CN1133581C - Process for preparing large-quantity nm-class carbon fibres by using growth promoter of sulfur - Google Patents
Process for preparing large-quantity nm-class carbon fibres by using growth promoter of sulfur Download PDFInfo
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- CN1133581C CN1133581C CNB991129032A CN99112903A CN1133581C CN 1133581 C CN1133581 C CN 1133581C CN B991129032 A CNB991129032 A CN B991129032A CN 99112903 A CN99112903 A CN 99112903A CN 1133581 C CN1133581 C CN 1133581C
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Abstract
The present invention relates to a method for preparing large quantities of nano carbon fibers by using a sulfur growth promoter. Benzene, CH4 and C2H2 are used as carbon sources, ferrocene and Ni (Co) 4 are used as catalysts, and hydrogen, helium and nitrogen are used as carrier gas. Sulfur-containing compounds, such as thiophene and H2S, are used as growth promoters, and the molar ratio to the carbon source and the carrier gas is controlled to be from 0.05 to 0.25. The molar ratio to carbon and sulphur is from 600 to 1300:1, and the molar ratio to the catalyst and the carbon source is from 0.008 to 0.015. The sulfur-containing compounds, hydrocarbon compounds and the catalysts are sufficiently mixed in a gas state to be carried in a reaction zone by the carrier gas at an even speed and are reserved in the reaction zone for 0.5 to 0.075 S, and nano carbon fiber grows under the condition of 1373 to 1473 K. The present invention has the advantages of high product yield, low cost and industrialization realization.
Description
The present invention relates to the technology of preparing of carbon fiber, a kind of method of using growth promoter of sulfur to prepare carbon nano fiber in a large number is provided especially.
Gas-phase grown nanometer carbon fibre (Vapor-grown carbon nanofibers, be called for short VGCNF) generally be to be catalyzer with magnesium-yttrium-transition metal Fe, Co, Ni and alloy thereof etc., with lower carbon number hydrocarbons compound etc. is carbon source, with hydrogen is carrier gas, a kind of nanoscale carbon fiber that generates under 873～1473K.Carbon nano fiber is a kind of very unique nano-carbon material, has many distinguished characteristics.Different is with general gas-phase growth of carbon fibre for it, carbon nano fiber except characteristic with common carbon fibers as: the performances such as low density, high ratio modulus, high specific strength, high conductivity, have also that defects count is considerably less, advantages such as specific surface area is big, conduct electricity very well, compact structure, be expected to be used for catalyzer and support of the catalyst, lithium-ion secondary cell anode material, electrical double layer capacitor electrodes, high-efficiency adsorbent, separating agent, structural reinforcement material etc.At present, the preparation of VGCNF mainly contains three kinds of methods: matrix method, spraying process and flowing catalyst method.So-called matrix method is that graphite or pottery are made matrix, imposes the nm-class catalyst particle and does " seed ", and high temperature feeds hydrocarbon compound gas down, and hydrocarbon gas decomposes and separates out nano-scale fiber shape carbon in a side of granules of catalyst under the effect of catalyzer.For example, N.M.Rodriguez sprays the superfine catalyst powder on matrix, promptly prepares the VGCNF of 50～80nm with so-called matrix method high temperature degradation hydrocarbon gas.This base catalyst method can be prepared high-quality VGCNF.But superfine catalyst particulate preparation is difficulty very, sprays inhomogeneously on matrix, and carbon nano fiber only grows having on the matrix of catalyzer, thereby output is also not really high, can not suitability for industrialized production.And spraying process is catalyzer and benzene mixed solution to be that liquid is vaporific to be sprayed at growing nano carbon fiber in the Reaktionsofen with micropump.G.G.Tibbetts successfully prepares the VGCNF of 50～100nn in a vertical stove with spraying process.Though this method provides the possibility of a large amount of preparation VGCNF, but because the ratio of catalyzer and hydrocarbon compound gas is difficult to optimize, the iron size distribution is inhomogeneous in the sprinkling process, and the granules of catalyst that sprays is difficult to exist with nanoscale form, therefore the nano-scale fiber proportion is few in the process of preparation fiber, and always generates with a large amount of carbon blacks.The inventor is general through applying for a Chinese patent 96115390.3, a kind of preparation method of gas-phase grown nanometer carbon fibre is provided, it is a carbon source with benzene, is catalyzer with the ferrocene, mixes under gaseous state and enters reaction zone, at 1000～1300 ℃ of following synthesis of nano carbon fibers, comparing with preceding method can be at low cost, and mass production goes out the high-purity high-quality carbon nano fiber, and yield reaches 5%, Fibre diameter is at 20～30nm, but the real suitability for industrialized production of distance still has certain distance.
