CN103480404B - 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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- CN103480404B CN103480404B CN201310445020.5A CN201310445020A CN103480404B CN 103480404 B CN103480404 B CN 103480404B CN 201310445020 A CN201310445020 A CN 201310445020A CN 103480404 B CN103480404 B CN 103480404B
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- 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
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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
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
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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 through macropore cementite of the strong three-dimensional of a kind of acid and alkali-resistance mechanical performance and its preparation method and application.
Background technology
Carbide by carbon and metal formed " filling a property alloy " (interstitial alloy), namely the carbon atom of small volume occupies the space of metallic atom closs packing layer, formation often there is simple crystal structure.
Carbide is the material that a class has very high fusing point and hardness, high heat endurance and mechanical stability, the at room temperature almost feature such as resistance to various chemical attacks.In addition, it also has the electricity similar with its base metal, magnetic property, and these character make them be widely used in the wear-resistant and field such as high-temperature component and nuclear reactor of machine cut, mineral mining, manufacture just.The Gaziev etc. of the former Soviet Union in 1961 reports and carrys out catalysis cyclohexane dehydrogenation benzene 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, and usually all carried out on noble metal before these reactions.Carbide has caused the great interest of people as a kind of new catalytic material, has 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 powdered carbon at high temperature (1500-2000 DEG C) carbonization.Due to the use of the sintering under high temperature and excess toner, surface cover by the very thick charcoal of one deck, so the carbide prepared by this method seldom has catalytic activity, therefore be restricted in catalytic applications.Use reducing gas subsequently instead and generally adopt 20vo1%CH
4-80vol%H
2, mist carbonization, although can specific surface be increased, sintering and catalyst on carbon deposition phenomenon be still difficult to be improved significantly.React with carbon gas again after at high temperature being gasified by metal oxide or metal and draw (chemical vapor deposition, CVD), then can obtain the carbide of large surface area.In addition, also Nano-Scaled Carbide particle can be obtained by plasma sputtering method.But these processes all need to carry out at high temperature, be an a large amount of catabiotic process, and 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 the experiment that carbide catalyst is used for biosynthesis oil also there is not yet bibliographical information.
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 the preparation method that described macropore iron-carbonide catalyst is provided.
Another object of the present invention is to provide described macropore iron-carbonide catalyst to be the application in fuel oil at catalysis biological Synthetic holography.
Of the present invention have an object to be to provide the described macropore iron-carbonide catalyst catalysis biological Synthetic holography of application to be 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, be that precursor power obtains with ferric nitrate, 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: 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.
Wherein preferred 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: 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 be warming up to 400-800 DEG C of insulation 4-8 hour both described macropore iron-carbonide catalyst.
According to macropore iron-carbonide catalyst of the present invention, the present invention is in order to make after catalyst drying heat transmission at 400-800 DEG C more even, can also quartz sand be used further as heat transfer carrier, the present invention preferably 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;
Wherein the present invention also further preferably, adds quartz sand mixing in the quartz ampoule being connected with inert gas.
Wherein quartz sand consumption can be determined according to catalyst amount and heating state, and without the need to particular determination, such as quartz sand and catalyst quality ratio can at 10-50:1.
Wherein it will be appreciated by persons skilled in the art that after insulation terminates, should by the catalyst separation of quartz sand and preparation;
Described is separated into this area routine operation, such as manually to pick, even can sieve according to the particle diameter of quartz sand and catalyst.
The macropore iron-carbonide catalyst described arbitrarily according to the present invention, described carboxyl acid modified poly (methyl methacrylate) micro-sphere can be commercially available acquisition, or be self-control, the present invention can comprise in the preparation of preferred described carboxyl acid modified poly (methyl methacrylate) micro-sphere: methyl methacrylate (MMA) is dissolved in reaction dissolvent, be heated to 60-90 DEG C, add potassium persulfate (KPS)/azodiisobutyronitrile (AIBN) aqueous solution prepared, add acrylic acid (AA), stirring reaction, filters and obtains described carboxyl acid modified poly (methyl methacrylate) micro-sphere;
According to macropore iron-carbonide catalyst of the present invention, wherein preferably described in the KPS/AIBN aqueous solution for preparing first be heated to 60-90 DEG C, then join and add in the reaction dissolvent of MMA;
The present invention further preferably the KPS/AIBN aqueous solution prepared first is heated to the temperature identical with reaction dissolvent, then join and add in the reaction dissolvent of MMA;
According to macropore iron-carbonide catalyst of the present invention, wherein also preferred MMA and AA volume ratio is 25:1; AIBN and KPS mass ratio is 1:0.6.
