WO2016011841A1 - 一种无载体催化剂及其制备方法和应用 - Google Patents

一种无载体催化剂及其制备方法和应用 Download PDF

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WO2016011841A1
WO2016011841A1 PCT/CN2015/079467 CN2015079467W WO2016011841A1 WO 2016011841 A1 WO2016011841 A1 WO 2016011841A1 CN 2015079467 W CN2015079467 W CN 2015079467W WO 2016011841 A1 WO2016011841 A1 WO 2016011841A1
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active metal
solution
metal oxide
reaction
catalyst
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French (fr)
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张燚
刘意
陈建峰
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北京化工大学
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • This invention relates to the field of catalysts. More specifically, it relates to an unsupported catalyst and a preparation method and application thereof.
  • CO hydrogenation catalytic conversion into liquid fuel or chemical is the core process of indirect conversion and utilization of non-oil-based carbon resources such as coal, coalbed methane, shale gas and biomass. Due to the complex and diverse products of CO hydroconversion, the selective regulation is extremely important. Taking the Fischer-Tropsch synthesis reaction of hydrogenation of CO to hydrocarbon as an example, the product conforms to the Anderson-Schulz-Flory (ASF) distribution on a conventional catalyst, which has a wide distribution and poor product selectivity. The development of a new type of Fischer-Tropsch catalyst with selective and controllable product is a challenging topic in this direction.
  • ASF Anderson-Schulz-Flory
  • coal-based natural gas is a process technology for producing natural gas from coal. It can convert coal into clean fuel CH 4 for long-distance transportation. It becomes an important way to alleviate the contradiction between supply and demand of natural gas and efficient and clean coal conversion.
  • the technology catalyzes the hydrogenation of carbon oxides (CO + CO 2 ) in the synthesis feed gas to methane (CH 4 ) by the principle of heterogeneous catalytic methanation.
  • Methanation technology is one of the core technologies of coal-based natural gas, and methanation catalyst is the basis for methanation process development. Ni-based catalyst has better catalytic activity of methanation, high selectivity and relatively low price.
  • Ni(CO) 4 nickel carbonyl
  • Heterogeneous catalytic reactions are reactions that occur on the surface of a catalyst and are therefore also referred to as surface catalysis or contact catalysis.
  • the auxiliary agent plays an important role in the heterogeneous catalytic reaction.
  • the auxiliary agent can be used as a catalyst carrier to disperse the nano metal particles, and the auxiliary agent can strongly influence the catalytic performance of the metal through the strong metal-support interaction (SMSI).
  • SMSI strong metal-support interaction
  • the active metal component is supported on the surface of the support and the adjuvant is part of the support. This makes a considerable part of the auxiliary agent covered by the active metal component, and the auxiliary agent can not contact with the reactant in the surface catalytic contact reaction, which greatly limits the effect of the auxiliary agent.
  • the first technical problem to be solved by the present invention is to provide an unsupported catalyst; it has good stability, is not easily deactivated, and has high catalytic performance.
  • the second technical problem to be solved by the present invention is to provide a preparation method of the above unsupported catalyst; the raw material is cheap, easy to obtain, simple in preparation process, low in cost, and suitable for industrial production.
  • a third technical problem to be solved by the present invention is to provide the use of the above unsupported catalyst.
  • the present invention adopts the following technical solutions:
  • An unsupported catalyst comprising: an active metal oxide and an auxiliary agent embedded on an outer surface thereof;
  • the active metal oxide is selected from one or more of the following oxides of metals: iron, cobalt, nickel, copper;
  • the auxiliary agent is selected from one or more of the following elements: iron, cobalt, nickel, copper, lanthanum, manganese, potassium, silver, calcium, magnesium, zirconium, aluminum, zinc, lanthanum, platinum, sodium, phosphorus, It exists in the form of a simple substance or an oxide.
  • the active metal oxide is soaked by an alcohol, an alcohol isomer or an aqueous carboxylic acid solution.
  • the active metal oxide is nano or micron in size; the auxiliaries are nanometer sized.
  • the active metal oxide has a particle diameter of from 20 nm to 5 mm
  • the auxiliary agent has a particle diameter of from 1 nm to 50 nm.
  • the active metal oxide has a particle size of from 50 nm to 1 ⁇ m; in this range, the catalytic activity of the unsupported catalyst is the highest.
  • the adjuvant has a mass fraction in the unsupported catalyst of from 0.1% by weight to 40% by weight. Too little additive may cause the additive effect to be insignificant. Too much additive may cover too much active site and affect the reactivity.
  • the adjuvant has a mass fraction of from 1% by weight to 20% by weight in the unsupported catalyst. Within this range, the matching of the adjuvant effect and the active site is optimal.
  • the mass fraction of the adjuvant in the unsupported catalyst refers to the ratio of the mass of the additive to the sum of the mass of the additive and the mass of the active metal oxide.
  • the mass fraction of the promoter in the catalyst can be adjusted by adjusting the concentration of the promoter precursor salt in the preparation of the unsupported catalyst.
  • the active metal oxide can be prepared by a hydrothermal/solvent thermal synthesis method, a precipitation method, a melting method, a sol-gel method or the like.
  • hydrothermal/solvent thermal synthesis is used, which has product purity High, good dispersion, easy to control particle size, and simple preparation process.
  • the preparation method of the above unsupported catalyst comprises the following steps:
  • the active metal oxide is selected from one or more of the following oxides of metals: iron, cobalt, nickel, copper;
  • the adjuvant is selected from one or more of the following elements: iron, cobalt, nickel, copper, cerium, manganese, potassium, silver, calcium, magnesium, zirconium, aluminum, zinc, cerium, platinum, sodium, phosphorus.
  • the impregnation process in the preparation of the catalyst is to infiltrate the liquid (ie, the active component) into the interior of the carrier void by capillary pressure; vacuum decompression is usually selected under vacuum, because when the vacuum is used, the internal and external pressure difference promotes the entry of the active component.
  • vacuum decompression is usually selected under vacuum, because when the vacuum is used, the internal and external pressure difference promotes the entry of the active component.
  • the vacuum can remove these impurities and moisture, thereby allowing more active components to enter the carrier and increasing the loading of the carrier.
  • the auxiliary agent is supported on the metal oxide, and the metal oxide is basically considered to be non-porous, it is only required to be dried under normal pressure, and thus, the preparation method of the present invention
  • the required reaction conditions are simple and more conducive to operation.
  • the temperature and time at atmospheric drying have an effect on the performance of the final catalyst. If the drying temperature is too low, it may cause solvent residue. If the drying temperature is too high, it will affect the valence state of the metal oxide.
  • the particles are agglomerated and agglomerated; if the drying time is too short, the drying may be insufficient, and if the drying time is too long, the particles may be further agglomerated.
