WO2019192079A1 - 用于费托合成反应的负载型ε/ε'碳化铁催化剂及其制备方法和费托合成的方法 - Google Patents

用于费托合成反应的负载型ε/ε'碳化铁催化剂及其制备方法和费托合成的方法 Download PDF

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WO2019192079A1
WO2019192079A1 PCT/CN2018/092084 CN2018092084W WO2019192079A1 WO 2019192079 A1 WO2019192079 A1 WO 2019192079A1 CN 2018092084 W CN2018092084 W CN 2018092084W WO 2019192079 A1 WO2019192079 A1 WO 2019192079A1
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catalyst
fischer
tropsch synthesis
temperature
preparation
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English (en)
French (fr)
Inventor
王鹏
张魁
吕毅军
林泉
冯波
门卓武
张奉波
孙琦
缪平
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China Energy Investment Corp Ltd
National Institute of Clean and Low Carbon Energy
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China Energy Investment Corp Ltd
National Institute of Clean and Low Carbon Energy
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Priority to RU2020133865A priority Critical patent/RU2760367C1/ru
Priority to JP2021501065A priority patent/JP6982216B2/ja
Priority to GB2015588.3A priority patent/GB2586404B/en
Priority to US17/044,694 priority patent/US11007510B2/en
Priority to EP18913867.0A priority patent/EP3778015A4/en
Publication of WO2019192079A1 publication Critical patent/WO2019192079A1/zh
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Priority to ZA2020/06772A priority patent/ZA202006772B/en
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Definitions

  • the invention relates to the field of Fischer-Tropsch synthesis reaction catalysts, in particular to a supported ⁇ / ⁇ ' iron carbide catalyst for Fischer-Tropsch synthesis reaction, a preparation method thereof and a Fischer-Tropsch synthesis method.
  • Fischer-Tropsch synthesis is an increasingly important energy conversion pathway in recent years, which converts the synthesis gas of carbon monoxide and hydrogen into liquid fuels and chemicals.
  • due to the indirect liquefaction technology of Fischer-Tropsch coal it can realize the clean utilization of coal and partially solve the problem of dependence on petroleum. It has become one of the preferred technologies for the clean utilization of petroleum and coal in China.
  • Fischer-Tropsch synthesis In addition to alkanes and alkenes, industrial Fischer-Tropsch synthesis also produces by-products of carbon dioxide (CO 2 ) and methane (CH 4 ).
  • the mechanism of the Fischer-Tropsch synthesis reaction is complex and has numerous steps such as CO dissociation, carbon (C) hydrogenation, CH x chain growth, and hydrogenation and dehydrogenation reactions leading to hydrocarbon product desorption and oxygen (O) removal.
  • the main purpose of the improved Fischer-Tropsch synthesis catalyst is to increase the selectivity of the target product, reduce the selectivity of by-products, increase the stability of the catalyst, and increase the life of the catalyst.
  • Iron is the cheapest transition metal used in the manufacture of Fischer-Tropsch synthesis catalysts.
  • the active phase of the iron-based Fischer-Tropsch synthesis catalyst is generally considered to be iron carbide.
  • Traditional iron-based catalysts have high water gas shift (CO + H 2 O ⁇ CO 2 + H 2 ) activity, so traditional iron-based catalysts usually have higher CO 2 selectivity as by-products, usually occupying carbon monoxide as a conversion raw material. %-45%. This is one of the main drawbacks of the Fischer-Tropsch synthesis iron-based catalyst.
  • the active phase of the synthetic iron-based Fischer-Tropsch synthesis catalyst - the pure phase of iron carbide is very difficult.
  • the change in the active phase of the iron-based catalyst is very complicated, which leads to considerable debate about the nature of the active phase and the Fischer-Tropsch reaction mechanism of the iron-based catalyst.
  • the different carbides observed under the Fischer-Tropsch synthesis reaction conditions include ⁇ -Fe 2 C, ⁇ '-Fe 2.2 C, Fe 7 C 3 , ⁇ -Fe 5 C 2 and ⁇ -Fe 3 C.
  • high temperature and low carbon chemical potentials ie high H 2 /CO ratios
  • high ⁇ C low H 2 /CO ratio
  • moderate temperature ⁇ 250 ° C
  • ⁇ -carbide is preferentially formed at a lower temperature, higher carbon chemical potential ⁇ C .
  • the iron-based Fischer-Tropsch synthesis temperature is 235-265 ° C, which is to improve the vapor saturation vapor pressure of by-products, obtain high-quality steam, and improve economic benefits.
  • this authoritative article shows that since ⁇ / ⁇ ' iron carbide is unstable above 200 °C, it cannot be used as a catalyst suitable for the modern Fischer-Tropsch synthesis industry.
  • CN104399501A provides a method for preparing nanoparticles of ⁇ -Fe 2 C suitable for low temperature Fischer-Tropsch synthesis reaction, the starting precursor of which is framework iron, and the reaction system is intermittent discontinuous reaction of polyethylene glycol solvent.
  • This catalyst has a CO 2 selectivity of 18.9% and a CH 4 selectivity of 17.3%.
  • the disadvantage is that it can only be applied to low temperatures below 200 ° C, and the reaction cannot be completed continuously. This means that the catalyst is not suitable for continuous production under modern Fischer-Tropsch synthesis industrial conditions.
  • the object of the present invention is to overcome the above-mentioned problems of the prior art and to provide a supported ⁇ / ⁇ ' iron carbide catalyst for Fischer-Tropsch synthesis reaction, a process for the preparation thereof and a Fischer-Tropsch synthesis process.
  • a first aspect of the present invention provides a method for producing a supported ⁇ / ⁇ ' iron carbide catalyst for a Fischer-Tropsch synthesis reaction, wherein the preparation method comprises:
  • step (3) The material obtained in step (2) and H 2 , CO pretreatment at a temperature of 90-185 ° C, the molar ratio of H 2 to CO is 1.2-2.8:1;
  • a supported ⁇ / ⁇ ' iron carbide catalyst for use in a Fischer-Tropsch synthesis reaction obtained by the production method of the present invention.
  • a third aspect of the present invention provides a method of Fischer-Tropsch synthesis comprising: contacting a synthesis feed gas with a catalyst under a Fischer-Tropsch synthesis reaction condition, wherein the catalyst is used in Fischer-Tropsch according to the second aspect of the present invention Supported ⁇ / ⁇ ' iron carbide catalyst for the synthesis reaction.
