JPS6312720A - Production of carbon fiber grown in gaseous phase - Google Patents
Production of carbon fiber grown in gaseous phaseInfo
- Publication number
- JPS6312720A JPS6312720A JP15083886A JP15083886A JPS6312720A JP S6312720 A JPS6312720 A JP S6312720A JP 15083886 A JP15083886 A JP 15083886A JP 15083886 A JP15083886 A JP 15083886A JP S6312720 A JPS6312720 A JP S6312720A
- Authority
- JP
- Japan
- Prior art keywords
- gas
- line
- converter
- carbon fiber
- separator
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 31
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 239000007792 gaseous phase Substances 0.000 title abstract 2
- 239000007789 gas Substances 0.000 claims abstract description 67
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 19
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000428 dust Substances 0.000 claims abstract description 17
- 238000011084 recovery Methods 0.000 claims abstract description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 239000011280 coal tar Substances 0.000 claims abstract description 7
- 239000000571 coke Substances 0.000 claims abstract description 7
- 239000006227 byproduct Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 12
- 235000013980 iron oxide Nutrition 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 9
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 claims description 6
- 239000002134 carbon nanofiber Substances 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 239000000498 cooling water Substances 0.000 abstract description 15
- 239000003054 catalyst Substances 0.000 abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- 239000007788 liquid Substances 0.000 abstract description 4
- 238000001816 cooling Methods 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 17
- 229910052799 carbon Inorganic materials 0.000 description 15
- 239000000835 fiber Substances 0.000 description 14
- 239000003921 oil Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 229910000805 Pig iron Inorganic materials 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 150000001454 anthracenes Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 150000003623 transition metal compounds Chemical class 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ZFTFAPZRGNKQPU-UHFFFAOYSA-N dicarbonic acid Chemical compound OC(=O)OC(O)=O ZFTFAPZRGNKQPU-UHFFFAOYSA-N 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- -1 reduction Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000001947 vapour-phase growth Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】 本発明は気相成長炭素Ｇｉ雑の製造方法に関する。[Detailed description of the invention] The present invention relates to a method for producing vapor-grown carbon and Gi miscellaneous.
［従来の技術］
気相成長炭素繊維は、有数物！１ｉｆｔ（ＰＡＮ系、ピ
ッチ系、レーヨン系等）を焼成して得られる炭素繊維に
比べ、機械的性質に優れている。特にこれを黒鉛化した
黒鉛化［は、引張強度として７００ＫＩ／ｍ２、引張弾
性率として７０ｉ／Ｎｘ２という極めて高い値を有して
いる。さらにこの気相成長炭素ｔｉ帷は、その高結晶性
および高配向性のため電気伝導性も高い。従ってその用
途は、構造材料を初めとして電気・電子材料、生体材料
など幅広く、注目すべき素材である。[Conventional technology] Vapor-grown carbon fiber is a leading product! It has superior mechanical properties compared to carbon fiber obtained by firing 1ift (PAN-based, pitch-based, rayon-based, etc.). In particular, the graphitized material has extremely high tensile strength of 700 KI/m2 and tensile modulus of 70 i/Nx2. Furthermore, this vapor-grown carbon Ti film has high electrical conductivity due to its high crystallinity and high orientation. Therefore, its applications are wide-ranging, including structural materials, electrical/electronic materials, and biomaterials, making it a noteworthy material.
