CN103480404A - Macroporous iron carbide catalyst, and preparation method and application thereof - Google Patents
Macroporous iron carbide catalyst, and preparation method and application thereof Download PDFInfo
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- CN103480404A CN103480404A CN201310445020.5A CN201310445020A CN103480404A CN 103480404 A CN103480404 A CN 103480404A CN 201310445020 A CN201310445020 A CN 201310445020A CN 103480404 A CN103480404 A CN 103480404A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
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Abstract
The invention provides a macroporous iron carbide catalyst, and a preparation method and application of the macroporous iron carbide catalyst. The iron carbide catalyst is prepared by using a carboxylic acid-modified polymethyl methacrylate microsphere as a template and ferric nitrate as a precursor; the pore diameter of the macroporous iron carbide catalyst is within the range of 50-1000 nm. According to the invention, the carboxylic acid-modified microsphere is used as the template, the ferric nitrate is used as the precursor, and direct roasting is carried out under the condition of a methanol and ethylene glycol mixed solution to prepare the three-dimensionally communicated iron carbide; the operation method is simple, the period is short and the cost is low.
Description
Technical field
The present invention relates to the preparation field of carbide catalyst, specifically, relate to a kind of macropore iron-carbonide catalyst and its preparation method and application, in particular, relate to the three-dimensional that a kind of acid and alkali-resistance mechanical performance is strong and connect macropore cementite and its preparation method and application.
Background technology
Carbide is that the carbon atom of small volume occupies the space of metallic atom closs packing layer by carbon and metal formed " filling a property alloy " (interstitial alloy), formation often there is simple crystal structure.
Carbide is that a class has very high fusing point and hardness, high heat endurance and mechanical stability, the material of the characteristics such as anti-various chemical attacks almost at room temperature.In addition, it also has electricity, the magnetic property similar with its base metal, and these character make that they are widely used in machine cut, mineral mining, manufacture is wear-resistant and the fields such as high-temperature component and nuclear reactor just.The Gaziev of the former Soviet Union in 1961 etc. has reported and has carried out catalysis cyclohexane dehydrogenation benzene processed with carbide, boride and silicide, a research group of France has just carried out 1 on tungsten carbide subsequently, 1, the work of 3-trimethyl cyclopentane dimethylbenzene processed, and be all to carry out on noble metal usually before these reactions.Carbide has caused people's very big interest as a kind of new catalytic material, fully shown the significance of its theoretical research and wide application prospect thereof in a series of reaction.
The preparation method of carbide has traditional powder metallurgy process, adopts metal oxide or its hydrate or metal dust as predecessor and at high temperature (1500-2000 ℃) carbonization of powdered carbon.Due to the use of the sintering under high temperature and excess toner, by one deck, very thick charcoal covers on surface, so the carbide prepared by this method seldom has catalytic activity, therefore be restricted on catalytic applications.Use subsequently reducing gas instead and generally adopt 20vo1%CH
4-80vol%H
2, the mist carbonization, although can increase specific surface, the carbon distribution phenomenon on sintering and catalyst still be difficult to be improved significantly.React with carbon gas again and draw (chemical vapor deposition, CVD) after at high temperature gasifying by metal oxide or metal, can obtain the carbide of large surface area.In addition, also can make the Nano-Scaled Carbide particle by the plasma sputtering method.But these processes all need to be carried out at high temperature, be an a large amount of catabiotic process, and the cementite pattern is single particle, preparation amount little (being less than 1 gram).
The carbide catalyst of pore passage structure all there is no report so far, and carbide catalyst also there is not yet bibliographical information for the experiment of biosynthesis oil.
Summary of the invention
One object of the present invention is to provide a kind of macropore iron-carbonide catalyst, and described macropore iron-carbonide catalyst acid and alkali-resistance mechanical performance is strong.
Another object of the present invention is to provide the preparation method of described macropore iron-carbonide catalyst.
A further object of the present invention is to provide the application of described macropore iron-carbonide catalyst in the catalysis biological synthesis gas is converted into fuel oil.
Of the present invention have a purpose to be to provide the described macropore iron-carbonide catalyst catalysis biological synthesis gas of application to be converted into the method for fuel oil.
