JPH03137098A - Production of silicon carbide whisker - Google Patents
Production of silicon carbide whiskerInfo
- Publication number
- JPH03137098A JPH03137098A JP27155289A JP27155289A JPH03137098A JP H03137098 A JPH03137098 A JP H03137098A JP 27155289 A JP27155289 A JP 27155289A JP 27155289 A JP27155289 A JP 27155289A JP H03137098 A JPH03137098 A JP H03137098A
- Authority
- JP
- Japan
- Prior art keywords
- group
- silicon carbide
- catalyst
- metals
- carbide whiskers
- 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
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 229910010271 silicon carbide Inorganic materials 0.000 title description 3
- 229910052751 metal Inorganic materials 0.000 claims abstract description 40
- 239000002184 metal Substances 0.000 claims abstract description 40
- 239000003054 catalyst Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 31
- KHDSWONFYIAAPE-UHFFFAOYSA-N silicon sulfide Chemical compound S=[Si]=S KHDSWONFYIAAPE-UHFFFAOYSA-N 0.000 claims abstract description 26
- 150000002739 metals Chemical class 0.000 claims abstract description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 11
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 8
- 239000011733 molybdenum Substances 0.000 claims abstract description 8
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 4
- 239000010941 cobalt Substances 0.000 claims abstract description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052802 copper Inorganic materials 0.000 claims abstract description 4
- 239000010949 copper Substances 0.000 claims abstract description 4
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052762 osmium Inorganic materials 0.000 claims abstract description 3
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 3
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 3
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 3
- 239000010948 rhodium Substances 0.000 claims abstract description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 3
- 239000010937 tungsten Substances 0.000 claims abstract description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 20
- 239000004480 active ingredient Substances 0.000 claims description 3
- 229910052702 rhenium Inorganic materials 0.000 claims description 2
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 2
- 230000009257 reactivity Effects 0.000 abstract description 3
- 239000012808 vapor phase Substances 0.000 abstract 2
- GRLYPOPFNDQSKV-UHFFFAOYSA-N rhenium ruthenium Chemical compound [Ru].[Re] GRLYPOPFNDQSKV-UHFFFAOYSA-N 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 25
- 238000006243 chemical reaction Methods 0.000 description 22
- 239000012159 carrier gas Substances 0.000 description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- -1 silicon halide compound Chemical class 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 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 5
- 229910052863 mullite Inorganic materials 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000011151 fibre-reinforced plastic Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000012779 reinforcing material Substances 0.000 description 3
- 238000010532 solid phase synthesis reaction Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 2
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000011226 reinforced ceramic Substances 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910000519 Ferrosilicon Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002483 hydrogen compounds Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000019086 sulfide ion homeostasis Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、繊維強化プラスチックス（ＦＲＰ） 、繊維
強化金属（ＦＲＭ）あるいは繊維強化セラミックス（Ｆ
ＲＣ）等の各種複合材料の補強材として有用な炭化ケイ
素ウィスカーの製造方法に関するものであり、さらに詳
しくは、特定の金属成分を組み合わせた多元触媒を使用
した気相法による製造方法に関する。Detailed Description of the Invention [Field of Industrial Application] The present invention is applicable to fiber reinforced plastics (FRP), fiber reinforced metals (FRM) or fiber reinforced ceramics (FRM).
The present invention relates to a method for producing silicon carbide whiskers useful as reinforcing materials for various composite materials such as RC), and more specifically, to a method for producing silicon carbide whiskers using a gas phase method using a multi-component catalyst in which specific metal components are combined.
［従来の技術］
炭化ケイ素ウィスカーは、高い強度と弾性率を有し、高
温における金属との反応性が低い、酸化性雰囲気下での
耐熱性が高い、溶融金属との濡れ性がよいなど、複合材
料の補強材として優れた特性を有してあり、広い分野に
おいて活用が期待されている材料である。[Prior Art] Silicon carbide whiskers have high strength and elastic modulus, low reactivity with metals at high temperatures, high heat resistance in oxidizing atmospheres, and good wettability with molten metals. It has excellent properties as a reinforcing material for composite materials, and is a material that is expected to be used in a wide range of fields.
従来、炭化ケイ素ウィスカーの製造方法として、固体状
の炭素及びケイ素化合物を反応させる固相法、あるいは
ハロゲン化ケイ素化合物又は硫化ケイ素と炭素化合物の
ガス状混合物を水素気流中で反応させる気相法など種々
の方法か知られている。Conventionally, methods for producing silicon carbide whiskers include a solid phase method in which solid carbon and a silicon compound are reacted, and a gas phase method in which a gaseous mixture of a silicon halide compound or a silicon sulfide and a carbon compound is reacted in a hydrogen stream. Various methods are known.
