CN103480404B - Macroporous iron carbide catalyst, and preparation method and application thereof - Google Patents

Abstract

The invention provides a macroporous iron carbide catalyst and its preparation method and application. The iron carbide catalyst is prepared from carboxylic acid-modified polymethyl methacrylate microspheres as a template and ferric nitrate as a precursor. The obtained The pore size of the macroporous iron carbide catalyst is 50-1000nm. The invention adopts carboxyl modified microspheres as a template, ferric nitrate as a precursor, and directly roasts under the condition of methanol and ethylene glycol solvent to prepare three-dimensional through iron carbide. The operation method is simple, the cycle is short, and the cost is low.

Description

A kind of macroporous iron carbide catalyst and its preparation method and application

technical field

The present invention relates to the field of preparation of carbide catalysts, specifically to a macroporous iron carbide catalyst and its preparation method and application, more specifically to a three-dimensional through macroporous iron carbide with strong acid and alkali resistance mechanical properties and Its preparation method and application.

Background technique

Carbide is an "interstitial alloy" formed by carbon and metal, that is, smaller carbon atoms occupy the gaps in the densely packed layer of metal atoms, and often have a simple crystal structure.

Carbide is a kind of substance with high melting point and hardness, extremely high thermal stability and mechanical stability, and almost resistant to various chemical corrosion at room temperature. In addition, it also has similar electrical and magnetic properties to its parent metal, and it is these properties that make them widely used in mechanical cutting, mineral mining, manufacturing anti-wear and high-temperature components, and nuclear reactors. In 1961, Gaziev of the former Soviet Union reported the use of carbides, borides and silicides to catalyze the dehydrogenation of cyclohexane to benzene, and then a French research team carried out 1,1,3-trimethyl Work on the synthesis of xylenes from cyclopentane, reactions that have previously been performed on noble metals. Carbide, as a new catalytic material, has aroused people's great interest, and has fully demonstrated its theoretical research significance and broad application prospects in a series of reactions.

The preparation method of carbide includes the traditional powder metallurgy method, which uses metal oxide, or its hydrate, or metal powder as the precursor and carbon powder to carbonize at high temperature (1500-2000 °C). Due to the sintering at high temperature and the use of excess carbon powder, the surface is covered by a thick layer of carbon, so the carbide prepared by this method has little catalytic activity, so its catalytic application is limited. Then switch to reducing gas and generally adopt 20vol% CH ₄ -80vol% H ₂ mixed gas for carbonization. Although the specific surface can be increased, it is still difficult to significantly improve the sintering and carbon deposition on the catalyst. By gasifying metal oxides or metals at high temperatures and then reacting with carbide gas (chemical vapor deposition, CVD), carbides with larger surface areas can be obtained. In addition, nanoscale carbide particles can also be prepared by plasma sputtering. However, these processes need to be carried out at high temperatures, which is a process that consumes a lot of energy, and the appearance of iron carbide is a single particle, and the preparation amount is not large (less than 1 gram).

Carbide catalysts with a pore structure have not been reported so far, and experiments on carbide catalysts for biosynthesis of oil have not been reported in the literature.

Contents of the invention

An object of the present invention is to provide a macroporous iron carbide catalyst, which has strong acid and alkali resistance and mechanical properties.

Another object of the present invention is to provide a preparation method of the macroporous iron carbide catalyst.

Another object of the present invention is to provide the application of the macroporous iron carbide catalyst in catalyzing the conversion of biosynthesis gas into fuel oil.

One purpose of the present invention is to provide a method for using the macroporous iron carbide catalyst to catalyze the conversion of biosynthesis gas into fuel oil.

In order to achieve the above object, on the one hand, the present invention provides a macroporous iron carbide catalyst, the iron carbide catalyst is prepared by using carboxylic acid modified polymethyl methacrylate microspheres as a template and using ferric nitrate as a precursor, The pore diameter of the obtained macroporous iron carbide catalyst is 50-1000nm.

