JPS60155507A - Continuous preparation of boron nitride - Google Patents
Continuous preparation of boron nitrideInfo
- Publication number
- JPS60155507A JPS60155507A JP1224584A JP1224584A JPS60155507A JP S60155507 A JPS60155507 A JP S60155507A JP 1224584 A JP1224584 A JP 1224584A JP 1224584 A JP1224584 A JP 1224584A JP S60155507 A JPS60155507 A JP S60155507A
- Authority
- JP
- Japan
- Prior art keywords
- furnace
- carbon
- reaction
- compound
- continuously
- 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.)
- Granted
Links
Abstract
Description
【発明の詳細な説明】 本発明は、窒化はう素の連続Ｉｌｒ］裂造法に関し。[Detailed description of the invention] The present invention relates to a continuous Ilr process for boron nitride.
特に、優れた物理的、化学的諸性質を有する六方晶形の
窒化はう素の遅１ａＦＪ製造方法に関する。In particular, the present invention relates to a method for producing slow 1aFJ of hexagonal nitrided boron having excellent physical and chemical properties.
六方晶形の窒化はう素は耐熱性、耐熱衝撃性−化学的安
定性、高熱伝導性、高電気絶縁性、潤滑特性に優れ、そ
め特性を活かして高温構造材、電気絶縁材、トランジス
ター、ＩＣ，マイクロ波用の放熱板あるいは耐摩耗材等
として広く使用されている。本発明は、この利用価値の
大きい六方晶形窒化はう素を製造する工業的に有利な新
規方法に係るものである。Hexagonal boron nitride has excellent heat resistance, thermal shock resistance, chemical stability, high thermal conductivity, high electrical insulation, and lubrication properties, and its thin properties can be used for high-temperature structural materials, electrical insulation materials, transistors, and ICs. It is widely used as a heat sink for microwaves or as a wear-resistant material. The present invention relates to a new industrially advantageous method for producing hexagonal boron nitride, which has great utility value.
従来、六方晶形窒化はう素の製造方法としては。Traditionally, hexagonal nitride is the manufacturing method for boron.
下肥反応式による方法が代表的なものとして知られてい
る。The method using the manure reaction formula is known as a representative method.
（１）２Ｂ十Ｎ２→２ＢＮ
（２） Ｂ、 Ｏ，＋ ＮＥ、十高融点物質（Ｏａ、
（ＰＯ４）り →Ｂ Ｎ
（３ン Ｂ］１３ ＋ ＮＨ３→Ｂ Ｎ＋ ３ Ｈｏｌ
（４） Ｎａ２Ｂ４０． ＋ ２００（ＮＨ２）２−（
５） Ｂ、０３＋３０十Ｎ、−＋ ２８Ｎ＋３００これ
ら製法の中で反応式（１）及び（３）の方法は、高価な
原料を必要とし、大量生産に不向であって工業的に採用
し難く、また、上記反応式（２）及び（４）による窒化
はう素の製法は、原料が安価で大量に生産できるため、
現在、工業的に実施されているが。(1) 2B ten N2 → 2BN (2) B, O, + NE, ten high melting point substance (Oa,
(PO4)ri →B N (3 N B]13 + NH3→B N+ 3 Hol
(4) Na2B40. +200(NH2)2-(
5) B, 03 + 30 1N, - + 28N + 300 Among these production methods, the methods of reaction formulas (1) and (3) require expensive raw materials, are unsuitable for mass production, and are difficult to adopt industrially. In addition, the method for producing boron nitride using the above reaction formulas (2) and (4) uses inexpensive raw materials and can be produced in large quantities.
Although it is currently being implemented industrially.
その製法は多くの工程を必要とし、特に高い気密性が要
求されるアンそニアガス雰囲気の窒化炉での処理を２段
階以上行なわねばならないので、連１ＦＡＦＩ調造は極
めて困難であり、事実、これらの製法はバッチ式のみが
採用されている。この多くの処理工程をバッチ式で行な
う場合には、設備費と製造費がかさむために製品＝スト
高となる欠点が避けられないものである。The manufacturing method requires many steps, and in particular requires two or more steps of treatment in a nitriding furnace in an anthonia gas atmosphere, which requires high airtightness. Only the batch method is used for manufacturing. When many of these processing steps are carried out in a batch manner, the drawback that equipment costs and manufacturing costs increase, resulting in high product cost is unavoidable.
また、反応式（５）に基づく窒化はう素の製造は。Moreover, the production of boron nitride based on reaction formula (5) is as follows.