固相法の例としては、もみ穀圧とカーボンブラックを、
非酸化性雰囲気中で１，３００〜１，７００℃で加熱、
反応させる方法（特開昭５７−２０９８１３など）があ
る。As an example of the solid phase method, rice grain pressure and carbon black are
Heating at 1,300-1,700°C in a non-oxidizing atmosphere,
There is a reaction method (such as Japanese Patent Application Laid-Open No. 57-209813).
また、気相法の例としては、金属又は金属化合物を気体
状で４００℃以上の反応器に導入し、同時に該反応器に
シラン化合物と炭化水素系化合物とを含有するガスを導
入することにより、該反応器中で炭化ケイ素ウィスカー
を生成させる方法（特開昭６１−２５７０００など）が
挙げられる。Further, as an example of the gas phase method, a metal or a metal compound is introduced in a gaseous state into a reactor at a temperature of 400°C or higher, and at the same time, a gas containing a silane compound and a hydrocarbon compound is introduced into the reactor. , a method of producing silicon carbide whiskers in the reactor (Japanese Unexamined Patent Publication No. 61-257000, etc.).
さらに、硫化ケイ素と炭化水素化合物を気相で反応させ
る方法が研究されており（江頭ら、窯業協会誌封、５３
５〜５４０（１９８５） ） 、この方法の改良法とし
て特開昭６３−２０６３９９及び特開昭６３−３１９３
００には、硫化ケイ素ガスを１，１３０〜］ 、５００
℃に保持された反応器にキャリヤガスを介して導入し、
空間に浮遊した生成様の存在下に炭化水素化合物と接触
させることにより炭化ケイ素ウィスカーを析出、成長さ
せる方法が提案されている。また、この方法においては
、生成核材として鉄、ニッケル、チタン、マンガン、コ
バルト、銅、バナジウム、クロム、アルミニウム及びシ
リコンなどの金属又はその化合物を使用することも開示
されている。Furthermore, a method of reacting silicon sulfide and hydrocarbon compounds in the gas phase has been studied (Egashira et al., Ceramics Association Journal, 53).
5-540 (1985)), and improved methods of this method are disclosed in JP-A-63-206399 and JP-A-63-3193.
00 contains silicon sulfide gas from 1,130 to 500
introduced via a carrier gas into a reactor maintained at °C;
A method has been proposed in which silicon carbide whiskers are precipitated and grown by bringing them into contact with a hydrocarbon compound in the presence of a product suspended in space. This method also discloses the use of metals such as iron, nickel, titanium, manganese, cobalt, copper, vanadium, chromium, aluminum, and silicon, or compounds thereof, as nucleating materials.
［発明が解決しようとする課題］
前記従来技術のうち、固相法による方法では、反応温度
が高い、粒状の炭化ケイ素が多量に副生ずる、未反応の
原料が残ることによる炭化ケイ素ウィスカーの純度低下
、などの問題点があった。[Problems to be Solved by the Invention] Among the above-mentioned conventional techniques, in the solid phase method, the reaction temperature is high, a large amount of granular silicon carbide is produced as a by-product, and the purity of silicon carbide whiskers is reduced due to the unreacted raw material remaining. There were problems such as a decline in
また、気相法については金属及び核材を用い、空間中で
炭化ケイ素ウィスカーを連続的に製造し得る点において
工業的価値が認められる。しかしながら、ハロゲン化ケ
イ素を用いる方法では、原料が高価で取り扱いも難しい
という問題があり、また、硫化ケイ素を用いる方法も炭
化ケイ素ウィスカーの収率は高々６０％程度であり、工
業的にはなお不十分であった。Furthermore, the gas phase method has industrial value in that it can continuously produce silicon carbide whiskers in space using a metal and a core material. However, the method using silicon halide has the problem that the raw material is expensive and difficult to handle, and the method using silicon sulfide has a yield of silicon carbide whiskers of about 60% at most, which is still unsuitable for industrial use. That was enough.
本発明の目的は、前記従来技術の問題点を解決し、高品
質の炭化ケイ素ウィスカーを高い収率で得ることができ
る工業的に有利な製造方法を提供することにある。An object of the present invention is to solve the problems of the prior art described above and to provide an industrially advantageous manufacturing method capable of obtaining high quality silicon carbide whiskers at a high yield.