According to the macroporous iron carbide catalyst of the present invention, the preparation of the macroporous iron carbide catalyst comprises: adding ferric nitrate to the methanol/ethylene glycol mixed solution, stirring to obtain ferric nitrate solution, and mixing carboxylic acid modified polyformaldehyde Add methyl acrylate microspheres into the obtained ferric nitrate solution for immersion, filter, dry, raise the temperature to 400-800° C. and keep it for 4-8 hours to obtain the macroporous iron carbide catalyst.

Wherein, preferably, the particle size of the carboxylic acid-modified polymethyl methacrylate microspheres is 50-600 nm.

Wherein the present invention preferably described ferric nitrate and methanol/ethylene glycol molar ratio is 1:1-3.

Wherein the present invention preferably said methanol and ethylene glycol volume ratio is 1:1.5-4.

According to the macroporous iron carbide catalyst of the present invention, the preparation of the macroporous iron carbide catalyst comprises: adding ferric nitrate to the methanol/ethylene glycol mixed solution, stirring for more than 2 hours to obtain ferric nitrate solution, and modifying the carboxylic acid Add polymethyl methacrylate microspheres to the obtained ferric nitrate solution for immersion, filter, dry at 50-100°C for 1-24 hours, raise the temperature at 0.5-2°C/min to 400-800°C and keep it for 4-8 hours to obtain the described Macroporous iron carbide catalyst.

According to the macroporous iron carbide catalyst of the present invention, in order to make the heat transfer of the catalyst more uniform at 400-800°C after drying, the present invention can further use quartz sand as the heat transfer carrier. Methyl methacrylate microspheres are added to the obtained ferric nitrate solution to impregnate, filter and dry, then add quartz sand and mix evenly, and then heat up to 400-800°C for 4-8 hours to obtain the macroporous iron carbide;

Among them, the present invention is further preferred to add quartz sand into the quartz tube with inert gas and mix well.

Among them, the amount of quartz sand can be determined according to the amount of catalyst and heating conditions, without special restrictions. For example, the mass ratio of quartz sand to catalyst can be 10-50:1.

Wherein it can be understood by those skilled in the art that after the heat preservation finishes, the quartz sand should be separated from the prepared catalyst;

The separation is a conventional operation in the field, for example, it can be manually sorted, or even sieved according to the particle diameters of the quartz sand and the catalyst.

According to any described macroporous iron carbide catalyst of the present invention, described carboxylic acid-modified polymethyl methacrylate microspheres can be commercially available, or for self-made, the present invention can preferably described carboxylic acid-modified polymethyl methacrylate The preparation of methyl methacrylate microspheres includes: dissolving methyl methacrylate (MMA) in the reaction solvent, heating to 60-90°C, adding the prepared potassium peroxodisulfate (KPS)/azobisisobutyronitrile ( AIBN) aqueous solution, adding acrylic acid (AA), stirring and reacting, and filtering to obtain the carboxylic acid-modified polymethyl methacrylate microspheres;

According to the macroporous iron carbide catalyst of the present invention, wherein preferably the prepared KPS/AIBN aqueous solution is first heated to 60-90° C., and then added to the reaction solvent added with MMA;

Further preferred in the present invention is that the prepared KPS/AIBN aqueous solution is first heated to the same temperature as the reaction solvent, and then added to the reaction solvent that has added MMA;

According to the macroporous iron carbide catalyst of the present invention, it is also preferred that the volume ratio of MMA and AA is 25:1; the mass ratio of AIBN and KPS is 1:0.6.

Macroporous iron carbide catalyst according to the present invention, wherein preferably said reaction solvent is acetone/water mixed solution;

Wherein it is also preferred that the mol ratio of MMA and acetone/water solution is 1:1-3;

Wherein it is further preferred that the volume ratio of acetone and water is 1:3;

According to the macroporous iron carbide catalyst of the present invention, after preferably adding AA, stir and react for 1.5h;

According to the macroporous iron carbide catalyst of the present invention, it is further preferred to carry out ultrasonic treatment after the stirring reaction, and then filter to obtain the carboxylic acid modified polymethyl methacrylate microspheres;

Among them, ultrasonic treatment for 1.5 h is further preferred.