一段反応で、原料の価格も安いという利点はあるが、一
般に、■反応収率が低い、■残留カーボンが多く、その
分離が必要である。０１２００〜１６００℃の高温反応
のため、従来技術ではバッチ反応となり、製造装置の大
型化一連続化が困難である。及び■温度分布の不均一性
に由来する品質のバラツキが極めて大きいなどの理由か
ら、工業的に不利とされ、固定炉又は小型回転炉による
小規模バッチ式が実用されているに過ぎず、特に。Although it has the advantage of being a one-stage reaction and the cost of raw materials is low, it generally requires (1) a low reaction yield, and (2) a large amount of residual carbon, which must be separated. Since the reaction is at a high temperature of 1,200 to 1,600°C, the conventional technology requires a batch reaction, making it difficult to increase the size of the production equipment and make it continuous. and ■ Due to extremely large variations in quality due to non-uniformity of temperature distribution, it is considered to be disadvantageous industrially, and only small-scale batch systems using fixed furnaces or small rotary furnaces are in practical use. .
上記（５）の反応式を利用する連続的製造法は到底考え
られなかったのである。A continuous production method using reaction formula (5) above was completely inconceivable.
しかし、優れた緒特性を有し、広い分野にゎたつて需要
が急速に伸びている高品質の六方晶形窒化はう素を大量
且つ安価に提供することは社会の大きな要望である。However, there is a great need in society to provide high-quality hexagonal boron nitride in large quantities and at low cost, which has excellent properties and whose demand is rapidly increasing in a wide range of fields.
従って１本発明の目的は、安価な原料を用い。Therefore, one object of the present invention is to use inexpensive raw materials.
六方晶形窒化はう素を連続的に製造する工業的方法を提
供するＫある。また、他の目的は、高純度且つ高結晶性
の六方晶形窒化はう素を安価に提供することにある。ま
た、更に他の目的は、上記反応式（５）の反応を効果的
に遂行させ、バラツキの小さい高品質の六方晶形窒化は
う素を高効率で製造しつる方法を提供することにある。Hexagonal nitridation provides an industrial method for producing boron continuously. Another object of the present invention is to provide hexagonal boron nitride with high purity and high crystallinity at a low cost. Still another object is to provide a method for efficiently carrying out the reaction of the above reaction formula (5) and producing high-quality hexagonal boron nitride with small variations with high efficiency.
その他の本発明の目的及び優れた諸効果は、以下の記載
から一層明らかになるであろう。Other objects and excellent effects of the present invention will become clearer from the following description.
本発明者らは、上記目的を達成すべく、特に。The present inventors particularly aimed to achieve the above object.
安価な出発原料を用い１段反応で六方晶窒化はう素を形
成させつる上記反応式（５）の方法について研究を重ね
た結果、極めて効率的で−しかも、従来＋３１−１ 、
ｌｒ ＴｔｆＴ 妬Ｌ ４−＆−＋イｌ ｓ ｆ−Ｔ
＋ 諺社１／ ’ｈ ＩＩ宣姑―の六方晶形窒化はう素
を製造しつることを知った。As a result of repeated research on the method of the above reaction formula (5), which forms hexagonal boron nitride in a one-step reaction using inexpensive starting materials, it has been found that it is extremely efficient - and +31-1 higher than conventional methods.
lr TtfT Jealous L 4-&-+Il s f-T
+ Proverbs 1/'h II I learned that Xuangu's hexagonal nitridation produces boron.
すなわち１本発明は、は５素化合物と炭素及び／又は炭
素化合物との混合物を、導入口と排出口を備えた加熱炉
の導入口から連続的に挿入し、窒素ガス又は窒素ガス含
有非酸化性ガスの向流接触条件下に、１，６５０〜２，
３００℃の温度に加熱して還元、窒化反応させ、該炉の
排出口から反応生成物を連続的に取出すことを特徴とす
る窒化はう素の連続的製造方法を提供する。In other words, the present invention provides a method in which a mixture of a penta-element compound and carbon and/or a carbon compound is continuously introduced through an inlet of a heating furnace equipped with an inlet and an outlet, and nitrogen gas or a nitrogen gas-containing non-oxidizing 1,650 to 2, under countercurrent contact conditions of reactive gases.
Provided is a method for continuously producing boron nitride, which is characterized by heating to a temperature of 300° C. to cause a reduction and nitriding reaction, and continuously taking out the reaction product from an outlet of the furnace.
本発明の方法に用いられるほう素化合物としては１例え
ば、はう酸、無水はう酸、シボ２ンやエチルボレート、
メチルボレート等の有機はう素化合物類を挙げることが
できるが１反応性と価格を考慮すれば、特にほう酸が好
ましい。また、炭素及び炭素化合物としては１例えば通
常のアセチレン・ブラック、チャンネル・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
１、Ｓ）！フェノールｓｉ貸−ポリエチレンーポリスチ
レン等の合成高分子等が挙げられるが、製品純度と経済
性からカーボン・プラックが好適に用いられる。Examples of the boron compounds used in the method of the present invention include 1, eg, halonic acid, fluoric anhydride, cibon, ethyl borate,
Examples include organic boron compounds such as methylborate, but boric acid is particularly preferred in view of reactivity and cost. In addition, carbon and carbon compounds include carbon such as ordinary acetylene black, channel black, graphite, charcoal, wood powder, tar, pitch, etc. 1)! Synthetic polymers such as phenol, silicone, polyethylene, and polystyrene may be used, but carbon plaque is preferably used in view of product purity and economical efficiency.