  • the main raw material iron source for the synthesis precursor can be a commercially available iron salt, and when the active phase carbide is synthesized, only the original reaction gas of the Fischer-Tropsch synthesis reaction system (CO and H) is used. 2 ) Yes, does not involve any other inorganic or organic reaction raw materials, greatly simplified compared with the existing literature technology;
  • the method of the present invention can prepare 100% pure active phase ⁇ / ⁇ ' iron carbide supported on a carrier, and the obtained supported ⁇ / ⁇ ' iron carbide catalyst is suitable for high temperature and high pressure (for example, 235-250 ° C Temperature, 2.3-2.5MPa pressure) continuous reactor, the reaction stability is extremely high, breaking the traditional literature theory "At a higher carbon chemical potential ⁇ C , ⁇ / ⁇ 'iron carbide needs to be less than 200 ° C under mild conditions Stable existence of theoretical technical barriers, which can achieve stable temperatures up to 250 ° C, and CO 2 selectivity is extremely low: under the industrial Fischer-Tropsch synthesis reaction conditions, high-pressure continuous reactor can be used to maintain a continuous stable reaction for more than 400h, the reaction product CO 2 selectivity below 5% (preferably less than 2.5%); at the same time, the selectivity of by-product CH 4 is also maintained at 13.5% (preferably less than 9.5%), effective product selectivity can reach 82 More than % (preferably more than 88%), it is very suitable for the
  • Example 2 is a transmission electron microscope TEM image of the precursor 1 in Example 1;
  • Example 3 is a high resolution transmission electron microscope HRTEM image of the precursor 1 in Example 1;
  • Figure 4 is an in-situ XRD pattern of the preparation process of the supported ⁇ / ⁇ ' iron carbide catalyst of Example 1;
  • Figure 5 is an in-situ XRD pattern of the supported ⁇ / ⁇ ' iron carbide catalyst obtained in Example 1;
  • Figure 6 is an in situ Mossbauer spectrum of the preparation process of the supported ⁇ / ⁇ ' iron carbide catalyst of Example 1.
  • a first aspect of the present invention provides a method for preparing a supported ⁇ / ⁇ ' iron carbide catalyst for a Fischer-Tropsch synthesis reaction, the preparation method comprising:
  • step (3) The material obtained in step (2) and H 2 , CO pretreatment at a temperature of 90-185 ° C, the molar ratio of H 2 to CO is 1.2-2.8:1;
  • the iron salt may be a water-soluble iron salt commonly used in the art, and may be a commercially available product.
  • the iron salt is at least iron nitrate, iron chloride, and ammonium ferrous sulfate.
  • the iron salt is at least iron nitrate, iron chloride, and ammonium ferrous sulfate.
  • the catalyst carrier may be conventionally selected in the art, for example, the catalyst carrier is at least one of silica, alumina, and titania. In the present invention, it is preferred that the catalyst carrier has a particle size of from 30 to 200 ⁇ m.
  • the impregnation is such that the iron content in the post-impregnation carrier after drying is from 10 to 30% by weight.
  • the impregnation may be a conventional choice in the art as long as the loading of iron in the impregnated support can be achieved, preferably, the impregnation is a saturated impregnation method.
  • the drying and calcining process comprises: first drying the impregnated carrier at 20-30 ° C for 0.5-4 h, then at a temperature of 35-80 ° C, and a vacuum of 250- Drying at 1200 Pa for 6-10 h, drying the dried material at 110-150 ° C for 3-24 h, and then baking the obtained material at a temperature of 300-550 ° C for 1-10 h.
  • the above drying process can be carried out in an oven which can be carried out in a muffle furnace.
  • the step (2) can simultaneously serve to in situ generate iron iron powder in the precursor and to perform surface purification treatment on the generated nano iron powder.
  • H 2 in the step (2) may be introduced into the reaction system in the form of a H 2 stream, and at the same time, the pressure of the precursor reduction treatment is controlled by controlling the pressure of the H 2 stream, preferably, step (2)
  • the pressure of the precursor reduction is from 0.1 to 15 atm, preferably from 0.3 to 2.6 atm, and the time is from 0.7 to 15 h, preferably from 1 to 12 h.
  • the amount of the H 2 may be selected according to the amount of the raw material to be treated.
  • the gas velocity of the H 2 is 600-25000 mL/h/g, more preferably 2800. -22000 mL/h/g.
  • H 2 and CO in the step (3) may be introduced into the reaction system in the form of a (H 2 + CO) mixed gas stream, and at the same time, the pretreatment is controlled by controlling the pressure of the (H 2 + CO) mixed gas stream.
  • the pressure of the process preferably, in the step (3), the pressure of the pretreatment is 0.05 to 7 atm, more preferably 0.08 to 4.5 atm, and the time is 15 to 120 min, more preferably 20 to 90 min.
  • the total gas velocity of the H 2 and CO is 300-12000 mL/h/g, more preferably 1500-9000 mL/h/g.
  • H 2 and CO in the step (4) may be introduced into the reaction system in the form of a (H 2 + CO) mixed gas stream, and at the same time, the carbide is controlled by controlling the pressure of the (H 2 + CO) mixed gas stream.
  • the pressure of the preparation process preferably, in the step (4), the carbide is prepared at a pressure of from 0.1 to 10 atm, preferably from 0.2 to 4.5 atm, for a period of from 1.5 to 15 h, preferably from 2.5 to 12 h.
  • the total gas velocity of the H 2 and CO is from 500 to 30,000 mL/h/g, more preferably from 3,000 to 25,000 mL/h/g.
  • the preparation method further comprises: raising the temperature of the pre-treated system to a temperature of 0.2 to 5 ° C/min to 200 to 300 ° C.
  • the resulting pure phase ⁇ / ⁇ ' iron carbide catalyst can be specifically better effective product selectivity in the Fischer-Tropsch synthesis reaction.
  • the temperature of the pre-treated system is raised to 210-290 ° C at a temperature increase rate of 0.2-2.5 ° C / min.
  • mL/h/g means an intake air volume per hour with respect to each gram of raw material, unless otherwise specified.
  • the process of precursor reduction, pretreatment and carbide preparation is carried out in a Fischer-Tropsch synthesis reactor.
  • the catalyst preparation and the Fischer-Tropsch synthesis share the same reactor. Therefore, the H 2 and CO raw materials in the catalyst preparation process can be the original raw materials of the Fischer-Tropsch synthesis reaction system, and do not require any additional activity.
  • the phase carbide preparation reaction device; the whole process of preparation can realize the preparation and synthesis reaction of the active phase in the same reactor in situ, and the operation steps are more simple.
  • the second aspect of the present invention provides a supported ⁇ / ⁇ ' iron carbide catalyst for the Fischer-Tropsch synthesis reaction obtained by the production method of the present invention.
  • the active phase of the supported ⁇ / ⁇ ' iron carbide catalyst has 100% pure phase ⁇ / ⁇ ' iron carbide.