For reaching above-mentioned purpose, on the one hand, the invention provides a kind of macropore iron-carbonide catalyst, described iron-carbonide catalyst is template by carboxyl acid modified poly (methyl methacrylate) micro-sphere, the ferric nitrate of take prepares as presoma, and the macropore iron-carbonide catalyst aperture of gained is 50-1000nm.
According to macropore iron-carbonide catalyst of the present invention, the preparation of described macropore iron-carbonide catalyst comprises: ferric nitrate is joined 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 ℃ the insulation 4-8 hour both described macropore iron-carbonide catalyst.
Wherein preferably described carboxyl acid modified poly (methyl methacrylate) micro-sphere particle diameter is particle diameter 50-600nm.
Wherein the preferred described ferric nitrate of the present invention and methyl alcohol/ethylene glycol mol ratio are 1:1-3.
Wherein the preferred described methyl alcohol of the present invention and ethylene glycol volume ratio are 1:1.5-4.
According to macropore iron-carbonide catalyst of the present invention, the preparation of described macropore iron-carbonide catalyst comprises: ferric nitrate is joined in methyl alcohol/ethylene glycol mixed solution, obtain iron nitrate solution more than stirring 2h, carboxyl acid modified poly (methyl methacrylate) micro-sphere is joined in the iron nitrate solution obtained and floods, filter, 50-100 ℃ of dry 1-24h, 0.5-2 ℃/min speed be warming up to 400-800 ℃ the insulation 4-8 hour both described macropore iron-carbonide catalyst.
According to macropore iron-carbonide catalyst of the present invention, the present invention is more even 400-800 ℃ of lower heat transmission in order to make after the catalyst drying, can also further use quartz sand as heat transfer carrier, after the present invention preferably joins carboxyl acid modified poly (methyl methacrylate) micro-sphere dipping in the iron nitrate solution obtained, filtration drying, first add quartz sand to mix, then be warming up to 400-800 ℃ of insulation and within 4-8 hour, obtain described macropore cementite;
Wherein the present invention also further preferably, adds quartz sand to mix in being connected with the quartz ampoule of inert gas.
Wherein the quartz sand consumption can be determined according to catalyst amount and heating state, and without particular determination, such as quartz sand and catalyst quality ratio can be at 10-50:1.
Wherein it will be appreciated by persons skilled in the art that after insulation finishes, should be by the catalyst separation of quartz sand and preparation;
Described this area routine operation that is separated into, for example can, for manually picking, even be sieved according to the particle diameter of quartz sand and catalyst.
Any described macropore iron-carbonide catalyst according to the present invention, described carboxyl acid modified poly (methyl methacrylate) micro-sphere can be commercially available acquisition, it is perhaps self-control, the present invention preferably preparation of described carboxyl acid modified poly (methyl methacrylate) micro-sphere comprises: methyl methacrylate (MMA) is dissolved in to reaction dissolvent, be heated to 60-90 ℃, add the potassium persulfate (KPS) for preparing/azodiisobutyronitrile (AIBN) aqueous solution, add acrylic acid (AA), stirring reaction, filter and obtain described carboxyl acid modified poly (methyl methacrylate) micro-sphere;
According to macropore iron-carbonide catalyst of the present invention, wherein preferably the described KPS/AIBN aqueous solution prepared first is heated to 60-90 ℃, then joins in the reaction dissolvent that has added MMA;
The present invention further preferably the KPS/AIBN aqueous solution prepared first is heated to the temperature identical with reaction dissolvent, then join in the reaction dissolvent that has added MMA;
According to macropore iron-carbonide catalyst of the present invention, wherein also preferred MMA and AA volume ratio are 25:1; AIBN and KPS mass ratio are 1:0.6.