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１通常の窒化反応に使用される触媒例、ｔ ハ鉄、
コバルト、ニッケル、カルシウム、マグネシウム、マン
ガン、七すプデン等の金属あるいはこれらの酸化物、炭
酸化物等の金属化合物の好適量が上記原料化合物に混用
できる。また、はう酸化合物と炭素及び／又は炭素化合
物の混合物は、あらかじめ造粒してもよいが、その際ポ
パール、精密、メチルセルｐ−ズ等の造粒バインダー等
を添加混合する事は何んら差支えない。In the method of the present invention, in order to make the nitriding reaction more efficient, (1) examples of catalysts used in ordinary nitriding reactions, (3) iron,
Suitable amounts of metals such as cobalt, nickel, calcium, magnesium, manganese, and hexaspodene, or metal compounds such as their oxides and carbonates can be mixed into the above-mentioned raw material compounds. In addition, the mixture of the oxalic acid compound and carbon and/or carbon compound may be granulated in advance, but at that time, a granulation binder such as Popal, Seimitsu, Methylcell P-s, etc. may not be added or mixed. There is no problem.
これらの成分の混合には１通常の混合機１例えば、ヘン
シェルミキサー、リボンミキサー、押出機等を用いるこ
とかでき、必要に応じて水分を添加したのち、混合−乾
燥を行う事もできる。又−主成分の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ｔｔｋＦＪＢ
１０で０．６〜１．２の範囲が採用される。ＯＫ対する
Ｂの重量が０．６よりも小さいと１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。For mixing these components, a conventional mixer such as a Henschel mixer, a ribbon mixer, an extruder, etc. can be used, and if necessary, after adding moisture, mixing and drying can be performed. Also, the mixing ratio of the main component boron compound and carbon and/or carbon compound is the element ttkFJB
10, a range of 0.6 to 1.2 is adopted. If the weight of B to OK is less than 0.6, the amount of carbon remaining after one reaction will increase, while if the mixing ratio of B is greater than 1.2, the reduction reaction of the boron compound before the nitrification reaction will be reduced. The proportions within the above weight ranges are preferable since this may result in insufficient nitriding, resulting in insufficient progress of nitriding and a decrease in yield.
更に好ましい割合は０．７〜１．０である。A more preferable ratio is 0.7 to 1.0.
本発明の方法においては、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用いられる。そ
のよ５な加熱炉としては。In the method of the present invention, a nitriding furnace is used as the nitriding heating reactor, which is equipped with an inlet for supplying a raw material and an outlet for taking out a reaction product that has been heated and reacted through the furnace. As a heating furnace like that.
形状忙制限はないが、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。Although there are no shape limitations, various commonly known vertical furnaces, fluidized bed furnaces, or tunnel furnaces can be conveniently used.
トンネル炉としては棚柵式プッシャー炉が特に好ましい
。これらの加熱ｐは６１本発明の方法における反応温度
に耐える炉材、１例えば炭Ｘ、炭化けい素、、窒化はう
素などの耐熱材料で構成される。As the tunnel furnace, a shelf-type pusher furnace is particularly preferred. These heating devices are made of heat-resistant materials such as 61 furnace materials that can withstand the reaction temperatures in the method of the present invention, such as charcoal, silicon carbide, and boron nitride.
本発明においては、原料混合物を加熱炉中を一定方向に
移動させ、同時にその移動方向とは反対の方向に窒素ガ
ス又は窒素含有非酸化性ガスを流しながら、該混合物を
該向流窒業ガスと接触条件下に、加熱反応させることが
極めて重要であり。In the present invention, the raw material mixture is moved in a certain direction in the heating furnace, and at the same time, while nitrogen gas or nitrogen-containing non-oxidizing gas is flowing in the opposite direction to the moving direction, the mixture is transferred to the countercurrent nitrogenous gas. It is extremely important to heat the reaction under contact conditions.
この要件と組合わせて、加熱反応を従来知られた反応温
度より高い１，６５０〜２，３００℃の温度範囲で行な
わせることが重要である。そのような高温加熱用熱源は
特に制限されないが、カーボンヒーターが好ましく用い
られる。加熱温度が１．６５０℃未満の場合には、窒化
反応が充分に進行し難く、また、２，３００℃を超える
と像化はう素以外の炭化はう素などの所望しない物質が
副生じ、目的物の純度及び収率が低下するので好ましく
ない。一方、ｉｉ！素又は窒素含有非酸化性ガスを原料
混合物の移動方向と同方向、すなわち並流状に流して接
触反応させると、混合物中の不純物。In combination with this requirement, it is important to carry out the heating reaction at a temperature range of 1,650 DEG to 2,300 DEG C., which is higher than previously known reaction temperatures. Such a heat source for high temperature heating is not particularly limited, but a carbon heater is preferably used. If the heating temperature is less than 1.650°C, the nitriding reaction will not proceed sufficiently, and if the heating temperature exceeds 2,300°C, undesired substances such as boron carbide will be produced as by-products. , is not preferable because the purity and yield of the target product decrease. On the other hand, ii! When a nitrogen-containing non-oxidizing gas is caused to flow in the same direction as the moving direction of the raw material mixture, that is, in parallel flow, to cause a contact reaction, impurities in the mixture.