The object of the present invention is to provide a kind of method of using growth promoter of sulfur to prepare carbon nano fiber in a large number, its product yield height, cost is low, can realize suitability for industrialized production.
The invention provides a kind of method of using growth promoter of sulfur to prepare carbon nano fiber in a large number, with benzene, CH
4, C
2H
2Be carbon source, with ferrocene, Ni (Co)
4Being catalyzer, is carrier gas with hydrogen, helium, nitrogen, it is characterized in that: with sulfocompound such as thiophene powder, H
2S is a growth stimulant, and the mol ratio of control carbon source and carrier gas is 0.05～0.25, and carbon and sulphur mol ratio are 600～1300: 1, and the mol ratio of catalyzer and carbon source is 0.008～0.015; The thorough mixing under gaseous state with sulfocompound hydrocarbon polymer and catalyzer is at the uniform velocity brought into reaction zone by carrier gas, keeps 0.5～0.075S in reaction zone, growing nano carbon fiber under 1373K～1473K.The invention provides a kind of novel method that can prepare high purity, high-quality carbon nano fiber in a large number, promptly add the growth promoter of sulfur legal system and be equipped with carbon nano fiber with flowing catalyst.Prepare carbon nano fiber with matrix method and spraying process and compare, have that technology is simple, cost is low, easy to prepare, help control, more help mass-produced advantage.
Normal conditions lower substrate method and spraying process can be prepared the carbon fiber of diameter below 100nm, but output and yield are low, and low difficult purification of product purity, and distribution of fiber diameters is inhomogeneous.And the flowing catalyst that combines matrix method and spraying process advantage adds the growth promoter of sulfur method, technology is simple, cost is low, easy to prepare, help control, be more conducive to mass production.At present, yet there are no with the thiophene benzole soln is carbon source and sulphur source, is carrier gas with hydrogen, is catalyst precursor with the ferrocene, successfully prepares report purified, diameter controlled growing nano carbon fiber in 5～500nm under 1373K～1473K in a large number.
The novel method of a large amount of preparation carbon nano fibers provided by the invention--flowing catalyst adds the growth promoter of sulfur method, catalyzer is not attached on the matrix, but introduce reaction chamber together with hydrocarbon gas, process differing temps district finishes the decomposition of catalyzer and hydrocarbon gas, separates out fibrous carbon with nanoscale form on catalyzer.Because the granules of catalyst that decomposites from organic compound can be distributed in the three-dimensional space, so output can be very big in its unit time, but continuous production helps industrialization.Entire reaction course is as follows: experiment is evaporated under the temperature of 473K in a large number with ferrocene, begin to decompose being higher than 673K, along with hydrogen, hydrocarbon compound gas and sulfocompound gas enter the high temperature reaction zone fe that is decomposed out, fe is collision mutually again, and be gathered into ultra-fine grain gradually, when condition suits, begin the VGCNF that grows.Wherein hydrogen divides two-way to feed, and a kind of through the benzene vapour producer, the one tunnel directly enters reaction chamber.The temperature of reaction chamber is by program temperature controller control, rise to 1100 ℃ with 25 ℃/min earlier after, again with 15 ℃/min, be raised to 1200 ℃, constant temperature 45min～1 hour.Add in right amount in the reaction process and contain growth promoter of sulfur, not only can stop the generation of impurity such as decolorizing carbon, carbon black effectively, and can stop the mutual collision of Fe atom, make the Fe particle that is gathered into thinner, be fit to growth VGCNF, increase output and the yield of VGCNF simultaneously greatly.Even add very a spot of growth promoter of sulfur that contains, the VGCNF of acquisition just can increase several times.After reaction finishes, feed N
2Protection when temperature drops to 250 ℃, is taken out product.Entire reaction keeps C
6H
6/ H
2Mol ratio 0.05～0.075, if sulfocompound is a thiophene, then thiophene is dissolved in the benzole soln, thiophene concentration remains on 0.05～1.0%, if sulfocompound is H
2S gas, then H
