CN1803280A - Ferriferous oxide for preparing nanometer carbon fiber and its preparation and uses - Google Patents
Ferriferous oxide for preparing nanometer carbon fiber and its preparation and uses Download PDFInfo
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- CN1803280A CN1803280A CN 200610023182 CN200610023182A CN1803280A CN 1803280 A CN1803280 A CN 1803280A CN 200610023182 CN200610023182 CN 200610023182 CN 200610023182 A CN200610023182 A CN 200610023182A CN 1803280 A CN1803280 A CN 1803280A
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Abstract
The invention discloses a making method and appliance of ferric oxide catalyst, which comprises the following steps: mixing the hybrid solution of bivalence and tervalence iron salt with excessive alkaline liquor at 85-95 deg C for 1-3 h; collecting the deposition to wash until the pH value is between 6.5 and 7.5; dispersing the filter cake in the organic solvent; filtering; drying the filter cake in the vacuum with even grain size at 10 nm. The invention displays narrow grain size, which can be applied to prepare nanometer carbon fiber.
Description
Technical field
The present invention relates to prepare catalyst and the preparation and the application of carbon nano-fiber.
Background technology
Unique and unusual physics, chemical property and potential application prospect thereof receives much concern carbon nano-fiber owing to it.Have several different methods to can be used for producing carbon nano-fiber, but the gas phase catalysis pyrolysismethod is simple to operate owing to the output height, small investment becomes at present the most possibly method of industrial mass production.This method is normally to load on different carriers such as Al
2O
3, SiO
2With magnesium-yttrium-transition metal Fe, Co, Ni and the alloy thereof of MgO etc. as catalyst, the particle of activity of such catalysts component requires usually less than 10nm, as carbon source, under 500～1200 ℃, prepare the carbon nano-fiber of diameter with the lower carbon number hydrocarbons compounds between 30～400nm.Carbon nano-fiber is expected as catalyst or catalyst carrier, galvanic anode, electrode for capacitors, structure reinforcing agent etc.; but when it is used as catalyst or catalyst carrier; remaining metallic catalyst regular meeting produces the catalytic reaction of its subsequent applications and disturbs in its preparation process, the metal of remnants is removed in therefore need the purge process after preparation is finished.
Because existing carbon nano-fiber preparation is often with Al
2O
3And SiO
2The Ni of load, Co, Fe are catalyst, therefore adopt concentrated base (KOH or NaOH) and concentrated acid (HNO usually
3Or HF) mode of heating for multiple times backflow removes catalyst carrier and reactive metal remaining in the carbon nano-fiber, but this operation is unfavorable in the application of catalytic field to its later stage through the fibre structure and the surface chemistry state of regular meeting's destruction carbon nano-fiber itself.Therefore develop the output height, cost is low, and the carbon nano-fiber growth catalyst that is easy to the later stage purge process simultaneously is significant further widening of the application of catalytic field to it.
Summary of the invention
The technical issues that need to address of the present invention are to disclose a kind of metal oxide and preparation and application that is used to prepare carbon nano-fiber, to overcome the defective that prior art exists.
The preparation method of nano-iron oxide of the present invention comprises the steps: the mixed aqueous solution of divalent iron salt and trivalent iron salt is mixed with excessive alkali lye, 85～95 ℃ were reacted 1～3 hour, the collecting precipitation thing, the pH that is washed to filtrate is 6.5～7.5, preferred 7, filter cake is dispersed in the organic solvent, organic solvent is selected from the unit alcohol of C1～C4, and preferred alcohol or isopropyl alcohol filter, filter cake 105～115 ℃ of dryings 8～16 hours, is promptly got catalyst of the present invention.
Divalent iron salt is selected from FeSO
4Or FeCl
2, trivalent iron salt is selected from Fe
2(SO
4)
3Or FeCl
3, the mol ratio of divalent iron salt and trivalent iron salt is 1: 1～1: 2, in the mixed aqueous solution of divalent iron salt and trivalent iron salt, the concentration of divalent iron salt and trivalent iron salt is 1～2M, the molar excess ratio of alkali lye is 1.05～1.5, and in the alkali lye, the concentration of alkali is that 1～10M is for suitable;
Alkali in the alkali lye is selected from NaOH or NH
3H
2O;
The molar excess ratio of alkali lye refers to, the ratio of the total mole of the mole of alkali and divalent iron salt and trivalent iron salt in the alkali lye.
The preparation method of metal oxide catalyst of the present invention is a kind of liquid phase coprecipitation method, and the metal oxide that is obtained is formed singlely, and average grain diameter is about 10nm, and narrow diameter distribution can be used as the catalyst for preparing carbon nano-fiber.