According to the macroporous iron carbide catalyst of the present invention, it is further preferred in the present invention to filter after the stirring reaction, place the filter cake in a centrifuge tube, centrifuge at a speed of 3000r/min for 10h, discard the supernatant, and After drying, carboxylic acid-modified polymethyl methacrylate microspheres were obtained.

According to the macroporous iron carbide catalyst of the present invention, it is further preferred in the present invention to perform ultrasonic treatment after the stirring reaction, then filter, place the filter cake in a centrifuge tube, and centrifuge at a speed of 3000r/min for 10h , discard the supernatant, and dry at room temperature to obtain carboxylic acid-modified polymethyl methacrylate microspheres.

According to the macroporous iron carbide catalyst of the present invention, the present invention further preferably dissolves MMA in the acetone/water mixed solution under the condition of isolated air, heats to 60-90°C, feeds inert gas, and adds prepared KPS /AIBN aqueous solution, add AA simultaneously, stir reaction, filter to obtain described carboxylic acid modified polymethyl methacrylate microsphere;

The isolated air condition described therein is a routine operation in the art, for example, the reaction vessel can be evacuated and then passed into an inert gas;

Wherein the present invention may preferably said inert gas is nitrogen or argon.

On the other hand, the present invention also provides a method for preparing the macroporous iron carbide catalyst of the present invention, the method comprising using carboxylic acid-modified polymethyl methacrylate microspheres as a template and preparing ferric nitrate as a precursor The macroporous iron carbide catalyst, the pore diameter of the obtained macroporous iron carbide catalyst is 50-1000nm.

According to the preparation method of the present invention, the preparation method comprises: adding ferric nitrate to the methanol/ethylene glycol mixed solution, stirring to obtain ferric nitrate solution, adding carboxylic acid modified polymethyl methacrylate microspheres to the Immerse in the ferric nitrate solution obtained, filter, dry, add quartz sand, mix and fill, raise the temperature to 400-800° C. and keep it for 4-8 hours to obtain the macroporous iron carbide catalyst.

Wherein, preferably, the particle size of the carboxylic acid-modified polymethyl methacrylate microspheres is 50-600 nm.

Wherein the present invention preferably described ferric nitrate and methanol/ethylene glycol molar ratio is 1:1-3.

Wherein the present invention preferably said methanol and ethylene glycol volume ratio is 1:1.5-4.

According to the preparation method of the present invention, the preparation method comprises: adding ferric nitrate into the methanol/ethylene glycol mixed solution, stirring for more than 2 hours to obtain ferric nitrate solution, and adding carboxylic acid-modified polymethyl methacrylate microspheres Add it into the obtained ferric nitrate solution for immersion, filter, dry at 50-100°C for 1-24h, add quartz sand and mix evenly for filling, raise the temperature at 0.5-2°C/min to 400-800°C and keep it for 4-8 hours to obtain the large Porous iron carbide catalyst.

According to the preparation method of the present invention, it is further preferred in the present invention to mix and fill with quartz sand in a quartz tube with an inert gas and mix and fill with quartz sand.

According to any of the preparation methods described in the present invention, the carboxylic acid-modified polymethyl methacrylate microspheres can be commercially available or self-made, and the present invention can preferably use the carboxylic acid-modified polymethyl methacrylate The preparation of ester microspheres includes: dissolving methyl methacrylate (MMA) in the reaction solvent, heating to 60-90°C, adding the prepared potassium peroxodisulfate (KPS)/azobisisobutyronitrile (AIBN) aqueous solution , adding acrylic acid (AA), stirring for reaction, and filtering to obtain the carboxylic acid-modified polymethyl methacrylate microspheres;

According to the preparation method of the present invention, preferably, the prepared KPS/AIBN aqueous solution is first heated to 60-90° C., and then added to the reaction solvent added with MMA;

Further preferred by the present invention is that the prepared KPS/AIBN aqueous solution is first heated to the same temperature as the reaction solvent, and then added to the reaction solvent that has added MMA;

According to the preparation method of the present invention, it is also preferred that the volume ratio of MMA and AA is 25:1; the mass ratio of AIBN and KPS is 1:0.6.

