CN102125844A - Method for preparing iron-carbon microsphere material and use thereof - Google Patents
Method for preparing iron-carbon microsphere material and use thereof Download PDFInfo
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- CN102125844A CN102125844A CN2010100228838A CN201010022883A CN102125844A CN 102125844 A CN102125844 A CN 102125844A CN 2010100228838 A CN2010100228838 A CN 2010100228838A CN 201010022883 A CN201010022883 A CN 201010022883A CN 102125844 A CN102125844 A CN 102125844A
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Abstract
The invention belongs to the field of material science, and relates to a method for preparing an iron-carbon microsphere material, in particular to a method for preparing an iron-carbon microsphere material for Fischer-Tropsch synthesis. The iron-carbon microsphere material is prepared from aqueous solution containing saccharides and ferric salts under the hydrothermal condition by a one-step reaction, and has a unique microstructure that iron oxide nano particles are dispersed into carbon microspheres uniformly. When used for the Fischer-Tropsch synthesis, a catalyst prepared from the iron-carbon microsphere material has the advantages of higher selectivity and stability and the like of hydrocarbon having over five carbon atoms compared with an unmodified iron catalyst reported in the prior art.
Description
Technical field
The invention belongs to material science, relate to the method for preparing iron charcoal micron ball material, be specifically related to a kind of preparation method who is used for the synthetic iron charcoal micron ball material of Fischer-Tropsch.
Background technology
Material with carbon element such as CNT, carbon nano-fiber, carbon nano rod, carbon ball, active carbon etc. are because its unique physics and chemical property and receive increasing concern in fields such as electricity, magnetics, optics, catalysis and drug delivery.But the preparation of carbon current material is generally relatively being carried out under the exacting terms, and as needs high temperature, high pressure, high-energy, prices of raw and semifnished materials costliness and complicated process of preparation etc., and these methods can cause the pollution of environment usually.Thereby, seek that a kind of prices of raw and semifnished materials are cheap, wide material sources, method are simple, the preparation method of the material with carbon element of consuming little energy, environmental protection has very important significance.
It is a kind of method that the carbon monoxide that coal, natural gas, living beings made by catalysis and hydrogen are converted into liquefied hydrocarbon that prior art discloses Fischer-Tropsch synthetic, the liquid fuel that is synthesized is made up of straight-chain hydrocarbons, alkene basically, having characteristics such as no sulphur, no nitrogen, no metal, no aromatic hydrocarbons, is the fuel oil and the chemicals of cleaning, environmental protection.One of key factor that Fischer-Tropsch is synthetic is to develop the catalyst of stability, active better, cheap, wide material sources.For this reason,, R﹠D institution and oil company research and develop both at home and abroad about all having dropped into huge financial resources, as (petrochemical technology economy such as Peking University, Shanxi coalification institute of the Chinese Academy of Sciences, the Dalian Chemistry and Physics Institute of the Chinese Academy of Sciences, group of Shenhua, Sasol company, Shell company, Exxon companies, 2004,19:8; The chemical industry progress, 2003,22:441).Wherein, the material with carbon element that adopts inertia has received researcher's concern as the catalyst carrier of Fischer-Tropsch synthesis, show when adopting CNT preferably as the carrier of iron the synthetic performance of Fischer-Tropsch (J.Am.Chem.Soc., 2008,130:9414).But CNT costs an arm and a leg, and the catalyst cupport method is also comparatively complicated.Thereby the researcher wishes to look for that a kind of preparation method is simple, raw material sources widely the iron Pd/carbon catalyst can in Fischer-Tropsch is synthetic, have a good application prospect.In view of the reserves of iron abundant, cheap, and in Fischer-Tropsch synthesis to the selectivity height of low-carbon alkene, tend to generate low catenanes, it will help the synthetic important raw material of industry such as ethene, propylene, butylene and the high-octane gasoline of preparation etc.Ferrum-based catalyst demonstrates the water gas shift reaction page or leaf and has higher activity simultaneously, will help low H
2The application of the synthesis gas of/CO ratio in Fischer-Tropsch is synthetic.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, propose a kind of method for preparing iron charcoal micron ball material.Relate in particular to that a kind of preparation method is simple, raw material sources extensively, active component is uniformly dispersed, load capacity and metal nanoparticle controlled amount, the preparation method of the new sections charcoal micron sphere catalyst that is used for Fischer-Tropsch synthesis that catalytic efficiency is high.