  • the alcohol is selected from one or more of the group consisting of methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, glycerol, butylene glycol.
  • the carboxylic acid is selected from one or more of the group consisting of formic acid, acetic acid, propionic acid, butyric acid.
  • the concentration of the alcohol, the alcohol isomer or the aqueous carboxylic acid solution is from 10% by weight to 100% by weight.
  • the active metal oxide is nano or micron in size.
  • the active metal oxide has a particle diameter of from 20 nm to 5 mm.
  • the active metal oxide has a particle size of from 50 nm to 1 ⁇ m; in this range, the catalytic activity of the unsupported catalyst is the highest.
  • the temperature and time of the immersion are not limited, and those skilled in the art can carry out according to the conventional operation. Preferably, it is soaked at 50-70 ° C for 1-3 h.
  • the temperature and time of the immersion need not be limited, and those skilled in the art can carry out according to the conventional operation. Preferably, it is soaked for 1-3 h at 20-40 °C.
  • the type of the precursor salt of the auxiliary agent is not limited, and may be any salt of each of the foregoing elements.
  • the concentration of the aqueous solution of the precursor salt of the auxiliary agent is not limited.
  • the active metal oxide can be prepared by a hydrothermal/solvent thermal synthesis method, a precipitation method, a melting method, a sol-gel method or the like. It is preferred to adopt a hydrothermal/solvent thermal synthesis method, which has the characteristics of high product purity, good dispersibility, easy control of particle size, and simple preparation process.
  • the active metal oxide is prepared by hydrothermal/solvent thermal synthesis, and comprises the following steps:
  • the solution C is heated in a sealed condition, 150-240 ° C for 10-20h to obtain a mixture D;
  • the mixture D is centrifuged, washed, and then dried at 60-200 ° C for 10-20h to obtain an active metal oxide
  • the solvent is one or more of water, ethanol, ethylene glycol, glycerol, 1-acet-2-ethylene glycol, DMF, THF, acetonitrile or ethylenediamine.
  • the precursor salt:surfactant:solvent ratio of the active metal is 7.4 mmol: 0.2-2 g: 40-80 ml. If the ratio is not in this range, the degree of hydrothermal reaction will be affected, and the size and uniformity of the obtained metal oxide particles will be affected.
  • the surfactant is one or more of cetyltrimethylammonium bromide, Triton X-100, and trisodium citrate.
  • the concentration of sodium acetate in solution B is from 0.5 to 2 mol/l. If the concentration of sodium acetate is too small, the hydrothermal reaction may be incompletely crystallized. If it is too large, the particles may be agglomerated and not uniform.
  • Steps I, II, and III can be carried out at room temperature.
  • step I The reactants are generally stirred in step II and step III.
  • Step IV is to move the solution C into a Teflon container and then heat it in a stainless steel autoclave. After the heating was completed, it was cooled to room temperature and then centrifuged again. The washing is to wash the precipitate with ethanol to remove the residual solvent and surfactant in the precipitate.
  • the present invention adopts the following technical solutions:
  • the carbon monoxide hydrogenation reaction comprises a Fischer-Tropsch synthesis reaction, a methanation reaction, a methanol synthesis reaction, a hydroformylation reaction, and an ethylene oxide oxo synthesis reaction.
  • the catalyst is used for the Fischer-Tropsch synthesis reaction and the methanation reaction after reduction.
  • the reduction has a reduction temperature of from 250 to 800 ° C and a pressure of from 0.1 to 2.0 MPa.
  • the invention combines the surface catalysis research of the model system with the interfacial catalysis research in the real catalytic material, and constructs a nano-structure auxiliary agent on the surface of the active metal to form a promoter-on-metal reverse catalytic system, and realizes the supporting agent and the active metal. Directly catalyze surface reactions.
  • the catalyst of the present invention does not contain a conventional catalyst carrier, but a nano-sized auxiliary agent is formed on the surface of the active metal oxide to form a structure in which the auxiliary agent is directly embedded in the surface of the active component particle.
  • the catalyst of the invention realizes efficient synergy between the supported auxiliary agent and the active metal oxide, and helps The agent can directly act on the surface of the active component to significantly enhance the promotion of the auxiliary agent, thereby effectively promoting the reduction of the active component, improving the reactivity and improving the catalytic reaction performance of the catalyst.
  • the catalyst of the invention has controllable reaction selectivity. Since the auxiliary agent forms a new interface on the surface of the active metal, the electron distribution on the surface of the active metal component can be adjusted by the auxiliary agent, thereby adjusting the hydrogenation effect and controlling the product. distributed.
  • the catalyst of the invention has good stability and is not easy to be deactivated. Due to the synergistic action of the auxiliary agent and the active metal and the new interface formed, the obtained catalyst has excellent carbon deposition resistance and oxidation resistance.
  • the preparation method of the catalyst of the invention is cheap, easy to obtain, simple in process, low in product cost, and suitable for industrial production.
  • Example 1 is an SEM image of a ferroferric oxide microsphere prepared in Example 1.
  • Example 2 is an XRD pattern of the ferroferric oxide microspheres prepared in Example 1.
  • Example 3 is an SEM image of the catalyst prepared in Example 1.
  • Example 4 is an XRD chart of the catalyst prepared in Example 1.
  • Figure 5 is a schematic view showing the structure of the catalyst of the present invention.
  • a method for preparing an iron-based inversion catalyst for Fischer-Tropsch synthesis comprising the steps of:
  • the solution was transferred to a Teflon container, sealed in a stainless steel autoclave, heated at 150 ° C for 10 h, and then cooled to room temperature; the product was centrifuged and washed three times with ethanol, then at 60 ° C. After drying for 10 hours, a ferroferric oxide microsphere was obtained with a diameter of about 250 nm.
  • Example 1 is an SEM image of a ferroferric oxide microsphere prepared in Example 1.
  • Example 2 is an XRD pattern of the ferroferric oxide microspheres prepared in Example 1.
  • the auxiliary agent accounts for 23% of the catalyst and the auxiliary size is about 5 nm.
  • Example 3 is an SEM image of the catalyst prepared in Example 1.
  • Example 4 is an XRD chart of the catalyst prepared in Example 1.
  • Figure 5 is a schematic view showing the structure of the catalyst of the present invention.
  • the obtained catalyst was the same as that of Example 1, and the reaction results are shown in Table 1.
  • the obtained catalyst was the same as the application method of Example 1, and the reaction results are shown in Table 1.
  • the solution was transferred to a Teflon container, sealed in a stainless steel autoclave, heated at 150 ° C for 10 h, and then cooled to room temperature; the product was centrifuged and washed three times with ethanol, then at 60 ° C. After drying for 10 h, iron cobalt oxide microspheres were obtained with a diameter of about 250 nm.