膿Ｉｒ珈瑯 壷へ七ヱ１１Ｌ今Ｅ實仁Ｉｆルは謙２−駒
ｌし炭素や他の金属不純物などのガス分圧が高くなり。If the pus is removed from the coffee pot, the partial pressure of gases such as carbon and other metal impurities will increase.
その結果％窒素分圧が低下し、窒化反応が迅速に進行し
なくなったり、生成物中に金属不純物を同伴してしまう
ので好しくない。従って１本発明の方法においては、窒
化用ガスは原料混合物の移動方向に逆行して向流接触さ
せることが重量であり。As a result, the % nitrogen partial pressure decreases, which is not preferable because the nitriding reaction does not proceed quickly or metal impurities are entrained in the product. Therefore, in the method of the present invention, it is important that the nitriding gas is brought into countercurrent contact with the raw material mixture in a direction opposite to the moving direction of the raw material mixture.
上記不都合が効果的に回避されるばかりでなく。Not only the above-mentioned inconveniences are effectively avoided.
導入原料混合物の予備加熱に有効に作用する付加効果も
得られる。上記の窒素ガスを含有する非酸化性ガスとし
ては１例えばアルゴン、ヘリウムなどの不活性ガスを挙
げることができるカζ窒素ガス濃度はできるだけ高いこ
とが望ましい。また。An additional effect is also obtained which effectively acts on the preheating of the introduced raw material mixture. Examples of the above-mentioned non-oxidizing gas containing nitrogen gas include inert gases such as argon and helium.It is desirable that the nitrogen gas concentration be as high as possible. Also.
本発明方法において窒素ガスとは１反応系において容易
に窒素ガスに変化しつる１例えばアンモニアなどを包含
する。In the method of the present invention, nitrogen gas includes gases that can be easily converted into nitrogen gas in a reaction system, such as ammonia.
本発明の方法において、窒素ガスの向流接触条件で加熱
反応させる原料混合物の反応時間は、温奢ｒ上つイ奢ｆ
ｂナス禍ｒ ；踏台１ ヘ９ ｒ＋此日［４◆ツまた、
向流させる９素ガス等は、前記不都合が伴わず、且つ窒
化反応に遅延等の不利益をもたらさない比較的低い流速
が有利に採用される。In the method of the present invention, the reaction time of the raw material mixture heated and reacted under countercurrent contact conditions of nitrogen gas is as follows:
b eggplant misfortune r ; stepping stone 1 h9 r + this day [4◆tsu also,
A relatively low flow rate of the 9-element gas or the like to be caused to flow counter-currently is advantageously used because it does not cause the above-mentioned disadvantages and does not cause disadvantages such as delay in the nitriding reaction.
本発明の方法は、前記したように、竪型加熱炉。As described above, the method of the present invention uses a vertical heating furnace.
又はトンネル炉、＠に棚積式プッシャー炉が好都合に利
用できる。それぞれの加熱炉の場合について説明すれば
、竪型加熱炉では炉頂部より原料を一定速度で供給し、
下部より非酸化性窒素含有ガスを向流になる様に導入し
、ヒーターで炉内を１．６５０〜２，３００℃に加熱し
反応させる。反応生成物は底部より１例えば四−タリー
パルプを介して連続的に一定速度で抜き出される。一方
−ガス入口から導入された非酸化性ガスは反応生成物を
冷却しなから一自体は熱せられ炉中を上昇し反応を進行
させ、上部の排気口より熱回収を行なったのち、排出さ
れる。Alternatively, a tunnel furnace or a stacked pusher furnace can be advantageously used. To explain the case of each heating furnace, in a vertical heating furnace, raw materials are supplied from the top of the furnace at a constant rate,
A non-oxidizing nitrogen-containing gas is introduced from the bottom in a countercurrent manner, and a heater is used to heat the inside of the furnace to 1.650-2,300°C to cause a reaction. The reaction product is continuously withdrawn from the bottom through, for example, a four-tally pulp at a constant rate. On the other hand, the non-oxidizing gas introduced from the gas inlet does not cool the reaction products, but rather heats itself and rises in the furnace to proceed with the reaction. After recovering heat from the upper exhaust port, it is discharged. Ru.
マタ、トンネル炉の棚積式ブツシャー炉ハ、トンネル状
の炉内の底部にレールを設け、このレール上に合板を載
せ、各合板上に前記の混合物を充填した匣鉢な積み１合
板を炉入口から出口方向へと移送する方式のものである
。棚積式プッシャー炉は炉本体に駆動部が無く１合板を
順次、押し出しグツシャーでレール上を移送させる為１
機械強度が不要（・本発明の様な高温反応下で主として
用いられる炭素材の使用ができるので極めて好都合であ
る。In the tunnel furnace, a shelf-type butsusha furnace is provided with a rail at the bottom of the tunnel-shaped furnace, a plywood is placed on the rail, and one stack of plywood filled with the above mixture is placed on each plywood in the furnace. This is a type of transport from the entrance to the exit. The shelf-type pusher furnace has no driving part in the furnace body, and the plywood is pushed out one by one and transferred on the rail with a gutsher.