According to macropore iron-carbonide catalyst of the present invention, wherein preferred described reaction dissolvent is the acetone/water mixed solution;
Wherein also the mol ratio of preferred MMA and acetone/water solution is 1:1-3;
Wherein the volume ratio of further preferred acetone and water is 1:3;
According to macropore iron-carbonide catalyst of the present invention, after wherein preferably adding AA, stirring reaction 1.5h;
According to macropore iron-carbonide catalyst of the present invention, wherein can also further preferably after stirring reaction, also carry out the ultrasonic wave processing, refilter and obtain described carboxyl acid modified poly (methyl methacrylate) micro-sphere;
Wherein further preferred ultrasonic wave is processed 1.5h.
According to macropore iron-carbonide catalyst of the present invention, the present invention further preferably, filters after stirring reaction, filter cake is placed in to centrifuge tube, with the centrifugal 10h of the rotating speed of 3000r/min, discard supernatant liquor, obtain carboxyl acid modified poly (methyl methacrylate) micro-sphere after drying at room temperature.
According to macropore iron-carbonide catalyst of the present invention, the present invention can also be further preferably, carry out the ultrasonic wave processing after stirring reaction, refilter, filter cake is placed in to centrifuge tube, with the centrifugal 10h of the rotating speed of 3000r/min, discard supernatant liquor, obtain carboxyl acid modified poly (methyl methacrylate) micro-sphere after drying at room temperature.
According to macropore iron-carbonide catalyst of the present invention, the present invention also further preferably is dissolved in the acetone/water mixed solution by MMA under the air-isolation condition, be heated to 60-90 ℃, pass into inert gas, add the KPS/AIBN aqueous solution prepared, add AA, stirring reaction, filter and obtain described carboxyl acid modified poly (methyl methacrylate) micro-sphere simultaneously;
Wherein said air-isolation condition is this area routine operation, for example can pass into inert gas for after reaction vessel is vacuumized again;
Wherein the present invention can preferred described inert gas be nitrogen or argon gas.
On the other hand, the present invention also provides the preparation method of macropore iron-carbonide catalyst of the present invention, described method comprises take carboxyl acid modified poly (methyl methacrylate) micro-sphere as template, the ferric nitrate of take prepares the macropore iron-carbonide catalyst as presoma, and the macropore iron-carbonide catalyst aperture of gained is 50-1000nm.
According to preparation method of the present invention, described preparation method comprises: ferric nitrate is joined 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, add quartz sand to mix filling, be warming up to 400-800 ℃ the insulation 4-8 hour both described macropore iron-carbonide catalyst.
Wherein preferably described carboxyl acid modified poly (methyl methacrylate) micro-sphere particle diameter is particle diameter 50-600nm.
Wherein the preferred described ferric nitrate of the present invention and methyl alcohol/ethylene glycol mol ratio are 1:1-3.
Wherein the preferred described methyl alcohol of the present invention and ethylene glycol volume ratio are 1:1.5-4.
According to preparation method of the present invention, described preparation method comprises: ferric nitrate is joined in methyl alcohol/ethylene glycol mixed solution, obtain iron nitrate solution more than stirring 2h, carboxyl acid modified poly (methyl methacrylate) micro-sphere is joined in the iron nitrate solution obtained and floods, filter, 50-100 ℃ of dry 1-24h, add quartz sand to mix filling, 0.5-2 ℃/min speed be warming up to 400-800 ℃ the insulation 4-8 hour both described macropore iron-carbonide catalyst.
According to preparation method of the present invention, it is in being connected with the quartz ampoule of inert gas that the present invention further preferably add quartz sand to mix to fill and quartz sand mixes filling.
Any described preparation method according to the present invention, described carboxyl acid modified poly (methyl methacrylate) micro-sphere can be commercially available acquisition, it is perhaps self-control, the present invention preferably preparation of described carboxyl acid modified poly (methyl methacrylate) micro-sphere comprises: methyl methacrylate (MMA) is dissolved in to reaction dissolvent, be heated to 60-90 ℃, add the potassium persulfate (KPS) for preparing/azodiisobutyronitrile (AIBN) aqueous solution, add acrylic acid (AA), stirring reaction, filter and obtain described carboxyl acid modified poly (methyl methacrylate) micro-sphere;
According to preparation method of the present invention, wherein preferably the described KPS/AIBN aqueous solution of crossing prepared first is heated to 60-90 ℃, then joins in the reaction dissolvent that has added MMA;
The present invention's mistake KPS/AIBN aqueous solution that further institute preferably will prepare first is heated to the temperature identical with reaction dissolvent, then joins in the reaction dissolvent that has added MMA;
According to preparation method of the present invention, wherein also preferred MMA and AA volume ratio are 25:1; AIBN is 1:0.6 with crossing the KPS mass ratio.