According to macropore iron-carbonide catalyst of the present invention, wherein preferred described reaction dissolvent is acetone/water mixed solution;
Wherein also the mol ratio of preferred MMA and acetone/water solution is 1:1-3;
Wherein preferably the volume ratio of acetone and water is 1:3 further;
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 preferably further after stirring reaction, also can also carry out ultrasonic wave process, refilter and obtain described carboxyl acid modified poly (methyl methacrylate) micro-sphere;
Wherein further preferably ultrasonic wave process 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 centrifuge tube, with the centrifugal 10h of the rotating speed of 3000r/min, discard supernatant liquor, after drying at room temperature, obtain carboxyl acid modified poly (methyl methacrylate) micro-sphere.
According to macropore iron-carbonide catalyst of the present invention, the present invention can also further preferably, ultrasonic wave process is carried out after stirring reaction, refilter, filter cake is placed in centrifuge tube, with the centrifugal 10h of the rotating speed of 3000r/min, discard supernatant liquor, after drying at room temperature, obtain carboxyl acid modified poly (methyl methacrylate) micro-sphere.
According to macropore iron-carbonide catalyst of the present invention, the present invention is also preferred to be further dissolved in MMA in acetone/water mixed solution under air-isolation condition, be heated to 60-90 DEG C, pass into inert gas, add the KPS/AIBN aqueous solution prepared, add AA, stirring reaction simultaneously, filter and obtain described carboxyl acid modified poly (methyl methacrylate) micro-sphere;
Wherein said air-isolation condition is this area routine operation, such as can pass into inert gas again after being vacuumized by reaction vessel;
Wherein the present invention can preferred described inert gas be nitrogen or argon gas.
On the other hand, present invention also offers the preparation method of macropore iron-carbonide catalyst of the present invention, described method comprises with carboxyl acid modified poly (methyl methacrylate) micro-sphere for template, be that precursor power obtains macropore iron-carbonide catalyst with ferric nitrate, the macropore iron-carbonide catalyst aperture of gained is 50-1000nm.
According to preparation method of the present invention, described preparation method 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, add quartz sand mixing fill, be warming up to 400-800 DEG C insulation 4-8 hour both described macropore iron-carbonide catalyst.
Wherein preferred 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: 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, add quartz sand mixing fill, 0.5-2 DEG C/min speed be warming up to 400-800 DEG C insulation 4-8 hour both described macropore iron-carbonide catalyst.
According to preparation method of the present invention, it is in the quartz ampoule being connected with inert gas that the present invention preferably adds quartz sand mixing filling further and quartz sand mixing is filled.
The preparation method described arbitrarily according to the present invention, described carboxyl acid modified poly (methyl methacrylate) micro-sphere can be commercially available acquisition, or be self-control, the present invention can comprise in the preparation of preferred described carboxyl acid modified poly (methyl methacrylate) micro-sphere: methyl methacrylate (MMA) is dissolved in reaction dissolvent, be heated to 60-90 DEG C, add potassium persulfate (KPS)/azodiisobutyronitrile (AIBN) aqueous solution prepared, add acrylic acid (AA), stirring reaction, filters and obtains described carboxyl acid modified poly (methyl methacrylate) micro-sphere;
According to preparation method of the present invention, wherein preferably described in the KPS/AIBN aqueous solution of crossing for preparing first be heated to 60-90 DEG C, then join and add in the reaction dissolvent of MMA;
The mistake KPS/AIBN aqueous solution prepared preferably first is heated to the temperature identical with reaction dissolvent by the present invention further institute, then joins and add in the reaction dissolvent of MMA;
According to preparation method of the present invention, wherein also preferred MMA and AA volume ratio is 25:1; AIBN is 1:0.6 with crossing KPS mass ratio.
According to preparation method of the present invention, wherein preferred described reaction dissolvent is acetone/water mixed solution;
Wherein also the mol ratio of preferred MMA methyl esters and acetone/water solution is 1:1-3;
Wherein preferably the volume ratio of acetone and water is 1:3 further;
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 preferably further after stirring reaction, also can also carry out ultrasonic wave process, refilter and obtain described carboxyl acid modified poly (methyl methacrylate) micro-sphere;
Wherein further preferably ultrasonic wave process 1.5h.