To put into fixed bed gas continuous-flow reacting furnace as the catalyst of above-mentioned step preparation, with argon gas and hydrogen mixed gas is reducing gases, 400～600 ℃ the reduction 0.5～9 hour after, the mixed air that feeds hydrocarbon or carbon monoxide and hydrogen is as carbon source, at 500～700 ℃, preferred 550～650 ℃, be incubated 4～24 hours.Wherein the volume ratio of argon gas and hydrogen is 5: 1～1: 2, and the flow of the mixture of argon gas and hydrogen is: 8～80m
3/ hour/kilogram catalyst, the volume ratio of carbon source and hydrogen are 10: 1～1: 1, and the flow of carbon source is: 6～60m
3/ hour/kilogram catalyst, reaction finishes back feeding argon gas cool to room temperature and promptly gets carbon nano-fiber, its diameter is 30-300nm, and diameter and pattern are mainly controlled by the technological parameters such as ratio of regulating reduction temperature, growth temperature, carbon source, hydrocarbon and hydrogen.
The carbon nano-fiber that is obtained by the present invention washs with deionized water after stirring 1 hour under with 10%～20% solid content under 40～60 ℃ with 1～4MHCl solution, repetition like this can obtain residual Fe content 5 times and be lower than 0.1% carbon nano-fiber, and the structure and the form of carbon nano-fiber are not subjected to any destruction simultaneously.
The invention provides technical scheme and prepare Preparation of catalysts and use has following advantage than the carbon nano-fiber of routine:
A) the nano-metal-oxide catalyst is formed simply, and preparation process is easy to operate, good reproducibility, and cost is lower.
B) can reach 5g～95g/gcat with the metal oxide of the present invention preparation as the carbon nano-fiber product specific yield of Preparation of Catalyst, be easy to realize large-scale production.
C) be easy in carbon nano-fiber later stage purge process, remove remaining metal, be particularly suitable for the application of catalytic field.
Description of drawings
Fig. 1 is transmission electron microscope (TEM) photo of the nano ferriferrous oxide that makes with the inventive method.
Fig. 2 is ESEM (SEM) photo of the carbon nano-fiber of embodiment 2.
Fig. 3 is ESEM (SEM) photo of the carbon nano-fiber of embodiment 3.
Fig. 4 is ESEM (SEM) photo of the carbon nano-fiber of embodiment 4.
Fig. 5 is ESEM (SEM) photo of the carbon nano-fiber of embodiment 5.
Fig. 6 is ESEM (SEM) photo of the carbon nano-fiber of embodiment 6.
Fig. 7 is ESEM (SEM) photo of the carbon nano-fiber of embodiment 7.
Fig. 8 is X-ray diffraction (XRD) collection of illustrative plates of the carbon nanofibers that makes with the inventive method.
The specific embodiment
Further specify the present invention below in conjunction with example.
Take by weighing 160gFeCl
2, be dissolved in deionized water, regulating pH with 0.1MHCl is 2, adds iron powder 20g, is warming up to 60 ℃, constant temperature 15 minutes, cooled and filtered, and with after the permanganimetric method demarcation preparation concentration, regulating its concentration is 1M.
Take by weighing FeCl
3.6H
20600g is dissolved in deionized water, and after the filtration, demarcating concentration and regulate concentration with permanganimetric method is 2M.
Respectively get 1MFeCl
2Solution 1L and 2MFeCl
3Solution 1L mixes.
Take by weighing 800gNaOH and be dissolved in deionized water configuration 10M solution 2L.
Mixed molysite solution and alkali lye are transferred to 2L reactive tank A and B respectively, the while of the reactant liquor in A and B force feed are gone into T type reaction tube and is transferred to reactor wore out 2 hours for 90 ℃ with the nitrogen pressure of 0.2MPa.Is 7 with sediment cooling back with the pH that hot deionized water is washed till filtrate, filter cake is dispersed in the ethanolic solution again filters at last, and filter cake is sent into 110 ℃ of dryings of vacuum drying oven 12 hours.The filter cake porphyrize of drying is promptly got catalyst of the present invention, and transmission electron microscope photo is observed (as Fig. 1) and is shown that the ferroferric oxide powder that obtains is the black cube particle less than 10 nanometers that particle diameter is evenly distributed.
Catalyst 1.0g is tiled in the quartz boat, and this quartz boat places reactor middle part constant temperature zone.At Ar: H
2=120: program is warming up to 600 ℃ in the mixed airflow of 40mL/min, and keeps 3 hours.Then gas is switched to reacting gas, CO: H
2=80: 20mL/min, temperature of reactor continue to keep 600 ℃, and growth course continues to switch to the argon gas of 80mL/min after 16 hours, stops heating, makes it naturally cool to room temperature, obtains black powder shape product 14.2g.The black powder shape product that obtains is carried out scanning electron microscopic observation respectively, see Fig. 2.The black powder product that obtains as seen from Figure 2 is that diameter is the carbon nano-fiber of 50～200nm, shows that through elementary analysis wherein the content of carbon surpasses 95%, and its XRD figure spectrum (as shown in Figure 8) shows that its degree of graphitization is very high.