According to preparation method of the present invention, wherein preferred described reaction dissolvent is the acetone/water mixed solution;
Wherein also the mol ratio of preferred MMA methyl esters and acetone/water solution is 1:1-3;
Wherein the volume ratio of further preferred acetone and water is 1:3;
According to preparation method of the present invention, after wherein preferably adding AA, stirring reaction 1.5h;
According to preparation method of the present invention, wherein can also further preferably after stirring reaction, also carry out the ultrasonic wave processing, refilter and obtain described carboxyl acid modified poly (methyl methacrylate) micro-sphere;
Wherein further preferred ultrasonic wave is processed 1.5h.
According to preparation method of the present invention, the present invention further preferably, filters after stirring reaction, filter cake is placed in to centrifuge tube, with the centrifugal 10h of the rotating speed of 3000r/min, discard supernatant liquor, obtain carboxyl acid modified poly (methyl methacrylate) micro-sphere after drying at room temperature.
According to preparation method of the present invention, the present invention can also be further preferably, carry out the ultrasonic wave processing after stirring reaction, refilter, filter cake is placed in to centrifuge tube, with the centrifugal 10h of the rotating speed of 3000r/min, discard supernatant liquor, obtain carboxyl acid modified poly (methyl methacrylate) micro-sphere after drying at room temperature.
According to preparation method of the present invention, the present invention also further preferably is dissolved in the acetone/water mixed solution by MAA under the air-isolation condition, be heated to 60-90 ℃, pass into inert gas, add the KPS/AIBN aqueous solution prepared, add AA, stirring reaction, filter and obtain described carboxyl acid modified poly (methyl methacrylate) micro-sphere simultaneously;
Wherein said air-isolation condition is this area routine operation, for example can pass into inert gas for after reaction vessel is vacuumized again;
Wherein the present invention can preferred described inert gas be nitrogen or argon gas.
On the one hand, the present invention also provides the application of described macropore iron-carbonide catalyst in the catalysis biological synthesis gas is converted into fuel oil again.
Another aspect, the present invention also provides and has applied the method that macropore iron-carbonide catalyst catalysis biological synthesis gas of the present invention is converted into fuel oil, and described method comprises: biosynthesis gas and described macropore iron-carbonide catalyst are carried out to the haptoreaction made fuel oil;
Wherein preferred described reaction condition comprises: 310 ℃ of reaction temperatures, air speed 2000h
-1, pressure 6.5MP
a;
Wherein more preferably first the macropore cementite is used for preparing fuel oil with biosynthesis gas haptoreaction through overactivation again;
Wherein further preferred described activation is activation under 310 ℃;
Wherein more preferably activate 2h.
Biosynthesis gas of the present invention is preferably as follows mol ratio composition: H
2: CO:CO
2: and CH
4: N
2=1:1:0.5-0.8:0.1:2-3.
In sum, the invention provides a kind of macropore iron-carbonide catalyst and its preparation method and application.Macropore iron-carbonide catalyst of the present invention has following advantage:
It is template that the present invention adopts carboxy-modified microballoon, take ferric nitrate as presoma, the three-dimensional cementite connected of roasting direct preparation under the condition of methyl alcohol ethylene glycol solvent, and method of operating is simple, and the cycle is short, and cost is low.The present invention has successfully prepared the macropore iron-carbonide catalyst first.
The accompanying drawing explanation
The FT-IR spectrum that Fig. 1 is the prepared carboxy-modified microsphere template of embodiment 1.
The SEM photo that Fig. 2 is the prepared carboxy-modified microsphere template of embodiment 1.
The particle diameter distribution map that Fig. 3 is the prepared carboxy-modified microsphere template of embodiment 1.
The FT-IR spectrum that Fig. 4 is the prepared cementite of embodiment 2.