According to preparation method of the present invention, the present invention further preferably, filters after stirring reaction, filter cake is placed in centrifuge tube, with the centrifugal 10h of the rotating speed of 3000r/min, discard supernatant liquor, after drying at room temperature, obtain carboxyl acid modified poly (methyl methacrylate) micro-sphere.
According to preparation method of the present invention, the present invention can also further preferably, ultrasonic wave process is carried out after stirring reaction, refilter, filter cake is placed in centrifuge tube, with the centrifugal 10h of the rotating speed of 3000r/min, discard supernatant liquor, after drying at room temperature, obtain carboxyl acid modified poly (methyl methacrylate) micro-sphere.
According to preparation method of the present invention, the present invention is also preferred to be further dissolved in MAA in acetone/water mixed solution under air-isolation condition, be heated to 60-90 DEG C, pass into inert gas, add the KPS/AIBN aqueous solution prepared, add AA, stirring reaction simultaneously, filter and obtain described carboxyl acid modified poly (methyl methacrylate) micro-sphere;
Wherein said air-isolation condition is this area routine operation, such as can pass into inert gas again after being vacuumized by reaction vessel;
Wherein the present invention can preferred described inert gas be nitrogen or argon gas.
Again on the one hand, present invention also offers described macropore iron-carbonide catalyst at catalysis biological Synthetic holography is the application in fuel oil.
Another aspect, present invention also offers application macropore iron-carbonide catalyst catalysis biological Synthetic holography of the present invention is the method for fuel oil, and described method comprises: biosynthesis gas and described macropore iron-carbonide catalyst are carried out haptoreaction made fuel oil;
Wherein preferred described reaction condition comprises: reaction temperature 310 DEG C, air speed 2000h
-1, pressure 6.5MP
a;
Wherein more preferably first macropore cementite is used for preparing fuel oil with biosynthesis gas haptoreaction through overactivation again;
Wherein preferably described further activation activates at 310 DEG C;
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 tool of the present invention has the following advantages:
The present invention adopts carboxy-modified microballoon to be template, take ferric nitrate as presoma, and the three-dimensional through cementite of roasting direct preparation under the condition of methyl alcohol ethylene glycol solvent, method of operating is simple, and the cycle is short, and cost is low.The present invention has successfully prepared macropore iron-carbonide catalyst first.
Accompanying drawing explanation
The FT-IR spectrum of the carboxy-modified microsphere template of Fig. 1 prepared by embodiment 1.
The SEM photo of the carboxy-modified microsphere template of Fig. 2 prepared by embodiment 1.
The grain size distribution of the carboxy-modified microsphere template of Fig. 3 prepared by embodiment 1.
The FT-IR spectrum of the cementite of Fig. 4 prepared by embodiment 2.
The XRD spectra of the cementite of Fig. 5 prepared by embodiment 2.
The TEM photo of the cementite of Fig. 6 prepared by embodiment 2.
The iron-carbonide catalyst of Fig. 7 prepared by embodiment 3 turns to the catalytic activity result of fuel oil to biosynthesis cyclostrophic.
Detailed description of the invention
Describe the beneficial effect of implementation process of the present invention and generation below by way of specific embodiment in detail, be intended to help reader to understand essence of the present invention and feature better, not as can the restriction of practical range to this case.
The preparation method of the carboxy-modified colloidal crystal template of embodiment 1
In the present embodiment, prepare carboxy-modified colloidal crystal template in accordance with the following methods:
(1) surfactant-free emulsion polymerization improved is adopted to prepare monodispersed carboxy-modified polymethyl methacrylate (c-PMMA) microballoon
50ml acetone and 150ml deionized water are added to agitator is housed, reflux condensing tube, temperature take into account N
2in the 1000ml four-hole boiling flask of tracheae, vacuumize rear logical N
2, adding volume ratio is that MMA and AA(two kinds of monomers of 25:1 are all refined through decompression distillation), and be heated to 80 DEG C.Take initator KPS0.27g and AIBN0.45g to be dissolved in 150ml water simultaneously, and add in four-hole boiling flask after being heated to 80 DEG C.N
2after the lower reaction 1.5h of protection, under stirring, naturally cool to room temperature, ultrasonic process 1.5h, suction filtration obtains c-PMMA polymer microballoon.Fig. 1 provides the FT-IR infrared absorption spectroscopy of this compound.
(2) adopt centrifugal deposition legal system for colloidal crystal template
C-PMMA microballoon is placed in centrifuge tube, with the centrifugal 10h of the rotating speed of 3000r/min, discards supernatant liquor, after drying at room temperature, obtain closelypacked modified PMMA colloidal crystal template.Fig. 2 provides the SEM photo of this colloidal crystal template.Fig. 3 provides the grain size distribution of this composite inorganic membranes.