気相成長炭素繊維は、従来固定床方式と呼ばれる方法で
製造されていた。この方法は、炉内に設置したムライト
、黒鉛等の基板に、５０〜２００人の粒径をもつ超微細
鉄粒子をシーディングし、この上に１０１０〜１３００
℃の温度で、ベンゼンなどの炭化水素ガス、水素及びキ
ャリヤガスからなる混合ガスを導入して、繊維を製造す
る技術である。しかしこの方法では基板表面の微妙な温
度ムラや、周囲のｍ維の密生度、さらにはガスが導入さ
れる反応管の入口への遠近などにより均一な糸径、ｕＡ
雑長、生成密度等を有する繊維を製造することは困難で
ある。しかも微細粒子の基板への分散、還元、繊維の成
長１次いで繊維の取出しという独立に実施を必要とする
プロセスを含むため、連続的な製造は不可能に近い。Vapor-grown carbon fibers have traditionally been produced using a method called a fixed bed method. In this method, a substrate made of mullite, graphite, etc. placed in a furnace is seeded with ultrafine iron particles with a particle size of 50 to 200 particles, and then ultrafine iron particles with a particle size of 1010 to 1300
This is a technology for manufacturing fibers by introducing a mixed gas consisting of a hydrocarbon gas such as benzene, hydrogen, and a carrier gas at a temperature of ℃. However, with this method, a uniform thread diameter and a
It is difficult to produce fibers having irregular length, production density, etc. Moreover, continuous production is nearly impossible because it involves processes that must be carried out independently: dispersion of fine particles onto a substrate, reduction, fiber growth, and then fiber removal.
これらの欠点を補うため、特開昭６０−５４９９８号及
び同６０−１８５８１１公報に記載された発明は、触媒
として有礪ｉｆｆ移金属化合物を使用する流動床方式に
よる製造方法を採用している。In order to compensate for these drawbacks, the inventions described in JP-A-60-54998 and JP-A-60-185811 adopt a production method using a fluidized bed method using an IFFF transfer metal compound as a catalyst.
この方法は有Ｒｉ！移金属化合物を蒸発させて、気相中
で遷移金属触媒を１能させることが特徴となっている。This method is useful! The feature is that the transition metal compound is evaporated to make the transition metal catalyst functional in the gas phase.
［発明が解決しようとする問題点］
しかしこれらの方法は、大旦生産用の大規模な熱交換器
等の設備投資及び炉内を１０１０〜１３００℃にするた
めの膨大な燃料に係る費用、並びに触媒として非常に高
価な有′ｅ！１遷移金属化合物を用いることなどのため
、安価な製造方法とはいい罷い。[Problems to be Solved by the Invention] However, these methods require large-scale equipment investment such as a heat exchanger for Daitan production, and the cost of a huge amount of fuel to heat the inside of the furnace to 1010 to 1300°C. Also, it is very expensive as a catalyst! Because it uses a single transition metal compound, it is not an inexpensive manufacturing method.
そこで本発明の目的は、気相酸二炭素ｌｌｎを安価にか
つ大量に供給できる製造方法を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a manufacturing method that can supply gaseous dicarbonate lln at low cost and in large quantities.
［問題点を解決するための手段］
本発明においては、これまで製鉄業においてせいぜい燃
料として用いられているにすぎなかった転炉ガスに着目
して、これを炭素繊維の気相成長の熱源として用い、か
つその中にダストとして含まれている鉄酸化物を触媒源
として利用するとともに、転炉ガス回収系を流動床式反
応器として使用することによって上記問題点の解決を図
っている。[Means for Solving the Problems] The present invention focuses on converter gas, which has so far been used only as a fuel in the steel industry, and uses it as a heat source for vapor phase growth of carbon fibers. The above-mentioned problems are solved by using the iron oxide contained in the iron oxide as a catalyst source as a catalyst source, and by using the converter gas recovery system as a fluidized bed reactor.
すなわち、この発明によれば、転炉に設置された転炉ガ
ス回収系内において転炉からの転炉ガスに水素含有ガス
を導入して該転炉ガス中にダストとして含まれている鉄
酸化物を順次金属鉄に還元し触媒を生成する。次いで転
炉ガス回収系内に炭素繊維原料を導入して金属鉄触媒と
接触させ炭素繊維を成長させる。That is, according to the present invention, hydrogen-containing gas is introduced into the converter gas from the converter in the converter gas recovery system installed in the converter to remove iron oxidation contained in the converter gas as dust. A catalyst is produced by sequentially reducing substances to metallic iron. Next, the carbon fiber raw material is introduced into the converter gas recovery system and brought into contact with the metal iron catalyst to grow carbon fibers.
