CN101245502B - Method for producing cochleiform carbon fiber with catalyst - Google Patents
Method for producing cochleiform carbon fiber with catalyst Download PDFInfo
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- CN101245502B CN101245502B CN2008101022360A CN200810102236A CN101245502B CN 101245502 B CN101245502 B CN 101245502B CN 2008101022360 A CN2008101022360 A CN 2008101022360A CN 200810102236 A CN200810102236 A CN 200810102236A CN 101245502 B CN101245502 B CN 101245502B
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- carbon fiber
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Abstract
The invention relates to a method which uses a catalyzer for preparing a twist carbon fiber and pertains to the field of carbon fiber preparation techniques. 30 to 50mg of hydrotalcite catalyzer is spread in a porcelain boat and then put into a horizontal quartz tube installed in a tube style heating furnace and nitrogen is pumped in the tube with the flow speed of 60-70ml/min; the temperature raises to 500-700 DEG C with the speed of 2-10 DEG C per minute and preserved for 20-60 minutes; then the acetylene is pumped in the catalyzer with the flow speed of 6-10ml/min at the temperature of 500-700 DEG C for the growth of carbon fiber and reaction for 1-2 hours, then cooled to chamber temperature along with the furnace, so as to obtain the twist carbon fiber; the twist carbon fiber comprises twist, chiral spiral and double helix carbon fibers. The method has the advantages that only acetylene is taken as a reducing gas and a carbon source for the growth of twist carbon fiber; the production cost is saved and the pollution to the environment is reduced substantially while the growth efficiency is enhanced. The twist, chiral spiral and double helix carbon fibers with even structure are finally obtained and the yield is higher, reaching 400-800 percent.
Description
Technical field
The invention belongs to the carbon fiber preparing technical field, particularly a kind of method with the Preparation of Catalyst screw carbon fibre.
Background technology
The special architectural feature of screw carbon fibre makes it have functions such as better elastic, strong mechanicalness and resistance to impact, at aspects such as storage hydrogen, absorption, microwave absorption, electricity potential widely application being arranged, is a kind of novel inorganic functional material of superior performance.Wherein coiled carbon fibers, chiral helical carbon fiber and double helix carbon fiber are typical screw carbon fibre, and all there is certain difference in they at aspects such as size pattern, structure, performances.
The most general preparation method of screw carbon fibre is that catalytic chemical vapor deposition technique is the CCVD method.The CCVD method has that equipment is simple, cost is low and course of reaction advantage such as control easily.Employed activity of such catalysts component is generally transition metal Ni, Fe, Cu in CCVD, or its alloy (S.Yang, X.Chen, M.Kusunoki, K.Yamamoto, H.Iwanaga, Carbon 43,2005,916-922; Yong Qin, Xin Jiang.J.Phys.Chem.B 109,2005,21749-21754; Yongkui Wen, Zengmin Shen.Carbon 39,2001,2369-2386), the catalyst of different activities component and structure can influence pattern, structure, productive rate and the performance of the screw carbon fibre of growth.Therefore, people constantly try to explore the influence of the various preparation methods of the easy preparation method of coiled carbon fibers and the catalyst that uses to its structure and composition, thereby carry out the controllable growth of carbon fibre material, in the hope of obtaining the screw carbon fibre of high-quality, excellent performance.
Present CCVD legal system is equipped with screw carbon fibre and adopts metal alloy or nano-metal particle as catalyst mostly, but owing to there is Preparation of Catalyst cost height, shortcomings such as metallic particles decentralization and particle size control difficulty are big, cause the carbon fiber thickness skewness that grows, had a strong impact on the uniformity and the productive rate of screw carbon fibre pattern.And, in CCVD, need introduce simultaneously usually sulfide or phosphide as cocatalyst to improve the growth of carbon fiber, this has not only increased preparation cost, but also has caused environmental hazard, is unfavorable for the large-scale production of screw carbon fibre.