  • a third aspect of the present invention provides a method of Fischer-Tropsch synthesis comprising: contacting a synthetic feed gas with a catalyst under a Fischer-Tropsch synthesis reaction condition, wherein the catalyst is a charge for the second aspect of the invention Supported ⁇ / ⁇ ' iron carbide catalyst for the synthesis reaction.
  • the supported ⁇ / ⁇ ' iron carbide catalyst of the present invention is used as a catalyst for Fischer-Tropsch synthesis, which can carry out a Fischer-Tropsch synthesis reaction under high temperature and high pressure.
  • the Fischer-Tropsch synthesis reaction conditions include: a temperature of 235-250 ° C, The pressure is 2.3-2.5 MPa.
  • the pressure refers to an absolute pressure, unless otherwise specified.
  • the Fischer-Tropsch synthesis is carried out in a high temperature and high pressure continuous reactor.
  • the supported ⁇ / ⁇ ' iron carbide catalyst of the present invention can realize a Fischer-Tropsch synthesis reaction which maintains a continuous stable reaction for more than 400 hours in a high temperature and high pressure continuous reactor.
  • This example is intended to illustrate the supported ⁇ / ⁇ ' iron carbide catalyst of the present invention and a process for the preparation thereof.
  • the change process from the precursor 1 ( ⁇ -Fe 2 O 3 phase) to the target carbide ( ⁇ / ⁇ ' iron carbide phase) can be clearly seen from Fig. 4; as can be seen from Fig. 5, the generation
  • the target product ⁇ / ⁇ ' iron carbide has good crystallinity, which corresponds well to all the characteristic peaks of ⁇ / ⁇ ' iron carbide, which is extremely pure and free from any other impurities.
  • FIG. 6 can clearly see the process of changing from the precursor to the target carbide and the process of high-temperature steam treatment.
  • Table 1 shows the specific data of phase transformation. It can be seen from Table 1 that the purity of the active phase ⁇ / ⁇ ' iron carbide in the target product prepared in Example 1 is 100%, after long-term operation after simulated industrialization conditions. Its purity is still 100%.
  • the process of the present invention can produce a supported catalyst of 100% pure active phase ⁇ / ⁇ ' iron carbide, while the supported ⁇ / ⁇ ' iron carbide catalyst obtained according to the preparation method of the present invention can stably exist at a high temperature of 250 ° C. Further, even after the simulated industrial high temperature and high pressure water vapor erosion, the active phase ⁇ / ⁇ ' iron carbide in the catalyst maintains 100% purity.
  • This example is intended to illustrate the supported ⁇ / ⁇ ' iron carbide catalyst of the present invention and a process for the preparation thereof.
  • ammonium ferrous sulfate solution (concentration is 0.08g/mL); and taking alumina carrier with particle size of 30-200 ⁇ m (Zhongguo Group Chemical Reagent Co., Ltd.) 8.0g , the above ammonium ferrous sulfate solution is saturated and impregnated on the alumina carrier, so that the impregnated carrier Fe content is 10% by weight, and placed at 20 ° C for 4 h;
  • This example is intended to illustrate the supported ⁇ / ⁇ ' iron carbide catalyst of the present invention and a process for the preparation thereof.
  • ferric chloride solution concentration: 0.1g/mL
  • titanium dioxide carrier Zhongguo Group Chemical Reagent Co., Ltd.
  • the precursor 3 is placed in a tubular Fischer-Tropsch synthesis reactor, and a H 2 flow having a gas velocity of 7000 mL/h/g and a pressure of 1.6 atm is introduced at a temperature of 420 ° C for 8 hours;
  • a supported ⁇ / ⁇ ' iron carbide catalyst was prepared according to the method of Example 1, except that in the step (4), the pressure of the H 2 stream was 15 atm.
  • the supported ⁇ / ⁇ ' iron carbide catalyst was designated as A4.
  • a supported ⁇ / ⁇ ' iron carbide catalyst was prepared in accordance with the method of Example 1, except that in step (4), the gas velocity of the H 2 stream was 600 mL/h/g.
  • the supported ⁇ / ⁇ ' iron carbide catalyst was designated as A5.
  • a supported ⁇ / ⁇ ' iron carbide catalyst was prepared in accordance with the method of Example 1, except that in the step (5), the pressure of the (H 2 + CO) stream was 7 atm.
  • the supported ⁇ / ⁇ ' iron carbide catalyst was designated as A6.
  • a supported ⁇ / ⁇ ' iron carbide catalyst was prepared according to the method of Example 1, except that in step (5), the gas velocity of the (H 2 +CO) stream was 300 mL/h/g.
  • the supported ⁇ / ⁇ ' iron carbide catalyst was designated as A7.
  • a supported ⁇ / ⁇ ' iron carbide catalyst was prepared in accordance with the method of Example 1, except that in step (6), the pressure of the (H 2 + CO) stream was 0.1 atm.
  • the supported ⁇ / ⁇ ' iron carbide catalyst was designated as A8.
  • a supported ⁇ / ⁇ ' iron carbide catalyst was prepared in accordance with the method of Example 1, except that in step (6), the gas velocity of the (H 2 +CO) stream was 30000 mL/h/g.
  • the supported ⁇ / ⁇ ' iron carbide catalyst was designated as A9.
  • a supported ⁇ / ⁇ ' iron carbide catalyst was prepared in the same manner as in Example 1, except that in the step (6), the heating rate was 5 ° C / min.
  • the supported ⁇ / ⁇ ' iron carbide catalyst was designated as A10.
  • a supported iron carbide catalyst was prepared in the same manner as in Example 1, except that the step (5) was carried out without directly carrying out the step (5).
  • the supported iron carbide catalyst was recorded as D1.
  • a supported iron carbide catalyst was prepared in the same manner as in Example 1, except that in the step (5), the molar ratio of H 2 to CO was 1.0.
  • the supported iron carbide catalyst was recorded as D2.
  • a supported iron carbide catalyst was prepared in the same manner as in Example 1, except that in the step (6), the molar ratio of H 2 to CO was 3.5.
  • the supported iron carbide catalyst was recorded as D3.
  • a supported iron carbide catalyst was prepared in accordance with the method of Example 1, except that the temperature of the pretreatment in the step (5) was 200 ° C, and the temperature of the carbide preparation in the step (6) was 310 °C.
  • the supported iron carbide catalyst was recorded as D4.
  • This comparative example is used to illustrate a method of preparing an iron carbide catalyst in the prior art (N. Lohitharn et al. / Journal of Catalysis 255 (2008) 104 - 113).