2The flow that S enters reaction tubes remains on 0.5～1ml/min, and the reaction mixture gas body remains on 0.5～0.75S in the residence time of reaction tubes.In general, when granules of catalyst moderate (2～50nm) time, the hydrocarbon compound gas that is adsorbed on the granules of catalyst surface decomposites carbon atom, carbon atom is dissolved in the granules of catalyst surface, in case the side at granules of catalyst has carbon atom to separate out with the graphite form, so just in the concentration gradient of catalyst particles plastochondria internal memory at carbon, the carbon atom of granules of catalyst opposite side just spreads to offside under the impellent effect of this concentration gradient, separates out carbon fiber.After the granules of catalyst surface was covered fully by carbon, catalyzer lost activity, and fiber stops growing.Characteristics of the present invention: 1. interpolation concentration, the C by growth stimulant such as control sulphur etc.
6H
6/ H
2Mol ratio and a large amount of preparation of mixed gas residence time carbon nano fibers.2. the sulphur in the sulfocompound gas has material impact to the output and the diameter of gained carbon nano fiber.By the control experiment condition, make its granules of catalyst that generates the different diameter size, thereby can prepare the VGCNF of different diameter as required.3. the VGCNF output of Sheng Chenging is big, yield is high, and the carbon yield can reach more than 30%.And the product purity height, diameter Distribution is even.4. add the product that the sulphur method can generate the last two kinds of shapes of macroscopic view with flowing catalyst: film like and bulk.Concrete generative process is as follows: in present method, because there are three temperature-rise periods in ferrocene, ferrocene begins volatilization when 438K, this moment, the ferrocene volatile quantity was fewer, in entering the process of flat-temperature zone, ferrocene decomposites fe, fe is very little owing to colliding the iron grain graininess that is gathered into mutually, when condition was suitable, fiber was with very fast speed growth, and the VGCNF diameter that generates is also very thin, be generally 5nm～20nm, the elongated fiber that moment grows out overlaps mutually and is blown out reaction zone by air-flow, and under the exit end near reaction tubes stops, becomes film.Along with its volatile quantity of rising of ferrocene temperature begins to increase, the mutual impingement area(s) of iron atom that decompose to be generated by ferrocene is gathered into the iron particle and grows up, at this moment Fibre diameter also begins to increase, and the fiber of growth afterwards rests in the stove under the effect of gravity, and the fibre stream mistake that generates after stoping, the fiber of generation rolls up bulk gradually.Like this, the VGCNF that obtains has two kinds of forms in appearance.A kind of is film like " fabric ", extremely thin; A kind of is block, flexible, as shown in drawings.
Below in conjunction with accompanying drawing in detail the present invention is described in detail.
Accompanying drawing 1 is the equipment synoptic diagram of preparation carbon nano fiber.
Accompanying drawing 2 is the photomacrograph of film like product.
Accompanying drawing 3 is the photomacrograph of block product.
Accompanying drawing 4 is the scanned photograph of film like product and block product.
Accompanying drawing 5 is the transmission electron microscope photo of film like product and block product.
Embodiment 1
Device is as accompanying drawing 1.
Carbon benzene flow 30ml/min, thiophene concentration is 0.55%, carrier gas H
2Total flux is 620ml/min, and catalyzer is a ferrocene, and weight is 0.6g.Reaction zone again with 15 ℃/min, rises to 1200 ℃, constant temperature 45min after rising to 1100 ℃ with 25 ℃/min earlier.
Product has two kinds of forms, and a kind of is film like " fabric ", extremely thin; A kind of is block, flexible.Observe under scanning electronic microscope, products obtained therefrom is pure, not carbon black.Observe at the transmission electron microscopy key, can be clear that the existence of hollow tube.And the distribution of fiber diameters of film like product is more even, and many tiny fibers are attached together and become pencil, and its fiber bundle diameters scope is 3～10nm, and also relatively evenly, its diameter range is 40～60nm to the diameter Distribution of block product carbon nano fiber.