  • the obtained catalyst was the same as the application method of Example 1, and the reaction results are shown in Table 1.
  • a preparation method of a cobalt-based inversion catalyst which can be used for Fischer-Tropsch synthesis comprising the following steps:
  • the solution was transferred to a Teflon container, sealed in a stainless steel autoclave, heated at 180 ° C for 20 h, and then cooled to room temperature; the product was centrifuged and washed three times with ethanol, then at 100 ° C. After drying for 15 h, a tricobalt tetraoxide microsphere was obtained.
  • a method for preparing a nickel-based inversion catalyst for methanation reaction comprising the steps of:
  • the solution was transferred to a Teflon container, sealed in a stainless steel autoclave, heated at 200 ° C for 20 h, and then cooled to room temperature; the product was centrifuged and washed three times with ethanol, then at 60 ° C. After drying for 15 h, nickel oxide microspheres were obtained.
  • the auxiliaries accounted for 21% by mass of the catalyst, the auxiliary size was about 10 nm, and the nickel oxide microspheres were about 100 nm.
  • a method for preparing a copper-based inversion catalyst for methanol synthesis reaction comprising the following steps:
  • the solution was transferred to a Teflon container, sealed in a stainless steel autoclave, heated at 240 ° C for 20 h, and then cooled to room temperature; the product was centrifuged and washed three times with ethanol, then at 200 ° C. After drying for 20 h, copper oxide nanoparticles were obtained.
  • the auxiliaries accounted for 10% by mass of the catalyst, the size of the auxiliaries was about 1 nm, and the size of the oxidized copper nano-particles was about 20 nm.
  • a method for preparing an iron-based inversion catalyst for Fischer-Tropsch synthesis comprises the following steps:
  • the iron ball is added to 6 ml of glycerin for soaking;
  • the auxiliaries accounted for 31% by mass of the catalyst and the auxiliary size was about 50 nm.
  • a method for preparing a cobalt-based inversion catalyst for carbonylation of 3-carbonylpropanal and 1,3-propanediol to ethylene oxide comprises the following steps:
  • the solution was transferred to a Teflon container, sealed in a stainless steel autoclave, heated at 150 ° C for 10 h, and then cooled to room temperature; the product was centrifuged and washed three times with ethanol, then at 60 ° C. After drying for 10 h, a cobalt tetraoxide microsphere was obtained.
  • Example 2 The same as in Example 1, except that the active metal oxide is prepared by a precipitation method, a sol-gel method, or a melting method, respectively.
  • Preparation of active metal oxide by precipitation method weigh iron nitrate according to 20wt% content of elemental iron in the final catalyst, prepare iron nitrate solution with 10wt% concentration with ethanol, stir and heat to 150°C in the vessel, constant After heating for 1 hour, the solution is cooled to room temperature, a certain amount of water is added, and a solution of 3 wt% iron nitrate is prepared. After mixing uniformly, it is slowly mixed with the sodium carbonate solution into the precipitation reactor to control the pH of the precipitate at 10 . After the end of the precipitation, it was aged for 2 hours. The precipitate was suction filtered, washed and dried. The drying temperature was 80 ° C, the temperature was kept for 48 hours, and then placed in a muffle furnace for calcination at a temperature of 500 ° C for 5 hours to obtain ferric oxide microspheres having a diameter of about 100nm.
  • Preparation of active metal oxide by melting method magnetite, hematite and reduced iron powder are mixed in a ratio of 1:1:1, and heated to a molten state in an arc induction graphite furnace under an argon atmosphere to form an alloy. After that, it was quickly transferred to water for quenching, and then mechanically broken to obtain precursor particles having a diameter of about 1 mm.
  • the additive used was changed to 0.31g potassium nitrate and 0.08g magnesium nitrate;
  • the obtained catalyst was the same as that of Example 1, and the results of the reaction are shown in Table 6.
  • Example 2 The same as Example 1, except that: 2. In the preparation of the catalyst: methanol was used instead of acetic acid at a concentration of 10% by weight. The results were similar to those of Example 1.
  • Example 2 The same as in Example 1, except that: 2. In the preparation of the catalyst: ethanol was used instead of acetic acid at a concentration of 20% by weight. The results were similar to those of Example 1.
  • Example 2 The same as in Example 1, except that: 2.
  • propanol was used instead of acetic acid at a concentration of 30% by weight. The results were similar to those of Example 1.
  • Example 2 The same as Example 1, except that: 2. In the preparation of the catalyst: butanol was used instead of acetic acid at a concentration of 44% by weight. The results were similar to those of Example 1.
  • Example 2 Same as Example 1, the difference is: 2, in the preparation of the catalyst: replacing the acetic acid with pentanol, the concentration It is 100% by weight. The results were similar to those of Example 1.
  • Example 2 The same as in Example 1, except that: 2.
  • propylene glycol was used instead of acetic acid at a concentration of 60% by weight. The results were similar to those of Example 1.
  • Example 2 The same as in Example 1, except that: 2. In the preparation of the catalyst: butanediol was used instead of acetic acid. The results were similar to those of Example 1.
  • Example 2 The same as in Example 1, except that: 2. In the preparation of the catalyst: formic acid was used instead of acetic acid. The results were similar to those of Example 1.
  • Example 2 The same as in Example 1, except that: 2. In the preparation of the catalyst: propionic acid was used instead of acetic acid. The results were similar to those of Example 1.
  • Example 2 The same as in Example 1, except that: 2. In the preparation of the catalyst: acetic acid was replaced by butyric acid. The results were similar to those of Example 1.