  • % CO 2 selectivity [number of moles of CO 2 in the discharge / (number of moles of CO in the feed - number of moles of CO in the discharge)] ⁇ 100%;
  • CO conversion % [(number of moles of CO in the feed - number of moles of CO in the feed) / number of moles of CO in the feed] x 100%;
  • CH 4 selectivity % [Q 4 moles in the discharge / (CO moles in the feed ⁇ CO conversion % (1-CO 2 selectivity %))] ⁇ 100%;
  • Effective product selectivity % 100% - CO 2 selectivity % - CH 4 selectivity %.
  • a catalyst having an active phase of 100% pure phase ⁇ / ⁇ ' iron carbide can be prepared by the production method of the present invention.
  • Effective product selectivity refers to product selectivity other than by-products CO 2 and CH 4 .
  • the supported ⁇ / ⁇ ' iron carbide catalyst prepared by the method of the present invention exhibits ultra-low CO 2 selectivity under industrial conditions, and preferably, the CO 2 selectivity can be low. At 2.5%, even close to zero; correspondingly, the iron carbide catalyst D5 prepared by the prior art has a CO 2 selectivity of up to 28.5% to 37.7% under the same industrial conditions.
  • the CH 4 selectivity of the active phase ⁇ / ⁇ ' iron carbide catalyst prepared by the method of the invention is less than 13.5% (preferably less than 9.5%), and the effective product selectivity can reach above 82% (preferred case)
  • the iron carbide catalyst D5 prepared by the prior art has higher CH 4 selectivity, lower effective product selectivity, and lower CO utilization efficiency.
  • the supported ⁇ / ⁇ ' iron carbide catalyst prepared by the method of the invention remains stable after the reaction for 400 hours, regardless of the CO conversion rate or the product selectivity.
  • the parameters of the iron carbide catalyst D5 prepared by the prior art all show significant decline, indicating that the stability of the supported ⁇ / ⁇ ' iron carbide catalyst prepared by the method of the invention is much better than that of the prior art. catalyst.

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Abstract

一种用于费托合成反应的负载型ε/ε'碳化铁催化剂及其制备方法和费托合成的方法。制备方法包括： (l)将催化剂载体在铁盐的水溶液中进行浸渍，并将浸渍后载体进行干燥、焙烧，得到催化剂前驱体； (2)将催化剂前驱体与H 2在温度为300-550℃下进行前驱体还原；(3)将步骤(2)得到的物料与H 2、CO 在温度为90-185℃下进行前处理，H 2与CO的摩尔比为1.2–2.8: 1；(4)将步骤(3)得到的物料与H 2、CO在温度为200-300℃下进行碳化物制备，H 2与CO 的摩尔比为1.0–3.2:1。该制备方法可以制备出活性相为100 ％纯相ε/ε'碳化铁的催化剂，该催化剂具有较低的CO 2和CH 4选择性以及较高的有效产物选择性。

Description

用于费托合成反应的负载型ε/ε’碳化铁催化剂及其制备方法和费托合成的方法 技术领域
本发明涉及费托合成反应催化剂领域，具体涉及一种用于费托合成反应的负载型ε/ε’碳化铁催化剂及其制备方法和费托合成的方法。
背景技术
我国一次能源结构的特点是富煤、缺油、少气，随着经济发展石油对外依存度不断攀升，2015年达到61％，严重影响着我国的能源安全。费托合成是近年来愈发重要的能源转化途径，它可将一氧化碳与氢气的合成气转化为液态燃料与化学品。近年，由于费托合成的煤间接液化技术可实现煤的清洁利用，并部分解决石油对外依存的问题，成为我国替代石油和煤炭清洁化利用的首选技术之一。经过多年努力，我国已实现16万吨/年铁基煤间接液化技术工业示范，兖矿100万吨/年、神华宁煤400万吨/年铁基煤间接液化厂在试运行。
费托合成的反应方程式如下：
(2n+1)H 2+nCO→C nH 2n+2+nH 2O      (1)，
2nH 2+nCO→C nH 2n+nH 2O        (2)。