Original position infusion process is adopted to prepare the compound of presoma and template
Stoichiometrically take a certain amount of ferric nitrate, be dissolved in methyl alcohol and ethylene glycol mixed solution (volume ratio 1:3), ferric nitrate and methyl alcohol/ethylene glycol mol ratio are that 1:2, magnetic agitation 2h obtain transparent and homogeneous solution, i.e. the precursor solution of catalyst.With the colloidal crystal template of this solution impregnation drying, to be impregnated completely after, unnecessary precursor solution suction filtration is removed.Colloidal crystal template after dipping is placed in vacuum drying chamber dry 20h at 80 DEG C, obtains the compound of colloidal crystal and presoma.
The preparation method of the three-dimensional through cementite of embodiment 2
(1) surfactant-free emulsion polymerization improved is adopted to prepare monodispersed carboxy-modified polymethyl methacrylate (c-PMMA) microballoon
50ml acetone and 150ml deionized water are added to agitator is housed, reflux condensing tube, temperature take into account N
2in the 1000ml four-hole boiling flask of tracheae, vacuumize rear logical N
2, MMA and the AA(two kinds of monomers adding certain volume ratio are all refined through decompression distillation), and be heated to 80 DEG C.Take a certain amount of initator KPS and AIBN to be dissolved in 150ml water simultaneously, and add in four-hole boiling flask after being heated to 80 DEG C.N
2after the lower reaction 1.5h of protection, under stirring, naturally cool to room temperature, ultrasonic process 1.5h, suction filtration obtains c-PMMA polymer microballoon.Fig. 1 provides the FT-IR infrared absorption spectroscopy of this compound.
(2) adopt centrifugal deposition legal system for colloidal crystal template
C-PMMA microballoon is placed in centrifuge tube, with the centrifugal 10h of the rotating speed of 3000r/min, discards supernatant liquor, after drying at room temperature, obtain closelypacked modified PMMA colloidal crystal template.Fig. 2 provides the SEM photo of this colloidal crystal template.Fig. 3 provides the grain size distribution of this composite inorganic membranes.
(3) original position infusion process is adopted to prepare the compound of presoma and template
Take Fe (NO
3)
29H
2o, is dissolved in 10ml methyl alcohol ethylene glycol mixed solution (volume ratio 1:2), and ferric nitrate and methyl alcohol/ethylene glycol mol ratio are that 1:3, magnetic agitation 2h obtain transparent and homogeneous solution, namely obtain the precursor solution of catalyst.With this solution impregnation 3g dried c-PMMA colloidal crystal template 10h, to be impregnated completely after, unnecessary precursor solution suction filtration is removed, then template is placed in vacuum drying chamber dried overnight at 80 DEG C.Fill with quartz sand mixing in the quartz ampoule being connected with inert gas, finally it is warming up in argon gas atmosphere 800 DEG C of roastings, and constant temperature 4h, obtain three-dimensional through iron-carbonide catalyst.Wherein argon gas flow velocity is 80ml/min, and heating rate is 1 DEG C/min.
Fig. 6 is the SEM photo of the through iron-carbonide catalyst of three-dimensional prepared by this example, and as can be seen from Figure, be macropore template with c-PMMA 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 the three-dimensional prepared of the present embodiment is through and infrared spectrum respectively as shown in Figure 4, Figure 5, its result show prepared by the present embodiment material in have cementite.
Embodiment 3 macropore iron-carbonide catalyst is 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.First catalyst embodiment 2 prepared activates 2h by biosynthesis gas at 310 DEG C.Operation condition is: temperature 310 DEG C, air speed 2000h
-1, pressure 6.5MPa.Experimental result as shown in Figure 7.Macropore iron-carbonide catalyst shows very high catalytic activity and stability, and the conversion ratio of CO remains on more than 90%, liquid fuel oil product selective more than 60%, and the sustained activity 500h of catalyst keeps basicly stable.It turns to the catalytic activity result of fuel oil as shown in Figure 7 to biosynthesis cyclostrophic.
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.
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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 |
| CN103030143A (en) * | 2012-08-09 | 2013-04-10 | 北京大学 | Iron carbide particle, and fabrication 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 regeneration flue gas combustion-supporting catalyst and preparation method |
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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 regeneration flue gas combustion-supporting catalyst and preparation method |
| 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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