The preparation method of the Fischer-Tropsch synthetic iron-based catalyst that the present invention proposes comprises the steps it;
At first adopt the mixed aqueous solution that contains carbohydrate and molysite through the synthetic presoma for preparing catalyst of hydro-thermal, make the iron carbon microspheres, ferriferous oxide is evenly dispersed in the carbon ball; Logical H2/Ar gaseous mixture reduction in tube furnace then, or under Ar atmosphere, carry out calcination process, make the catalyst that is used for Fischer-Tropsch synthesis.
The synthetic catalyst of Fischer-Tropsch that is used for of the present invention preparation is made up of iron and material with carbon element, is 1 with the gross weight of catalyst, and then the weight of iron is 0.01～0.40, and preferred 0.03～0.30.
Among the present invention, the molar ratio range of described iron/carbohydrate is 1: 20～5: 1.
Among the present invention, in 0～50 ℃ temperature range, carbohydrate and molysite be dissolved in the water respectively obtain the corresponding aqueous solution, after two kinds of solution mix the stirring certain hour, be transferred in the band teflon-lined water heating kettle, then water heating kettle placed 50～300 ℃ baking oven hydrothermal treatment consists 0.5～240 h.Take out water heating kettle, cool off naturally, filter, wash, dry, make the presoma of catalyst.
Carbohydrate of the present invention comprises sucrose, glucose and fructose etc., preferred 0.5～2 mol/L of carbohydrate concentration of aqueous solution.
The present invention adopts ferric nitrate as source of iron, preferred 1～3 mol/L of molysite aqueous solution concentration.
Preferred 50 ℃～250 ℃ of the temperature range of hydro-thermal reaction of the present invention; More preferably hydrothermal temperature is 60～200 ℃.
Preferred 1～96 h of hydro-thermal time of the present invention.
Among the present invention, the reduction of catalyst is carried out in tube furnace, and reducing condition is: H
2/ Ar flow velocity is 20～60ml/min, preferred 30～50 ml/min; Reduction temperature is 200～600 ℃, preferred 300～500 ℃; Recovery time is 180～2880 min, preferred 300～1440 min.
The iron charcoal micron sphere catalyst that the inventive method makes, the active component Fe nanometer particles is dispersed in the carbon micro-spheres.Show that through transmission electron microscope photo the Fe nanometer particles decentralization in the carbon micro-spheres is very high, uniform particle diameter.
The iron charcoal micron sphere catalyst that the inventive method makes is estimated its activity by following method:
Fischer-Tropsch synthesis carries out in the high-pressure flow fixed-bed micro-reactor.The stainless steel reaction bore is 10mm, and length is 470 mm, and beds is positioned at the electric tube furnace flat-temperature zone, and thermocouple places the beds middle part by sleeve pipe.Reacting gas or pretreatment gas are accurately regulated flow by mass flowmenter, and Fischer-Tropsch synthetic adopts gas-chromatography to analyze.
Evaluation result shows that the new sections charcoal micron sphere catalyst that the present invention makes has shown good stable and C in Fischer-Tropsch synthesis
5+Selectivity, its C
5+Selectivity is higher than the result on the not modified Fe fischer-tropsch synthetic catalyst that has bibliographical information now, has shown good prospects for application.
For the ease of understanding, below will describe in detail of the present invention by concrete drawings and Examples.It needs to be noted, instantiation and accompanying drawing only are in order to illustrate, obviously those of ordinary skill in the art can illustrate according to this paper, within the scope of the invention the present invention is made various corrections and change, and these corrections and change are also included in the scope of the present invention.
Description of drawings
Fig. 1: the pattern of glucosyl group iron charcoal micron ball material sample.
Fig. 2: the TEM photo of its microscopic appearance of glucosyl group iron charcoal micron ball material.
Fig. 3: the pattern of sucrose base iron charcoal micron ball material sample.
Fig. 4: the pattern of fructosyl iron charcoal micron ball material sample.