Abstract

一种无载体催化剂及其制备方法。其中所述催化剂包括：活性金属氧化物和嵌在其外表面上的助剂；所述活性金属氧化物选自下列金属的氧化物中的一种或多种：铁、钴、镍、铜；所述助剂选自下列元素中的一种或多种：铁、钴、镍、铜、铑、锰、钾、银、钙、镁、锆、铝、锌、钌、铂、钠、磷，所述助剂以单质或氧化物形式存在。

Description

一种无载体催化剂及其制备方法和应用 技术领域
本发明涉及催化剂领域。更具体地，涉及一种无载体催化剂及其制备方法和应用。
背景技术
CO加氢催化转化制成液体燃料或化学品是煤、煤层气、页岩气及生物质等非油基碳资源间接转化利用的核心过程。因CO加氢转化反应的产物复杂多样，其选择性的调控极其重要。以CO加氢制碳氢化合物的费托合成反应为例，在传统催化剂上其产物服从Anderson-Schulz-Flory(ASF)分布，该分布宽，产物选择性差。研制产物选择性可调控的新型费托催化剂是该方向上的一大挑战性课题。
再以煤制天然气为例，煤制天然气是以煤为原料生产天然气的工艺技术，可以将煤炭转化为便于远距离输送的清洁燃料CH4，成为缓解天然气供需矛盾和煤炭高效清洁转化的重要途径之一。该技术是通过多相催化甲烷化反应原理，将合成原料气中的碳氧化合物(CO+CO2)催化加氢生成甲烷(CH4)。甲烷化技术是煤制天然气的核心技术之一，甲烷化催化剂是甲烷化工艺开发的基础。Ni基催化剂具有比较好的甲烷化催化活性，选择性高，且价格相对廉价；缺点是其对硫十分敏感，易中毒失活，在催化甲烷化反应的同时也会 发生积炭反应使催化剂失活，而且在一定温度范围内可同CO反应生成Ni(CO)4(羰基镍)，使活性组分流失。国内外的研究人员针对Ni基催化剂的缺点做了大量的研究工作使实际生产中Ni基催化剂的缺点得以避免。
多相催化反应是发生于催化剂表面的反应，因此也称表面催化或接触催化。助剂在多相催化反应中发挥着重要作用，助剂可以被用作催化剂载体来分散纳米金属粒子，同时助剂能够通过金属-载体的强相互作用(SMSI)强烈地影响金属的催化性能。在传统的催化剂体系中，是将活性金属组分负载于载体表面，助剂是作为载体的一部分。这使得有相当部分的助剂被活性金属组分覆盖，在表面催化接触反应中助剂无法与反应物接触发挥作用，大大限制了助剂的效果。
因此，需要提供一种稳定性好，不易失活且催化性能高的催化剂。
发明内容
本发明要解决的第一个技术问题是提供一种无载体催化剂；它具有良好的稳定性，不易失活，且催化性能高。
本发明要解决的第二个技术问题是提供上述无载体催化剂的制备方法；它的原料廉价、易得，制备工艺简单，成本低，适于工业化生产。
本发明要解决的第三个技术问题是提供上述无载体催化剂的应用。
为解决上述第一个技术问题，本发明采用下述技术方案：
一种无载体催化剂，包括：活性金属氧化物和嵌在其外表面上的助剂；
所述活性金属氧化物选自下列金属的氧化物中的一种或多种：铁、钴、镍、铜；
所述助剂选自下列元素中的一种或多种：铁、钴、镍、铜、铑、锰、钾、银、钙、镁、锆、铝、锌、钌、铂、钠、磷，以单质或氧化物形式存在。
优选地，所述活性金属氧化物经醇、醇的异构体或羧酸水溶液浸泡处理。
优选地，所述活性金属氧化物为纳米或微米尺寸；所述助剂为纳米尺寸。
更优选地，所述活性金属氧化物的粒径为20nm-5mm，所述助剂的粒径为1nm-50nm。
最优选地，所述活性金属氧化物的粒径为50nm-1μm；在此范围内时，无载体催化剂的催化活性最高。
优选地，所述助剂在无载体催化剂中的质量分数为0.1wt％-40wt％。助剂含量太少可能导致助剂效应不显著，助剂含量太多可能会覆盖过多活性位，影响反应活性。
更优选地，所述助剂在无载体催化剂中的质量分数为1wt％-20wt％。在此范围内，助剂效应和活性位的匹配最佳。
本文中，助剂在无载体催化剂中的质量分数指助剂质量与助剂质量和活性金属氧化物质量之和的比。可通过调节无载体催化剂制备过程中助剂前驱体盐的浓度来调节催化剂中助剂的质量分数。
所述活性金属氧化物可采用水热/溶剂热合成法、沉淀法、熔融法、溶胶凝胶法等等方法来制备得到。优选采用水热/溶剂热合成法，其具有产物纯度 高、分散性好、粒度易控制、制备过程较简单等特点。
为解决上述第二个技术问题，本发明采用下述技术方案：
上述无载体催化剂的制备方法，包括如下步骤：
1)用醇、醇的异构体或羧酸水溶液浸泡活性金属氧化物，之后在60-180℃干燥12-48h，得到改性后活性金属氧化物；
2)用助剂的前驱体盐的水溶液浸泡步骤1)得到的改性后活性金属氧化物，之后在60-180℃干燥12-48h，得到无载体催化剂；
所述活性金属氧化物选自下列金属的氧化物中的一种或多种：铁、钴、镍、铜；
所述助剂选自下列元素中的一种或多种：铁、钴、镍、铜、铑、锰、钾、银、钙、镁、锆、铝、锌、钌、铂、钠、磷。
一般，在催化剂制备中的浸渍过程是通过毛细管压力使液体(即活性组分)渗透到载体空隙内部；通常会选择减压抽真空浸渍，因为使用真空时，内外压力差会促进活性组分进入到载体空隙内部，且由于载体上的孔内有杂质和水分，真空可以清除这些杂质和水分，进而相对能使更多的活性组分进入载体内，增加载体的负载量。但在本催化体系中，由于助剂是负载在金属氧化物上，而这些金属氧化物可基本认为是无孔的，因此只需在常压下干燥处理即可，这样，本发明的制备方法要求的反应条件很简单，更利于操作。
常压干燥时的温度和时间对最终催化剂的性能有影响。若干燥温度过低则可能会导致溶剂残留，若干燥温度过高则会影响金属氧化物的价态，并导 致颗粒烧结团聚等；若干燥时间过短则会导致干燥的不充分，若干燥时间过长则可能导致颗粒进一步生长团聚。
优选地，步骤1)中，所述醇选自下列物质中的一种或多种：甲醇、乙醇、丙醇、丁醇、戊醇、乙二醇、丙二醇、丙三醇、丁二醇。
优选地，步骤1)中，所述羧酸选自下列物质中的一种或多种：甲酸、醋酸、丙酸、丁酸。
优选地，步骤1)中，所述醇、醇的异构体或羧酸水溶液的浓度为10wt％-100wt％。
优选地，步骤1)中，所述活性金属氧化物为纳米或微米尺寸。