Summary of the invention
The invention reside in provides a kind of method with the Preparation of Catalyst screw carbon fibre, overcomes the metallic particles decentralization and the unmanageable shortcoming of particle size of the traditional carbon fibres preparation cost height and the traditional catalyst of using.
The method for preparing screw carbon fibre is directly to use hydrotalcite as catalyst, need not feed hydrogen and noxious material, the acetylene that utilization is introduced in course of reaction decomposes the roasting catabolite of the hydrogen in-situ reducing hydrotalcite that is produced, the carbon that is produced in the cracking of original position absorption simultaneously directly carries out the growth of carbon fibre material.This process is after the catalyst decomposes, reduction, catalysis, absorption are carried out synchronously, and easy and simple to handle, pollution-free, productive rate is higher.
Layered double hydroxide (Layered Double Hydroxides is called for short LDHs) is the anionic clay that a class has layer structure.The chemical composition of hydrotalcite has following general formula: [M
2+ 1-xM
3+ x(OH)
2]
X+(A
N-)
X/nMH
2O, wherein M
2+And M
3+Be respectively divalence and trivalent metal cation, be positioned on the main body laminate; A
N-Be interlayer anion; X is M
3+/ (M
2++ M
3+) molar ratio; M is the molar weight of intermediary water molecule.But the characteristics of bound water talcum laminate The Nomenclature Composition and Structure of Complexes microcosmic modulation of the present invention, can introduce Ni, Cu activity or help active specy to its laminate by design, obtain the specific hydrotalcite that laminate contains definite composition by urea hydro-thermal Preparation by Uniform Precipitation, and carry out the growth of screw carbon fibre as catalyst.Because active specy high degree of dispersion and evenly distributing on molecular level has not only improved the reactivity of catalyst in the hydrotalcite, and can assign to realize control by the metal group of different proportion in the control hydrotalcite to the screw carbon fibre growth.
A kind of method with the Preparation of Catalyst coiled carbon fibers:
30～50mg hydrotalcite catalyst is tiled in the porcelain boat, put into the horizontal quartz ampoule that is arranged in tubular heater then, feeding flow velocity is the nitrogen of 60～70ml/min, be incubated 20～60min after being warming up to 500～700 ℃ with the speed of 2～10 ℃/min, the acetylene gas that feeds flow velocity then and be 6～10ml/min under this temperature carries out the growth of carbon fiber, reaction 1～2h cools to room temperature at last with the furnace and obtains screw carbon fibre.
Acetylene carries out the screw carbon fibre growth as carbon source simultaneously, has typical spiral, chiral helical or double helix carbon fiber to generate in the carbon product.Fibre diameter is 200～250nm in the coiled carbon fibers that is generated; Fibre diameter is at 80～120nm in the chiral helical carbon fiber, and caliber is smooth, and evenly screw diameter is 80～120nm, and revolving distance is 120～180nm; Fibre diameter is 400～600nm in the double helix carbon fiber, and screw diameter is 2～4um, and the double helix pipe range is 40～50um; The productive rate of catalytic growth coiled carbon fibers (mass percent of the carbon that every gram catalyst generates) can reach 400～800%.
The concrete preparation method of this catalyst is as follows:
A. contain bivalent metal ion M with the deionized water preparation
2+With trivalent metal ion M
3+Mixing salt solution, [M wherein
2+]/[M
3+]=1～4, and the total mol concentration of each metal ion species is 0.4～1.2M; M wherein
2+Be Ni
2+, Cu
2+In one or both, or contain Mg
2+M
3+Be Al
3+, Fe
3+In one or both; Acid ion in the mixing salt solution can be NO
3 -, Cl
-Or SO
4 2-In any one or a few.