［課題を解決するための手段］
本発明者らは、硫化ケイ素と炭化水素化合物との反応に
より炭化ケイ素ウィスカーを製造する方法について鋭意
検討の結果、特定の金属成分を組み合わせた多元触媒を
使用することにより前記目的が達成できることを見出し
、本発明を完成した。[Means for Solving the Problems] As a result of intensive study on a method for producing silicon carbide whiskers by the reaction between silicon sulfide and a hydrocarbon compound, the present inventors used a multi-component catalyst combining specific metal components. The inventors have discovered that the above object can be achieved by doing so, and have completed the present invention.
本発明は、炭化水素化合物及び硫化ケイ素を原料とし、
気相法により炭化ケイ素ウィスカーを製造する方法にお
いて、触媒として■族金属に属する鉄、ニッケル、コバ
ルト、ルテニウム、ロジウム、パラジウム、オスミウム
、イリジウム、白金、及びＩＢ金金属属する銅よりなる
群（Ａ群）から選ばれる二種以上の金属とモリブデン、
ルテニウム、レニウム及びタングステンよりなる群（Ｂ
群）から選ばれる一種以上の金属とを有効成分とする多
元触媒を使用することを特徴とする炭化ケイ素ウィスカ
ーの製造方法である。The present invention uses hydrocarbon compounds and silicon sulfide as raw materials,
In a method for producing silicon carbide whiskers by a gas phase method, a group consisting of iron, nickel, cobalt, ruthenium, rhodium, palladium, osmium, iridium, platinum, and copper belonging to IB gold metals, which belong to Group I metals, is used as a catalyst. ) and molybdenum,
The group consisting of ruthenium, rhenium and tungsten (B
This is a method for producing silicon carbide whiskers, which is characterized by using a multi-component catalyst containing as an active ingredient one or more metals selected from group 1).
本発明の方法においては、触媒として前記金属成分を担
体上に混合担持させた多元触媒を使用する。In the method of the present invention, a multi-component catalyst in which the aforementioned metal components are mixed and supported on a carrier is used as a catalyst.
この多元触媒は各金属成分の単体金属又はこれらの金属
の酸化物、炭化物、硫化物、ハロゲン化物、硫酸塩、硝
酸塩などの無機化合物あるいは数式Ｍ（Ｃ２Ｈ５）ｎで
表されるメタロセンなどの有機金属化合物を担体上に混
合付着させたのち熱分解及び／又は還元により各金属の
混合物あるいは一部合金の形で担持させたものである。This multi-component catalyst is a single metal of each metal component, an inorganic compound such as an oxide, carbide, sulfide, halide, sulfate, or nitrate of these metals, or an organic metal such as a metallocene represented by the formula M(C2H5)n. After the compounds are mixed and deposited on a carrier, they are supported in the form of a mixture or a partial alloy of each metal by thermal decomposition and/or reduction.
各金属の使用割合は、Ｂ群の金属に対するＡ群の金属の
比率がモル比で０．５〜１０．０かつＡ群中の最大成分
が残りの成分に対して１０．０以下の比率となるような
範囲が好ましい。金属成分の構成比率が前記の範囲を外
ねると反応率が低くなり、炭化ケイ素ウィスカーの収率
が低下するので好ましくない。これらの多元触媒の中で
Ａ群の金属として鉄（Ｆｅ）およびニッケル（Ｎｉ）を
使用し、Ｂ群の金属としてモリブデン（ＭＯ）を使用し
た三元触媒が、反応性も高く、取り扱いも容易で特に優
れた組み合わせである。The ratio of each metal to be used is such that the ratio of Group A metal to Group B metal is 0.5 to 10.0 in molar ratio, and the ratio of the largest component in Group A to the remaining components is 10.0 or less. It is preferable that the range is as follows. If the composition ratio of the metal components is outside the above range, the reaction rate will be low and the yield of silicon carbide whiskers will be reduced, which is not preferable. Among these multi-way catalysts, three-way catalysts that use iron (Fe) and nickel (Ni) as group A metals and molybdenum (MO) as group B metals have high reactivity and are easy to handle. This is a particularly excellent combination.
触媒を担持させる担体の材質としては、炭化ケイ素ウィ
スカーの生成反応に悪影響を及ぼすものでなければ特に
制限は無く、アルミナ、ムライト等のセラミックス材料
あるいは黒鉛、ガラス状炭素等の炭素材料などが用いら
れるが、その中でムライト系のセラミックス等の５ｉｎ
２成分を含有する材料が特に好適である。これは、材料
の構成成分の一部である５ｉｎ２が炭化ケイ素ウィスカ
ーの生成に好結果を与えるためと推定される。担体の形
状は、炭化ケイ素ウィスカーがこの担体を基板として生
成し、成長するので、あとの生成物の単離の容易な表面
形状のものが好ましい。通常は反応器の器壁をそのまま
利用すればよく、反応容積を大きくする場合にはムライ
ト製ボールなどの簡単な構造の充填物を入れるか、管状
の反応器を組み合わせた多管反応器を使用すればよい。There is no particular restriction on the material of the carrier on which the catalyst is supported, as long as it does not adversely affect the formation reaction of silicon carbide whiskers, and ceramic materials such as alumina and mullite, or carbon materials such as graphite and glassy carbon are used. However, among them, 5 inches of mullite ceramics etc.