除烷烃和烯烃外，工业费托合成还会产生副产物二氧化碳(CO 2)和甲烷(CH 4)。费托合成反应的机理复杂，步骤繁多，诸如CO解离、碳(C)加氢、CH x链增长，以及导致烃产物脱附与氧(O)移除的加氢与脱氢反应。从实际应用的角度来看，改进费托合成催化剂的主要目的是提高目标产品的选择性，降低副产物的选择性以及增加催化剂稳定性，提高催化剂寿命。
铁是用于制造费托合成催化剂中最便宜的过渡金属。铁基费托合成催化剂的活性相通常被认为是铁碳化物。传统铁基催化剂具有很高的水煤气变换(CO+H 2O→CO 2+H 2)活性，因此传统铁基催化剂通常会有较高的副产物CO 2选择性，通常占有转化原料一氧化碳的25％-45％。这成为费托合成反应铁基催化剂的主要缺点之一。
合成铁基费托合成催化剂的活性相——纯相的碳化铁难度很高。铁基催化剂的活性相的变化非常复杂，这导致其活性相本质和铁基催化剂的费托合成反应机理存在着相当大的争论。在费托合成反应条件下观察到的不同的碳化物包括ε-Fe 2C、ε′-Fe 2.2C、Fe 7C 3、 χ-Fe 5C 2与θ-Fe 3C。2010年发表在顶级期刊Journal of the American Chemical Society(JACS)上的文章《Stability and reactivity ofε-χ-θiron carbide catalyst phases in Fischer–Tropsch synthesis:Controllingμ C》中对各种碳化铁的生成条件做了十分系统的计算与实验，如图1所示，碳化铁相变的发生(ε–χ–θ相变)依赖于根据温度和H 2/CO比例。具体地说，高温和低碳化学势(μ C)，即高H 2/CO比例通常导致θ-Fe 3C优先形成；相反地，高μ C(低H 2/CO比例)和中等温度(～250℃)则导向χ-Fe 5C 2的形成；ε-碳化物则是优先在较低温度、更高的碳化学势μ C下形成。
该文章的主要观点如图1所示，文章中采用了Fe 2O 3作为起始的前驱体，在费托合成反应气氛下做了一系列实验，并以XRD和同步辐射原位XAS测试其相变。在较高的碳化学势μ C下，ε/ε’碳化铁需在温和条件～200℃生成及稳定存在，而当接近于250℃时，则会转化为热力学稳定的χ-Fe 5C 2。在工业费托合成生产中，铁基费托合成温度为235-265℃，这是为了使副产的蒸汽饱和蒸气压提高，得到高品质蒸汽，提高经济效益。换言之，这篇权威性的文章表明，由于ε/ε’碳化铁在200℃以上不稳定，因此无法作为适用于现代费托合成工业的催化剂使用。
在2015发表在《Nature》子刊《Nature communication》的文章《Metal organic framework-mediated synthesis of highly active and stable Fischer-Tropsch catalysts》对碳化物做了合成尝试，并成功合成了χ-Fe 5C 2。这是一种可以适用于现代费托合成工业温度的催化剂，然而其CO 2选择性高达46％，这意味着其CO的利用效率理论最高值仅为54％，效率较低。
CN104399501A提供了适用于低温费托合成反应的ε-Fe 2C的纳米颗粒制备方法，其起始的前驱体为骨架铁，反应体系为聚乙二醇溶剂的间歇性非连续反应。这种催化剂的CO 2选择性为18.9％，CH 4的选择性为17.3％。其缺点为只能应用于200℃以下低温，反应无法连续完成。这意味该催化剂不适用于现代费托合成工业条件下的连续生产。
上述技术中，均存在着制备工艺复杂、原料较为昂贵、催化剂稳定性不佳，以及CO 2或CH 4副产物选择性过高的问题。
发明内容
本发明的目的是为了克服现有技术存在的上述技术问题，提供一种用于费托合成反应的负载型ε/ε’碳化铁催化剂及其制备方法和费托合成的方法。
为了实现上述目的，本发明第一方面提供一种用于费托合成反应的负载型ε/ε’碳化 铁催化剂的制备方法，其中，该制备方法包括：
(1)将催化剂载体在铁盐的水溶液中进行浸渍，并将浸渍后载体进行干燥、焙烧，得到催化剂前驱体；
(2)将所述催化剂前驱体与H 2在温度为300-550℃下进行前驱体还原；
(3)将步骤(2)得到的物料与H 2、CO在温度为90-185℃下进行前处理，H 2与CO的摩尔比为1.2-2.8：1；
(4)将步骤(3)得到的物料与H 2、CO在温度为200-300℃下进行碳化物制备，H 2与CO的摩尔比为1.0-3.2：1。
本发明第二方面提供由本发明所述的制备方法得到的用于费托合成反应的负载型ε/ε’碳化铁催化剂。
本发明第三方面提供一种费托合成的方法，包括：在费托合成反应条件下，将合成原料气与催化剂接触，其中，所述催化剂为本发明第二方面所述的用于费托合成反应的负载型ε/ε’碳化铁催化剂。
本发明具有以下技术效果：
(1)所需原料简便易得、成本低廉：合成前驱体主要原料铁源可以为市售铁盐，合成活性相碳化物时，仅利用费托合成反应体系的原有反应气(CO与H 2)即可，不涉及任何其它无机或有机物反应原料，与现有文献技术相比大大简化；
(2)操作步骤简便，优选的实施方式中，碳化物催化剂的制备与费托合成共用同一个反应器，因此，无需任何额外的活性相碳化物制备反应装置；制备的整个过程，仅需前驱体还原、前处理和碳化物制备三步，可在同一反应器内原位实现活性相的制备与合成反应；
(3)本发明的方法可以制备出负载在载体上的100％纯度的活性相ε/ε’碳化铁，所得负载型ε/ε’碳化铁催化剂适用于高温高压(例如，235-250℃的温度、2.3-2.5MPa的压力)连续反应器，反应稳定性极高，打破了传统文献理论“在较高的碳化学势μ C下，ε/ε’碳化铁需在温和的条件小于200℃稳定存在”的理论技术壁垒，其可实现稳定温度高达250℃，且CO 2选择性极低：在工业费托合成反应条件下，可使用高压连续反应器保持连续稳定反应400h以上，反应产物CO 2选择性在5％以下(优选情况下可以达到2.5％以下)；同时，副产物CH 4的选择性也保持在13.5％(优选情况下可以达到9.5％以下)，有效产物选择性可达到82％以上(优选情况下可以达到88％以上)，十分适用于现代煤化工费托合成大工业高效产出油蜡产品使用。
附图说明
图1是现有技术中的碳化铁转化关系图；
图2是实施例1中的前驱体1的透射电子显微镜TEM图；
图3是实施例1中的前驱体1的高分辨透射电子显微镜HRTEM图；
图4是实施例1的负载型ε/ε’碳化铁催化剂制备过程的原位XRD图；
图5是实施例1得到的负载型ε/ε’碳化铁催化剂的原位XRD图；
图6是实施例1的负载型ε/ε’碳化铁催化剂制备过程的原位穆斯堡尔谱图。
具体实施方式
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。
本发明第一方面提供一种用于费托合成反应的负载型ε/ε’碳化铁催化剂的制备方法，该制备方法包括：
(1)将催化剂载体在铁盐的水溶液中进行浸渍，并将浸渍后载体进行干燥、焙烧，得到催化剂前驱体；