Mechanical strength is not required (-This is extremely advantageous because it allows the use of carbon materials that are mainly used in high-temperature reactions such as in the present invention.
本発明の方法によれば、安価な原料から一段反応により
、高純度、高結晶性の六方晶形窒化はう素を高反応率且
つ連続的に製造することができるので１本発明は優れた
工業的価値及び実用性を有する。According to the method of the present invention, high purity, highly crystalline hexagonal boron nitride can be produced continuously at a high reaction rate through a one-step reaction from inexpensive raw materials. It has practical value and practicality.
次に具体例により本発明を更に詳細に説明する。Next, the present invention will be explained in more detail using specific examples.
実施例１゜
カーボンヒーターを備えた容量３００ｔの通常の竪型加
熱炉を用いた。Example 1 A normal vertical heating furnace with a capacity of 300 tons and equipped with a carbon heater was used.
まず原料として、はう酸５００Ｋｆ、アセチレン・ブラ
ック１１０〜及び酸化カルシウム５０Ｋｆをポリビニル
アルコール１．０チ水溶液５０１と共に混練均質化し、
直径５ｍ、長さ３０１１Ｅのベレットに造粒して、１５
０℃の温度に加熱し完全に脱水乾燥調製した。これを炉
の上部導入口から供給し。First, as raw materials, 500Kf of halonic acid, 110~ of acetylene black, and 50Kf of calcium oxide are kneaded and homogenized with 1.0% of polyvinyl alcohol aqueous solution 501,
Granulated into a pellet with a diameter of 5 m and a length of 3011E, 15
It was heated to a temperature of 0°C and completely dehydrated and dried. This is supplied from the upper inlet of the furnace.
炉の下部のガス供給口から窒素ガスを１２０ ｔ／ｍｉ
ｎ の割合で導入しながら、炉の中央部の周壁なカーボ
ンヒーターで約２，０００℃に加熱して反応を開始した
。反応開始３時間後に炉の底部の排出口のロータリーバ
ルブを連続的に操作しながら反応生成物である窒化はう
素をＩＫｐ／Ｈｒの割合で取り出した。Nitrogen gas is supplied from the gas supply port at the bottom of the furnace at 120 t/mi.
The reaction was started by heating to about 2,000° C. with a carbon heater in the peripheral wall at the center of the furnace while introducing the reactor at a rate of n. Three hours after the start of the reaction, boron nitride, a reaction product, was taken out at a ratio of IKp/Hr while continuously operating the rotary valve at the outlet at the bottom of the furnace.
反応は２４時間行なったが、極めて順調であった。又−
得られた生成物は５％塩酸水で洗浄後。The reaction was carried out for 24 hours and was extremely successful. Again-
The obtained product was washed with 5% hydrochloric acid water.
熱水でろ液が中性にな）脩芒甲ツ０℃、１０時間乾燥し
た。この物の平均的な分析結果はＸ線回折では六方晶形
の窒化はう素であって、黒鉛化指数（Ｇ・１値）１．６
５の結晶性に優れた物であり。The filtrate was made neutral with hot water) and dried at 0°C for 10 hours. The average analysis result of this material is that the hexagonal nitride is boron by X-ray diffraction, and the graphitization index (G・1 value) is 1.6.
It has excellent crystallinity.
化学分析の結果では残留カーボン０．０４１Ｂ、 ０３
Ｑ；、０８％、窒素含量５６．１％と純度の高いもので
ある事を示した。又、３時間毎の生成物の分析値のバラ
ツキを調べたところ、カーボン０．００８東Ｂ、Ｏ８０
，００５に窒素含量０．１５チ以内で分析誤差範囲内で
あり、生成物間の品質１のバラツキはほとんど無視出来
るものであった。The results of chemical analysis showed that the residual carbon was 0.041B, 03
Q;08% and nitrogen content 56.1%, indicating high purity. In addition, when we investigated the dispersion of the analysis values of the product every 3 hours, we found that carbon was 0.008 East B, O80
, 005, the nitrogen content was within 0.15 inches, which was within the analytical error range, and the variation in quality between the products was almost negligible.
尚、従来のバッチ式では通常どの分析値も５〜２０チ位
のバラツキが見られた。In addition, in the conventional batch method, there was usually a variation of about 5 to 20 inches in every analytical value.
又、総合収率は理論値の９７．８％と高く優れたもので
あった。Moreover, the overall yield was as high as 97.8% of the theoretical value, which was excellent.
同一容積のパッチ炉に比べ生産性は約１５倍であった。Productivity was approximately 15 times higher than that of a patch furnace with the same volume.
なお、上記黒鉛化指数（Ｇ−１値）は。In addition, the graphitization index (G-1 value) is as follows.