The XRD spectra that Fig. 5 is the prepared cementite of embodiment 2.
The TEM photo that Fig. 6 is the prepared cementite of embodiment 2.
Fig. 7 is that the prepared iron-carbonide catalyst of embodiment 3 turns to the catalytic activity result of fuel oil to the biosynthesis cyclostrophic.
The specific embodiment
Below describe the beneficial effect of implementation process of the present invention and generation in detail by specific embodiment, be intended to help the reader to understand better essence of the present invention and characteristics, but not as the restriction to this case practical range.
The preparation method of embodiment 1 carboxy-modified colloidal crystal template
In the present embodiment, prepare in accordance with the following methods carboxy-modified colloidal crystal template:
(1) adopt standby monodispersed carboxy-modified polymethyl methacrylate (c-PMMA) microballoon of improved emulsifier-free emulsion polymerization legal system
50ml acetone and 150ml deionized water are added to and agitator, reflux condensing tube, temperature are housed take into account N
2in the 1000ml four-hole boiling flask of tracheae, vacuumize rear logical N
2, add MMA and two kinds of monomers of AA(that volume ratio is 25:1 all to make with extra care through decompression distillation), and be heated to 80 ℃.Take initator KPS0.27g and AIBN0.45g simultaneously and be dissolved in 150ml water, and add in four-hole boiling flask after being heated to 80 ℃.N
2after the lower reaction 1.5h of protection, naturally cool to room temperature under stirring, ultrasonic processing 1.5h, suction filtration obtains the c-PMMA polymer microballoon.Fig. 1 provides the FT-IR infrared absorption spectroscopy of this compound.
(2) adopt the standby colloidal crystal template of centrifugal deposition legal system
The c-PMMA microballoon is placed in to centrifuge tube, with the centrifugal 10h of the rotating speed of 3000r/min, discards supernatant liquor, obtain closelypacked modified PMMA colloidal crystal template after drying at room temperature.Fig. 2 provides the SEM photo of this colloidal crystal template.Fig. 3 provides the particle diameter distribution map of this compound microballoon.
Adopt the original position infusion process to prepare the compound of presoma and template
Take a certain amount of ferric nitrate by stoichiometric proportion, be dissolved in methyl alcohol and ethylene glycol mixed solution (volume ratio 1:3), ferric nitrate and methyl alcohol/ethylene glycol mol ratio is 1:2, and magnetic agitation 2h obtains transparent and homogeneous solution, i.e. the precursor solution of catalyst.With the colloidal crystal template of this solution impregnation drying, to be impregnated fully after, unnecessary precursor solution suction filtration is removed.Colloidal crystal template after dipping is placed in to vacuum drying chamber dry 20h under 80 ℃, obtains the compound of colloidal crystal and presoma.
The preparation method of the embodiment 2 three-dimensional cementite that connect
(1) adopt standby monodispersed carboxy-modified polymethyl methacrylate (c-PMMA) microballoon of improved emulsifier-free emulsion polymerization legal system
50ml acetone and 150ml deionized water are added to and agitator, reflux condensing tube, temperature are housed take into account N
2in the 1000ml four-hole boiling flask of tracheae, vacuumize rear logical N
2, add the MMA of certain volume ratio and two kinds of monomers of AA(all to make with extra care through decompression distillation), and be heated to 80 ℃.Take a certain amount of initator KPS and AIBN simultaneously and be dissolved in 150ml water, and add in four-hole boiling flask after being heated to 80 ℃.N
2after the lower reaction 1.5h of protection, naturally cool to room temperature under stirring, ultrasonic processing 1.5h, suction filtration obtains the c-PMMA polymer microballoon.Fig. 1 provides the FT-IR infrared absorption spectroscopy of this compound.
(2) adopt the standby colloidal crystal template of centrifugal deposition legal system
The c-PMMA microballoon is placed in to centrifuge tube, with the centrifugal 10h of the rotating speed of 3000r/min, discards supernatant liquor, obtain closelypacked modified PMMA colloidal crystal template after drying at room temperature.Fig. 2 provides the SEM photo of this colloidal crystal template.Fig. 3 provides the particle diameter distribution map of this compound microballoon.