(2)将所述催化剂前驱体与H 2在温度为300-550℃下进行前驱体还原；
(3)将步骤(2)得到的物料与H 2、CO在温度为90-185℃下进行前处理，H 2与CO的摩尔比为1.2-2.8：1；
(4)将步骤(3)得到的物料与H 2、CO在温度为200-300℃下进行碳化物制备，H 2与CO的摩尔比为1.0-3.2：1。
本发明中，所述铁盐可以为本领域中常用的能够溶于水的铁盐，可以为市售品，例如，所述铁盐为硝酸铁、氯化铁和硫酸亚铁铵中的至少一种。
本发明中，所述催化剂载体可以为本领域的常规选择，例如，所述催化剂载体为二氧化硅、氧化铝和二氧化钛中的至少一种。本发明中，优选所述催化剂载体的粒度为30-200μm。
本发明中，优选地，所述浸渍使得干燥后的浸渍后载体中的铁含量为10-30重量％。所述浸渍可以为本领域的常规选择，只要能够使得浸渍后的载体中铁的负载量达到要求 即可，优选地，所述浸渍为饱和浸渍法。
根据本发明的一种优选实施方式，所述干燥、焙烧的过程包括：首先将所述浸渍后载体在20-30℃干燥0.5-4h，然后在温度为35-80℃、真空度为250-1200Pa下烘干6-10h，将烘干后的物料在110-150℃下干燥3-24h，再将得到的物料在温度为300-550℃下焙烧1-10h。上述烘干的过程可以在烘箱中进行，所述焙烧的过程可以在马弗炉中进行。
本发明中，步骤(2)可以同时起到将前驱体中的铁原子原位生成纳米铁粉以及对生成的纳米铁粉进行表面净化处理的作用。
本发明中，步骤(2)中的H 2可以以H 2流的形式通入反应体系中，同时，通过控制H 2流的压力来控制前驱体还原处理的压力，优选地，步骤(2)中，所述前驱体还原的压力为0.1-15大气压，优选为0.3-2.6大气压，时间为0.7-15h，优选为1-12h。
本发明中，所述H 2的用量可以根据待处理的原料的量进行选择，优选地，步骤(2)中，所述H 2的气速为600-25000mL/h/g，更优选为2800-22000mL/h/g。
本发明中，步骤(3)中的H 2和CO可以以(H 2+CO)混合气流的形式通入反应体系中，同时，通过控制(H 2+CO)混合气流的压力来控制前处理过程的压力，优选地，步骤(3)中，所述前处理的压力为0.05-7大气压，更优选为0.08-4.5大气压，时间为15-120min，更优选为20-90min。
本发明中，优选地，步骤(3)中，所述H 2与CO的总气速为300-12000mL/h/g，更优选为1500-9000mL/h/g。
本发明中，步骤(4)中的H 2和CO可以以(H 2+CO)混合气流的形式通入反应体系中，同时，通过控制(H 2+CO)混合气流的压力来控制碳化物制备过程的压力，优选地，步骤(4)中，所述碳化物制备的压力为0.1-10大气压，优选为0.2-4.5大气压，时间为1.5-15h，优选为2.5-12h。
本发明中，优选地，步骤(4)中，所述H 2与CO的总气速为500-30000mL/h/g，更优选为3000-25000mL/h/g。
根据本发明的一种优选实施方式，所述制备方法还包括：将所述前处理后的体系温度以0.2-5℃/min的升温速率升温至200-300℃。在该优选实施方式中，得到的纯相ε/ε’碳化铁催化剂在费托合成反应中可以具体更好的有效产物选择性。进一步优选地，将所述前处理后的体系温度以0.2-2.5℃/min的升温速率升温至210-290℃。
本发明中，在无特殊说明的情况下，“mL/h/g”是指相对于每克原料，每小时的进气体积。
根据本发明的一种优选实施方式，所述前驱体还原、前处理和碳化物制备的过程在费托合成反应器中进行。在该优选实施方式中，催化剂制备与费托合成共用同一个反应器，因此，催化剂制备过程中的H 2和CO原料可以为费托合成反应体系的原有原料，并且，无需任何额外的活性相碳化物制备反应装置；制备的整个过程可在同一反应器内原位实现活性相的制备与合成反应，操作步骤更加简便。
本发明第二方面提供了由本发明所述的制备方法得到的用于费托合成反应的负载型ε/ε’碳化铁催化剂。该负载型ε/ε’碳化铁催化剂的活性相具有100％纯相的ε/ε’碳化铁。
本发明第三方面提供了一种费托合成的方法，包括：在费托合成反应条件下，将合成原料气与催化剂接触，其中，所述催化剂为本发明第二方面所述的用于费托合成反应的负载型ε/ε’碳化铁催化剂。
采用本发明的负载型ε/ε’碳化铁催化剂作为费托合成的催化剂，其可以在高温高压下进行费托合成反应，例如，所述费托合成反应条件包括：温度为235-250℃，压力为2.3-2.5MPa。
本发明中，在未作特殊说明的情况下，所述压力指的是绝对压力。
本发明中，优选地，所述费托合成在高温高压连续反应器中进行。本发明的负载型ε/ε’碳化铁催化剂可以实现费托合成反应在高温高压连续反应器中保持连续稳定反应400h以上。
以下将通过实施例对本发明进行详细描述。
以下实施例和对比例中，为方便对比，所有相同的原料均来自同一公司，实际操作时并不限于此一家公司原料。
实施例1
该实施例用于说明本发明的负载型ε/ε’碳化铁催化剂及其制备方法。
(1)取九水硝酸铁晶体，完全溶解于纯净水中制成硝酸铁溶液(浓度为0.12g/mL)；另取10.0g粒度为30-200μm的二氧化硅载体(购自国药集团化学试剂有限公司，硅载体)，将上述硝酸铁溶液饱和浸渍于二氧化硅载体上，使得浸渍后的载体Fe含量为30重量％，30℃放置干燥0.5h；
(2)将上述浸渍后载体放入真空烘箱，真空度设为250Pa，温度35℃，烘干10h，而后入110℃烘箱干燥24h；
(3)将上述已干燥的浸渍后载体入马弗炉焙烧，温度500℃，时间1h，得到前驱体1；
(4)将上述前驱体1放入管式费托合成反应器，在温度550℃下，通入气速2800mL/h/g、压力为2.6大气压的H 2流，反应1h；
(5)将反应器内温度降至185℃，同时将H 2流切换为摩尔比H 2/CO＝1.2、气速9000mL/h/g、总压力为0.08大气压的(H 2+CO)气流，前处理反应90min；
(6)将反应器内气流切换为摩尔比H 2/CO＝3.2、气速25000mL/h/g、总压力为0.2大气压的(H 2+CO)气流，同时以2.5℃/min的升温速率，稳定升温至290℃，保持2.5h。得到负载型ε/ε’碳化铁催化剂，记为A1。
对该实施例进行以下测试：
1)对前驱体1进行透射电子显微镜TEM测试与高分辨透射电子显微镜(HRTEM)测试，其结果如图2和图3所示。
2)采取原位XRD检测技术，即上述催化剂制备过程中同时使用X射线衍射仪(购自Rigaku公司，型号为D/max-2600/PC)对物料的晶相变化做监测，结果如图4-5所示。
其中，由图4可以清楚得看到由前驱体1(α-Fe 2O 3物相)至目标碳化物(ε/ε’碳化铁物相)的变化过程；由图5可以看出，生成的目标产物ε/ε’碳化铁结晶度好，很好地对应了ε/ε’碳化铁的所有特征峰，纯粹度极高，无任何其它杂质。