Ｘ１１１回折のピーク面積をめ１次式より算出したもの
である。Ｇ−Ｉ値が低いものほど結晶化が進んでいる事
を示す。The peak area of X111 diffraction was calculated using the linear equation. The lower the G-I value, the more advanced the crystallization is.
（１０２）面積 実施例２゜ ブツシャ一部及び炉外壁以外のヒーター、匣鉢。(102) Area Example 2゜ Heater and sagger other than part of the bush and the outer wall of the furnace.
台板、炉内壁、レール等は全て炭素材質で製作されてい
る棚積式プッシャー炉（外形：ｌ、５００Ｘｘ、５ｏｏ
ｘ３ｏｏｏｍｍ）に、窒業ガス６０ ｔＡｎｉｎを炉出
口方向から原料混合物と向流に流し、炉圧を１００ｍｍ
Ａｑになる様調節した。その炉内中央１．０００龍を２
，０００℃の均熱帯になる様にカーボンヒーターを制御
し、この炉内に合板に設置された匣鉢（２００ｘ２００
ｘ１５０ｍｍ）中へ１鉢当すほう酸５００ｐ、アセチレ
ン・プラック１１０１酸化マグネシウム１００ｇの混合
物を仕込み、１鉢／３０分サイクルで匣鉢なプッシャー
で炉中へ順次移送し、この操作を２４０時間連続して行
なって窒化は５累を連続的に製造した。The bed plate, furnace inner walls, rails, etc. are all made of carbon material (external size: l, 500Xx, 5oo
x3oomm), 60 tAnin of nitrogen gas was flowed countercurrently to the raw material mixture from the direction of the furnace exit, and the furnace pressure was set to 100 mm.
It was adjusted to be Aq. 1.000 dragons in the center of the furnace 2
A carbon heater was controlled to create a soaking zone of ,000℃, and a sagger (200 x 200
A mixture of 500 p of boric acid and 100 g of acetylene plaque 1101 magnesium oxide per pot was charged into a 1 pot (150 mm x 150 mm), and the mixture was transferred to the furnace using a sagger pusher in a cycle of 1 pot/30 minutes, and this operation was continued for 240 hours. The nitriding was carried out successively in five cycles.
得ヒれた生成物は５％塩酸水で洗浄し１次いで熱水でろ
液が中性になるまで洗ったのち、１５０℃の温度で１０
時間乾燥した。得られた物はＸ線回折の結果、六方晶形
の窒化はう素であって、黒鉛化指数１．５０の極めて結
晶性の優れた物であることが確認された。又−化学分析
の結果は残留カーボン０．０３係、ＢＯ０，０９％−窒
素含量３
５６．２７％の平均値を示した。なお、各匣鉢間の化学
分析値のバラツキは各々、Ｑ、００５％。The obtained product was washed with 5% hydrochloric acid, first washed with hot water until the filtrate became neutral, and then heated at 150°C for 10 minutes.
Dry for an hour. As a result of X-ray diffraction, the obtained product was confirmed to be hexagonal boron nitride with extremely excellent crystallinity and a graphitization index of 1.50. Also, the results of chemical analysis showed an average value of residual carbon of 0.03%, BO of 0.09%, and nitrogen content of 356.27%. In addition, the variation in chemical analysis values between each sagger is Q, 005%.
０．００３％、 ０．１０％以下で分析誤差内であり。0.003%, 0.10% or less, which is within analytical error.
生成物の品質のバラツキはほとんど無視出来るものであ
った。従来のバッチ式では１通常上記各成分の分析値は
いずれも５〜２０チ位のバラツキが見られる。又、総合
収率は理論値の９８．５％と高く、優れたものであった
。この方法は、同一容積の炉を用いてパッチ方式で窒化
はう素を製造した場合の約１０倍の生産性であった。The variation in product quality was almost negligible. In the conventional batch method, the analysis values of each of the above-mentioned components usually vary by about 5 to 20 degrees. Moreover, the overall yield was as high as 98.5% of the theoretical value, which was excellent. This method was approximately 10 times more productive than producing boron nitride using the patch method using a furnace of the same volume.
実施例３〜７及び比較例１〜５
を
実施例２で用いたプツシャーラキ用して、第１辰中に示
すような反応温度条件又はほう素化合物と炭素材との重
量割合を変えたものなどの一連の実験を行ない、各反応
生成物の分析結果を下掲第１ｆｆにまとめて示す。なお
、分析は１反応生成物を塩酸水処理及び熱水洗浄し乾燥
したものについてのものである。また、参考のために、
前記実施例２を対応併記した。Examples 3 to 7 and Comparative Examples 1 to 5 were used in the same way as in Example 2, but the reaction temperature conditions or the weight ratio of the boron compound and the carbon material were changed as shown in the first column. A series of experiments were conducted, and the analysis results of each reaction product are summarized in Section 1ff below. The analysis was conducted on the product obtained by treating the reaction product with hydrochloric acid, washing with hot water, and drying. Also, for reference,
The corresponding example 2 is also listed.