B, urea is added in the above mixing salt solution, the molar concentration rate of urea and all metal cations is between 3～6; The mixing salt solution that will add urea then is placed in the water heating kettle, under static condition in 120～150 ℃ of hydro-thermal reaction 15～24h; With the product isolated by filtration, spend deionised water, drying is 15～20 hours under 60～70 ℃, obtains catalyst LDHs, and its molecular formula is [M
2+ 1-XM
3+ X(OH)
2]
X+(CO
3 2-)
X/2MH
2O;
Can form mixture after this screw carbon fibre catalyst for growth roasting, Main Ingredients and Appearance is the composite oxides of metal oxide and spinel structure thereof.Catalyst uses the back with the quality percentage composition that elementary analysis and the test of X-photoelectron spectroscopy draw each component of product to be respectively: the composite oxides 35～65% of active elemental metal 35～65%, spinel structure.The active elemental metal is one or both among Ni and the Cu, and they are to obtain by the hydrogen in-situ reducing LDHs catabolite that the acetylene cracking is produced; Spinelle type composite oxides is with M
2+M
3+ 2O
4Form exists, wherein M
2+Be Ni
2+And Cu
2+In one or both, M
3+Be Fe
3+, Al
3+In one or both.
The present invention has following remarkable result:
The present invention only utilizes acetylene simultaneously to carry out the growth of screw carbon fibre as reducing gas and carbon source, can be when improving growth usefulness, and save production cost significantly and reduce environmental pollution.In addition, utilize urea homogeneous precipitation under hydrothermal condition to generate the high hydrotalcite catalyst of degree of crystallinity, can effectively control the even distribution of active component, and hydrotalcite has overcome preparation cost height and metallic particles decentralization and the unmanageable shortcoming of particle size that the conventional metals catalyst exists through accessing The Nomenclature Composition and Structure of Complexes even metal nano particle on microcosmic behind the roasting reduction.
The specific embodiment:
Embodiment 1:
With 80ml deionized water, 0.7755g Ni (NO
3)
26H
2O, 0.5002g Al (NO
3)
37H
2Adding 0.7928g urea was made mixed solution after O was mixed with salting liquid.Put into the inner bag of the polyflon of 100ml, in autoclave, seal.Put into 120 ℃ baking oven crystallization 15 hours, take out inner bag at last.Reaction finishes the back suction filtration, spends twice, 70 ℃ of drying of deionised water 15 hours.
To put into quartz ampoule behind the above-mentioned hydrotalcite 50mg threading porcelain boat for preparing, feed nitrogen (60ml/min), speed with 2 ℃/min is warming up to 700 ℃, continue to feed the acetylene (flow of acetylene and nitrogen is respectively 6ml/min and 60ml/min) of 1h behind the insulation 20min again, cool to room temperature at last with the furnace and obtain chiral helical carbon fiber.Two spiral nanometer carbon fibers of symmetric growth are respectively left-handed and dextrorotation, and its fibre diameter, screw diameter and helix length are all identical.The most chiral helical carbon fiber spiral shells footpath and the pitch that are generated are even, and the fiber diameter of carbon fiber is about 100nm, and average screw diameter on average revolves distance for about 150nm about 110nm, and productive rate reaches 423%.
Embodiment 2:
With 80ml deionized water, 0.3785g NiSO
46H
2O, 0.0372g Cu (NO
3)
23H
2O, 0.6506gMgCl
26H
2O and 0.3863g AlCl
36H
2Adding 1.5375g urea was made mixed solution after O was mixed with salting liquid.Put into the inner bag of the polyflon of 100ml, put into autoclave and seal.Put into 150 ℃ baking oven crystallization 24 hours, take out inner bag at last.Reaction finishes the back suction filtration, spends twice, 70 ℃ of drying of deionised water 20 hours.