更优选地，步骤1)中，所述活性金属氧化物的粒径为20nm-5mm。
最优选地，所述活性金属氧化物的粒径为50nm-1μm；在此范围内时，无载体催化剂的催化活性最高。所述步骤1)中，浸泡的温度和时间无须限定，本领域技术人员按照常规操作进行即可。优选地，在50-70℃浸泡1-3h。
所述步骤2)中，浸泡的温度和时间无须限定，本领域技术人员按照常规操作进行即可。优选地，在20-40℃浸泡1-3h。
所述步骤2)中，助剂的前驱体盐的类型不作限制，可以是前述各元素的任意盐。助剂的前驱体盐的水溶液的浓度不作限制。
所述活性金属氧化物可采用水热/溶剂热合成法、沉淀法、熔融法、溶胶凝胶法等等方法来制备得到。优选采用水热/溶剂热合成法，其具有产物纯度高、分散性好、粒度易控制、制备过程较简单等特点。
优选地，所述活性金属氧化物采用水热/溶剂热合成法制备得到，包括以下步骤：
I将活性金属的前驱体盐(可为任意盐)和表面活性剂溶于溶剂，得到溶液A；
II将乙酸钠溶于溶剂，得到溶液B；
III将溶液B加入溶液A中，得到溶液C；溶液A和溶液B的用量比为活性金属的前驱体盐：乙酸钠＝1.95g：20-160mmol；
IV将溶液C在密闭条件、150-240℃加热10-20h，得到混合液D；
V将混合液D离心分离，洗涤，之后在60-200℃下干燥10-20h，得到活性金属氧化物；
步骤I和步骤II中，所述溶剂为水、乙醇、乙二醇、丙三醇、1-缩-2-乙二醇、DMF、THF、乙腈、乙二胺中的一种或多种。
优选地，步骤I中，活性金属的前驱体盐∶表面活性剂∶溶剂的用量比为7.4mmol∶0.2-2g∶40-80ml。用量比不在此范围会影响水热反应的程度，得到的金属氧化物颗粒大小以及均一程度会受到影响。
优选地，步骤I中，所述表面活性剂为十六烷基三甲基溴化铵、曲拉通X-100、柠檬酸三钠中的一种或几种。
优选地，步骤II中，溶液B中乙酸钠的浓度为0.5-2mol/1。乙酸钠浓度过小可能会导致水热反应结晶不完全，过大可能会导致颗粒较大结块，不均一。
步骤I、II、III在室温下进行即可。为了保证各反应物充分接触，步骤I、 步骤II、步骤III中一般将反应物进行搅拌。
步骤IV是将溶液C移至聚四氟乙烯容器内，之后密闭在不锈钢高压反应釜中加热。加热完成后，冷却至室温，然后再进行离心分离。洗涤是将沉淀物用乙醇洗涤，以除去沉淀物中残留的溶剂和表面活性剂。
为解决上述第三个技术问题，本发明采用下述技术方案：
上述无载体催化剂的应用，其可应用于一氧化碳加氢反应中。
优选地，所述一氧化碳加氢反应包括费托合成反应、甲烷化反应、甲醇合成反应、氢甲酰化反应、环氧乙烷羰基合成反应。
更优选地，所述催化剂经还原后用于费托合成反应及甲烷化反应。
最优选地，所述还原的还原温度为250-800℃、压力为0.1-2.0MPa。
优选地，所述催化剂应用在费托合成反应及甲烷化反应中时的反应条件为：反应温度240-750℃、反应压力0.1-8.5MPa、合成气空速500-15000h-1(V/V)，合成气H2/CO＝0.8-3。
本发明的有益效果如下：
本发明将模型体系的表面催化研究和真实催化材料中的界面催化研究相结合，在活性金属表面构建纳米结构助剂形成promoter-on-metal反转催化体系，实现担载的助剂与活性金属直接催化表面反应。
1、本发明的催化剂不含常规的催化剂载体，而是在活性金属氧化物表面构建纳米尺寸的助剂，形成助剂直接镶嵌在活性组分颗粒表面的结构。
2、本发明的催化剂实现了担载的助剂与活性金属氧化物的高效协同，助 剂能直接作用于活性组分表面使得助剂的促进作用得到显著增强，进而有效促进活性组分的还原，提高反应活性，提高了催化剂的催化反应性能。
3、本发明的催化剂具有可控的反应选择性，由于助剂在活性金属表面形成新的界面，可通过助剂来调节活性金属组分表面的电子分布状况，进而调节加氢效果，控制产物分布。
4、本发明的催化剂具有良好的稳定性，不易失活，由于助剂与活性金属的协同作用及形成的新界面，使得到的催化剂具有优异的抗积碳和抗氧化性能。
5、本发明的催化剂的制备方法使用的原料廉价、易得，工艺简单，产品成本低，适于工业化生产。
附图说明
图1为实施例1中制备的四氧化三铁微球SEM图。
图2为实施例1中制备的四氧化三铁微球XRD图。
图3为实施例1中制备的催化剂的SEM图。
图4为实施例1中制备的催化剂的XRD图。
图5为本发明的催化剂的结构示意图。
具体实施方式
下面结合附图及实施例对本发明进一步加以说明。
实施例1
一种可用于费托合成的铁基反转催化剂的制备方法，包括如下步骤：
1、制备活性金属氧化物纳微颗粒：
称取1.95g三氯化铁和0.2g柠檬酸三钠，混合后加入40ml乙二醇，搅拌0.5h得到溶液A；
称取4g乙酸钠溶于40ml丙三醇中，搅拌0.5h得到溶液B；
将B溶液缓慢添加到A溶液中，并持续搅拌3h；
将上述溶液移至聚四氟乙烯容器内，密闭在不锈钢高压反应釜中，在150℃下加热反应10h，再冷却至室温；将上述产物离心分离后，用乙醇洗涤3次，后在60℃下干燥10h，得到四氧化三铁微球，直径约为250nm。
图1为实施例1中制备的四氧化三铁微球SEM图。
图2为实施例1中制备的四氧化三铁微球XRD图。
2、制备催化剂：
1)量取6ml醋酸，加入去离子水配制成浓度为50wt％的醋酸溶液；然后用该溶液浸泡1.5g上述得到的四氧化三铁微球；之后放入干燥箱中干燥，干燥温度120℃，恒温48h，获得改性后的四氧化三铁微球；
2)称取0.01g硝酸钾、0.35g硝酸锰和0.08g硝酸铜，混合后加入4ml水，配制成溶液，将该溶液浸泡改性后的四氧化三铁微球，然后放入干燥箱中干燥，干燥温度150℃，恒温12h，得到费托合成铁基反转催化剂。
其中，助剂占催化剂的质量分数为23％，助剂尺寸约为5nm。
图3为实施例1中制备的催化剂的SEM图。
图4为实施例1中制备的催化剂的XRD图。
图5为本发明的催化剂的结构示意图。
3、催化剂的应用：