The specific embodiment
Embodiment 1: preparation glucosyl group iron charcoal micron ball material
3.75 g glucose are dissolved in the 20 ml deionized waters 4.545 g Fe (NO
3)
39H
2O is dissolved in the 10 ml deionized waters, mixes rapidly again, changes in the band teflon-lined water heating kettle.Place 80 ℃ of baking oven hydro-thermals to synthesize certain hour water heating kettle, take out the nature cooling then, filtration, washing, drying.The pattern of gained sample as shown in Figure 1, the TEM photo of its microscopic appearance is as shown in Figure 2.
Embodiment 2: preparation sucrose base iron charcoal micron ball material
With 3.75 g sucrose dissolved in 20 ml deionized waters, 4.545 g Fe (NO
3)
39H
2O is dissolved in the 10 ml deionized waters, mixes rapidly again, changes in the band teflon-lined water heating kettle.Place 80 ℃ of baking oven hydro-thermals to synthesize certain hour water heating kettle, take out the nature cooling then, filtration, washing, drying.The pattern of gained sample as shown in Figure 3.
Embodiment 3: preparation fructosyl iron charcoal micron ball material
3.75 g fructose are dissolved in the 20 ml deionized waters 4.545 g Fe (NO
3)
3.9H
2O is dissolved in the 10 ml deionized waters, mixes rapidly again, changes in the band teflon-lined water heating kettle.Place 80 ℃ of baking oven hydro-thermals to synthesize certain hour water heating kettle, take out the nature cooling then, filtration, washing, drying.The pattern of gained sample as shown in Figure 4.
Embodiment 4: at H
2Reduce the catalyst reaction performance evaluation of handling under/Ar the atmosphere
With the catalyst after the oven dry through compressing tablet, sieve, get 40～60 purposes and partly pack in the reaction tube, logical H
2/ Ar (volume ratio 5%) gaseous mixture is at 400 ℃ of following in-situ reducing 24 h, and gas flow is 50 ml/min, and heating rate is 2 ℃/min.The gained catalyst is designated as Fe
xO
y@C-H
2/ Ar.Fischer-Tropsch synthesis carries out under the following conditions: P=2.0 MPa, and T=270 ℃, gas flow rate is 16.7 ml/min, the unstripped gas mole consists of H
2/ CO=2, the catalyst loading amount is 2 g.Recovery time is 1440 min.Reaction result is as shown in table 1.
Embodiment 5: the catalyst reaction performance evaluation of carrying out calcination process under Ar atmosphere
Evaluating catalyst is similar to evaluation embodiment 1.With the catalyst after the oven dry through compressing tablet, sieve, get the 40-60 purpose and partly pack in the reaction tube, logical Ar gas is at 400 ℃ of following original position roasting 24 h, gas flow is 50 ml/min, heating rate is 2 ℃/min.The gained catalyst is designated as Fe
xO
y@C-Ar.Fischer-Tropsch synthesis carries out under the following conditions: P=2.0 MPa, and T=270 ℃, gas flow rate is 16.7 ml/min, the unstripped gas mole consists of H
2/ CO=2, the catalyst loading amount is 2 g.Roasting time is 1440 min.Reaction result is as shown in table 1.
The result shows that the iron charcoal micron sphere catalyst that the present invention makes has shown good stable and C in Fischer-Tropsch synthesis
5+Selectivity, its C
5+Selectivity is higher than the result on the not modified Fe fischer-tropsch synthetic catalyst that has bibliographical information now, has shown good prospects for application.
Table 1 is that new sections charcoal micron sphere catalyst is at H
2Reduction back or the Fischer-Tropsch synthesis performance after the Ar roasting under/the Ar atmosphere.
Table 1
Claims (10)
1. a method for preparing iron charcoal micron ball material is characterized in that it comprises the steps; At first adopt the mixed aqueous solution that contains carbohydrate and molysite through the synthetic presoma for preparing catalyst of hydro-thermal, make the iron carbon microspheres, then logical H in tube furnace
2The reduction of/Ar gaseous mixture, or under Ar atmosphere, carry out calcination process, make the catalyst that is used for Fischer-Tropsch synthesis.
2. by the described method of claim 1, it is characterized in that adopt ferric nitrate as source of iron, described carbohydrate is selected from sucrose, glucose or fructose; The molar ratio range of described iron/carbohydrate is 1: 20～5: 1.