To put into quartz ampoule behind the above-mentioned hydrotalcite 40mg threading porcelain boat for preparing, feed nitrogen (65ml/min), speed with 5 ℃/min is warming up to 700 ℃, continue to feed the acetylene (flow of acetylene and nitrogen is respectively 6ml/min and 65ml/min) of 1h30min behind the insulation 30min again, cool to room temperature at last with the furnace and obtain chiral helical carbon fiber and double helix carbon fiber product.The fiber diameter of chiral helical carbon fiber is about 115nm, and average screw diameter on average revolves apart from being about 140nm about 100nm, and the carbon fiber of uniform diameter is the chirality symmetry grows up, and accounts for 20% of gross production rate.What occur in a large number simultaneously is even regular double helix micron carbon fiber.The double helix carbon fiber by two fibre diameters be about 500nm carbon filament in pairs, form with axial vortex in the same way, when tight circumvolution, then form a no gap coil.The average screw diameter of the double spiral tube that forms is about 3um, and average pipe range is about 41um, accounts for about 80% of gross production rate.The gross output productive rate reaches 796%.
Embodiment 3:
With 80ml deionized water, 1.2836g NiCl
26H
2O, 0.1498g CuSO
45H
2O, 0.7503gAl (NO
3)
37H
2Adding 1.5856g urea was made mixed solution after O was mixed with salting liquid.Put into the inner bag of the polyflon of 100ml, put into autoclave and seal.Put into 150 ℃ baking oven crystallization 20 hours, take out inner bag at last.Reaction finishes the back suction filtration, spends twice, 60 ℃ of drying of deionised water 15 hours.
To put into quartz ampoule behind the above-mentioned hydrotalcite 45mg threading porcelain boat for preparing, feed nitrogen (60ml/min), speed with 10 ℃/min is warming up to 500 ℃, continue to feed the acetylene (flow of acetylene and nitrogen is respectively 6ml/min and 60ml/min) of 1h30min behind the insulation 50min again, cool to room temperature at last with the furnace and finally obtain the generation of double helix carbon fiber.Even regular double helix carbon fiber by two fibre diameters be about 500nm carbon filament in pairs, form with axial vortex in the same way, when tight circumvolution, then form a no gap coil, smooth surface.The average screw diameter of the double spiral tube that forms is about 2.5um, and average spiral pipe range is that productive rate reaches 652% about 46um.
Embodiment 4:
With 80ml deionized water, 0.7886g NiCl
26H
2O, 0.404g Fe (NO
3)
39H
2Adding 1.2012g urea was made mixed solution after O was mixed with salting liquid.Put into the inner bag of the polyflon of 100ml, put into autoclave and seal.Put into 120 ℃ baking oven crystallization 24 hours, take out inner bag at last.Reaction finishes the back suction filtration, spends twice, 70 ℃ of drying of deionised water 20 hours.
To put into quartz ampoule behind the above-mentioned hydrotalcite 50mg threading porcelain boat for preparing, feed nitrogen (70ml/min), speed with 5 ℃/min is warming up to 700 ℃, continue to feed the acetylene (flow of acetylene and nitrogen is respectively 10ml/min and 70ml/min) of 2h behind the insulation 60min again, cool to room temperature at last with the furnace and obtain coiled carbon fibers.Fiber diameter is about 250nm, and productive rate is 440%.
Claims (2)
1. method with the Preparation of Catalyst coiled carbon fibers: it is characterized in that, 30～50mg hydrotalcite catalyst is tiled in the porcelain boat, put into the horizontal quartz ampoule that is arranged in tubular heater then, feeding flow velocity is the nitrogen of 60～70ml/min, be incubated 20～60min after being warming up to 500～700 ℃ with the speed of 2～10 ℃/min, the acetylene gas that feeds flow velocity then and be 6～10ml/min under this temperature carries out the growth of carbon fiber, reaction 1～2h cools to room temperature at last with the furnace and obtains screw carbon fibre; Screw carbon fibre comprises chiral helical and double helix carbon fiber;
The preparation method of described hydrotalcite catalyst is:
A. contain bivalent metal ion M with the deionized water preparation
2+With trivalent metal ion M
3+Mixing salt solution, [M wherein
2+]/[M
3+]=1～4, and the total mol concentration of each metal ion species is 0.4～1.2M; M wherein
2+Be Ni
2+, Cu
2+In one or both; M
3+Be Al
3+, Fe
3+In one or both; Acid ion in the mixing salt solution is NO
3 -, Cl
-Or SO
4 2-In any one or a few;
B, urea is added in the above mixing salt solution, the molar concentration rate of urea and all metal cations is between 3～6; The mixing salt solution that will add urea then is placed in the water heating kettle, under static condition in 120～150 ℃ of hydro-thermal reaction 15～24h; With the product isolated by filtration, spend deionised water, drying is 1 5～20 hours under 60～70 ℃, obtains hydrotalcite catalyst, and its molecular formula is: [M
2+ 1-XM
3+ X(OH)
2]
X+(CO
3 2-)
X/2MH
2O.