According to the preparation method of the present invention, wherein preferably the reaction solvent is acetone/water mixed solution;

Wherein it is also preferred that the mol ratio of MMA methyl ester and acetone/water solution is 1:1-3;

Wherein it is further preferred that the volume ratio of acetone and water is 1:3;

According to the preparation method of the present invention, preferably after AA is added, the reaction is stirred for 1.5 h;

According to the preparation method of the present invention, it is further preferred to perform ultrasonic treatment after the stirring reaction, and then filter to obtain the carboxylic acid-modified polymethyl methacrylate microspheres;

Among them, ultrasonic treatment for 1.5 h is further preferred.

According to the preparation method of the present invention, it is further preferred in the present invention to filter after stirring and reacting, place the filter cake in a centrifuge tube, centrifuge at a speed of 3000r/min for 10h, discard the supernatant, and dry at room temperature to obtain Carboxylic acid modified polymethyl methacrylate microspheres.

According to the preparation method described in the present invention, the present invention can further preferably carry out ultrasonic treatment after the stirring reaction, then filter, place the filter cake in a centrifuge tube, centrifuge at a speed of 3000r/min for 10h, discard The supernatant was dried at room temperature to obtain carboxylic acid-modified polymethyl methacrylate microspheres.

According to the preparation method of the present invention, the present invention further preferably dissolves MAA in the acetone/water mixed solution under the condition of isolated air, heats to 60-90°C, passes inert gas, and adds the prepared KPS/AIBN aqueous solution , while adding AA, stirring the reaction, and filtering to obtain the carboxylic acid modified polymethyl methacrylate microspheres;

The isolated air condition described therein is a routine operation in the art, for example, the reaction vessel can be evacuated and then passed into an inert gas;

Wherein the present invention may preferably said inert gas is nitrogen or argon.

In another aspect, the present invention also provides the application of the macroporous iron carbide catalyst in catalyzing the conversion of biosynthesis gas into fuel oil.

In another aspect, the present invention also provides a method for applying the macroporous iron carbide catalyst of the present invention to catalyze the conversion of biosynthesis gas into fuel oil, the method comprising: performing a contact reaction between biosynthesis gas and the macroporous iron carbide catalyst fuel oil;

Among them, the preferred reaction conditions include: reaction temperature 310°C, space velocity 2000h ^-1 , pressure _6.5MPa ;

Among them, it is more preferable to first activate the macroporous iron carbide and then use it to contact and react with biosynthesis gas to prepare fuel oil;

Wherein it is further preferred that the activation is activated at 310°C;

Among them, activation for 2 h is more preferred.

The biosynthesis gas of the present invention preferably has the following molar ratio composition: H ₂ :CO:CO ₂ , :CH ₄ :N ₂ =1:1:0.5-0.8:0.1:2-3.

In summary, the present invention provides a macroporous iron carbide catalyst and its preparation method and application. The macroporous iron carbide catalyst of the present invention has the following advantages:

The invention adopts carboxyl modified microspheres as a template, ferric nitrate as a precursor, and directly roasts under the condition of methanol and ethylene glycol solvent to prepare three-dimensional through iron carbide. The operation method is simple, the cycle is short, and the cost is low. The invention successfully prepares macroporous iron carbide catalyst for the first time.

Description of drawings

Figure 1 is the FT-IR spectrum of the carboxyl-modified microsphere template prepared in Example 1.

FIG. 2 is an SEM photo of the carboxyl-modified microsphere template prepared in Example 1.

FIG. 3 is a particle size distribution diagram of the carboxyl-modified microsphere template prepared in Example 1. FIG.

Fig. 4 is the FT-IR spectrum of the iron carbide prepared in embodiment 2.

Fig. 5 is the XRD spectrogram of the iron carbide prepared in Example 2.

Fig. 6 is the TEM photograph of the iron carbide prepared in embodiment 2.

Fig. 7 is the result of the catalytic activity of the iron carbide catalyst prepared in Example 3 for converting biosynthesis gas into fuel oil.