Embodiment 3
As embodiment 2, the mixed air that difference is to adopt ethene and hydrogen obtains carbon nano-fiber 22.3g as carbon source.Its stereoscan photograph as shown in Figure 3.
Embodiment 4
As embodiment 2, difference is CO: H
2=80: 10mL/min obtains carbon nano-fiber 12.9g.Its stereoscan photograph as shown in Figure 4.
Embodiment 5
As embodiment 2, difference is CO: H
2=80: 40mL/min obtains carbon nano-fiber 12.1g.Its stereoscan photograph as shown in Figure 5.
Embodiment 6
As embodiment 2, difference is that reaction temperature is 550 ℃, obtains carbon nano-fiber 14.1g.Its stereoscan photograph as shown in Figure 6.
Embodiment 7
As embodiment 2, difference is that reduction temperature is 400 ℃, obtains carbon nano-fiber 12.7g.Its stereoscan photograph as shown in Figure 7.
Claims (10)
1. be used to prepare the nano-iron oxide Preparation of catalysts method of carbon nano-fiber, it is characterized in that, comprise the steps: the mixed aqueous solution of divalent iron salt and trivalent iron salt is mixed with excessive alkali lye, 85～95 ℃ were reacted 1～3 hour, the collecting precipitation thing, and the pH that is washed to filtrate is 6.5～7.5, filter cake is dispersed in the organic solvent, filter, filter cake 105～115 ℃ of dryings 8～16 hours, is promptly got catalyst of the present invention.
2. method according to claim 1 is characterized in that divalent iron salt is selected from FeSO
4Or FeCl
2, trivalent iron salt is selected from Fe
2(SO
4)
3Or FeCl
3
3. method according to claim 2 is characterized in that, the mol ratio of divalent iron salt and trivalent iron salt is 1: 1～1: 3.
4. method according to claim 3 is characterized in that, the molar excess ratio of alkali lye is 1.05～1.5.
5. method according to claim 1 is characterized in that the alkali in the alkali lye is selected from NaOH or NH
3.H
2O.
6. method according to claim 1 is characterized in that, organic solvent is selected from the unit alcohol of C1～C4.
7. a nano-iron oxide catalyst that is used to prepare carbon nano-fiber is characterized in that, is to adopt each described method preparation of claim 1～6.
8. the described catalyst of claim 7 is used to prepare the method for carbon nano-fiber, the steps include: the mixture of argon gas and hydrogen is contacted with catalyst, temperature is 500～700 ℃, time is that the flow of the mixture of 0.5～6 hour argon gas and hydrogen is: 8～80m3/ hour. the kilogram catalyst, and the volume ratio of argon gas and hydrogen is 5: 1～1: 2; Import carbon source insulation 4～24 hours then, the volume ratio of carbon source and hydrogen is 10: 1～1: 1, and the flow of carbon source and hydrogen mixture is: 6～60m
3/ hour. the kilogram catalyst, cooling promptly gets carbon nano-fiber.
9. method according to claim 8 is characterized in that, said carbon source is CO or hydrocarbon.
10. method according to claim 8 is characterized in that carbon source contacts with catalyst with hydrogen, and temperature is 550～650 ℃.
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| CN 200610023182 CN1803280A (en) | 2006-01-10 | 2006-01-10 | Ferriferous oxide for preparing nanometer carbon fiber and its preparation and uses |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103764554A (en) * | 2011-09-30 | 2014-04-30 | 三菱综合材料株式会社 | Carbon nanofibers encapsulting metal cobalt, and production method therefor |
| CN104003369A (en) * | 2014-05-09 | 2014-08-27 | 上海大学 | Method for preparing carbon nano-tube from iron oxide catalyst |
-
2006
- 2006-01-10 CN CN 200610023182 patent/CN1803280A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103764554A (en) * | 2011-09-30 | 2014-04-30 | 三菱综合材料株式会社 | Carbon nanofibers encapsulting metal cobalt, and production method therefor |
| CN103764554B (en) * | 2011-09-30 | 2016-03-30 | 三菱综合材料株式会社 | Include carbon nanofiber and the manufacture method thereof of cobalt metal |
| US9505622B2 (en) | 2011-09-30 | 2016-11-29 | Mitsubishi Materials Corporation | Carbon nanofibers encapsulating metal cobalt, and production method therefor |
| CN104003369A (en) * | 2014-05-09 | 2014-08-27 | 上海大学 | Method for preparing carbon nano-tube from iron oxide catalyst |
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