以下添附図面を参照して、本発明をさらに詳しく説明す
る。The present invention will be described in more detail below with reference to the accompanying drawings.
添附図面は、本発明の方法を実施するために用いられる
転炉ガス回収系を示している。The accompanying drawings show a converter gas recovery system used to carry out the method of the invention.
銑鉄の精練に用いる転炉１の転炉ガス排出口には排ガス
ライン１３が取付けられている。ライン１３の中途には
転炉側から順に水素含有ガス（還元ガス）導入管２１及
び炭素繊維原料導入管１４及び冷却水導入管１５が設け
られている。ライン１３の冷却水導入管１５との接続箇
所からさらに進んだところに気水分離機６が設けられて
いる。An exhaust gas line 13 is attached to a converter gas outlet of a converter 1 used for refining pig iron. In the middle of the line 13, a hydrogen-containing gas (reducing gas) introduction pipe 21, a carbon fiber raw material introduction pipe 14, and a cooling water introduction pipe 15 are provided in order from the converter side. A steam-water separator 6 is provided further from the connection point of the line 13 with the cooling water introduction pipe 15.
この分［１６には気体成分の流路１６が接続している。A gas component flow path 16 is connected to this portion [16].
この流路１６はガスホルダー（図示せず）に通じており
、途中にフィルター２１を介してブロア１１が設置され
ている。他方気水分離機６に接続した液体成分の流路１
７はデカンタ−７に通じている。デカンタ−７には分離
された冷却水をライン１３に導入する前記
導入管１５の他端が接続している。デカンタ−７の底部
に接続したもう一つの流路１８は分Ｍｔ’１８に通じて
いる。この分１１１ｉ１８には炭素ｍＮの回収路１つと
ダス［−の回収炉２０が接続している。This flow path 16 communicates with a gas holder (not shown), and a blower 11 is installed with a filter 21 interposed therebetween. On the other hand, the liquid component flow path 1 connected to the steam/water separator 6
7 leads to decanter 7. The other end of the introduction pipe 15 for introducing the separated cooling water into the line 13 is connected to the decanter 7. Another channel 18 connected to the bottom of the decanter 7 leads to the minute Mt'18. One carbon mN recovery path and a das[- recovery furnace 20 are connected to this portion 111i18.
転炉１において銑鉄の酸化精練時に発生する転炉ガスに
は、鉄酸化物を含む微細なダストが含有されている。通
常転炉ガス中には鉄酸化物が１．０〜１．５％の割合で
含まれている。この転炉ガスはブロア１１の吸引により
排出口から排ガスライン１３に導入される。転炉ガスは
、通常１０〜１５万Ｎｒｒｔ３の流量で吸引する。ライ
ン１３の入口２においては転炉ガスの温度は１４００℃
以上であり、転炉内に吹き込まれた酸素の濃度は４％以
下になっている。酸素の濃度が低いことは後に行うダス
ト中の鉄酸化物の還元に都合がよい。転炉ガスは、ライ
ン１３内を進むにつれて冷却されていく。転炉ガスの温
度が１１００〜１４００℃になる箇所に水素含有ガス導
入管２１を設けておき、これを通して０．５〜５．０Ｎ
ＴｒＬ３の流量で水素含有ガス３を吹き込む。Converter gas generated during oxidation and scouring of pig iron in the converter 1 contains fine dust containing iron oxides. Normally, iron oxide is contained in the converter gas at a rate of 1.0 to 1.5%. This converter gas is introduced into the exhaust gas line 13 from the discharge port by suction by the blower 11 . Converter gas is usually sucked in at a flow rate of 100,000 to 150,000 Nrrt3. At the inlet 2 of line 13, the temperature of the converter gas is 1400°C.