Detailed ways

The implementation process and beneficial effects of the present invention are described in detail below through specific examples, aiming to help readers better understand the essence and characteristics of the present invention, and not as a limitation to the scope of implementation of this case.

Embodiment 1 The preparation method of carboxyl modified colloidal crystal template

In this example, the carboxyl-modified colloidal crystal template was prepared according to the following method:

(1) Preparation of monodisperse carboxyl-modified polymethylmethacrylate (c-PMMA) microspheres by improved soap-free emulsion polymerization

Add 50ml of acetone and 150ml of deionized water into a 1000ml four-neck flask equipped with a stirrer, reflux condenser, thermometer and _N2 gas tube, and then pass _N2 after vacuuming, and add MMA and AA with a volume ratio of 25:1 ( Both monomers were purified by vacuum distillation) and heated to 80°C. At the same time, 0.27g of initiator KPS and 0.45g of AIBN were weighed and dissolved in 150ml of water, heated to 80°C and added to a four-necked flask. After reacting for 1.5 h under the protection of N ₂ , it was naturally cooled to room temperature under stirring, ultrasonically treated for 1.5 h, and c-PMMA polymer microspheres were obtained by suction filtration. Figure 1 provides the FT-IR infrared absorption spectrum of the complex.

(2) Preparation of colloidal crystal templates by centrifugal deposition method

The c-PMMA microspheres were placed in a centrifuge tube, centrifuged at a speed of 3000r/min for 10h, the supernatant was discarded, and dried at room temperature to obtain a tightly packed modified PMMA colloidal crystal template. Figure 2 provides the SEM photograph of the colloidal crystal template. Figure 3 provides a particle size distribution diagram of the composite microspheres.

Precursor-template composites prepared by in-situ impregnation

Weigh a certain amount of ferric nitrate according to the stoichiometric ratio, dissolve it in the mixed solution of methanol and ethylene glycol (volume ratio 1:3), the molar ratio of ferric nitrate and methanol/ethylene glycol is 1:2, stir magnetically for 2 hours to get uniform Transparent solution, that is, the precursor solution of the catalyst. The dry colloidal crystal template is impregnated with the solution, and after the impregnation is complete, the excess precursor solution is removed by suction filtration. The impregnated colloidal crystal template was placed in a vacuum oven and dried at 80° C. for 20 h to obtain a composite of the colloidal crystal and the precursor.

The preparation method of the iron carbide of embodiment 2 three-dimensional penetration

(1) Preparation of monodisperse carboxyl-modified polymethylmethacrylate (c-PMMA) microspheres by improved soap-free emulsion polymerization

Add 50ml of acetone and 150ml of deionized water into a 1000ml four-neck flask equipped with a stirrer, reflux condenser, thermometer and _N2 air tube, and then pass _N2 after vacuuming, and add a certain volume ratio of MMA and AA (two single body were purified by distillation under reduced pressure), and heated to 80 ° C. At the same time, a certain amount of initiator KPS and AIBN was weighed and dissolved in 150ml of water, heated to 80°C and added to a four-necked flask. After reacting for 1.5 h under the protection of N ₂ , it was naturally cooled to room temperature under stirring, ultrasonically treated for 1.5 h, and c-PMMA polymer microspheres were obtained by suction filtration. Figure 1 provides the FT-IR infrared absorption spectrum of the complex.

(2) Preparation of colloidal crystal templates by centrifugal deposition method

The c-PMMA microspheres were placed in a centrifuge tube, centrifuged at a speed of 3000r/min for 10h, the supernatant was discarded, and dried at room temperature to obtain a tightly packed modified PMMA colloidal crystal template. Figure 2 provides the SEM photograph of the colloidal crystal template. Figure 3 provides a particle size distribution diagram of the composite microspheres.