(3) adopt the original position infusion process to prepare the compound of presoma and template
Take Fe (NO
3)
29H
2o, be dissolved in 10ml methyl alcohol ethylene glycol mixed solution (volume ratio 1:2), and ferric nitrate and methyl alcohol/ethylene glycol mol ratio is 1:3, and magnetic agitation 2h obtains transparent and homogeneous solution, obtains the precursor solution of catalyst.With the dried c-PMMA colloidal crystal template of this solution impregnation 3g 10h, to be impregnated fully after, unnecessary precursor solution suction filtration is removed, then template is placed in to vacuum drying chamber 80 ℃ of lower dried overnight.Mix filling with quartz sand in being connected with the quartz ampoule of inert gas, finally it being warming up in argon gas atmosphere to 800 ℃ of roastings, and constant temperature 4h, the three-dimensional iron-carbonide catalyst connected obtained.Wherein the argon gas flow velocity is 80ml/min, and heating rate is 1 ℃/min.
The SEM photo of the iron-carbonide catalyst that three-dimensional prepared for this example by Fig. 6 connects, as can be seen from Figure, take c-PMMA as the macropore template in the present embodiment, the cementite of preparation has regular three-dimensional macroporous structure, and average pore size is 300nm, and duct is uniform sequential.The X ray diffracting spectrum of the iron-carbonide catalyst that three-dimensional prepared by the present embodiment connects and infrared spectrum respectively as shown in Figure 4, Figure 5, its result show prepared by the present embodiment material in cementite is arranged.
Embodiment 3 macropore iron-carbonide catalysts are catalytically conveted to the catalytic performance result of fuel oil to biosynthesis gas
The gas composition of biosynthesis gas is 20%H
2, 19%CO, 12%CO
2, 2%CH
4and 49%N
2.At first the catalyst of embodiment 2 preparations is activated to 2h by biosynthesis gas under 310 ℃.Operation condition is: 310 ℃ of temperature, air speed 2000h
-1, pressure 6.5MPa.Experimental result as shown in Figure 7.The macropore iron-carbonide catalyst has shown very high catalytic activity and stability, and the conversion ratio of CO remains on more than 90%, and the selective of liquid fuel oil product surpasses 60%, and the activity of catalyst continues 500h and keeps basicly stable.Its catalytic activity result that biosynthesis cyclostrophic is turned to fuel oil as shown in Figure 7.
Claims (10)
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, and the ferric nitrate of take prepares as presoma, and the macropore iron-carbonide catalyst aperture of gained is 50-1000nm.
2. macropore iron-carbonide catalyst according to claim 1, it is characterized in that, the preparation of described macropore iron-carbonide catalyst comprises: ferric nitrate is joined in methyl alcohol/ethylene glycol mixed solution, wherein preferably ferric nitrate and methyl alcohol/ethylene glycol mol ratio are 1:1-3, stirring obtains iron nitrate solution, and carboxyl acid modified poly (methyl methacrylate) micro-sphere is joined in the iron nitrate solution obtained and floods, and filters, drying, be warming up to 400-800 ℃ the insulation 4-8 hour both described macropore iron-carbonide catalyst; Wherein preferred described methyl alcohol and ethylene glycol volume ratio are 1:1.5-4.
3. macropore iron-carbonide catalyst according to claim 2, it is characterized in that, the preparation of described macropore iron-carbonide catalyst comprises: ferric nitrate is joined in methyl alcohol/ethylene glycol mixed solution, obtain iron nitrate solution more than stirring 2h, carboxyl acid modified poly (methyl methacrylate) micro-sphere is joined in the iron nitrate solution obtained and floods, filter, 50-100 ℃ of dry 1-24h, 0.5-2 ℃/min speed be warming up to 400-800 ℃ of insulation 4-8 hour both described macropore cementite.