3)采取原位穆斯堡尔谱检测技术，即上述催化剂制备过程中同时使用穆斯堡尔谱(Transmission  57Fe， 57Co(Rh)源正弦速度谱仪，下同)对物料的成分变化做监测，并且对目标产物活性相ε/ε’碳化铁做了在反应气中添加250℃饱和蒸气压水蒸气的处理(高温水汽处理)，模拟工业化条件长周期运转后的情况。通过原位穆斯堡尔谱监测可以清楚地看到，由前驱体1至目标碳化物的变化过程以及经过高温水汽处理来模拟工业化条件长周期运转后的情况。结果见图6和表1。
其中，图6可以清楚地看到由前驱体至目标碳化物的变化过程以及经过高温水汽处理的过程。
表1统计了物相转化的具体数据，由表1可以看出，实施例1制备得到的目标产物中的活性相ε/ε’碳化铁的纯度为100％，经过模拟工业化条件长周期运转后，其纯度依然为100％。这说明本发明的方法可以制备出100％纯度活性相ε/ε’碳化铁的负载型催化剂，同时按照本发明的制备方法得到的负载型ε/ε’碳化铁催化剂能在高温250℃稳定存在，进一步地，即使经过模拟工业高温高压水蒸气侵蚀，该催化剂中的活性相ε/ε’碳化 铁依然保持着100％的纯度。
表1
Figure PCTCN2018092084-appb-000001
实施例2
该实施例用于说明本发明的负载型ε/ε’碳化铁催化剂及其制备方法。
(1)取硫酸亚铁铵晶体，完全溶解于纯净水中制成硫酸亚铁铵溶液(浓度为0.08g/mL)；另取粒度30-200μm氧化铝载体(国药集团化学试剂有限公司)8.0g，将上述硫酸亚铁铵溶液饱和浸渍于氧化铝载体上，使得浸渍后的载体Fe含量为10重量％，20℃放置干燥4h；
(2)将上述浸渍后载体放入真空烘箱，真空度设为1200Pa，温度80℃，烘干6h，而后入110℃烘箱干燥3h；
(3)将上述已干燥的浸渍后载体入马弗炉焙烧，温度300℃，时间10h，得到前驱体2；
(4)将上述前驱体2放入管式费托合成反应器，在温度300℃下，通入气速22000mL/h/g、压力为0.3大气压的H 2流，反应12h；
(5)将反应器内温度降至90℃，同时将H 2流切换为摩尔比H 2/CO＝2.8、气速1500mL/h/g、总压力为4.5大气压的(H 2+CO)气流，前处理反应20min；
(6)将反应器内气流切换为摩尔比H 2/CO＝1.0、气速3000mL/h/g、总压力为4.5大气压的(H 2+CO)气流，同时以0.2℃/min的升温速率，稳定升温至210℃，保持12h。得到负载型ε/ε’碳化铁催化剂，记为A2。
实施例3
该实施例用于说明本发明的负载型ε/ε’碳化铁催化剂及其制备方法。
(1)取氯化铁晶体，完全溶解于纯净水中制成氯化铁溶液(浓度为0.1g/mL)；另取11.0g粒度30-200μm二氧化钛载体(国药集团化学试剂有限公司)，将上述氯化铁溶液饱和浸渍于二氧化钛载体上，使得浸渍后的载体Fe含量为19重量％，25℃放置干燥2h；
(2)将上述浸渍后载体放入真空烘箱，真空度设为450Pa，温度70℃，烘干9h，而后入130℃烘箱干燥5h；
(3)将上述已干燥的浸渍后载体入马弗炉焙烧，温度500℃，时间6h，得到前驱体3；
(4)将上述前驱体3放入管式费托合成反应器，在温度420℃下，通入气速7000mL/h/g、压力为1.6大气压的H 2流，反应8h；
(5)将反应器内温度降至127℃，同时将H 2流切换为摩尔比H 2/CO＝2.3、气速5000mL/h/g、总压力为0.5大气压的(H 2+CO)气流，前处理反应80min；
(6)将反应器内气流切换为摩尔比H 2/CO＝2.7、气速5000mL/h/g、总压力为2.5大气压的(H 2+CO)气流，同时以1℃/min的升温速率，稳定升温至280℃，保持8h。得到负载型ε/ε’碳化铁催化剂，记为A3。
实施例4
按照实施例1的方法制备负载型ε/ε’碳化铁催化剂，不同的是，步骤(4)中，H 2流的压力为15大气压。将得到负载型ε/ε’碳化铁催化剂记为A4。
实施例5
按照实施例1的方法制备负载型ε/ε’碳化铁催化剂，不同的是，步骤(4)中，H 2流的气速为600mL/h/g。将得到负载型ε/ε’碳化铁催化剂记为A5。
实施例6
按照实施例1的方法制备负载型ε/ε’碳化铁催化剂，不同的是，步骤(5)中，(H 2+CO)流的压力为7大气压。将得到负载型ε/ε’碳化铁催化剂记为A6。
实施例7
按照实施例1的方法制备负载型ε/ε’碳化铁催化剂，不同的是，步骤(5)中，(H 2+CO)流的气速为300mL/h/g。将得到负载型ε/ε’碳化铁催化剂记为A7。
实施例8
按照实施例1的方法制备负载型ε/ε’碳化铁催化剂，不同的是，步骤(6)中，(H 2+CO)流的压力为0.1大气压。将得到负载型ε/ε’碳化铁催化剂记为A8。
实施例9
按照实施例1的方法制备负载型ε/ε’碳化铁催化剂，不同的是，步骤(6)中，(H 2+CO)流的气速为30000mL/h/g。将得到负载型ε/ε’碳化铁催化剂记为A9。
实施例10
按照实施例1的方法制备负载型ε/ε’碳化铁催化剂，不同的是，步骤(6)中，升温速率为5℃/min。将得到负载型ε/ε’碳化铁催化剂记为A10。
对比例1
按照实施例1的方法制备负载型碳化铁催化剂，不同的是，不进行步骤(5)，直接将步骤(4)得到的物料按照步骤(6)处理。将得到负载型碳化铁催化剂记为D1。
对比例2
按照实施例1的方法制备负载型碳化铁催化剂，不同的是，步骤(5)中，H 2与CO的摩尔比为1.0。将得到负载型碳化铁催化剂记为D2。
对比例3
按照实施例1的方法制备负载型碳化铁催化剂，不同的是，步骤(6)中，H 2与CO的摩尔比为3.5。将得到负载型碳化铁催化剂记为D3。
对比例4
按照实施例1的方法制备负载型碳化铁催化剂，不同的是，步骤(5)中的前处理的温度为200℃，步骤(6)中的碳化物制备的温度为310℃。将得到负载型碳化铁催化剂记为D4。
对比例5
该对比例用于说明现有技术(N.Lohitharn et al./Journal of Catalysis 255(2008)104–113)制备碳化铁催化剂的方法。
(1)按照100Fe/5Cu/17Si的摩尔比例，将原料0.6mol/L的Fe(NO 3) 3·9H 2O、CuN 2O 6·3H 2O混合，加入60mL H 2O溶解，另取Si(OC 2H 5) 4，加入40mL丙醇中溶解。将上述得到的两种溶液混合，并加热至83±3℃；
(2)预热2.7mol/L NH 4OH溶液至83±3℃；
(3)将步骤(2)得到的NH 4OH溶液连续加入步骤(1)得到的混合溶液中，剧烈搅拌，直至产生沉淀，沉淀终点保持pH＝8-9。在室温下老化17小时，以1.3-1.5L去离子水彻底洗涤除去NH 3，至pH＝7-8。将洗涤后的沉淀物在110℃下干燥18-24小时，并在空气中300℃煅烧5小时，并在2小时冷却至室温；