2. the described method of claim 1 is characterized in that, described hydrotalcite catalyst is directly used in the growth of screw carbon fibre, and after decomposing under 500～700 ℃ the temperature, reduction, cracking, catalytic reaction are carried out synchronously; Acetylene is simultaneously as reducing gas and carbon source.
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|---|---|---|---|
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|---|---|---|---|
| CN2008101022360A CN101245502B (en) | 2008-03-19 | 2008-03-19 | Method for producing cochleiform carbon fiber with catalyst |
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| CN101245502B true CN101245502B (en) | 2010-06-23 |
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| CN101814604B (en) * | 2010-01-08 | 2012-07-25 | 北京化工大学 | Noble-metal/composite metal oxide/ carbon nanometer tubular electro-catalyst and preparation method and application |
| CN101820066B (en) * | 2010-03-26 | 2012-10-17 | 北京化工大学 | Single metal/multi-wall carbon nano tube type composite material, preparation method and application thereof |
| CN101822986B (en) * | 2010-03-31 | 2012-05-09 | 北京化工大学 | Preparation method of catalyst capable of controlling growth of carbon nano pipe and carbon fibre |
| CN103015165A (en) * | 2012-12-05 | 2013-04-03 | 中南大学 | Novel carbon fiber with spiral structure and preparation method thereof |
| CN103590141B (en) * | 2013-08-26 | 2015-09-16 | 国家纳米科学中心 | A kind of silver-glutathione chirality nanofiber and preparation method thereof |
| CN104386676B (en) * | 2014-11-05 | 2017-09-26 | 北京化工大学 | A kind of preparation method of graphene |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1748862A (en) * | 2005-08-29 | 2006-03-22 | 天津大学 | Process for preparing carbon nano tube and carbon onion by Ni/Al catalyst chemical gas phase deposition |
| WO2006055679A2 (en) * | 2004-11-16 | 2006-05-26 | Hyperion Catalysis International, Inc. | Method for preparing single walled carbon nanotubes |
| CN1272240C (en) * | 2004-12-13 | 2006-08-30 | 关君正 | Method for preparing spiral carbon nano pipe |
| CN1995503A (en) * | 2006-01-06 | 2007-07-11 | 北京化工大学 | Method for preparing spiral nano carbon fiber |
-
2008
- 2008-03-19 CN CN2008101022360A patent/CN101245502B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006055679A2 (en) * | 2004-11-16 | 2006-05-26 | Hyperion Catalysis International, Inc. | Method for preparing single walled carbon nanotubes |
| CN1272240C (en) * | 2004-12-13 | 2006-08-30 | 关君正 | Method for preparing spiral carbon nano pipe |
| CN1748862A (en) * | 2005-08-29 | 2006-03-22 | 天津大学 | Process for preparing carbon nano tube and carbon onion by Ni/Al catalyst chemical gas phase deposition |
| CN1995503A (en) * | 2006-01-06 | 2007-07-11 | 北京化工大学 | Method for preparing spiral nano carbon fiber |
Non-Patent Citations (2)
| Title |
|---|
| 田媛媛.层状化合物及其复合金属氧化物薄膜的制备与性能研究.北京化工大学,2007,24、29、52. * |
| 谭茜.层状前体法制备新型碳纳米管生长催化剂的研究.北京化工大学,2005,全文. * |
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