Particularly suitable are materials containing two components. This is presumed to be because 5in2, which is a part of the constituent components of the material, gives good results to the formation of silicon carbide whiskers. Since silicon carbide whiskers are generated and grown using this carrier as a substrate, the carrier preferably has a surface shape that facilitates isolation of the subsequent product. Normally, the wall of the reactor can be used as is, but if the reaction volume is to be increased, a simple packing such as mullite balls can be used, or a multi-tubular reactor combined with tubular reactors can be used. do it.
本発明の方法において硫化ケイ素と共に原料として使用
する炭化水素化合物としては、メタン、エタン、プロパ
ン等のパラフィン系炭化水素化合物、エチレン、プロピ
レン等のオレフィン系炭化水素化合物、アセチレン、ア
リレン等のアセチレン系炭化水素化合物、ベンゼン、ト
ルエン等の芳香族炭化水素化合物、シクロパラフィン、
シクロオレフィン等の脂環族炭化水素化合物あるいはこ
れらの混合物が挙げられる。このうち、反応効率やウィ
スカーの収率などの点から、メタン、エタン、プロピレ
ン等の低分子量の炭化水素化合物を用いるのが望ましい
。また、これらの炭化水素化合物は気体の形でキャリヤ
ガスと共に系内に導入して反応させるが、炭化水素化合
物の物性あるいは取扱、装置上の制約などで気体での供
給が不都合な場合には液体あるいは反応に悪影響を与え
ない溶媒の溶液としてキャリヤガスと共に反応器内へ供
給し、同装置内で気化させてもよい。Hydrocarbon compounds used as raw materials together with silicon sulfide in the method of the present invention include paraffin hydrocarbon compounds such as methane, ethane, and propane, olefin hydrocarbon compounds such as ethylene and propylene, and acetylene hydrocarbon compounds such as acetylene and arylene. Hydrogen compounds, aromatic hydrocarbon compounds such as benzene and toluene, cycloparaffins,
Examples include alicyclic hydrocarbon compounds such as cycloolefins and mixtures thereof. Among these, from the viewpoint of reaction efficiency and whisker yield, it is desirable to use low molecular weight hydrocarbon compounds such as methane, ethane, and propylene. In addition, these hydrocarbon compounds are introduced into the system together with a carrier gas in the form of a gas and reacted, but if it is inconvenient to supply them in the form of a gas due to the physical properties of the hydrocarbon compound, handling, or restrictions on equipment, liquid Alternatively, it may be supplied into the reactor together with a carrier gas as a solution of a solvent that does not adversely affect the reaction, and vaporized within the same apparatus.
もう一つの原料である硫化ケイ素は、あらかじめフェロ
シリコンと硫黄を反応させる等の方法で製造したものを
加熱気化させ、キャリヤガスと共に系内に導入すること
によって供給される。あるいは、この硫化ケイ素は、金
属ケイ素を反応器の１ 、０００〜１，４００℃に維持
された導入管の先端部に保持し、キャリヤガスで希釈さ
れた硫化水素ガスを反応させ反応器内に導入することに
よって生成が可能であり、本反応器以外に硫化ケイ素の
製造装置や気化装置を設ける必要がなく、効率よく操作
をすすめることかできる。Silicon sulfide, which is another raw material, is supplied by heating and vaporizing a product produced in advance by reacting ferrosilicon and sulfur, etc., and introducing it into the system together with a carrier gas. Alternatively, this silicon sulfide can be produced by holding metal silicon at the tip of an inlet tube maintained at 1,000 to 1,400°C in a reactor, and reacting hydrogen sulfide gas diluted with a carrier gas into the reactor. Production is possible by introducing silicon sulfide, and there is no need to provide a silicon sulfide production device or vaporization device other than this reactor, and the operation can be carried out efficiently.
