JPS616117A - Molding of starting material for manufacturing sic or metallic si - Google Patents

Abstract

PURPOSE:To improve the yield of Si by increasing the amount of C in the peripheral parts of moldings of an SiO2-C mixture as compared with the average C content of the moldings so as to fix SiO formed during a reaction for manufacturing metallic Si or SiC. CONSTITUTION:The weight ratio of SiO2/C in the central parts of moldings of a mixture contg. SiO2 and C as principal components is increased as compared with the average weight ratio of SiO2/C in the moldings, and the weight ratio of SiO2/C in the outside peripheral parts is decreased. The resulting moldings have a two-layered structure contg. much C in the outer layers. SiO formed chiefly in the central parts during a reaction for manufacturing metallic Si or SiC is fixed by the outside peripheral parts without scattering, so the yield of Si is improved and the consumption unit of electric power required to manufacture SiC can be reduced.

Description

【発明の詳細な説明】 く光用の目的〉 産業上の利用分野 本発明はＳｉＣあるいは金属Ｓ１製造用原料成型物に係
り、詳しくは、ＳｉＣや金属３１等がぎわめで製品歩留
りよく製造できかつ大巾に電力原単位も低減できる原料
成型物に係る。[Detailed Description of the Invention] Purpose of Lighting> Industrial Field of Application The present invention relates to a raw material molded product for producing SiC or metal S1, and more specifically, it is a molded product that is made of SiC, metal S1, etc., and can be produced with a high product yield. It relates to raw material moldings that can significantly reduce the electricity consumption rate.

従　　来　　の　　技　　術 金１ｉｉｓｉは従来粒状の３１０２および炭素（例えば
コークス）を電気炉に装入し、２０００℃以上の温度に
ｂＯ熱し、ＳｉＯ２と炭素を反応させる口とにより製造
され−（きた。また、ＳｉＣはＳｉＯ２と炭素の混合物
を大気を遮断して電気的に加熱し、５１０２と炭素を反
応させることにより製造されている。両者の反応はそれ
ぞれ、 ＳｉＯ２＋２Ｃ→Ｓｉ＋２ＧＯ・・・・（１）Ｓｉｎ２
−１　３０→ＳｉＣ＋２ＧＯ・・・・（２）上記（１）
、（２）式によって示されるが、実際には、これら反応
に削随して、どうしても、Ｓｌの並酸化物て゛あるＳｉ
Ｏが（３）式の反応により生成づる。Conventional technology Gold 1IIS has conventionally been produced by charging granular 3102 and carbon (e.g. coke) into an electric furnace, heating it to a temperature of 2000° C. or higher, and causing SiO2 and carbon to react. In addition, SiC is manufactured by electrically heating a mixture of SiO2 and carbon while blocking the atmosphere, and reacting 5102 with carbon.The reactions between the two are as follows: SiO2+2C→Si+2GO... (1) Sin2
-1 30→SiC+2GO...(2) Above (1)
, (2), but in reality, as a result of these reactions, Si, which is a sub-oxide of Sl, is inevitably produced.
O is produced by the reaction of formula (3).

５１０２イーＣ−＋ＳｉＯ＋ＧＯ・・・・・（３）しが
し、このＳｉＯが生成すると、ＳｉＯは蒸気圧が高いた
め、ＳｉＯが外部に放散し、成品の歩留りの低下、電力
原単位の１臂をもたらし、例えば、アーク炉での金属Ｓ
１製造における歩留り（、、Ｌ約８５％程瓜できわめて
低い。5102 E-C-+SiO+GO...(3) However, when this SiO is generated, SiO has a high vapor pressure, so it dissipates to the outside, reducing the yield of the product and reducing the power consumption per unit. For example, metal S in an arc furnace
1. The yield in production is extremely low for melons (approximately 85%).

発明が解決しようとする問題点 要づるに、本発明は上記欠点の解決を目的としているが
、具体的には、金属３１等の製造時のＳｉＯの生成によ
る成品歩留り低下や、電力原単位の低下等の問題点を解
決することを目的としている。Problems to be Solved by the Invention In short, the present invention aims to solve the above-mentioned drawbacks, but specifically, the reduction in product yield due to the generation of SiO during the production of metal 31, etc., and the reduction in the power consumption rate. The purpose is to solve problems such as the decline in

〈発明の構成〉 問題点を解決するための 手段ならひにその作用 本発明は、金属Ｓ１やＳｉＣ等の！！！７造時のＳｉＯ
の生成の抑制が困難であるため、直接その抑制を行なわ
ずに生成させるが、生成づるＳｉＯは飛散することなく
効率よく捕捉されしかも金属Ｓ１ヤＳｉＣ等に転化でき
る構造の原料成型物を提案ゴる。<Structure of the Invention> The present invention is a means to solve the problem. ! ! SiO at the time of 7 construction
Since it is difficult to suppress the generation of SiO, we have proposed a raw material molded product with a structure that allows it to be generated without directly suppressing it, but the generated SiO can be efficiently captured without scattering and can be converted into metal S1 or SiC. Ru.