取催化剂1g用合成气(H2/CO＝1)于固定床中还原，还原条件为500℃，0.1MPa，5000h-1(V/V)，恒温10h；还原完成后，将已还原好的催化剂在氮气流中降至室温，然后将氮气切换成合成气(H2/CO＝1)，开始进行费托合成反应；反应条件为280℃，1.5MPa，2500h-1(V/V)，反应结果见表1。
实施例2
与实施例1相同，区别在于：
2、制备催化剂中：
1)干燥温度60℃，恒温12h；
2)干燥温度60℃，恒温24h。
得到的催化剂与实施例1的应用相同，反应结果见表1。
实施例3
与实施例1相同，区别在于：
2、制备催化剂中：
1)干燥温度180℃，恒温24h；
2)干燥温度180℃，恒温48h。
得到的催化剂与实施例1的应用方法相同，反应结果见表1。
实施例4
与实施例1相同，区别在于：
1、制备活性金属氧化物纳微颗粒：
称取1.05g三氯化铁、0.9g硝酸钴和0.2g柠檬酸三钠，混合后加入40ml乙二醇，搅拌0.5h得到溶液A；
称取4g乙酸钠溶于40ml丙三醇中，搅拌0.5h得到溶液B；
将B溶液缓慢添加到A溶液中，并持续搅拌3h；
将上述溶液移至聚四氟乙烯容器内，密闭在不锈钢高压反应釜中，在150℃下加热反应10h，再冷却至室温；将上述产物离心分离后，用乙醇洗涤3次，后在60℃下干燥10h，得到铁钴氧化物微球，直径约为250nm。
得到的催化剂与实施例1的应用方法相同，反应结果见表1。
表1 费托合成催化剂反应结果
Figure PCTCN2015079467-appb-000001
实施例5
一种可用于费托合成的钴基反转催化剂制备方法，包括如下步骤：
制备活性金属氧化物纳微颗粒：
称取1.95g硝酸钴和0.8g柠檬酸三钠，混合后加入80ml乙醇，搅拌0.5h得到溶液A；
称取6g乙酸钠溶于60ml 1-缩-2-乙二醇中，搅拌0.5h得到溶液B；
将B溶液缓慢添加到A溶液中，并持续搅拌0.5h；
将上述溶液移至聚四氟乙烯容器内，密闭在不锈钢高压反应釜中，在180℃下加热反应20h，再冷却至室温；将上述产物离心分离后，用乙醇洗涤3次，后在100℃下干燥15h，得到四氧化三钴微球。
制备催化剂：
称取1.5g四氧化三钴微球加入6ml乙二醇进行浸泡；
然后放入干燥箱中干燥，干燥温度150℃，恒温24h，获得改性后的四氧化三钴微球；
称取0.01g硝酸镁、0.15g硝酸铁、0.75g硝酸锰和0.08g硝酸锌，混合后加入4ml水，配制成溶液，将该溶液浸泡改性后的四氧化三钴微球；
然后放入干燥箱中干燥，干燥温度150℃，恒温12h，得到费托合成钴基反转催化剂。
助剂占催化剂的质量分数为40％，助剂尺寸约为50nm，四氧化三钴微球尺寸约为500nm。
催化剂的应用：
取催化剂1g用H2于固定床中还原，还原条件为400℃，0.1MPa，5000h-1(V/V)，恒温10h；还原完成后，将已还原好的催化剂在氮气流中降至室温，然后将氮气切换成合成气(H2/CO＝2)，开始进行费托合成反应；反应条件为240℃，1.0MPa，2500h-1(V/V)，反应结果见表2。
表2 费托合成催化剂反应结果
Figure PCTCN2015079467-appb-000002
实施例6
一种用于甲烷化反应的镍基反转催化剂制备方法，包括如下步骤：
制备活性金属氧化物纳微颗粒：
称取1.95g硝酸镍和0.8g十六烷基三甲基溴化铵，混合后加入80ml水，搅拌0.5h得到溶液A；
称取4g乙酸钠溶于60ml乙腈中，搅拌0.5h得到溶液B；
将B溶液缓慢添加到A溶液中，并持续搅拌0.5h；
将上述溶液移至聚四氟乙烯容器内，密闭在不锈钢高压反应釜中，在200℃下加热反应20h，再冷却至室温；将上述产物离心分离后，用乙醇洗涤3次，后在60℃下干燥15h，得到氧化镍微球。
制备催化剂：
称取1.5g氧化镍微球加入6ml丙三醇进行浸泡；
然后放入干燥箱中干燥，干燥温度120℃，恒温12h，获得改性后的氧化镍微球；
称取0.01g三氯化钌、0.25硝酸铝、0.08g硝酸钴和0.05g碳酸钙，混合后加入4ml水，配制成溶液，将该溶液浸泡改性后的微球；
然后放入干燥箱中干燥，干燥温度150℃，恒温12h，得到甲烷化反应镍基反转催化剂。
助剂占催化剂的质量分数为21％，助剂尺寸约为10nm，氧化镍微球尺寸约为100nm。
催化剂的应用：
取上述催化剂1g用H2于固定床中还原，还原条件为300℃，0.1MPa，5000h-1(V/V)，恒温10h；还原完成后，将已还原好的催化剂在氮气流中降至室温，然后将氮气切换成合成气(H2/CO＝2)，开始进行甲烷化反应；反应条件为600℃，5MPa，2500h-1(V/V)，反应转化率大于99％。
实施例7
一种用于甲醇合成反应的铜基反转催化剂制备方法，包括如下步骤：
制备活性金属氧化物纳微颗粒：
称取1.95g硝酸铜和2.0g曲拉通X-100，混合后加入60ml DMF，搅拌0.5h得到溶液A；
称取6g乙酸钠溶于60ml乙二胺中，搅拌0.5h得到溶液B；
将B溶液缓慢添加到A溶液中，并持续搅拌0.5h；
将上述溶液移至聚四氟乙烯容器内，密闭在不锈钢高压反应釜中，在240℃下加热反应20h，再冷却至室温；将上述产物离心分离后，用乙醇洗涤3次，后在200℃下干燥20h，得到氧化铜纳微颗粒。
催化剂制备：
称取1.5g氧化铜纳微颗粒加入6ml乙二醇进行浸泡；
然后放入干燥箱中干燥，干燥温度150℃，恒温24h，获得改性后的氧化铜纳微颗粒；
称取0.1g硝酸锌、0.01g硝酸银、0.05g硝酸铝和0.01g硝酸氧锆，混合后加 入4ml水，配制成溶液，将该溶液浸泡到改性后的氧化铜纳微颗粒中；
浸渍完成后放入干燥箱中干燥，干燥温度150℃，恒温12h，获得甲醇合成铜基反转催化剂。
助剂占催化剂的质量分数为10％，助剂尺寸约为1nm，氧化铜纳微颗粒尺寸约为20nm。
催化剂的应用：
取催化剂1g用混合气(V(H2)/V(N2)＝5∶95)按150℃，180℃，210℃和240℃的升温程序于固定床中还原后，降温，将还原气切换成合成气(V(H2)/V(CO)/V(CO2)/V(N2)＝65.9/27.1/2.9/4.1)，开始进行甲醇合成反应。反应条件为210℃-270℃，3.0MPa，7500h-1(V/V)，反应结果见表3。