3. by the described method of claim 1, it is characterized in that described molysite aqueous solution concentration is 1～3mol/L; The carbohydrate concentration of aqueous solution is 0.5～2mol/L.
4. by the described method of claim 1, it is characterized in that described hydrothermal temperature scope is 50 ℃～250 ℃.
5. by the described method of claim 1, it is characterized in that described hydrothermal temperature scope is 60～200 ℃.
6. by the described method of claim 1, it is characterized in that the described hydro-thermal time is 0.5～240h.
7. by the described method of claim 1, it is characterized in that the described hydro-thermal time is 1～96h.
8. by the described method of claim 1, it is characterized in that the reduction of described catalyst is carried out in tube furnace, reducing condition is: H
2/ Ar flow velocity is 20～60ml/min; Reduction temperature is 200～600 ℃; Recovery time is 180～2880min.
9. by the described method of claim 8, it is characterized in that, in the described reducing condition: H
2/ Ar flow velocity is 30～50ml/min; Reduction temperature is 300～500 ℃; Recovery time is 300～1440min.
10. by the described method of claim 1, it is characterized in that described catalyst is made up of iron and material with carbon element, wherein, is 1 with the gross weight of catalyst, and then the weight of iron is 0.01～0.40.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102773106A (en) * | 2012-07-24 | 2012-11-14 | 宁夏大学 | Catalyst for preparing low carbon olefin by synthetic gas as well as preparation method and application of catalyst |
| CN102974350A (en) * | 2012-11-27 | 2013-03-20 | 复旦大学 | Graphene-supported metallic oxide nanometer material as well as preparation method and application thereof |
| CN106881059A (en) * | 2017-02-04 | 2017-06-23 | 中国科学技术大学苏州研究院 | A kind of preparation method of iron/carbon composite |
| CN111389400A (en) * | 2020-03-23 | 2020-07-10 | 广东石油化工学院 | Preparation method of catalyst for fused salt electrochemical synthesis of ammonia |
| EP3789111A1 (en) * | 2019-09-05 | 2021-03-10 | Evonik Operations GmbH | Materials comprising carbon-embedded iron nanoparticles, processes for their manufacture, and use as heterogeneous catalysts |
-
2010
- 2010-01-15 CN CN2010100228838A patent/CN102125844A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102773106A (en) * | 2012-07-24 | 2012-11-14 | 宁夏大学 | Catalyst for preparing low carbon olefin by synthetic gas as well as preparation method and application of catalyst |
| CN102974350A (en) * | 2012-11-27 | 2013-03-20 | 复旦大学 | Graphene-supported metallic oxide nanometer material as well as preparation method and application thereof |
| CN102974350B (en) * | 2012-11-27 | 2015-06-17 | 复旦大学 | Graphene-supported metallic oxide nanometer material as well as preparation method and application thereof |
| CN106881059A (en) * | 2017-02-04 | 2017-06-23 | 中国科学技术大学苏州研究院 | A kind of preparation method of iron/carbon composite |
| CN106881059B (en) * | 2017-02-04 | 2019-10-08 | 中国科学技术大学苏州研究院 | A kind of preparation method of iron/carbon composite |
| EP3789111A1 (en) * | 2019-09-05 | 2021-03-10 | Evonik Operations GmbH | Materials comprising carbon-embedded iron nanoparticles, processes for their manufacture, and use as heterogeneous catalysts |
| WO2021043861A1 (en) * | 2019-09-05 | 2021-03-11 | Evonik Operations Gmbh | Materials comprising carbon-embedded iron nanoparticles, processes for their manufacture, and use as heterogeneous catalysts |
| CN114340785A (en) * | 2019-09-05 | 2022-04-12 | 赢创运营有限公司 | Material comprising carbon-intercalated iron nanoparticles, method for the production thereof and use as heterogeneous catalyst |
| CN111389400A (en) * | 2020-03-23 | 2020-07-10 | 广东石油化工学院 | Preparation method of catalyst for fused salt electrochemical synthesis of ammonia |
| CN111389400B (en) * | 2020-03-23 | 2022-09-27 | 广东石油化工学院 | Preparation method of catalyst for fused salt electrochemical synthesis of ammonia |
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Application publication date: 20110720 |