炭化水素化合物と硫化ケイ素の使用割合は、硫化ケイ素
１モルに対し炭化水素化合物１〜１０モルの範囲が好ま
しい。炭化水素化合物のモル比が１未満では反応率が低
くなり、また、１０モル比を超えても反応率はそれ以上
向上せず、炭化水素化合物のロスが多くなるので好まし
くない。The ratio of the hydrocarbon compound and silicon sulfide used is preferably in the range of 1 to 10 moles of hydrocarbon compound per 1 mole of silicon sulfide. If the molar ratio of the hydrocarbon compound is less than 1, the reaction rate will be low, and if it exceeds 10 molar ratio, the reaction rate will not improve any further and the loss of the hydrocarbon compound will increase, which is not preferable.
炭化水素化合物及び硫化ケイ素を反応器へ導入するため
のキャリヤガスとしては、窒素のような活性の低いガス
または不活性ガスで希釈されていてもよい水素などの還
元性ガスを用いるが、このうち水素ガスまたは水素と窒
素の混合ガスが特に好ましい。As a carrier gas for introducing hydrocarbon compounds and silicon sulfide into the reactor, a reducing gas such as hydrogen, which may be diluted with a less active gas such as nitrogen or an inert gas, is used. Particularly preferred is hydrogen gas or a mixed gas of hydrogen and nitrogen.
本発明の方法で使用する反応装置としては特に限定はさ
れないが、例えば、第１図に示すような炭化水素化合物
、硫化ケイ素及び触媒成分の導入管と排ガスの導出管を
具えた反応管を、縦型の電気炉中に設置した構成のもの
が好適に用いられる。該反応装置の材質については、容
器内部か１．０００℃以上の高温になるため例えばムラ
イト及びアルミナなどの耐熱性の材料を用いることがで
きる。また導入管、導出管の材質としては例えばアルミ
ナが使用できる。Although the reaction apparatus used in the method of the present invention is not particularly limited, for example, a reaction tube equipped with an inlet tube for hydrocarbon compounds, silicon sulfide, and catalyst components and an outlet tube for exhaust gas as shown in FIG. A structure installed in a vertical electric furnace is preferably used. As for the material of the reactor, heat-resistant materials such as mullite and alumina can be used, since the inside of the container reaches a high temperature of 1.000° C. or more. Further, as the material for the inlet pipe and the outlet pipe, for example, alumina can be used.
次に本発明の製造方法をプロセスに従って説明する。Next, the manufacturing method of the present invention will be explained according to the process.
先ず、反応に先立ち、反応器内に触媒を担持させる。触
媒の担持方法としては、前記各金属の単体又はその金属
化合物を１，１００〜１，４００℃の高温度に保持され
た反応器内へ導入し、担体上へ担持させる。この場合、
フェロセン、ニラケロセン、二硫化モリブデン等の昇華
性のある物質は蒸気圧を利用し、加熱状態で窒素等の不
活性ガスや水素等の還元性ガスをキャリヤガスとして系
内に導入して担持させる。蒸気圧の低い化合物の場合に
は溶液あるいはスラリーの形で反応器内へ噴霧する方法
が好適である。各成分はそれぞれ単独で反応器内へ導入
してもよいが、あらかじめ混合した状態で導入してもよ
い。各種化合物の形で反応器内へ担持された金属成分は
還元性キャリヤガスによって還元され、金属の形で触媒
作用を示すものと思われる。First, prior to the reaction, a catalyst is supported in a reactor. As a method for supporting the catalyst, each of the above-mentioned metals or their metal compounds are introduced into a reactor maintained at a high temperature of 1,100 to 1,400°C, and supported on a carrier. in this case,
Sublimable substances such as ferrocene, kerosene, and molybdenum disulfide are supported by using vapor pressure and introducing an inert gas such as nitrogen or a reducing gas such as hydrogen as a carrier gas into the system under heating. In the case of compounds with low vapor pressure, it is preferable to spray them into the reactor in the form of a solution or slurry. Each component may be introduced into the reactor individually, or may be introduced in a pre-mixed state. It is believed that the metal components supported in the reactor in the form of various compounds are reduced by the reducing carrier gas and exhibit catalytic activity in the form of metals.
触媒の使用量は、反応させる硫化ケイ素１モルに対し金
属成分の合計量で０．０００２〜０．００１モルが好ま
しい。使用量が０．０００２モル未満では反応が速やか
に進行せず、またｏ、ｏｏｔモルを超えてもそれ以上の
効果はない。The amount of the catalyst used is preferably 0.0002 to 0.001 mol in total of the metal components per 1 mol of silicon sulfide to be reacted. If the amount used is less than 0.0002 mol, the reaction will not proceed quickly, and if it exceeds o or oot mol, there will be no further effect.
次に反応帯域の温度を１，１３０〜１，５００℃、好ま
しくは１，２００〜１，４００℃とした反応器内へ原料
の炭化水素化合物及び硫化ケイ素を導入して反応を開始
させる。炭化水素化合物はキャリヤガスとともに反応器
内へ導入される。また硫化ケイ素は前述のようにあらか
じめ調整し加熱気化させたものをキャリヤガスによって
反応器へ導入するか、あるいは、反応器の導入管先端部
に固定した金属ケイ素にキャリヤガスで希釈した硫化水
素ガスを反応させて導入する。Next, the raw material hydrocarbon compound and silicon sulfide are introduced into a reactor whose reaction zone temperature is 1,130 to 1,500°C, preferably 1,200 to 1,400°C, to start the reaction. Hydrocarbon compounds are introduced into the reactor along with a carrier gas. In addition, silicon sulfide can be prepared in advance as described above and heated and vaporized before being introduced into the reactor using a carrier gas, or hydrogen sulfide gas diluted with a carrier gas can be added to metal silicon fixed at the tip of the introduction tube of the reactor. react and introduce.
反応器内へ導入する原料混合物の濃度及び通ガス速度は
反応器の大きさ、形状、反応温度等の他の条件との組合
わせで適宜室められる。通常、原料混合物及びキャリヤ
ガスを含む全ガス中の硫化ケイ素の濃度は１〜５ｍｏｌ
’ｌ；、炭化水素化合物の濃度は５〜３０ ｒｎｏ１９
６の範囲とするのが好ましい。The concentration of the raw material mixture introduced into the reactor and the gas passing rate are determined as appropriate in combination with other conditions such as the size, shape, and reaction temperature of the reactor. Usually, the concentration of silicon sulfide in the total gas including the raw material mixture and carrier gas is 1 to 5 mol.
'l;, the concentration of hydrocarbon compounds is 5-30 rno19
It is preferable to set it as the range of 6.
原料混合物の反応帯域における滞留時間を左右する通ガ
ス速度は、０．Ｏｆ＋〜０．２４ｃｍ／ｓｅｃとする。The gas passing rate, which determines the residence time of the raw material mixture in the reaction zone, is 0. Of+ to 0.24 cm/sec.
通ガス速度が０．０６ｃｆｆｌ／ｓｅｃ未満では単位時
間当たりの炭化ケイ素ウィスカーの生成量が少なく、ま
た、０．２４ｃｍ７ｓｅｃを超えると炭化ケイ素ウィス
カーの収率が大幅に低下するので好ましくない。If the gas passing rate is less than 0.06 cffl/sec, the amount of silicon carbide whiskers produced per unit time is small, and if it exceeds 0.24 cm/7 sec, the yield of silicon carbide whiskers will decrease significantly, which is not preferable.
本発明の方法によって得られる炭化ケイ素ウィスカーは
、ウィスカー中に触媒粒子の混入がほとんどなく高純度
で、平均直径が０．１〜１．０μｍ、長さ２０〜３００
μｍ１かつアスペクト比１００以上の形状を有しており
、繊維強化プラスチックス、繊維強化金属あるいは繊維
強化セラミックス等の各！４複合材料の補強材として好
適である。The silicon carbide whiskers obtained by the method of the present invention have high purity with almost no catalyst particles mixed in the whiskers, have an average diameter of 0.1 to 1.0 μm, and a length of 20 to 300 μm.
It has a shape of μm1 and an aspect ratio of 100 or more, and is made of fiber-reinforced plastics, fiber-reinforced metals, fiber-reinforced ceramics, etc. 4 Suitable as a reinforcing material for composite materials.
以下、実施例により本発明の方法をさらに具体的に説明
する。Hereinafter, the method of the present invention will be explained in more detail with reference to Examples.
［実施例１．２及び比較例１，２］
第１図に示すような、縦型電気炉１中に、上、下端をシ
リコンゴム栓２，３でシールした内径５２ｍｍ、長さ１
，５００ ｍｍのムライト製反応管４を設置し、内径１
０１Ｉｌｆｆｌのアルミナ管を上端のゴム栓に４本（導
入管５〜８）、下端のゴム栓に１本（排ガス導出管９）
取り付けたものを反応器とした。[Example 1.2 and Comparative Examples 1 and 2] A vertical electric furnace 1 as shown in FIG.
, 500 mm mullite reaction tube 4 was installed, and the inner diameter was 1.
Four alumina tubes of 01Iffl are attached to the rubber plugs at the upper end (inlet pipes 5 to 8), and one to the rubber plug at the lower end (exhaust gas outlet pipe 9).
The attached item was used as a reactor.
［触媒の調製］
反応器を第２図に示すような温度分布となるように加熱
しておき、充分量のフェロセン及びニラケロセンを５０
１の容器中に入れ、６０℃に加温しておき、キャリヤガ
スとして５０ ｍｌ／ｍｉｎの水素を３０分間通すこと
によって気化フェロセン及びニラケロセンを導入管５か
ら反応器内へ導入し、反応管内壁に所定量の鉄及びニッ
ケルを担持させた。モリブデン成分については、予め二
硫化モリブデンを導入管７の先端部に固定しておき、こ
の先端部を約１，１００℃の温度域に保持し、フェロセ
ン及びニラケロセンと同時に、導入管７から２５１１／
ｍｉｎの窒素ガスを３０分かけて導入することにより反
応器内へ導入し、担持させた。[Preparation of Catalyst] A reactor was heated so that the temperature distribution was as shown in Figure 2, and a sufficient amount of ferrocene and nilakerosene was added at 50°C.
1 and heated to 60°C, vaporized ferrocene and nirakerosene were introduced into the reactor through the introduction tube 5 by passing hydrogen at 50 ml/min as a carrier gas for 30 minutes, and the inner wall of the reaction tube was heated. was made to support a predetermined amount of iron and nickel. Regarding the molybdenum component, molybdenum disulfide is fixed in advance at the tip of the introduction tube 7, and this tip is maintained at a temperature range of approximately 1,100°C.
It was introduced into the reactor by introducing nitrogen gas of min. over 30 minutes, and was supported.
［反応］
触媒を担持させ、第２図のような温度分布に加熱された
反応器内に、気体状のメタン及び硫化ケイ素（ＳｉＳ）
をキャリヤガスとともに２時間を要して導入し、反応さ
せた。メタンは２０ ｍｌ／＋ｕｉｎのメタンガスを１
１５ｍｌ／ｗｉｎの水素ガスと共に導入管６より導入し
、硫化ケイ素は、導入管８の先端部に金属ケイ素を固定
しておき、この先端部を１，２００℃の温度域に保持し
、導入管８より３１ＩＩｌ／ｍ１ｒ１の硫化水素と１５
ｍｌ／ｍｉｎの水素の混合ガスを導入することにより硫
化ケイ素を生成させながら導入した。[Reaction] Gaseous methane and silicon sulfide (SiS) are placed in a reactor in which a catalyst is supported and heated to a temperature distribution as shown in Figure 2.
was introduced together with a carrier gas over a period of 2 hours and allowed to react. For methane, add 20 ml/+uin of methane gas to 1
Silicon sulfide is introduced from the introduction tube 6 together with 15 ml/win of hydrogen gas. Metallic silicon is fixed at the tip of the introduction tube 8, and this tip is maintained in a temperature range of 1,200°C. 8 to 31 IIl/ml hydrogen sulfide and 15
By introducing a mixed gas of hydrogen at a rate of ml/min, silicon sulfide was introduced while being generated.
反応終了後、室温まで冷却し、生成したウィスカーを回
収した。得られた生成物は、Ｘ線回折測定の結果、β型
の炭化ケイ素ウィスカーであることが確認された。After the reaction was completed, the mixture was cooled to room temperature and the generated whiskers were collected. As a result of X-ray diffraction measurement, the obtained product was confirmed to be β-type silicon carbide whiskers.
触媒の使用比率を変えた実施例及び比較例の結果を表１
に示す。表１の結果から、本発明の多元触媒を使用すれ
ば、従来知られていた単一あるいは２成分触媒に比較し
て著しく高い収率で炭化ケイ素ウィスカーが得られるこ
とがわかる。なお、ここで示した収率は、次の式により
計算した。Table 1 shows the results of examples and comparative examples in which the ratio of catalyst used was changed.
Shown below. The results in Table 1 show that silicon carbide whiskers can be obtained in significantly higher yields by using the multi-component catalyst of the present invention than by conventionally known single or two-component catalysts. Note that the yield shown here was calculated using the following formula.
収率（’り ＝ （（Ｓａｃウィスカー収ｆｆ１）／（
消費Ｓｉ量から計算したＳｉＣ量））Ｘ１００表１
［実施例３］
二硫化モリブデンの代りに塩化ルテニウムを使用し、窒
素ガスの流量を１０ ｍｌ／ｎ＋ｉｎとした他は実施例
１と同様に操作し、炭化ケイ素ウィスカーを製造した。Yield ('ri = ((Sac whisker yield ff1)/(
Amount of SiC calculated from the amount of Si consumed)) and produced silicon carbide whiskers.