As above, the concentration of oxygen blown into the converter is 4% or less. A low concentration of oxygen is convenient for the later reduction of iron oxides in the dust. The converter gas is cooled as it travels through the line 13. A hydrogen-containing gas introduction pipe 21 is provided at a location where the temperature of the converter gas is 1100 to 1400°C, and a 0.5 to 5.0 N
Hydrogen-containing gas 3 is blown in at a flow rate of TrL3.
水素含有ガス中の水素ガスの含有割合は２０％以上、好
ましくは５０％以上がよい。これにはコークス炉ガスを
用いると大量生産に都合がよい。この処理によって転炉
ガスにダストとして含まれている鉄酸化物（主にＦｅＯ
からなり、他にＦｅ２Ｏ３を含む。）を金属鉄に還元し
、炭素繊維製造のための触媒として用いる。この場合鉄
酸化物の粒径は０．００５〜１．０μｍであるが、この
粒径は炭素ｔ［の成長に適している。The content of hydrogen gas in the hydrogen-containing gas is preferably 20% or more, preferably 50% or more. The use of coke oven gas is convenient for mass production. This treatment removes iron oxides (mainly FeO) contained in the converter gas as dust.
It also contains Fe2O3. ) is reduced to metallic iron and used as a catalyst for carbon fiber production. In this case, the particle size of the iron oxide is 0.005 to 1.0 μm, which is suitable for the growth of carbon t[.
次に炭素繊維原料導入管１４を通じて炭素ａｌＮ原料４
を５〜２０ｔ／ｈの流量で吹き込み、上記金属鉄触媒と
接触させ炭素繊維を気相成長させる。Next, the carbon alN raw material 4 is passed through the carbon fiber raw material introduction pipe 14.
is blown at a flow rate of 5 to 20 t/h, and brought into contact with the metal iron catalyst to grow carbon fibers in a vapor phase.
炭素繊維の成長のためには、反応温度は１０１０〜１２
００℃がよいので、導入管１４の位置をそれに合せて設
定する。この結果はぼ瞬時に炭素繊維が成長する。For carbon fiber growth, the reaction temperature is between 1010 and 12
Since a temperature of 00° C. is preferable, the position of the introduction tube 14 is set accordingly. As a result, carbon fibers grow almost instantly.
炭素繊維原料としては炭化水素その他あらゆる有礪化合
物が用いられるが、収率の観点から芳香族化合物が好ま
しい。特にコークス炉からの副産物である粗軽油類、ナ
フタリン、中油、アントラセン油、重油、ピッチ及びコ
ールタール並びにこれらの水素化物、及びこれらの混合
物は、ベンゼンに比べて非常に安価で、しかも大量に供
給することが可能である。ざらにヘテロ原子を含有する
ものも使用可能であり、特に硫黄を含有するチオフェン
類、チオール類及びチオフェノール類を用いると、生成
速度が速く有用である。Although hydrocarbons and all other solid compounds can be used as carbon fiber raw materials, aromatic compounds are preferred from the viewpoint of yield. In particular, crude light oils, naphthalene, middle oil, anthracene oil, heavy oil, pitch and coal tar, their hydrides, and mixtures thereof, which are by-products from coke ovens, are much cheaper than benzene and can be supplied in large quantities. It is possible to do so. Those containing heteroatoms can also be used, and sulfur-containing thiophenes, thiols, and thiophenols are particularly useful because of their rapid production rate.
こうして成長した炭素繊維を含む転炉ガスを、デカンタ
−７からの冷却水５で１００℃以下に冷却する。これに
より、微細な綿状の炭素！ｌ維が、未反応鉄酸化物を含
むダストとともに冷却水によって補促される。The converter gas containing the carbon fibers thus grown is cooled to 100° C. or lower with cooling water 5 from the decanter 7. This creates fine cotton-like carbon! The fibers are supplemented by cooling water along with dust containing unreacted iron oxides.