Embodiment 2
Device is as accompanying drawing 1.
Carbon benzene flow 40ml/min, thiophene concentration is 1%, carrier gas H
2Total flux is 600ml/min, and catalyzer is a ferrocene, and weight is 0.7g.Reaction zone again with 15 ℃/min, rises to 1200 ℃, constant temperature 45min after rising to 1100 ℃ with 25 ℃/min earlier.
Product has two kinds of forms, and a kind of is film like " fabric ", extremely thin; A kind of is block, flexible.Observe under scanning electronic microscope, products obtained therefrom is pure, not carbon black.At transmission electron microscope observation, can be clear that the existence of hollow tube.And the distribution of fiber diameters of film like product is more even, and many tiny fibers are attached together and become pencil, and its fiber bundle diameters scope is 5～10nm, and also relatively evenly, its diameter range is 80～100nm to the diameter Distribution of block product carbon nano fiber.
Embodiment 3
Device is as accompanying drawing 1.
Carbon benzene flow 36ml/min, thiophene concentration is 0.15%, carrier gas H
2Total flux is 600ml/min, and catalyzer is a ferrocene, and weight is 0.6g.Reaction zone rises to 1100 ℃ with 25 ℃/min earlier; After, again with 15 ℃/min, rise to 1200 ℃, constant temperature 45min.
Product has two kinds of forms, and a kind of is film like " fabric ", extremely thin; A kind of is block, flexible.Observe under scanning electronic microscope, products obtained therefrom is pure, not carbon black.At transmission electron microscope observation, can be clear that the existence of hollow tube.And the distribution of fiber diameters of film like product is more even, and many tiny fibers are attached together and become pencil, and its fiber bundle diameters scope is 3～10nm, and also relatively evenly, its diameter range is 130～150nm to the diameter Distribution of block product carbon nano fiber.
Embodiment 4
Device is as accompanying drawing 1.
Carbon benzene flow 30ml/min, thiophene concentration is 0.55%, carrier gas H
2Total flux is 500mlmin, and catalyzer is a ferrocene, and weight is 0.75g.Reaction zone again with 15 ℃/min, rises to 1200 ℃, constant temperature 45min after rising to 1100 ℃ with 25 ℃/min earlier.
Product has two kinds of forms, and a kind of is film like " fabric ", extremely thin; A kind of is block, flexible.Observe under scanning electronic microscope, products obtained therefrom is pure, not carbon black.At transmission electron microscope observation, can be clear that the existence of hollow tube.And the distribution of fiber diameters of film like product is more even, and many tiny fibers are attached together and become pencil, and its fiber bundle diameters scope is 5～10nm, and also relatively evenly, its diameter range is 145～160nm to the diameter Distribution of block product carbon nano fiber.
Embodiment 5
Device is as accompanying drawing 1.
Carbon benzene flow 40ml/min, thiophene concentration is 0.15%, carrier gas H
2Total flux is 600ml/min, and catalyzer is a ferrocene, and weight is 0.65g.Reaction zone again with 15 ℃/min, rises to 1200 ℃, constant temperature 45min after rising to 1100 ℃ with 25 ℃/min earlier.
Product has two kinds of forms, and a kind of is film like " fabric ", extremely thin; A kind of is block, flexible.Observe under scanning electronic microscope, products obtained therefrom is pure, not carbon black.At transmission electron microscope observation, can be clear that the existence of hollow tube.And the distribution of fiber diameters of film like product is more even, and many tiny fibers are attached together and become pencil, and its fiber bundle diameters scope is 5～10nm, and also relatively evenly, its diameter range is 195～208nm to the diameter Distribution of block product carbon nano fiber.
Embodiment 6
Device is as accompanying drawing 1.
Carbon benzene flow 35ml/min, thiophene concentration is 0.05%, carrier gas H
2Total flux is 600ml/min, and catalyzer is a ferrocene, and weight is 0.7g.Reaction zone again with 15 ℃/min, rises to 1200 ℃, constant temperature 45min after rising to 1100 ℃ with 25 ℃/min earlier.