(3) Prepare the composite of precursor and template by in situ impregnation method

Weigh Fe(NO ₃ ) ₂ ·9H ₂ O, dissolve it in 10ml methanol ethylene glycol mixed solution (volume ratio 1:2), ferric nitrate and methanol/ethylene glycol molar ratio is 1:3, stir magnetically for 2h to get A homogeneous transparent solution, that is, the precursor solution of the catalyst is obtained. The solution was used to impregnate 3 g of the dried c-PMMA colloidal crystal template for 10 h. After the impregnation was complete, the excess precursor solution was removed by suction filtration, and then the template was dried overnight at 80° C. in a vacuum oven. Mix and fill it with quartz sand in a quartz tube with an inert gas, and finally heat it up to 800°C in an argon atmosphere and bake it at a constant temperature for 4 hours to obtain a three-dimensionally penetrated iron carbide catalyst. The argon flow rate is 80ml/min, and the heating rate is 1°C/min.

Fig. 6 is the SEM photo of the iron carbide catalyst that three-dimensionally penetrates prepared in this example, as can be seen from the figure, in the present embodiment, c-PMMA is used as a macroporous template, and the prepared iron carbide has a regular three-dimensional macroporous structure, with an average The pore diameter is 300nm, and the pores are uniform and orderly. The X-ray diffraction pattern and infrared spectrum of the three-dimensional penetrating iron carbide catalyst prepared in this example are shown in Figure 4 and Figure 5 respectively, and the results show that iron carbide is contained in the material prepared in this example.

Example 3 Catalytic Performance Result of Macroporous Iron Carbide Catalyst Converting Biosynthesis Gas into Fuel Oil

The gas composition of the biosyngas is 20% H ₂ , 19% CO, 12% CO ₂ , 2% CH ₄ and 49% N ₂ . The catalyst prepared in Example 2 was first activated by biosyngas at 310° C. for 2 hours. The reaction operating conditions are: temperature 310°C, space velocity 2000h ^-1 , pressure 6.5MPa. The experimental results are shown in Figure 7. The macroporous iron carbide catalyst showed high catalytic activity and stability, the conversion rate of CO remained above 90%, the selectivity of liquid fuel oil products exceeded 60%, and the activity of the catalyst remained basically stable for 500 hours. The results of its catalytic activity for the conversion of biosyngas to fuel oil are shown in Figure 7.

Claims (34)

1. a macropore iron-carbonide catalyst, is characterized in that, described iron-carbonide catalyst is template by carboxyl acid modified poly (methyl methacrylate) micro-sphere, is that precursor power obtains with ferric nitrate, and the macropore iron-carbonide catalyst aperture of gained is 50-1000nm; The preparation of described macropore iron-carbonide catalyst comprises: joined by ferric nitrate in methyl alcohol/ethylene glycol mixed solution, stirring obtains iron nitrate solution, carboxyl acid modified poly (methyl methacrylate) micro-sphere is joined in the iron nitrate solution obtained and floods, filter, drying, is warming up to 400-800 DEG C of insulation and within 4-8 hour, namely obtains described macropore iron-carbonide catalyst.

2. macropore iron-carbonide catalyst according to claim 1, is characterized in that, ferric nitrate and methyl alcohol/ethylene glycol mol ratio are 1:1-3.

3. macropore iron-carbonide catalyst according to claim 1, is characterized in that, described methyl alcohol and ethylene glycol volume ratio are 1:1.5-4.

4. macropore iron-carbonide catalyst according to claim 1, it is characterized in that, the preparation of described macropore iron-carbonide catalyst comprises: joined by ferric nitrate in methyl alcohol/ethylene glycol mixed solution, stir more than 2h and obtain iron nitrate solution, carboxyl acid modified poly (methyl methacrylate) micro-sphere is joined in the iron nitrate solution obtained and floods, filter, 50-100 DEG C of dry 1-24h, 0.5-2 DEG C/min speed is warming up to 400-800 DEG C of insulation and within 4-8 hour, namely obtains described macropore cementite.

5. macropore iron-carbonide catalyst according to claim 1, it is characterized in that, the preparation of described macropore iron-carbonide catalyst also comprises: carboxyl acid modified poly (methyl methacrylate) micro-sphere is joined in the iron nitrate solution obtained flood, filter and drying after, first add quartz sand mixing, then be warming up to 400-800 DEG C of insulation and within 4-8 hour, obtain described macropore cementite.