しかる後、転炉ガスと炭素繊維およびダストを含む冷却
水とを気水分離機６で分離し、転炉ガスはブロア１１に
より流路１６を通じフィルター２２を介してガスホルダ
ーに移送される。他方、分離された冷却水は、デカンタ
−７により水とダストおよび炭素繊維の混合物とに分離
される。回収された水は冷却水導入管１５から排ガスラ
イン１３内に循環される。また、分離されたダストおよ
び炭素繊維の混合物は、流路１８から分離］８に導入さ
れ、炭素繊維とダストとに分離される。Thereafter, the converter gas and cooling water containing carbon fibers and dust are separated by a steam separator 6, and the converter gas is transferred by a blower 11 through a flow path 16 to a gas holder via a filter 22. On the other hand, the separated cooling water is separated into water, dust, and a mixture of carbon fibers by a decanter 7. The recovered water is circulated into the exhaust gas line 13 from the cooling water introduction pipe 15. Further, the separated mixture of dust and carbon fibers is introduced from the flow path 18 into the separation section 8, where it is separated into carbon fibers and dust.
分離された炭素繊維９は回収路１９から回収され、また
ダスト１０は回収路２０から回収される。The separated carbon fibers 9 are recovered from a recovery path 19, and the dust 10 is recovered from a recovery path 20.
［実施例コ
以下に図面に示した装置を用いた本発明の詳細な説明す
る。[Embodiment] The present invention will be described in detail below using the apparatus shown in the drawings.
ＬＵＬ二
２５０ト＞転炉１から生ずる転炉ガスを、１０万ＮＴｒ
Ｌ３／ｈの流量で排ガス回収ライン１３に導入した。こ
の際ライン１３の入口２における温度は１４５０℃であ
り、酸素の濃度は３％に低下していた。転炉ガスはライ
ン１３中を進むにつれて冷却されていった。排ガスの温
度が１３００℃になったところで、転炉ガスに対して１
０容量％のコークス炉ガス（水素含有ガス）３を導入し
た。LUL2250 > converter gas generated from converter 1 to 100,000 NTr
It was introduced into the exhaust gas recovery line 13 at a flow rate of L3/h. At this time, the temperature at the inlet 2 of the line 13 was 1450° C., and the oxygen concentration had decreased to 3%. The converter gas was cooled as it progressed through line 13. When the exhaust gas temperature reaches 1300℃, 1
0% by volume of coke oven gas (hydrogen-containing gas) 3 was introduced.
その直後、排ガスとの反応温度が１１００℃程度になる
ように吹き込み位置と流量を調整しながら。Immediately after that, while adjusting the blowing position and flow rate so that the reaction temperature with the exhaust gas is about 1100°C.
転炉ガス１ＮＴｒＬ３に対し１．７７Ｋｇの割合に相当
するコールタール４を吹き込んだ。この結果的０．１秒
で微細な綿状の炭素［１１ｆｆｉが生成した。Coal tar 4 corresponding to a ratio of 1.77 kg was blown into the converter gas 1 NTrL3. As a result, fine flocculent carbon [11ffi] was generated in 0.1 seconds.
炭素繊維を含む排ガスは、次に冷却水５で冷却し１００
℃以下にした。次にこの炭素繊維、排ガス及びダストを
含んだ冷却水を気水分離機６で気水分離した。分離され
た炭素繊維とダストを含んだ冷却水はデカンタ−７に移
し、ここで炭素繊維９とダスト１０からなる混合物を冷
却水から分離した。混合物を除いた冷却水５は、回収し
て再度使用した。混合物は分離８１８により、炭素ｍ維
９とダスト１０に分離し、炭素繊維を回収した。The exhaust gas containing carbon fibers is then cooled with cooling water 5 and
below ℃. Next, the cooling water containing the carbon fibers, exhaust gas, and dust was separated into steam and water by a steam-water separator 6. The cooling water containing the separated carbon fibers and dust was transferred to a decanter 7, where a mixture of carbon fibers 9 and dust 10 was separated from the cooling water. The cooling water 5 from which the mixture was removed was collected and used again. The mixture was separated into carbon fibers 9 and dust 10 by separation 818, and the carbon fibers were recovered.