Product has two kinds of forms, and a kind of is film like " fabric ", extremely thin; A kind of is block, flexible.Observe under scanning electronic microscope, products obtained therefrom is pure, not carbon black.At transmission electron microscope observation, can be clear that the existence of hollow tube.And the distribution of fiber diameters of film like product is more even, and many tiny fibers are attached together and become pencil, and its fiber bundle diameters scope is 5～10nm, and also relatively evenly, its diameter range is 240～255nm to the diameter Distribution of block product carbon nano fiber.
Embodiment 7
Device is as accompanying drawing 1.
Carbon benzene flow 45ml/min, thiophene concentration is 0.15%, carrier gas H
2Total flux is 600ml/min, and catalyzer is a ferrocene, and weight is 0.67g.Reaction zone again with 15 ℃/min, rises to 1200 ℃, constant temperature 45min after rising to 1100 ℃ with 25 ℃/min earlier.
Product has two kinds of forms, and a kind of is film like " fabric ", extremely thin; A kind of is block, flexible.Observe under scanning electronic microscope, products obtained therefrom is pure, not carbon black.At transmission electron microscope observation, can be clear that the existence of hollow tube.And the distribution of fiber diameters of film like product is more even, and many tiny fibers are attached together and become pencil, and its fiber bundle diameters scope is 3～10nm, and also relatively evenly, its diameter range is 300nm to the diameter Distribution of block product carbon nano fiber.
Embodiment 8
Device is as accompanying drawing 1.
Carbon CH
4Flow 240ml/min, H
2The S flow is 0.5ml/min, carrier gas H
2Total flux is 550ml/min, and catalyzer is a ferrocene, and weight is 0.6g.Reaction zone again with 15 ℃/min, rises to 1200 ℃, constant temperature 45min after rising to 1100 ℃ with 25 ℃/min earlier.
Product has two kinds of forms, and a kind of is film like " fabric ", extremely thin; A kind of is block, flexible.Observe under the scanning electron microscopy key, products obtained therefrom is pure, not carbon black.At transmission electron microscope observation, can be clear that the existence of hollow tube.And the distribution of fiber diameters of film like product is more even, and many tiny fibers are attached together and become pencil, and its fiber bundle diameters scope is 5～10nm, and also relatively evenly, its diameter range is 100nm to the diameter Distribution of block product carbon nano fiber.
Embodiment 9
Device is as accompanying drawing 1.
Carbon CH
4Flow 180ml/min, H
2The S flow is 1ml/min, carrier gas H
2Total flux is 600ml/min, and catalyzer is a ferrocene, and weight is 0.6g.Reaction zone again with 15 ℃/min, rises to 1200 ℃, constant temperature 45min after rising to 1100 ℃ with 25 ℃/min earlier.
Product has two kinds of forms, and a kind of is film like " fabric ", extremely thin; A kind of is block, flexible.Observe under scanning electronic microscope, products obtained therefrom is pure, not carbon black.Now examine at transmission electron microscope, can be clear that the existence of hollow tube.And the distribution of fiber diameters of film like product is more even, and many tiny fibers are attached together and become pencil, and its fiber bundle diameters scope is 5～10nm, and also relatively evenly, its diameter range is 70～80nm to the diameter Distribution of block product carbon nano fiber.
Embodiment 10
Device is as accompanying drawing 1.
Carbon CH
4Flow 180ml/min, H
2The S flow is 1ml/min, carrier gas H
2Total flux is 550ml/min, and catalyzer is Ni (Co)
4, weight is 0.55g.Reaction zone again with 15 ℃/min, rises to 1200 ℃, constant temperature 45min after rising to 1100 ℃ with 25 ℃/min earlier.
Product has two kinds of forms, and a kind of is film like " fabric ", extremely thin; A kind of is block, flexible.Observe under scanning electronic microscope, products obtained therefrom is pure, does not conform to carbon black.At transmission electron microscope observation, can be clear that the existence of hollow tube.And the distribution of fiber diameters of film like product is more even, and many tiny fibers are attached together and become pencil, and its fiber bundle diameters scope is 5～10nm, and also relatively evenly, its diameter range is 65nm to the diameter Distribution of block product carbon nano fiber.