Claims (1)
合物を、導入口と排出口を備えた加熱炉の ３゜導入口
から連続的に挿入し、窒素ガス又は窒素ガス含有非酸化
性ガスの向流接触条件下に。 １、６５０〜＆３００℃の温度に加熱して還元。 窒化反応させ、該炉の排出口から反応生成物を連続的に
取出すことを特徴とする窒化はう素の連続的製造方法。 ２、はう素化合物がほう酸である特許請求の範囲第１項
記載の方法。 ３、はう素化合物と炭素及び／又は炭素化合物との混合
割合が１元素成分比Ｂ：０＝Ｏ１６〜１−２：１の重ａ
ｍ煕で凱ス破詐饋すの箭開笛１項記載の方法。 ４、加熱炉が竪型炉である特許請求の範囲第１項記載の
方法。 ５、加熱炉がトンネル型の棚積式プッシャー炉である特
許請求の範囲第１項記載の方法。[Claims] 1. A mixture of a boronate compound and carbon and/or a carbon compound is continuously inserted into a heating furnace equipped with an inlet and an outlet through a 3° inlet, and nitrogen gas or nitrogen is added. Under conditions of countercurrent contact with gas-containing non-oxidizing gases. 1. Reduction by heating to a temperature of 650~300℃. 1. A method for continuously producing boron nitride, which comprises carrying out a nitriding reaction and continuously taking out the reaction product from an outlet of the furnace. 2. The method according to claim 1, wherein the boronate compound is boric acid. 3. The mixing ratio of the boronate compound and carbon and/or carbon compound is a weight a with a one-element component ratio of B:0=O16 to 1-2:1
The method described in Paragraph 1 of the method of opening the whistle of the Kaisu fraud in m-hi. 4. The method according to claim 1, wherein the heating furnace is a vertical furnace. 5. The method according to claim 1, wherein the heating furnace is a tunnel-type stacked pusher furnace.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1224584A JPS60155507A (en) | 1984-01-26 | 1984-01-26 | Continuous preparation of boron nitride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1224584A JPS60155507A (en) | 1984-01-26 | 1984-01-26 | Continuous preparation of boron nitride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60155507A true JPS60155507A (en) | 1985-08-15 |
| JPH0211521B2 JPH0211521B2 (en) | 1990-03-14 |
Family
ID=11799977
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1224584A Granted JPS60155507A (en) | 1984-01-26 | 1984-01-26 | Continuous preparation of boron nitride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60155507A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6256307A (en) * | 1985-09-05 | 1987-03-12 | Tokuyama Soda Co Ltd | Production of powder mixed with boron nitride |
| JPH11322310A (en) * | 1998-05-11 | 1999-11-24 | Sumitomo Electric Ind Ltd | Cubic boron nitride polycrystalline abrasive grain and its production |
| EP1053973A1 (en) * | 1999-05-19 | 2000-11-22 | Advanced Ceramics Corporation | Spherical boron nitride process, system and product of manufacture |
| 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 |
| WO2011021366A1 (en) * | 2009-08-20 | 2011-02-24 | 株式会社カネカ | Process for production of spheroidized boron nitride |
| JP2012111657A (en) * | 2010-11-24 | 2012-06-14 | Denki Kagaku Kogyo Kk | Boron nitride powder, method for producing the same, composition containing the same, and heat dissipative material |
| WO2013065556A1 (en) | 2011-11-02 | 2013-05-10 | 株式会社カネカ | Process for continuous production of boron nitride powder |
| WO2014109134A1 (en) * | 2013-01-10 | 2014-07-17 | 株式会社カネカ | Hexagonal boron nitride, and resin molded article having high thermal conductivities which is produced using same |
| EP2855401A4 (en) * | 2012-05-30 | 2015-06-03 | Auckland Uniservices Ltd | Production of bn-composite materials |
| JP2016060661A (en) * | 2014-09-17 | 2016-04-25 | 株式会社トクヤマ | Boron nitride powder and method for producing the same |
| JP2016088799A (en) * | 2014-11-04 | 2016-05-23 | 株式会社トクヤマ | Method of producing boron nitride powder |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB870084A (en) * | 1958-03-24 | 1961-06-14 | United States Borax Chem | Method of manufacturing boron nitride |
| JPS5347320A (en) * | 1976-10-13 | 1978-04-27 | Nippon Musical Instruments Mfg | Manufacturing of magnetic material |
| JPS55158176A (en) * | 1979-05-24 | 1980-12-09 | Showa Denko Kk | Manufacture of boron nitride filled carbon product |
| JPS5888107A (en) * | 1981-11-16 | 1983-05-26 | Denki Kagaku Kogyo Kk | Continuous preparation of alpha-type silicon nitride |
-
1984
- 1984-01-26 JP JP1224584A patent/JPS60155507A/en active Granted
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB870084A (en) * | 1958-03-24 | 1961-06-14 | United States Borax Chem | Method of manufacturing boron nitride |
| JPS5347320A (en) * | 1976-10-13 | 1978-04-27 | Nippon Musical Instruments Mfg | Manufacturing of magnetic material |