こうして１回の仕込みについて、原料のコールタールに
対して１２％の収率で綿状の炭素ｌ！帷が得られた。こ
の繊維を２８００℃で黒鉛化したところ、糸径０．−３
μｍ、糸長５００μｍの黒鉛化繊維が得られた。また破
断面は同心円構造を有していた。この黒鉛化ｍ雑の引張
強度は５１０に９／１、メ
実施例１と同様な設備並びに水素含有ガス及び炭素ＩＩ
Ｉ！原料の吹き込み条件下において、コールタールの代
りに粗軽油０．８５に９を吹き込んだ。In this way, for one charge, the yield of 12% of the raw material coal tar is 1 flocculent carbon! A veil was obtained. When this fiber was graphitized at 2800°C, the yarn diameter was 0. -3
Graphitized fibers with a yarn length of 500 μm were obtained. Moreover, the fracture surface had a concentric structure. The tensile strength of this graphitized material was 510 to 9/1, using the same equipment as in Example 1, hydrogen-containing gas, and carbon II.
I! Under the raw material blowing conditions, 9 was blown into 0.85 of crude light oil instead of coal tar.
その結果原料の粗軽油に対して１０％の収率で綿状の炭
素ｔｆｉ維が得られた。この繊維を２８００℃で黒鉛化
したところ、糸径０．２μｍ１糸長３００μｍの黒鉛化
繊維が（停られた。この黒鉛（ヒ繊帷の引張強度は５１
０ Ｋｌ／ ｔｎｒａ２、引張弾性率は６０ｔ／ＨＲ２
であった。As a result, flocculent carbon TFI fibers were obtained at a yield of 10% based on the crude light oil used as the raw material. When this fiber was graphitized at 2800°C, a graphitized fiber with a thread diameter of 0.2 μm and a thread length of 300 μm was obtained.The tensile strength of this graphite fiber was 51
0 Kl/tnra2, tensile modulus is 60t/HR2
Met.
友ｍ
実施例１と同様な設備並びに水素含有ガス及び炭素！Ｉ
Ｎ原料の吹き込み条件下において、コールタールの代り
に水添アントラセン油１．９に９を吹き込んだ。その結
果原料の水添アントラセン油に対して１３％の収率で綿
状の炭素１Ｇ維が得られた。Friend m Same equipment as Example 1, hydrogen-containing gas and carbon! I
Under the conditions of N raw material blowing, 9 was blown into hydrogenated anthracene oil 1.9 instead of coal tar. As a result, cotton-like carbon 1G fibers were obtained at a yield of 13% based on the raw material hydrogenated anthracene oil.
このｌ！帷を２８００℃で黒鉛化したところ、糸径０．
３μｍ、糸長６００μｍの黒鉛化４Ｇ維が得られた。こ
の黒鉛化ｍ維の引張強度は７００匈／ｓ＋２、引張弾性
率は７０ｔ／ｍ２であった。This l! When the cloth was graphitized at 2800°C, the yarn diameter was 0.
Graphitized 4G fibers of 3 μm and yarn length of 600 μm were obtained. The graphitized m-fiber had a tensile strength of 700/s+2 and a tensile modulus of 70 t/m2.