6. macropore iron-carbonide catalyst according to claim 5, is characterized in that, described in add quartz sand mixing be add in the quartz ampoule being connected with inert gas quartz sand mixing.

7. the macropore iron-carbonide catalyst according to claim 1 ~ 6 any one, it is characterized in that, the preparation of described carboxyl acid modified poly (methyl methacrylate) micro-sphere comprises: methyl methacrylate is dissolved in reaction dissolvent, be heated to 60-90 DEG C, add the potassium persulfate/azodiisobutyronitrile aqueous solution prepared, add acrylic acid, stirring reaction, filter and obtain described carboxyl acid modified poly (methyl methacrylate) micro-sphere.

8. macropore iron-carbonide catalyst according to claim 7, is characterized in that, the wherein said potassium persulfate/azodiisobutyronitrile aqueous solution prepared first is heated to 60-90 DEG C, then joins and add in the reaction dissolvent of methyl methacrylate.

9. macropore iron-carbonide catalyst according to claim 7, it is characterized in that, the preparation of described carboxyl acid modified poly (methyl methacrylate) micro-sphere comprises: be dissolved in by methyl methacrylate in acetone/water mixed solution, be heated to 60-90 DEG C, add the potassium persulfate/azodiisobutyronitrile aqueous solution prepared, add acrylic acid, stirring reaction 1.5h simultaneously, filter and obtain described carboxyl acid modified poly (methyl methacrylate) micro-sphere.

10. macropore iron-carbonide catalyst according to claim 9, is characterized in that, wherein the mol ratio of methyl methacrylate and acetone/water solution is 1:1-3.

11. macropore iron-carbonide catalysts according to claim 9, is characterized in that, wherein the volume ratio of acetone and water is 1:3.

12. macropore iron-carbonide catalysts according to claim 9, is characterized in that, after stirring reaction 1.5h, also carry out ultrasonic wave process, cold filtration obtains described carboxyl acid modified poly (methyl methacrylate) micro-sphere.

13. macropore iron-carbonide catalysts according to claim 12, is characterized in that, described ultrasonic wave is treated to process 1.5h.

14. macropore iron-carbonide catalysts according to claim 9, it is characterized in that, the preparation of described carboxyl acid modified poly (methyl methacrylate) micro-sphere comprises: be dissolved under air-isolation condition in acetone/water mixed solution by methyl methacrylate, be heated to 60-90 DEG C, pass into inert gas, add the potassium persulfate/azodiisobutyronitrile aqueous solution prepared, add acrylic acid simultaneously, stirring reaction, filters and obtains described carboxyl acid modified poly (methyl methacrylate) micro-sphere.

The preparation method of macropore iron-carbonide catalyst described in 15. 1 kinds of claims 1, described iron-carbonide catalyst is template by carboxyl acid modified poly (methyl methacrylate) micro-sphere, be that precursor power obtains with ferric nitrate, the macropore iron-carbonide catalyst aperture of gained is 50-1000nm; The preparation of described macropore iron-carbonide catalyst comprises: joined by ferric nitrate in methyl alcohol/ethylene glycol mixed solution, stirring obtains iron nitrate solution, carboxyl acid modified poly (methyl methacrylate) micro-sphere is joined in the iron nitrate solution obtained and floods, filter, drying, be warming up to 400-800 DEG C insulation 4-8 hour both described macropore iron-carbonide catalyst.

16. preparation methods according to claim 15, is characterized in that, ferric nitrate and methyl alcohol/ethylene glycol mol ratio are 1:1-3.

17. preparation methods according to claim 15, is characterized in that, described methyl alcohol and ethylene glycol volume ratio are 1:1.5-4.

18. preparation methods according to claim 15, it is characterized in that, the preparation of described macropore iron-carbonide catalyst comprises: joined by ferric nitrate in methyl alcohol/ethylene glycol mixed solution, stir more than 2h and obtain iron nitrate solution, carboxyl acid modified poly (methyl methacrylate) micro-sphere is joined in the iron nitrate solution obtained and floods, filter, 50-100 DEG C of dry 1-24h, 0.5-2 DEG C/min speed is warming up to 400-800 DEG C of insulation and within 4-8 hour, namely obtains described macropore cementite.