4. according to the described macropore iron-carbonide catalyst of claim 2 or 3, it is characterized in that, the preparation of described macropore iron-carbonide catalyst also comprises: after carboxyl acid modified poly (methyl methacrylate) micro-sphere being joined to dipping in the iron nitrate solution obtained, filtration drying, first add quartz sand to mix, then be warming up to 400-800 ℃ of insulation and within 4-8 hour, obtain described macropore cementite; Wherein preferably in being connected with the quartz ampoule of inert gas, add quartz sand to mix.
5. according to the described macropore iron-carbonide catalyst of claim 1～4 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 to reaction dissolvent, be heated to 60-90 ℃, add the potassium persulfate for preparing/azodiisobutyronitrile aqueous solution, add acrylic acid, stirring reaction, filter and obtain described carboxyl acid modified poly (methyl methacrylate) micro-sphere; Wherein preferably the described potassium persulfate prepared/azodiisobutyronitrile aqueous solution first is heated to 60-90 ℃, then joins in the reaction dissolvent that has added methyl methacrylate.
6. macropore iron-carbonide catalyst according to claim 5, it is characterized in that, the preparation of described carboxyl acid modified poly (methyl methacrylate) micro-sphere comprises: methyl methacrylate is dissolved in the acetone/water mixed solution, wherein the mol ratio of preferable methyl methyl acrylate and acetone/water solution is 1:1-3, be heated to 60-90 ℃, add the potassium persulfate for preparing/azodiisobutyronitrile aqueous solution, add acrylic acid simultaneously, stirring reaction 1.5h, filter and obtain described carboxyl acid modified poly (methyl methacrylate) micro-sphere; Wherein preferably the volume ratio of acetone and water is 1:3; Preferably after stirring reaction 1.5h, also carry out the ultrasonic wave processing, preferred process 1.5h, cold filtration obtains described carboxyl acid modified poly (methyl methacrylate) micro-sphere.
7. macropore iron-carbonide catalyst according to claim 6, it is characterized in that, the preparation of described carboxyl acid modified poly (methyl methacrylate) micro-sphere comprises: by methyl methacrylate, under the air-isolation condition, be dissolved in the acetone/water mixed solution, be heated to 60-90 ℃, pass into inert gas, add the potassium persulfate for preparing/azodiisobutyronitrile aqueous solution, add acrylic acid simultaneously, stirring reaction, filter and obtain described carboxyl acid modified poly (methyl methacrylate) micro-sphere.
8. the preparation method of the described macropore iron-carbonide catalyst of claim 1～7 any one.
9. the application of the described macropore iron-carbonide catalyst of claim 1～7 any one in the catalysis biological synthesis gas is converted into fuel oil; The main component of preferred described biosynthesis gas is H
2: CO:CO
2: and CH
4: N
2=1:1:0.5-0.8:0.1:2-3.
10. application rights requires the described macropore iron-carbonide catalyst of 1～7 any one catalysis biological synthesis gas to be converted into the method for fuel oil, it is characterized in that, described method comprises: biosynthesis gas and described macropore iron-carbonide catalyst are carried out to the haptoreaction made fuel oil; Wherein said reaction condition comprises: 310 ℃ of reaction temperatures, air speed 2000h
-1, pressure 6.5MPa; Wherein more preferably first the macropore cementite is used for preparing fuel oil with biosynthesis gas haptoreaction through overactivation again; Wherein preferred described activation is activation under 310 ℃, wherein more preferably activates 2h.
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| CN1895777A (en) * | 2005-07-14 | 2007-01-17 | 北京化工大学 | Porous molecular-sieve catalyst for assembling carbide and its preparation |
| CN1895778A (en) * | 2005-07-14 | 2007-01-17 | 北京化工大学 | Porous molecular sieve catalyst for assembling tungsten carbide and its preparation |
| CN102443454A (en) * | 2010-10-12 | 2012-05-09 | 中国石油化工股份有限公司 | Oxygen carrier of chemical-looping combustion and preparation method and application thereof |
| CN103182314A (en) * | 2011-12-30 | 2013-07-03 | 中国石油天然气股份有限公司 | Catalytic cracking regenerated flue gas combustion-supporting catalyst and preparation method thereof |
| CN103030143A (en) * | 2012-08-09 | 2013-04-10 | 北京大学 | Iron carbide particle, and fabrication method and application thereof |
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