表3 甲醇合成催化剂反应结果
催化剂 CO转化率(％) 烃选择性(％) CO2选择性(％) 甲醇选择性(％)
实施例7 40.9 0.7 0.8 98.5
实施例8
一种用于费托合成的铁基反转催化剂制备方法，包括如下步骤：
称取2g熔融法制备的铁球(主要成分为磁铁矿)，铁球的粒径为500微米。
催化剂制备：
将铁球加入6ml丙三醇进行浸泡；
然后放入干燥箱中干燥，干燥温度120℃，恒温12h，获得改性后的铁球；
称取0.01g硝酸镍、0.02g氯铂酸、0.55g硝酸锰和0.08g硝酸铜，混合后加入4ml水，配制成溶液，将该溶液浸泡到熔融铁球中；
然后放入干燥箱中干燥，干燥温度150℃，恒温12h，获得费托合成铁基 反转催化剂。
助剂占催化剂的质量分数为31％，助剂尺寸约为50nm。
催化剂的应用：
取上述催化剂1g用合成气(H2/CO＝1)于固定床中还原，还原条件为300℃，0.1MPa，5000h-1(V/V)，恒温10h；还原完成后，将已还原好的催化剂在氮气流中降至室温，然后将氮气切换成合成气(H2/CO＝1)，开始进行费托合成反应；反应条件为350℃，1.5MPa，2500h-1(V/V)，反应结果见表4。
表4 费托合成催化剂反应结果
Figure PCTCN2015079467-appb-000003
实施例9
一种用于环氧乙烷羰基合成3-羰基丙醛和1，3-丙二醇的钴基反转催化剂制备方法，包括如下步骤：
制备活性金属氧化物纳微颗粒：
称取1.95g硝酸钴和0.2g柠檬酸三钠，混合后加入40ml乙二醇，搅拌0.5h得到溶液A；
称取4g乙酸钠溶于40ml丙三醇中，搅拌0.5h得到溶液B；
将B溶液缓慢添加到A溶液中，并持续搅拌0.5h；
将上述溶液移至聚四氟乙烯容器内，密闭在不锈钢高压反应釜中，在150℃下加热反应10h，再冷却至室温；将上述产物离心分离后，用乙醇洗涤3次，后在60℃下干燥10h，得到四氧化三钴微球。
催化剂制备：
量取6ml乙二醇，加入去离子水配制成浓度为50wt％的乙二醇溶液；称取1.5g四氧化三钴微球加入乙二醇溶液进行浸泡；
然后放入干燥箱中干燥，干燥温度120℃，恒温48h，获得改性后的四氧化三钴微球；
称取0.01g三氯化铑、0.1g碳酸钠、0.2g三苯基膦和0.08g硝酸钾，混合后加入4ml水，配制成溶液，将该溶液浸泡到改性后的四氧化三钴微球中；
然后放入干燥箱中干燥，干燥温度150℃，恒温12h，获得羰基合成钴基反转催化剂。
催化剂的应用：
在反应釜中加入0.5g催化剂、100ml甲苯和20ml氯苯，并加入环氧乙烷20gm，将反应釜密封后通入11.0MPa H2/CO＝1的合成气，直接程序升温至110℃温度下，反应4小时。冷却后，泄压取样分析。环氧乙烷转化率70％，3-羰基丙醛的选择性52.5％，1，3-丙二醇的选择性42.1％，3-羰基丙醛和1，3-丙二醇的总选择性94.6％。
实施例10-12
同实施例1，区别在于，所述活性金属氧化物分别由沉淀法、溶胶凝胶法、熔融法制备得到。
沉淀法制备活性金属氧化物：按最终催化剂中单质铁20wt％含量称取硝酸铁，与乙醇配制成浓度10wt％的硝酸铁溶液，在容器中搅拌加热至150℃，恒 温1小时后，待溶液降至室温，加入一定量的水，配制成浓度3wt％的硝酸铁溶液，混合均匀后，与碳酸钠溶液慢慢混合进入沉淀反应器中，控制沉淀PH值在10。沉淀结束后老化2小时。将沉淀抽滤、洗涤干净后干燥，干燥温度为80℃，恒温48小时，再放入马弗炉中焙烧，焙烧温度为500℃，恒温5小时，得到三氧化二铁微球，直径约为100nm。
溶胶凝胶法制备活性金属氧化物：取2.0g Fe(NO3)3·9H2O和3.5g聚乙二醇溶于100mL蒸馏水中，在超声振荡条件下，缓慢滴入20ml碳酸铵溶液和20ml十二烷基磺酸钠溶液，得到氢氧化铁胶体。用蒸馏水和无水乙醇交替洗涤4次，再经过真空干燥得到前驱体。然后，将样品置于管式炉中在400℃下焙烧4h，即获得纳米三氧化二铁微球，直径约为40nm。
熔融法制备活性金属氧化物：将磁铁矿、赤铁矿和还原铁粉按等1∶1∶1混合，在氩气气氛下在电弧感应石墨炉中加热至熔融态，形成合金。之后迅速转移至水中急冷，然后机械破碎得到前驱体颗粒，直径约为1mm。
表5 费托合成催化剂反应结果
Figure PCTCN2015079467-appb-000004
实施例13
与实施例1相同，区别在于：
2、制备催化剂中：
所用助剂改为0.31g硝酸钾、0.08g硝酸镁；
得到的催化剂与实施例1的应用相同，反应结果见表6。
表6 费托合成催化剂反应结果
Figure PCTCN2015079467-appb-000005
由上表可看出，当使用K和Mg为助剂时，它们能促进CO的吸附性能，进而促进链增长反应，使产物分布向长链产物移动，表明本发明的催化剂具有可控的反应选择性。
实施例14
与实施例1相同，区别在于：2、制备催化剂中：用甲醇代替醋酸，浓度为10wt％。结果与实施例1类似。
实施例15
与实施例1相同，区别在于：2、制备催化剂中：用乙醇代替醋酸，浓度为20wt％。结果与实施例1类似。
实施例16
与实施例1相同，区别在于：2、制备催化剂中：用丙醇代替醋酸，浓度为30wt％。结果与实施例1类似。
实施例17
与实施例1相同，区别在于：2、制备催化剂中：用丁醇代替醋酸，浓度为44wt％。结果与实施例1类似。
实施例18
与实施例1相同，区别在于：2、制备催化剂中：用戊醇代替醋酸，浓度 为100wt％。结果与实施例1类似。
实施例19
与实施例1相同，区别在于：2、制备催化剂中：用丙二醇代替醋酸，浓度为60wt％。结果与实施例1类似。
实施例20
与实施例1相同，区别在于：2、制备催化剂中：用丁二醇代替醋酸。结果与实施例1类似。
实施例21
与实施例1相同，区别在于：2、制备催化剂中：用甲酸代替醋酸。结果与实施例1类似。
实施例22
与实施例1相同，区别在于：2、制备催化剂中：用丙酸代替醋酸。结果与实施例1类似。
实施例23