19. preparation methods according to claim 15, it is characterized in that, the preparation of described macropore iron-carbonide catalyst also comprises: carboxyl acid modified poly (methyl methacrylate) micro-sphere is joined in the iron nitrate solution obtained flood, filter and drying after, first add quartz sand mixing, then be warming up to 400-800 DEG C of insulation and within 4-8 hour, obtain described macropore cementite.

20. preparation methods according to claim 19, is characterized in that, described in add quartz sand mixing be add in the quartz ampoule being connected with inert gas quartz sand mixing.

21. preparation methods according to claim 15 ~ 20 any one, it is characterized in that, the preparation of described carboxyl acid modified poly (methyl methacrylate) micro-sphere comprises: methyl methacrylate is dissolved in reaction dissolvent, be heated to 60-90 DEG C, add the potassium persulfate/azodiisobutyronitrile aqueous solution prepared, add acrylic acid, stirring reaction, filter and obtain described carboxyl acid modified poly (methyl methacrylate) micro-sphere.

22. preparation methods according to claim 21, is characterized in that, the wherein said potassium persulfate/azodiisobutyronitrile aqueous solution prepared first is heated to 60-90 DEG C, then join and add in the reaction dissolvent of methyl methacrylate.

23. preparation methods according to claim 21, it is characterized in that, the preparation of described carboxyl acid modified poly (methyl methacrylate) micro-sphere comprises: be dissolved in by methyl methacrylate in acetone/water mixed solution, be heated to 60-90 DEG C, add the potassium persulfate/azodiisobutyronitrile aqueous solution prepared, add acrylic acid, stirring reaction 1.5h simultaneously, filter and obtain described carboxyl acid modified poly (methyl methacrylate) micro-sphere.

24. preparation methods according to claim 23, is characterized in that, wherein the mol ratio of methyl methacrylate and acetone/water solution is 1:1-3.

25. preparation methods according to claim 23, is characterized in that, wherein the volume ratio of acetone and water is 1:3.

26. preparation methods according to claim 23, is characterized in that, after stirring reaction 1.5h, also carry out ultrasonic wave process, and cold filtration obtains described carboxyl acid modified poly (methyl methacrylate) micro-sphere.

27. preparation methods according to claim 26, is characterized in that, described ultrasonic wave is treated to process 1.5h.

28. preparation methods according to claim 23, it is characterized in that, the preparation of described carboxyl acid modified poly (methyl methacrylate) micro-sphere comprises: be dissolved under air-isolation condition in acetone/water mixed solution by methyl methacrylate, be heated to 60-90 DEG C, pass into inert gas, add the potassium persulfate/azodiisobutyronitrile aqueous solution prepared, add acrylic acid simultaneously, stirring reaction, filters and obtains described carboxyl acid modified poly (methyl methacrylate) micro-sphere.

Macropore iron-carbonide catalyst described in 29. claim 1 ~ 14 any one is the application in fuel oil at catalysis biological Synthetic holography.

30. application according to claim 29, is characterized in that, the main component of described biosynthesis gas is H ₂: CO:CO ₂: and CH ₄: N ₂=1:1:0.5-0.8:0.1:2-3.

31. application rights require that described in 1 ~ 14 any one, macropore iron-carbonide catalyst catalysis biological Synthetic holography is the method for fuel oil, it is characterized in that, described method comprises: biosynthesis gas and described macropore iron-carbonide catalyst are carried out haptoreaction made fuel oil; Wherein said reaction condition comprises: reaction temperature 310 DEG C, air speed 2000h ^-1, pressure 6.5MPa.

32. methods according to claim 31, is characterized in that, are wherein first macropore cementite to be used for preparing fuel oil with biosynthesis gas haptoreaction through overactivation again.

33. methods according to claim 32, is characterized in that, wherein said activation activates at 310 DEG C.

34. methods according to claim 33, is characterized in that, are wherein activation 2h.