| JPS55158176A (en) * | 1979-05-24 | 1980-12-09 | Showa Denko Kk | Manufacture of boron nitride filled carbon product |
| JPS5888107A (en) * | 1981-11-16 | 1983-05-26 | Denki Kagaku Kogyo Kk | Continuous preparation of alpha-type silicon nitride |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6256307A (en) * | 1985-09-05 | 1987-03-12 | Tokuyama Soda Co Ltd | Production of powder mixed with boron nitride |
| JPH11322310A (en) * | 1998-05-11 | 1999-11-24 | Sumitomo Electric Ind Ltd | Cubic boron nitride polycrystalline abrasive grain and its production |
| EP1053973A1 (en) * | 1999-05-19 | 2000-11-22 | Advanced Ceramics Corporation | Spherical boron nitride process, system and product of manufacture |
| US6348179B1 (en) | 1999-05-19 | 2002-02-19 | University Of New Mexico | Spherical boron nitride process, system and product of manufacture |
| 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 |
| US8617503B2 (en) | 2009-08-20 | 2013-12-31 | Kaneka Corporation | Process for production of spheroidized boron nitride |
| WO2011021366A1 (en) * | 2009-08-20 | 2011-02-24 | 株式会社カネカ | Process for production of spheroidized boron nitride |
| JP5673539B2 (en) * | 2009-08-20 | 2015-02-18 | 株式会社カネカ | Method for producing spheroidized boron nitride |
| JP2012111657A (en) * | 2010-11-24 | 2012-06-14 | Denki Kagaku Kogyo Kk | Boron nitride powder, method for producing the same, composition containing the same, and heat dissipative material |
| WO2013065556A1 (en) | 2011-11-02 | 2013-05-10 | 株式会社カネカ | Process for continuous production of boron nitride powder |
| JPWO2013065556A1 (en) * | 2011-11-02 | 2015-04-02 | 株式会社カネカ | Continuous production method of boron nitride powder |
| EP2774893A4 (en) * | 2011-11-02 | 2015-11-25 | Kaneka Corp | Process for continuous production of boron nitride powder |
| EP2855401A4 (en) * | 2012-05-30 | 2015-06-03 | Auckland Uniservices Ltd | Production of bn-composite materials |
| WO2014109134A1 (en) * | 2013-01-10 | 2014-07-17 | 株式会社カネカ | Hexagonal boron nitride, and resin molded article having high thermal conductivities which is produced using same |
| JPWO2014109134A1 (en) * | 2013-01-10 | 2017-01-19 | 株式会社カネカ | Hexagonal boron nitride and high thermal conductive resin molding using the same |
| JP2016060661A (en) * | 2014-09-17 | 2016-04-25 | 株式会社トクヤマ | Boron nitride powder and method for producing the same |
| JP2016088799A (en) * | 2014-11-04 | 2016-05-23 | 株式会社トクヤマ | Method of producing boron nitride powder |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0211521B2 (en) | 1990-03-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103305739B (en) | A kind of high nitrogen VN alloy VN18 and production method thereof | |
| JPS60155507A (en) | Continuous preparation of boron nitride | |
| JPS6112844B2 (en) | ||
| US4818511A (en) | Process and apparatus for producing non-oxide compounds | |
| KR20110112334A (en) | Method for producing high-purity silicon nitride | |
| US4619905A (en) | Process for the synthesis of silicon nitride | |
| KR880005286A (en) | Continuous manufacturing process of high purity ultra fine aluminum nitride by carbon-nitridation of alumina | |
| US4511666A (en) | Process for producing beta'-silicon aluminum oxynitride (B'-SiAlON) | |
| JPS6111886B2 (en) | ||
| JPS61286207A (en) | Production of boron nitride | |
| CN104986749A (en) | Pushing type dynamic continuous preparing method for My(CXN1-X) powder and sintering device | |
| AU560369B2 (en) | Method of making yttrium silicon oxynitrides | |
| JPH0416502A (en) | Production of boron nitride | |
| JPH028964B2 (en) | ||
| JPS5884108A (en) | Manufacture of high purity alpha-type silicon nitride | |
| JPH0483706A (en) | Production of boron nitride | |
| WO2005070822A1 (en) | Continuous pusher-type furnacing system for the production of high-quality uniform boron nitride | |
| JP2726703B2 (en) | Method for producing aluminum nitride powder | |
| JP3585302B2 (en) | Manufacturing method of aluminum nitride | |
| IL104435A (en) | Continuous process for the preparation of silicon nitride by carbonitriding and silicon nitride obtained thereby | |
| US20030101850A1 (en) | Continuous procedure for the manufacture of powdered materials | |
| JP3539777B2 (en) | Manufacturing method of aluminum nitride | |
| JPH08245206A (en) | Boron carbonitride compound and method for synthesizing the same | |
| JPH0463802B2 (en) | ||
| JPH02192408A (en) | Production of aluminum nitride powder |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |