JPH0483706A - Production of boron nitride - Google Patents
Production of boron nitrideInfo
- Publication number
- JPH0483706A JPH0483706A JP19669090A JP19669090A JPH0483706A JP H0483706 A JPH0483706 A JP H0483706A JP 19669090 A JP19669090 A JP 19669090A JP 19669090 A JP19669090 A JP 19669090A JP H0483706 A JPH0483706 A JP H0483706A
- Authority
- JP
- Japan
- Prior art keywords
- carbon
- compound
- boron
- boron nitride
- mixture
- 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
- 229910052582 BN Inorganic materials 0.000 title claims abstract description 24
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 40
- 150000001639 boron compounds Chemical class 0.000 claims abstract description 39
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 36
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 239000008187 granular material Substances 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 10
- -1 diborane Chemical compound 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 150000001722 carbon compounds Chemical class 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 18
- 239000000843 powder Substances 0.000 abstract description 8
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 abstract description 7
- 239000004327 boric acid Substances 0.000 abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 abstract description 3
- KUGSJJNCCNSRMM-UHFFFAOYSA-N ethoxyboronic acid Chemical compound CCOB(O)O KUGSJJNCCNSRMM-UHFFFAOYSA-N 0.000 abstract description 2
- MLSKXPOBNQFGHW-UHFFFAOYSA-N methoxy(dioxido)borane Chemical compound COB([O-])[O-] MLSKXPOBNQFGHW-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011363 dried mixture Substances 0.000 abstract 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 abstract 1
- 239000011369 resultant mixture Substances 0.000 abstract 1
- 238000005121 nitriding Methods 0.000 description 21
- 238000000034 method Methods 0.000 description 15
- 239000006229 carbon black Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920006184 cellulose methylcellulose Polymers 0.000 description 1
- 239000006231 channel black Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000002023 wood Substances 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、ほう素化合物と炭素及び／又は炭素化合物と
の混合物を窒素雰囲気下で窒化して窒化ほう素を製造す
る方法に関し、更に詳述するとほう素化合物と炭素及び
／又は炭素化合物との混合方法を改良して純度の良い窒
化ほう素を製造する方法に関する。Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a method for producing boron nitride by nitriding a mixture of a boron compound and carbon and/or a carbon compound in a nitrogen atmosphere. Specifically, the present invention relates to a method for producing boron nitride of high purity by improving the method of mixing a boron compound with carbon and/or a carbon compound.
〔従来の技術及び発明が解決しようとする課題〕従来よ
り、ほう素化合物と炭素及び／又は炭素化合物との混合
物を竪型炉やトンネル型の棚積式式プッシャー炉を用い
て連続的に窒素雰囲気下で窒化する方法が知られている
（特開昭６０１５５０７号公報）。[Prior art and problems to be solved by the invention] Conventionally, a mixture of boron compounds and carbon and/or carbon compounds has been continuously heated with nitrogen using a vertical furnace or a tunnel-type shelf-type pusher furnace. A method of nitriding in an atmosphere is known (Japanese Unexamined Patent Publication No. 6015507).
しかし、従来の方法は、ほう素化合物と炭素及び／又は
炭素化合物とを各々粉末で単純に混合していたため、連
続的に窒化する方法ではほう素化合物粉末と炭素及び／
又は炭素化合物粉末との混合物が比重の違い等により不
均質になり易く、このため窒化後の窒化ほう素粉末中に
未反応の炭素が残留することがあり、窒化ほう素の純度
を低下させる原因になっていた。しかも、混合後の粉末
を窒化する際、窒化温度がほう素化合物の融点よりはる
かに高いためにほう素化合物が溶融して流れ出してしま
い、混合物の表面積が減少し、窒素との接触面積が減少
する結果、反応が十分に進行しなくなり、この点でも未
反応物が残り易いものであった。また二の場合、この傾
向は窒化時に１つの容器に仕込む量が増えるほど顕著に
あられれ。However, in the conventional method, the boron compound and the carbon and/or carbon compound were simply mixed in powder form.
Alternatively, the mixture with carbon compound powder tends to become inhomogeneous due to differences in specific gravity, etc., and for this reason, unreacted carbon may remain in the boron nitride powder after nitriding, which causes a decrease in the purity of boron nitride. It had become. Moreover, when the mixed powder is nitrided, the nitriding temperature is much higher than the melting point of the boron compound, so the boron compound melts and flows out, reducing the surface area of the mixture and the contact area with nitrogen. As a result, the reaction did not proceed sufficiently, and unreacted substances tended to remain in this respect as well. In the second case, this tendency becomes more pronounced as the amount charged into one container increases during nitriding.
これを防くためには仕込量を制限する必要かあるので、
生産性の低下を招いていた。In order to prevent this, it is necessary to limit the amount of preparation.
This was causing a decline in productivity.
これらの不具合を防止するため、ほう素化合物と炭素及
び／又は炭素化合物との混合物にポリビニルアルコール
水溶液等を加えて、この混合物をペレット化する方法が
知られているが、この方法は水を用いるために水溶液が
増粘し、炭素及び／又は炭素化合物との混合物との濡れ
が悪く、均一に混合できないという問題がある上、水分
の蒸発に多くの熱量を要し、不経済であった。In order to prevent these problems, a method is known in which an aqueous polyvinyl alcohol solution or the like is added to a mixture of a boron compound and carbon and/or a carbon compound, and this mixture is pelletized, but this method uses water. This causes the aqueous solution to thicken, resulting in poor wettability with the mixture with carbon and/or carbon compounds, making it impossible to mix uniformly. In addition, a large amount of heat is required to evaporate water, making it uneconomical.
一方、ほう素化合物をアンモニア等の還元性雰囲気下で
加熱して窒化ほう素を得る方法では上述した問題が生し
ないが、反応が低温で行なわれるため高結晶性の粉末を
得ることが難しく、このため窒化終了後に生成物を再加
熱するなどの対策が必要であった。On the other hand, the method of obtaining boron nitride by heating a boron compound in a reducing atmosphere such as ammonia does not cause the above-mentioned problems, but it is difficult to obtain highly crystalline powder because the reaction takes place at a low temperature. Therefore, it was necessary to take measures such as reheating the product after nitriding.
本発明は上記事情に鑑みなされたもので、ほう素化合物
と炭素及び／又は炭素化合物との混合物を窒素雰囲気下
で窒化して窒化ほう素を製造する方法において、炭素等
が未反応物として残留することを可及的に防止し、高品
質な窒化ほう素粉末を生産性良く得ることのできる窒化
ほう素の製造方法を提供することを目的とする。The present invention was made in view of the above circumstances, and is a method for producing boron nitride by nitriding a mixture of a boron compound and carbon and/or a carbon compound in a nitrogen atmosphere, in which carbon, etc. remain as unreacted substances. It is an object of the present invention to provide a method for producing boron nitride that can prevent such problems as much as possible and obtain high-quality boron nitride powder with good productivity.
〔課題を解決するための手段及び作用〕本発明者は上記
目的を達成するため鋭意検討を重ねた結果、ほう素化合
物と炭素及び／又ｌ′！炭素化合物とを該ほう素化合物
の一部又は全部が溶解可能な有機溶媒と共に混合し、こ
れを乾燥造粒してほう素化合物と炭素、炭素化合物との
混合顆粒を窒素雰囲気下で加熱して窒化ほう素を得るこ
とが有効であることを知見した。[Means and effects for solving the problem] As a result of intensive studies to achieve the above object, the present inventors discovered that boron compounds, carbon and/or l'! A carbon compound is mixed with an organic solvent in which part or all of the boron compound can be dissolved, and this is dried and granulated, and the mixed granules of the boron compound, carbon, and the carbon compound are heated in a nitrogen atmosphere. It was found that it is effective to obtain boron nitride.
即ち、ほう酸等のほう素化合物とカーボンブラック等の
炭素や炭素化合物とをメタノール等の有機溶媒と共に混
合することにより、原料の混合カニ湿式で行なわれ、ま
た、原料の一つであるほう素化合物の一部又は全部が有
機溶媒中に溶けた状態であるため、水を用いた場合と異
なり溶液の増粘もなく、粘度が低いため、均一に原料を
混合することができ、特に炭素源としてカーボンブラン
クを用いた場合、従来の水溶液と異なり濡れが良く、し
かもカーボンブラックの比重がほう酸等のほう素化合物
に比へて極端に小さいため、通常の混合方法ではカーボ
ンブラックとほう酸等のほう素化合物との均一な混合が
望めないものであったが、カーホンブラックとほう酸等
のほう素化合物とをメタノール等の有機溶媒と共に混合
した場合、有機溶媒中のほう素化合物が乾燥時にカーホ
ンブラックを核として析出するため、カーボンブラック
の表面をほう素化合物が十分に濡らした状態となること
を知見した。更に、上述したように従来の混合粉末を用
いる窒化方法では、窒化温度がほう素化合物の融点をは
るかに超えるため、ほう素化合物が溶融して流れ出てし
まい、混合物の表面積が減少し、このため窒素との接触
面積が減少し反応が十分に進行しなくなり、未反応物が
残り易いものであったが、上述した有機溶媒による湿式
混合後の原料を顆粒状とすることにより、ほう素化合物
が溶融しても十分な表面積を有し、従って窒化の反応が
十分に進行し、このため−ボート内の原料の仕込量を増
やした場合にも炭素等の未反応物が残らず、生産性が向
上すると共に、得られる窒化ほう素が高品質であること
を見い出し、本発明をなすに至ったものである
従って、本発明は、ほう素化合物と炭素及び／又は炭素
化合物との混合物を窒素雰囲気下に加熱して、窒化ほう
素化合物を製造する方法において、ほう素化合物の一部
又は全部を有機溶媒に溶解すると共に、該溶液に炭素及
び／又は炭素化合物を混合し、次いでこれを乾燥、造粒
してほう素化合物と炭素及び／又は炭素化合物との混合
顆粒を製造し、この顆粒を窒素雰囲気下に加熱するよう
にしたことを特徴とする窒化ほう素の製造方法を提供す
る。That is, the raw material is wet-mixed by mixing a boron compound such as boric acid and carbon or a carbon compound such as carbon black with an organic solvent such as methanol. Because part or all of it is dissolved in an organic solvent, there is no thickening of the solution unlike when water is used, and the viscosity is low, so raw materials can be mixed uniformly, and it is especially useful as a carbon source. When carbon blank is used, unlike conventional aqueous solutions, it has good wettability, and the specific gravity of carbon black is extremely small compared to boron compounds such as boric acid. However, when carbon black and a boron compound such as boric acid are mixed together with an organic solvent such as methanol, the boron compound in the organic solvent becomes carbon black when dried. It was discovered that the boron compound precipitates as a nucleus, so that the surface of the carbon black is sufficiently wetted with the boron compound. Furthermore, as mentioned above, in the conventional nitriding method using mixed powder, the nitriding temperature far exceeds the melting point of the boron compound, so the boron compound melts and flows out, reducing the surface area of the mixture. The contact area with nitrogen was reduced, the reaction did not proceed sufficiently, and unreacted substances tended to remain. However, by making the raw materials into granules after wet mixing with the above-mentioned organic solvent, the boron compound can be reduced. It has a sufficient surface area even when melted, so the nitriding reaction progresses sufficiently, and therefore even when the amount of raw materials charged in the boat is increased, no unreacted substances such as carbon remain, increasing productivity. The inventors have discovered that the obtained boron nitride is of high quality and has led to the present invention. Therefore, the present invention provides a method for preparing a mixture of a boron compound and carbon and/or a carbon compound in a nitrogen atmosphere. In the method of manufacturing a boron nitride compound by heating below, part or all of the boron compound is dissolved in an organic solvent, carbon and/or a carbon compound is mixed in the solution, and then this is dried, A method for producing boron nitride is provided, characterized in that mixed granules of a boron compound and carbon and/or a carbon compound are produced by granulation, and the granules are heated in a nitrogen atmosphere.
以下、本発明について更に詳しく説明する。The present invention will be explained in more detail below.
本発明の窒化ほう素の製造方法は、上述したように原料
としてほう素化合物と炭素及び／又は炭素化合物とを有
機溶媒を用いて湿式混合し、これを乾燥造粒した顆粒を
使用するものである。As described above, the method for producing boron nitride of the present invention uses granules obtained by wet-mixing a boron compound and carbon and/or carbon compound as raw materials using an organic solvent, and drying and granulating the mixture. be.
ここで、ほう素化合物としては、例えばほう酸、無水ほ
う酸、ジボランやエチルボレート、メチルボレート等の
有機ほう窒化合物類を挙げることができるが、これらの
中でほう酸が最も好適に用いられる。Examples of the boron compound include organic boron compounds such as boric acid, boric anhydride, diborane, ethyl borate, and methyl borate, and among these, boric acid is most preferably used.
また、炭素又は炭素化合物としては、例えば通常のアセ
チレンブラック、チャンネルブラック等のカーボンブラ
ック、グラファイト等の炭素や木炭、木粉、タール、ピ
ッチ、あるいはフェノール樹脂、ポリエチレン、ポリス
チレン等の合成高分子物質等が挙げられるが、製品純度
と経済性からカーボンブラックが好適に用いられる。Examples of carbon or carbon compounds include carbon black such as ordinary acetylene black and channel black, carbon such as graphite, charcoal, wood flour, tar, pitch, and synthetic polymer substances such as phenol resin, polyethylene, and polystyrene. However, carbon black is preferably used in terms of product purity and economical efficiency.
また、ほう素化合物と炭素及び／又は炭素化合物の混合
割合は、元素重量比Ｂ／Ｃで０．６〜１．２の範囲が採
用される。Ｃに対するＢの重量が０．６よりも小さいと
、反応後の残留カーボンが多くなり、一方、Ｂの混合割
合が１．２よりも大きいと窒化反応前のほう素化合物の
還元反応が不充分となり、ひいては窒化が充分に進行せ
ず、収率が低下してしまうので、上記重量範囲割合が好
ましく、更に好ましい割合は０．６〜］であ０゜
なお、本発明の方法においては、窒化反応をより効率的
にするため、通常の窒化反応に使用される触媒、例えば
鉄、コバルト、ニッケル、カルシウム、マグネシウム、
マンガン、モリブデン等の金属あるいはこれらの酸化物
、炭酸化合物等の金属化合物の常用量が上記原料化合物
に混用できる。Moreover, the mixing ratio of the boron compound and carbon and/or carbon compound is in the range of 0.6 to 1.2 in element weight ratio B/C. If the weight of B to C is less than 0.6, there will be a large amount of carbon remaining after the reaction, while if the mixing ratio of B is greater than 1.2, the reduction reaction of the boron compound before the nitriding reaction will be insufficient. As a result, the nitriding does not proceed sufficiently and the yield decreases. Therefore, the above weight range ratio is preferable, and the more preferable ratio is 0.6 to 0. To make the reaction more efficient, catalysts used in common nitriding reactions, such as iron, cobalt, nickel, calcium, magnesium,
Conventional amounts of metals such as manganese and molybdenum or metal compounds such as their oxides and carbonate compounds can be mixed with the above raw material compounds.
次に、有機溶媒としては、上述したほう素化合物の一部
又は全部が溶解可能なものを使用するものであり、例え
ばメタノール、エタノール、プロパツール、インプロパ
ツール、ブタノール、イソブタノール、ヘプタツール、
オクタツール、グリセリン等の脂肪族アルコール、ベン
ジルアルコール、フェネチルアルコール等の芳香族アル
コールなどが挙げられるが、これらのなかではメタノー
ルが、粘度が低く、カーボンとの濡れや分散性も良く、
沸点も低いため扱い易く、しかも経済的であるので、最
も好適に用いられる。Next, the organic solvent used is one in which some or all of the boron compounds mentioned above can be dissolved, such as methanol, ethanol, propatool, impropatol, butanol, isobutanol, heptatool,
Examples include aliphatic alcohols such as octatool and glycerin, and aromatic alcohols such as benzyl alcohol and phenethyl alcohol, but among these, methanol has a low viscosity and has good wettability and dispersibility with carbon.
It has a low boiling point, is easy to handle, and is economical, so it is most preferably used.
本発明においては、上述したほう素化合物と炭素及び／
又は炭素化合物とを上述した有機溶媒と共に混合し、こ
れを乾燥造粒した顆粒を窒化原料とするものである。In the present invention, the above-mentioned boron compound and carbon and/or
Or a carbon compound is mixed with the above-mentioned organic solvent, and granules obtained by drying and granulating the mixture are used as the nitriding raw material.
ここで、有機溶媒の使用量は、ほう素化合物の一部又は
全部を溶解して炭素や炭素化合物と均一に混合できれば
良く、特に制限されないが、通常ほう素化合物と炭素及
び／又は炭素化合物との合計１００重量部に対し、１０
０〜２０００重量部、好ましくは５００〜１５００重量
部の配合量とすることができる。Here, the amount of organic solvent used is not particularly limited as long as it can dissolve part or all of the boron compound and mix uniformly with the carbon and/or carbon compound, but usually the boron compound and the carbon and/or carbon compound are mixed together. For a total of 100 parts by weight, 10
The amount may be 0 to 2000 parts by weight, preferably 500 to 1500 parts by weight.
また、混合方法も特に制限されず、通常の混合方法、例
えばボールミル、ニーダ−、エクストルーダー等を用い
ることができる。更に、乾燥造粒方法も特に制限されな
いが、乾燥と顆粒状に造粒することを同時に行なえる点
で、スプレードライヤーが好適に用いられる。造粒効果
を上げるために、各種バインダーを併用することができ
る。バインダーとしてはＰＶＡ、ＣＭＣ、メチルセルロ
ースが例示される。Further, the mixing method is not particularly limited, and ordinary mixing methods such as a ball mill, kneader, extruder, etc. can be used. Further, the drying and granulating method is not particularly limited, but a spray dryer is preferably used since it can perform drying and granulating at the same time. Various binders can be used in combination to increase the granulation effect. Examples of the binder include PVA, CMC, and methylcellulose.
このようにして得られたほう素化合物と炭素及び／又は
炭素化合物との混合顆粒は更に必要により粉砕して好ま
しくは粒径１００〜５００４＋１１１の顆粒状として窒
化に供する。The thus-obtained mixed granules of boron compound and carbon and/or carbon compound are further pulverized if necessary and subjected to nitriding in the form of granules preferably having a particle size of 100 to 5004+111.
次に、窒化方法はパノ千式、連続式を問わずいずれの方
法も採用し得るが、本発明の方法によって得られた原料
は不均一化を生じないため、特に連続式窒化方法が好適
に採用される。Next, although any nitriding method can be used, regardless of whether it is a pano-thousand method or a continuous method, the continuous nitriding method is particularly preferable because the raw material obtained by the method of the present invention does not cause non-uniformity. Adopted.
この場合、窒化加熱反応炉として、原料物質を供給する
導入口と炉中を通って加熱反応した反応生成物を取出す
排出口を備えた窒化炉が好適に用いられる。そのような
加熱炉としては、形状に制限はないが、通常知られた各
種の竪型炉や流動床炉又はトンネル炉が好都合に使用で
き、トンネル炉としては棚積式プッシャー類が特に好ま
しい。In this case, as the nitriding heating reactor, a nitriding furnace equipped with an inlet for supplying raw material and an outlet for taking out the reaction product that has passed through the furnace and has been heated and reacted is preferably used. Although there are no restrictions on the shape of such a heating furnace, various commonly known vertical furnaces, fluidized bed furnaces, or tunnel furnaces can be conveniently used, and shelf-type pushers are particularly preferred as tunnel furnaces.
これらの加熱炉は、本発明の方法における反応温度に耐
える炉材、例えば炭素、炭化けい素、窒化ほう素などの
耐熱材料で構成される。These heating furnaces are constructed of a furnace material that can withstand the reaction temperatures in the method of the present invention, such as heat-resistant materials such as carbon, silicon carbide, boron nitride, and the like.
また、窒素雰囲気は窒素ガスだけとしてもよく、あるい
は窒素ガスに例えばアルゴン、ヘリウムなどの不活性ガ
スを混合したものであってもよく、更に窒素カスとして
は反応系において容易に窒素ガスに変化し得るもの、例
えばアンモニアガスなどでもよい。In addition, the nitrogen atmosphere may be made of only nitrogen gas, or may be a mixture of nitrogen gas and an inert gas such as argon or helium. Furthermore, the nitrogen gas is easily converted into nitrogen gas in the reaction system. For example, ammonia gas or the like may be used.
なお、窒化反応は通常１７００〜２０００℃で、１〜５
時間で行なうことができる。In addition, the nitriding reaction is usually carried out at 1700 to 2000°C and 1 to 5
It can be done in time.
以上説明したように、本発明の窒化ほう素の製造方法に
よれば、炭素等の不純物が極めて少ない高品質な窒化ほ
う素粉束を生産性良く、しかも確実に製造できるもので
ある。As explained above, according to the method for producing boron nitride of the present invention, a high-quality boron nitride powder bundle containing extremely few impurities such as carbon can be produced reliably and with high productivity.
以下、実施例及び比較例を示し、本発明を更に具体的に
説明するが、本発明は下記実施例に制限されるものでは
ない。EXAMPLES Hereinafter, the present invention will be explained in more detail by showing examples and comparative examples, but the present invention is not limited to the following examples.
ほう９９００ ｇとカーボンブラック４００ｇとをメタ
ノール５ｐ中でボールミルを用いて３時間部合した。9,900 g of carbon black and 400 g of carbon black were combined in 5 parts of methanol using a ball mill for 3 hours.
混合後のスラリーをスプレードライヤーを用いて乾燥と
造粒を同時に行ない、粒径５００−前後の顆粒を得た。The mixed slurry was simultaneously dried and granulated using a spray dryer to obtain granules with a particle size of approximately 500 mm.
この顆粒を黒鉛製容器に充填し、棚積式プッシャー炉（
外形： １５００Ｘ１５００Ｘ８０００＋ｎｏ）にＮ２
カス６０Ｑ／分を炉出口方向から原料混合物と向流に流
し、最高温度１９００℃で３時間窒化を行なった。The granules were filled into a graphite container and placed in a shelf-type pusher furnace (
External size: 1500X1500X8000+N2
Nitriding was carried out at a maximum temperature of 1900° C. for 3 hours by flowing the waste 60 Q/min countercurrently to the raw material mixture from the direction of the furnace exit.
ほう酸９００ｇとカーボンブラック４００ｇとを１％ポ
リビニルアルコール水溶液５Ｑ中でボールミルを用いて
３時間部合したが水溶液は増粘し、またカーボンブラッ
クとの濡れも悪いものであった。900 g of boric acid and 400 g of carbon black were combined in a 1% polyvinyl alcohol aqueous solution 5Q for 3 hours using a ball mill, but the aqueous solution thickened and had poor wetting with carbon black.
混合後のスラリーを真空乾燥及び造粒機を用いて乾燥・
造粒したが、得られたものはまま粉が生じ、均一な顆粒
状粒子は得られなかった。The slurry after mixing is vacuum dried and dried using a granulator.
Although granulation was carried out, the resulting product was a powder, and uniform granular particles could not be obtained.