Claims (3)
1. method of using growth promoter of sulfur to prepare carbon nano fiber in a large number is with benzene, CH
4, C
2H
2Be carbon source, with ferrocene, Ni (Co)
4Being catalyzer, is carrier gas with hydrogen, helium, nitrogen, it is characterized in that: with sulfocompound such as thiophene, H
2S is a growth stimulant, and the mol ratio of control carbon source and carrier gas is 0.05～0.25, and carbon and sulphur mol ratio are 600～1300: 1, and the mol ratio of catalyzer and carbon source is 0.008～0.015; The thorough mixing under gaseous state with sulfocompound hydrocarbon polymer and catalyzer is at the uniform velocity brought into reaction zone by carrier gas, keeps 0.5～0.075S in reaction zone, growing nano carbon fiber under 1373K～1473K.
2. prepare the method for carbon nano fiber in a large number according to the described use growth promoter of sulfur of claim 1, it is characterized in that: sulfocompound is a thiophene, when carbon source is benzene, when thiophene is dissolved in certain solution thiophene weight concentration 0.05～1.0%.
3. prepare the method for carbon nano fiber according to the described use growth promoter of sulfur of claim 1 in a large number, it is characterized in that: when sulfocompound is H
2During S, H
2The amount that S enters reaction zone is 0.5～1ml/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB991129032A CN1133581C (en) | 1999-05-06 | 1999-05-06 | Process for preparing large-quantity nm-class carbon fibres by using growth promoter of sulfur |
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|---|---|---|---|
| CNB991129032A CN1133581C (en) | 1999-05-06 | 1999-05-06 | Process for preparing large-quantity nm-class carbon fibres by using growth promoter of sulfur |
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| CN1133581C true CN1133581C (en) | 2004-01-07 |
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| CNB991129032A Expired - Fee Related CN1133581C (en) | 1999-05-06 | 1999-05-06 | Process for preparing large-quantity nm-class carbon fibres by using growth promoter of sulfur |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7878449B2 (en) | 2004-06-21 | 2011-02-01 | Ltas Holdings, Llc | Mass transfer system for stabilizing an airship and other vehicles subject to pitch and roll moments |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100387515C (en) * | 2005-05-31 | 2008-05-14 | 财团法人工业技术研究院 | Method for fabricating Nano carbon fibers |
| CN100402419C (en) * | 2006-08-02 | 2008-07-16 | 太原理工大学 | Method of preparing nano-carbon fiber using coal tar asphalt as raw material |
| CN104659377A (en) * | 2013-11-21 | 2015-05-27 | 青岛润鑫伟业科贸有限公司 | Production method of electrode for battery |
| CN110438589A (en) * | 2019-08-15 | 2019-11-12 | 南京林业大学 | A kind of high heat conducting nano carbon fiber production method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56118913A (en) * | 1980-02-26 | 1981-09-18 | Shohachi Kawakado | Preparation of carbon fiber growing in vapor phase in high yield |
| JPS63182415A (en) * | 1987-01-19 | 1988-07-27 | Asahi Chem Ind Co Ltd | Production of carbonaceous fiber |
| JPH0314623A (en) * | 1988-11-07 | 1991-01-23 | Asahi Chem Ind Co Ltd | Production of carbon fiber |
-
1999
- 1999-05-06 CN CNB991129032A patent/CN1133581C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56118913A (en) * | 1980-02-26 | 1981-09-18 | Shohachi Kawakado | Preparation of carbon fiber growing in vapor phase in high yield |
| JPS63182415A (en) * | 1987-01-19 | 1988-07-27 | Asahi Chem Ind Co Ltd | Production of carbonaceous fiber |
| JPH0314623A (en) * | 1988-11-07 | 1991-01-23 | Asahi Chem Ind Co Ltd | Production of carbon fiber |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7878449B2 (en) | 2004-06-21 | 2011-02-01 | Ltas Holdings, Llc | Mass transfer system for stabilizing an airship and other vehicles subject to pitch and roll moments |
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