与实施例1相同，区别在于：2、制备催化剂中：用丁酸代替醋酸。结果与实施例1类似。
实施例24
与实施例1相同，区别在于：
3、催化剂的应用：
取催化剂1g用合成气(H2/CO＝1)于固定床中还原，还原条件为250℃， 2.0MPa，5000h-1(V/V)，恒温10h；还原完成后，将已还原好的催化剂在氮气流中降至室温，然后将氮气切换成合成气(H2/CO＝1)，开始进行费托合成反应；反应条件为240℃，0.1MPa，500h-1(V/V)。结果与实施例1类似。
实施例25
与实施例1相同，区别在于：
3、催化剂的应用：
取催化剂1g用合成气(H2/CO＝1)于固定床中还原，还原条件为800℃，1.0MPa，5000h-1(V/V)，恒温10h；还原完成后，将已还原好的催化剂在氮气流中降至室温，然后将氮气切换成合成气(H2/CO＝1)，开始进行费托合成反应；反应条件为750℃，8.5MPa，15000h-1(V/V)。结果与实施例1类似。
实施例26
与实施例1相同，区别在于：
3、催化剂的应用：
取催化剂1g用合成气(H2/CO＝1)于固定床中还原，还原条件为500℃，1.0MPa，5000h-1(V/V)，恒温10h；还原完成后，将已还原好的催化剂在氮气流中降至室温，然后将氮气切换成合成气(H2/CO＝1)，开始进行费托合成反应；反应条件为400℃，4.0MPa，5000h-1(V/V)。结果与实施例1类似。
显然，本发明的上述实施例仅仅是为清楚地说明本发明所作的举例，而并非是对本发明的实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无法对所有 的实施方式予以穷举。凡是属于本发明的技术方案所引伸出的显而易见的变化或变动仍处于本发明的保护范围之列。

Claims (10)

  1. 一种无载体催化剂，其特征在于，包括：活性金属氧化物和嵌在其外表面上的助剂；
    所述活性金属氧化物选自下列金属的氧化物中的一种或多种：铁、钴、镍、铜；
    所述助剂选自下列元素中的一种或多种：铁、钴、镍、铜、铑、锰、钾、银、钙、镁、锆、铝、锌、钌、铂、钠、磷，以单质或氧化物形式存在。
  2. 根据权利要求1所述的一种无载体催化剂，其特征在于，所述活性金属氧化物经醇、醇的异构体或羧酸水溶液浸泡处理。
  3. 根据权利要求1所述的一种无载体催化剂，其特征在于，所述活性金属氧化物为纳米或微米尺寸；所述助剂为纳米尺寸；
    更优选地，所述活性金属氧化物的粒径为20nm-5mm，所述助剂的粒径为1nm-50nm；
    最优选地，所述活性金属氧化物的粒径为50nm-1μm。
  4. 根据权利要求1所述的一种无载体催化剂，其特征在于，所述助剂在无载体催化剂中的质量分数为0.1wt％-40wt％；
    更优选地，所述助剂在无载体催化剂中的质量分数为1wt％-20wt％。
  5. 如权利要求1-4任一所述的无载体催化剂的制备方法，其特征在于，包括如下步骤：
    1)用醇、醇的异构体或羧酸水溶液浸泡活性金属氧化物，之后在60-180℃干燥12-48h，得到改性后活性金属氧化物；
    2)用助剂的前驱体盐的水溶液浸泡步骤1)得到的改性后活性金属氧化物，之后在60-180℃干燥12-48h，得到无载体催化剂；
    所述活性金属氧化物选自下列金属的氧化物中的一种或多种：铁、钴、镍、铜；
    所述助剂选自下列元素中的一种或多种：铁、钴、镍、铜、铑、锰、钾、银、钙、镁、锆、铝、锌、钌、铂、钠、磷。
  6. 根据权利要求5所述的无载体催化剂的制备方法，其特征在于，步骤1)中，所述醇选自下列物质中的一种或多种：甲醇、乙醇、丙醇、丁醇、戊醇、乙二醇、丙二醇、丙三醇、丁二醇；所述羧酸选自下列物质中的一种或多种：甲酸、醋酸、丙酸、丁酸。
  7. 根据权利要求5所述的无载体催化剂的制备方法，其特征在于，步骤1)中，所述醇、醇的异构体或羧酸水溶液的浓度为10wt％-100wt％。
  8. 根据权利要求5所述的无载体催化剂的制备方法，其特征在于，所述活性金属氧化物采用水热/溶剂热合成法、沉淀法、熔融法、溶胶凝胶法来制备得到；
    优选地，所述活性金属氧化物采用水热/溶剂热合成法制备得到，包括以下步骤：
    I将活性金属的前驱体盐和表面活性剂溶于溶剂，得到溶液A；
    II将乙酸钠溶于溶剂，得到溶液B；
    III将溶液B加入溶液A中，得到溶液C；溶液A和溶液B的用量比为活性金属的前驱体盐：乙酸钠＝1.95g：20-160mmol；
    IV将溶液C在密闭条件、150-240℃加热10-20h，得到混合液D；
    V将混合液D离心分离，洗涤，之后在60-200℃下干燥10-20h，得到活性金属氧化物；
    步骤I和步骤II中，所述溶剂为水、乙醇、乙二醇、丙三醇、1-缩-2-乙二醇、DMF、THF、乙腈、乙二胺中的一种或多种；
    更优选地，步骤I中，活性金属的前驱体盐：表面活性剂：溶剂的用量比为7.4mmol：0.2-2g：40-80ml；步骤I中，所述表面活性剂为十六烷基三甲基溴化铵、曲拉通X-100、柠檬酸三钠中的一种或几种；步骤II中，溶液B中乙酸钠的浓度为0.5-2mol/l。
  9. 如权利要求1-8任一所述的无载体催化剂的应用，该无载体催化剂可应用于一氧化碳加氢反应中。
  10. 根据权利要求9所述的无载体催化剂的应用，所述一氧化碳加氢反应包括费托合成反应、甲烷化反应、甲醇合成反应、氢甲酰化反应、环氧乙烷羰基合成反应；
    优选地，所述催化剂经还原后用于费托合成反应及甲烷化反应；更优选地，所述还原的还原温度为250-800℃、压力为0.1-2.0MPa；
    优选地，所述催化剂应用在费托合成反应及甲烷化反应中时的反应条件为：反应温度240-750℃、反应压力0.1-8.5MPa、合成气空速500-15000h-1(V/V)，合成气H2/CO＝0.8-3。
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