この顆粒状粒子を実施例と同様に窒化した。These granular particles were nitrided in the same manner as in the example.
次に、実施例、比較例で得られた窒化ほう素について元
素分析を行なった。その結果を第１表に示す。Next, elemental analysis was performed on the boron nitride obtained in Examples and Comparative Examples. The results are shown in Table 1.
第 １ 表
第１表の結果かられかるように、実施例で得られた窒化
ほう素中の不純物は実質的にわずかのＢ２０．のみであ
り、しかもこのＢ２０７は容易に除去することができる
ものである。Table 1 As can be seen from the results in Table 1, the impurities in the boron nitride obtained in the examples were substantially small in B20. Moreover, this B207 can be easily removed.
これに対し、比較例で得られた窒化ほう素には不純物と
してＢ２０．のほかに、除去し難い炭素が残留している
ものであった。In contrast, the boron nitride obtained in the comparative example contained B20. In addition to this, there was some residual carbon that was difficult to remove.
出願人 信越化学工業 株式会社 代理人 弁理士 小 島 隆 司Applicant: Shin-Etsu Chemical Co., Ltd. Agent: Patent Attorney Takashi Kojima
Claims (1)
物を窒素雰囲気下に加熱して、窒化ほう素化合物を製造
する方法において、ほう素化合物の一部又は全部を有機
溶媒に溶解すると共に、該溶液に炭素及び／又は炭素化
合物を混合し、次いでこれを乾燥、造粒してほう素化合
物と炭素及び／又は炭素化合物との混合顆粒を製造し、
この顆粒を窒素雰囲気下に加熱するようにしたことを特
徴とする窒化ほう素の製造方法。1. A method for producing a boron nitride compound by heating a mixture of a boron compound and carbon and/or a carbon compound in a nitrogen atmosphere, in which part or all of the boron compound is dissolved in an organic solvent, and Mixing carbon and/or a carbon compound with the solution, then drying and granulating it to produce mixed granules of a boron compound and carbon and/or a carbon compound,
A method for producing boron nitride, characterized in that the granules are heated in a nitrogen atmosphere.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19669090A JPH0483706A (en) | 1990-07-25 | 1990-07-25 | Production of boron nitride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19669090A JPH0483706A (en) | 1990-07-25 | 1990-07-25 | Production of boron nitride |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0483706A true JPH0483706A (en) | 1992-03-17 |
Family
ID=16361977
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19669090A Pending JPH0483706A (en) | 1990-07-25 | 1990-07-25 | Production of boron nitride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0483706A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005070822A1 (en) * | 2004-01-14 | 2005-08-04 | Paint & Powder Technologies Llc | Continuous pusher-type furnacing system for the production of high-quality uniform boron nitride |
| JP2007031170A (en) * | 2005-07-22 | 2007-02-08 | National Institute For Materials Science | Boron nitride-based porous body and its manufacturing method |
| JP2016088799A (en) * | 2014-11-04 | 2016-05-23 | 株式会社トクヤマ | Method of producing boron nitride powder |
| CN108251801A (en) * | 2016-12-29 | 2018-07-06 | 宁波江丰电子材料股份有限公司 | The preparation method of magnesia, zinc oxide mixed-powder |
-
1990
- 1990-07-25 JP JP19669090A patent/JPH0483706A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005070822A1 (en) * | 2004-01-14 | 2005-08-04 | Paint & Powder Technologies Llc | Continuous pusher-type furnacing system for the production of high-quality uniform boron nitride |
| JP2007031170A (en) * | 2005-07-22 | 2007-02-08 | National Institute For Materials Science | Boron nitride-based porous body and its manufacturing method |
| JP2016088799A (en) * | 2014-11-04 | 2016-05-23 | 株式会社トクヤマ | Method of producing boron nitride powder |
| CN108251801A (en) * | 2016-12-29 | 2018-07-06 | 宁波江丰电子材料股份有限公司 | The preparation method of magnesia, zinc oxide mixed-powder |
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