担持された塩化ルテニウム、フェロセン及びニラケロセ
ンの量はそれぞれ０゜９ｍｇ 。The amount of supported ruthenium chloride, ferrocene and nilakerosene was 0.9 mg each.
０．８ ｍｇ及び０．８ｍｇで、Ｒｕ：Ｆｅ：Ｎｉのモ
ル比率は１：１＝１であった。得られた炭化ケイ素ウィ
スカーの平均径は０．３μｍ、平均長さ６０μ田で収率
は８６．５％であった。At 0.8 mg and 0.8 mg, the molar ratio of Ru:Fe:Ni was 1:1=1. The obtained silicon carbide whiskers had an average diameter of 0.3 μm, an average length of 60 μm, and a yield of 86.5%.
［発明の効果］
本発明の方法によれば、従来の方法に比較して不純物の
混入の少ない炭化ケイ素ウィスカーを高収率で得ること
ができる。また、−度担持させた触媒は、生成したウィ
スカーを回収したのち、そのまま繰り返し使用が可能で
あり、本発明の方法は工業的に極めて有利な方法という
ことができる。[Effects of the Invention] According to the method of the present invention, silicon carbide whiskers with less contamination of impurities can be obtained in high yield compared to conventional methods. Further, the catalyst supported on the catalyst can be used repeatedly as it is after collecting the generated whiskers, and the method of the present invention can be said to be an extremely advantageous method from an industrial perspective.
第１図は、本発明で使用する反応器の１例を示す装置の
断面図である。
１・・・縦型電気炉 ２，３００．シリョンゴム栓
４・・・反応管 ５〜８・・・導入管９・・・
排ガス導出管
第２図は、実施例において加熱された反応器内の温度分
布を示すグラフである。FIG. 1 is a sectional view of an apparatus showing one example of a reactor used in the present invention. 1... Vertical electric furnace 2,300. Rubber stopper 4...Reaction tube 5-8...Introduction tube 9...
Exhaust gas outlet pipe FIG. 2 is a graph showing the temperature distribution inside the heated reactor in the example.
Claims (3)
法により炭化ケイ素ウィスカーを製造する方法において
、触媒としてＶIII族金属に属する鉄、ニッケル、コバ
ルト、ルテニウム、ロジウム、パラジウム、オスミウム
、イリジウム、白金及びＩＢ金属に属する銅よりなる群
（Ａ群）から選ばれる二種以上の金属とモリブデン、ル
テニウム、レニウム及びタングステンよりなる群（Ｂ群
）から選ばれる一種以上の金属とを有効成分として含有
する多元触媒を使用することを特徴とする炭化ケイ素ウ
ィスカーの製造方法。(1) In a method for producing silicon carbide whiskers by a gas phase method using hydrocarbon compounds and silicon sulfide as raw materials, iron, nickel, cobalt, ruthenium, rhodium, palladium, osmium, iridium, and platinum belonging to group VIII metals are used as catalysts. and two or more metals selected from the group consisting of copper belonging to the IB metals (group A) and one or more metals selected from the group consisting of molybdenum, ruthenium, rhenium, and tungsten (group B) as active ingredients. A method for producing silicon carbide whiskers, characterized by using a multi-component catalyst.
モル数に換算して（Ａ群）／（Ｂ群）＝０．５〜１０．
０かつＡ群中の最大成分のモル数が残りの成分のモル数
に対して１０．０以下の比率である請求項（１）に記載
の方法。(2) The ratio of the groups to which the metals used in the multi-component catalyst belong is (Group A)/(Group B) = 0.5 to 10 in terms of the number of moles of metal.
The method according to claim 1, wherein the number of moles of the largest component in Group A is 10.0 or less with respect to the number of moles of the remaining components.
成分から成る三元触媒である請求項（１）に記載の方法
。(3) The method according to claim 1, wherein the multi-way catalyst is a three-way catalyst comprising molybdenum, iron and nickel as active ingredients.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27155289A JPH03137098A (en) | 1989-10-20 | 1989-10-20 | Production of silicon carbide whisker |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27155289A JPH03137098A (en) | 1989-10-20 | 1989-10-20 | Production of silicon carbide whisker |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03137098A true JPH03137098A (en) | 1991-06-11 |
Family
ID=17501660
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27155289A Pending JPH03137098A (en) | 1989-10-20 | 1989-10-20 | Production of silicon carbide whisker |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03137098A (en) |
-
1989
- 1989-10-20 JP JP27155289A patent/JPH03137098A/en active Pending
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