［発明の効果］
以上説明したように、本発明によれば、転炉ガス回収系
を流動床式反応器として利用し、転炉ガスの顕熱を炭素
ｔｌａｌｌの熱源とに利用しているので、大量生産によ
って気相成長炭素ｕＡＮを製造する際に新たに設備投資
をしたり、あらたに熱源を設置することが不要になる。[Effects of the Invention] As explained above, according to the present invention, the converter gas recovery system is used as a fluidized bed reactor, and the sensible heat of the converter gas is used as a heat source for carbon tlall. , Mass production eliminates the need for new equipment investment or new heat source installation when manufacturing vapor-grown carbon uAN.
また、転炉ガス中にダストとして含まれる鉄酸化物を水
素を含有するガスで還元することにより安価な金属触媒
を得ることができる。したがって気相成長炭素を安価に
製造することが可能になる。In addition, an inexpensive metal catalyst can be obtained by reducing iron oxides contained in converter gas as dust with a hydrogen-containing gas. Therefore, it becomes possible to manufacture vapor-grown carbon at low cost.
図は本発明の方法を実施する上で用いて好適な転炉ガス
回収系の概略図である。
１・・・・・・転炉、３・・・・・・水素含有ガス、４
・・・・・・炭素繊維原料、５・・・・・・冷却水、６
・・・・・・気水分離機、７・・・・・・デカンタ−１
８・・・・・・分離類、１１・・・・・・ブロア。The figure is a schematic diagram of a converter gas recovery system suitable for use in carrying out the method of the present invention. 1...Converter, 3...Hydrogen-containing gas, 4
...Carbon fiber raw material, 5...Cooling water, 6
...Sea water separator, 7 ... Decanter 1
8... Separation, 11... Blower.
Claims (3)
転炉からの転炉ガスに水素含有ガスを導入して該転炉ガ
ス中にダストとして含まれている鉄酸化物を順次金属鉄
に還元し、しかる後該転炉ガス回収系内に炭素繊維原料
を導入して該金属鉄と接触させ炭素繊維を成長させるこ
とを特徴とする気相成長炭素繊維の製造方法。(1) In the converter gas recovery system installed in the converter, hydrogen-containing gas is introduced into the converter gas from the converter to sequentially remove iron oxides contained in the converter gas as dust. A method for producing vapor-grown carbon fiber, which comprises reducing the carbon fiber to metallic iron, and then introducing a carbon fiber raw material into the converter gas recovery system and bringing it into contact with the metallic iron to grow carbon fiber.
ールタールである特許請求の範囲第１項記載の方法(2) The method according to claim 1, wherein the hydrocarbon is coal tar, which is a byproduct from a coke oven.
求の範囲第１項記載の方法。(3) The method according to claim 1, wherein the hydrogen-containing gas is coke oven gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15083886A JPS6312720A (en) | 1986-06-27 | 1986-06-27 | Production of carbon fiber grown in gaseous phase |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15083886A JPS6312720A (en) | 1986-06-27 | 1986-06-27 | Production of carbon fiber grown in gaseous phase |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6312720A true JPS6312720A (en) | 1988-01-20 |
Family
ID=15505482
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15083886A Pending JPS6312720A (en) | 1986-06-27 | 1986-06-27 | Production of carbon fiber grown in gaseous phase |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6312720A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01290570A (en) * | 1988-05-18 | 1989-11-22 | Showa Denko Kk | Production of carbon-fiber formed heat insulating material |
| JPH0280619A (en) * | 1988-09-12 | 1990-03-20 | Nkk Corp | Production of carbon fiber |
| JPH02165512A (en) * | 1988-12-16 | 1990-06-26 | Kitagawa Kogyo Kk | Flat cable |
-
1986
- 1986-06-27 JP JP15083886A patent/JPS6312720A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01290570A (en) * | 1988-05-18 | 1989-11-22 | Showa Denko Kk | Production of carbon-fiber formed heat insulating material |
| JPH0280619A (en) * | 1988-09-12 | 1990-03-20 | Nkk Corp | Production of carbon fiber |
| JPH02165512A (en) * | 1988-12-16 | 1990-06-26 | Kitagawa Kogyo Kk | Flat cable |
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