(4)筛分出粒径<90μm的物料，在典型工业催化剂活化条件H 2/CO摩尔比1.0，总气速5000mL/h/g，260℃下，活化12h，即得碳化铁催化剂，将该催化剂记为D5。
测试例
(1)采用穆斯堡尔谱法分别测定产物催化剂A2-A10和D1-D5的活性相中的ε’-Fe 2.2C/ε-Fe 2C物相的摩尔含量。结果如表2所示。
(2)在反应气摩尔比H 2/CO＝1.5，压力2.4MPa，温度235℃，(H 2+CO)总气速20000mL/h/g的条件下，分别将产物催化剂A1-A10、D1-D5与反应气H 2和CO接触进行费托合成反应。监测反应10h和400h时催化剂的活性和产物选择性。其中，
CO 2选择性％＝[出料中CO 2摩尔数/(进料中CO摩尔数-出料中CO摩尔数)]×100％；
CO转化率％＝[(进料中CO摩尔数-出料中CO摩尔数)/进料中CO摩尔数]×100％；
CH 4选择性％＝[出料中CH 4摩尔数/(进料中CO摩尔数×CO转化率％(1-CO 2选择性％))]×100％；
有效产物选择性％＝100％-CO 2选择性％-CH 4选择性％。
结果如表3所示。
表2
Figure PCTCN2018092084-appb-000002
Figure PCTCN2018092084-appb-000003
由表2的结果可以看出，采用本发明的制备方法能制备出活性相为100％纯相ε/ε’碳化铁的催化剂。
表3
Figure PCTCN2018092084-appb-000004
1：以上选择性均基于CO总转化量；
2：有效产物选择性指除副产物CO 2与CH 4以外的产物选择性。
通过表3的结果可以看出，本发明的方法所制备的负载型ε/ε’碳化铁催化剂在工业条件下展示出超低的CO 2选择性，优选的情况下，CO 2选择性可以低于2.5％，甚至接近于零；相对应地，通过现有技术制备的碳化铁催化剂D5在相同工业条件下的CO 2选择性高达28.5％-33.7％。
同时，本发明的方法所制备的活性相ε/ε’碳化铁催化剂的CH 4选择性均低于13.5％(优选情况下低于9.5％)，有效产物选择性可达到82％以上(优选情况下可以达到88％ 以上)；而通过现有技术制备的碳化铁催化剂D5的CH 4选择性较高，有效产物选择性较低，CO利用效率低下。
最后，对比第10小时与第400小时的实验数据可知，本发明方法所制备的负载型ε/ε’碳化铁催化剂在反应400h之后，不论是CO转化速率还是产物选择性均保持稳定，无明显变化；而通过现有技术制备的碳化铁催化剂D5的各项参数均出现明显下滑，说明本发明方法所制备的负载型ε/ε’碳化铁催化剂稳定性大大优于现有技术中的碳化铁催化剂。
以上详细描述了本发明的优选实施方式，但是，本发明并不限于此。在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，包括各个技术特征以任何其它的合适方式进行组合，这些简单变型和组合同样应当视为本发明所公开的内容，均属于本发明的保护范围。

Claims (10)

  1. 一种用于费托合成反应的负载型ε/ε’碳化铁催化剂的制备方法，其特征在于，该制备方法包括：
    (1)将催化剂载体在铁盐的水溶液中进行浸渍，并将浸渍后载体进行干燥、焙烧，得到催化剂前驱体；
    (2)将所述催化剂前驱体与H 2在温度为300-550℃下进行前驱体还原；
    (3)将步骤(2)得到的物料与H 2、CO在温度为90-185℃下进行前处理，H 2与CO的摩尔比为1.2-2.8：1；
    (4)将步骤(3)得到的物料与H 2、CO在温度为200-300℃下进行碳化物制备，H 2与CO的摩尔比为1.0-3.2：1。
  2. 根据权利要求1所述的制备方法，其中，所述铁盐为硝酸铁、氯化铁和硫酸亚铁铵中的至少一种；
    优选地，所述浸渍使得干燥后的浸渍后载体中的铁含量为10-30重量％；
    优选地，所述干燥、焙烧的过程包括：首先将所述浸渍后载体在20-30℃干燥0.5-4h，然后在温度为35-80℃、真空度为250-1200Pa下烘干6-10h，将烘干后的物料在110-150℃下干燥3-24h，再将得到的物料在温度为300-550℃下焙烧1-10h。
  3. 根据权利要求1或2所述的制备方法，其中，所述催化剂载体为二氧化硅、氧化铝和二氧化钛中的至少一种；
    优选地，所述催化剂载体的粒度为30-200μm。
  4. 根据权利要求1或2所述的制备方法，其中，步骤(2)中，所述前驱体还原的压力为0.1-15大气压，优选为0.3-2.6大气压，时间为0.7-15h，优选为1-12h；
    进一步优选地，步骤(2)中，所述H 2的气速为600-25000mL/h/g，更优选为2800-22000mL/h/g。
  5. 根据权利要求1或2所述的制备方法，其中，步骤(3)中，所述前处理的压力为0.05-7大气压，优选为0.08-4.5大气压，时间为15-120min，优选为20-90min；
    进一步优选地，步骤(3)中，所述H 2与CO的总气速为300-12000mL/h/g，更优 选为1500-9000mL/h/g。
  6. 根据权利要求1或2所述的制备方法，其中，步骤(4)中，所述碳化物制备的压力为0.1-10大气压，优选为0.2-4.5大气压，时间为1.5-15h，优选为2.5-12h；
    优选地，步骤(4)中，所述H 2与CO的总气速为500-30000mL/h/g，更优选为3000-25000mL/h/g。
  7. 根据权利要求1或2所述的制备方法，其中，所述制备方法还包括：将所述前处理后的体系温度以0.2-5℃/min的升温速率升温至200-300℃；
    优选地，将所述前处理后的体系温度以0.2-2.5℃/min的升温速率升温至210-290℃。
  8. 根据权利要求1或2所述的制备方法，其中，所述前驱体还原、前处理和碳化物制备的过程在费托合成反应器中进行。
  9. 由权利要求1-8中任意一项所述的制备方法得到的用于费托合成反应的负载型ε/ε’碳化铁催化剂。
  10. 一种费托合成的方法，包括：在费托合成反应条件下，将合成原料气与催化剂接触，其特征在于，所述催化剂为权利要求9所述的用于费托合成反应的负载型ε/ε’碳化铁催化剂；
    优选地，所述费托合成在高温高压连续反应器中进行。
PCT/CN2018/092084 2018-04-02 2018-06-21 用于费托合成反应的负载型ε/ε'碳化铁催化剂及其制备方法和费托合成的方法 Ceased WO2019192079A1 (zh)

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