的一种； 在成品催化剂中， 各金属组分的重量百分比为： 第一种金属组分: 10〜35%， 第二种金属组分： 0.5〜10%； 第三种组分： 0.02〜2%， 余量为载体； 载体为 多孔材料， 其组分是纳米二氧化硅或氧化铝， 其形状为球形； 其孔径在 l〜20nm， 比表 面积为 300〜500m2/g， 其中活性组分的粒径在 0.5〜20nm。
2. 根据权利要求 1所述的基于多孔材料限域的费托合成钴基纳米催化剂，其特征在 于： 金属组分重量百分比为： 第一种金属组分： 15〜30%， 第二种金属组分 1%〜5%； 第三种金属组分： 0.05%〜2%， 余量为载体。
3. 根据权利要求 1或 2所述的多孔材料限域的用于费托合成的钴基催化剂，其特征 在于： 所述的载体为多孔材料， 其孔径在 l〜10nm， 比表面积为 300〜400m2/g， 其中活 性组分的粒径在 0.5〜5nm。
4. 根据权利要求 1或 2所述的基于多孔材料限域的费托合成钴基纳米催化剂，其特 征在于： 所述的载体为多孔材料， 其孔径在 10〜15nm， 比表面积为 400〜500m2/g， 其 中活性组分的粒径在 6nm〜15nm。
5. 根据权利要求 1或 2所述的基于多孔材料限域的费托合成钴基纳米催化剂，其特 征在于： 所述的载体为多孔材料， 其孔径在 10〜20nm， 比表面积为 400〜500m2/g， 其 中活性组分的粒径在 16〜20nm。
6.权利要求 1〜5所述的基于多孔材料限域的费托合成钴基纳米催化剂的制备方法， 其制备方法采用有机凝胶模板法， 包括如下步骤： 1 )原料选取： 按各组份重量百分比选取正硅酸乙酯或硝酸铝、第一种金属钴的水溶 性盐类、 第二种金属组分和第三种金属组分的硝酸盐或亚硝酰基硝酸盐及凝胶模板剂备 用；
2)将模板剂溶解在极性溶剂中，然后在恒温下向上述溶液中加入含有各种金属盐的 水溶液， 加入适量氨水调节 pH值到 8〜10， 恒温搅拌 0.1〜3小时；
3 ) 向上述溶液中加入计算量的正硅酸乙酯或硝酸铝， 并继续恒温搅拌 3-24小时；
4) 对上述反应物在 90〜150°C下进行喷雾干燥， 得到有机一无机杂化材料；
5 ) 将喷雾干燥后的粉末放入马弗炉中， 在 300〜750°C焙烧 3h-12h， 制得成品催化 剂。
7. 根据权利要求 6所述的基于多孔材料限域的费托合成钴基纳米催化剂的制备方法 如下：
步骤 4) 利用溶胶凝胶模板法制备得到的凝胶在 110〜150°C喷雾干燥得到有机一无 机杂化材料。
8. 根据权利要求 6或 Ί所述的基于多孔材料限域的费托合成钴基纳米催化剂的制备 方法如下：
步骤 5 ) 将喷雾干燥后的粉末放入马弗炉中， 在 350〜700°C焙烧 51！〜 10h， 制得成 品催化剂。
9. 根据权利要求 6或 7所述的基于多孔材料限域的费托合成钴基纳米催化剂的制备 方法， 其特征在于： 所用的凝胶模板剂是含有胺基的两亲性线形高分子。
10. 根据权利要求 6或 Ί所述的基于多孔材料限域的费托合成钴基纳米催化剂的制 备方法， 其特征在于： 配置溶液时， 所用的第一种活性金属组分钴的盐为硝酸钴、 乙酸 钴或碳酸钴； 第二种金属组分的盐为金属的硝酸盐； 第三种金属组分的盐为金属的硝酸
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