すなわち、本発明は主として５１０２とＣとの混合物か
ら成る成型物であって、この成型物の平均のＳｉＯ２／
Ｃの重量比に対し、中心部のＳｉＯ２／Ｃの重量比を人
きくかつ外周部のＳｉＯ２／Ｃの重量比を小さく構成し
て成ることを特徴とする。That is, the present invention is a molded product mainly composed of a mixture of 5102 and C, and the average SiO2/
It is characterized in that the weight ratio of SiO2/C in the central part is set to be high and the weight ratio of SiO2/C in the outer peripheral part is small relative to the weight ratio of C.

そこで、この構成ならひにその作用につき更に詳しく説
明すると、次の通りである。Therefore, the operation of this configuration will be explained in more detail as follows.

まず、５１０２および、炭素から金属Ｓｉを製造する揚
台の反１，６は上述の（１）式で示される。けれども、
実際に小型電気炉内に３１０２とＣＩ！：混合して装入
し、高温で反応させると、金属Ｓ１の他にもＳｉＣや、
更にはＳｉＯが生成し、とくに、Ｓ　ｉ　０１．Ｌフユ
ームとなって、電気炉外へ排出される。そこて、このＳ
ｉＯをＣあるいはＳｉＣと反応させると、前当のＣの場
合は、金ｆｉｓｔ　Ｊ　ＳｉＣ，後者のＳｉＣの場合は
金属Ｓｉが゛それぞれ生成することを確認した。この反
応をみると、生成した５１０（ま、ＣあるいはＳｉＣと ＳｉＯ４−Ｃ−Ｉ　Ｓｉ　＋Ｇｏ・・・・・（４）Ｓｉ
Ｏ＋２Ｏ−３ｉＣ＋ＧＯ・・・・・（５）ＳｉＯ−１−
３ｉＣ→２Ｓｉ＋ＧＯ・・・・・（６）のＪ、うな反応
を起こすことが判った。更に、このような反応は、生成
物が固体あるいは液体であり、がっ、蒸気圧がＳｉＯと
比較して低いため、Ｓｌの歩留り向上のため有益であっ
た。First, 5102 and the lift platform 1, 6 for producing metal Si from carbon are expressed by the above equation (1). However,
Actually 3102 and CI in a small electric furnace! : When mixed and charged and reacted at high temperature, in addition to metal S1, SiC,
Furthermore, SiO is generated, especially SiO1. It becomes L fume and is discharged outside the electric furnace. There, this S
It was confirmed that when iO is reacted with C or SiC, gold fist J SiC is produced in the case of the former C, and metallic Si is produced in the case of the latter SiC. Looking at this reaction, the generated 510 (well, C or SiC and SiO4-C-I Si + Go... (4) Si
O+2O-3iC+GO...(5) SiO-1-
3iC→2Si+GO...J in (6) was found to cause a similar reaction. Furthermore, such a reaction was beneficial for improving the yield of Sl because the product was solid or liquid and had a lower vapor pressure than SiO.

しかしながら、現実の電気炉内においては、（４）、（
５）、（６）式で示されるＳｉＯ消費反応と同時に（３
１Ｘ”、で示されるＳｉＯ生成反応が起き、このため、
ＳｉＯが外部へ放散Ｊ−るのを完全に止めることは困難
であった。However, in an actual electric furnace, (4), (
At the same time as the SiO consumption reaction shown by equations (5) and (6), (3
1X", a SiO production reaction occurs, and therefore,
It has been difficult to completely prevent SiO from dissipating to the outside.

そこで、本発明者等は、（３）式によるＳｉＯの生成は
ＳｉＯ２の存在づる場所で起こるのに対し、（４）、（
５）　＜：ｊらひに（６）式によるＳｉＯの固定は、Ｃ
またはＳｉＣが存在Ｊる場所で起こることに着目し、金
属Ｓ１やＳｉＣ等の製造用原料を主としてＳｉＯ２とＣ
とがら成る混合物の成型物とし、その成型物の中心部若
しくは内部を実質的に８１０２が多く、壬してこの部分
をＳｉＯ生成帯とし、この生成帯の外周にＣが過剰に存
在する領域を配置した構造の原料成型物を開発した。Therefore, the present inventors concluded that, whereas the generation of SiO according to equation (3) occurs at the location where SiO2 exists, (4), (
5) <:j Rahini The fixation of SiO by formula (6) is C
Or, focusing on the fact that SiC occurs where SiC exists, we mainly use SiO2 and C as raw materials for manufacturing metal S1 and SiC.
A molded product of a mixture consisting of spikes, the center or inside of the molded product has a substantial amount of 8102, this part is used as a SiO generation zone, and a region in which C is excessively present is arranged around the outer periphery of this generation zone. We have developed a raw material molded product with a similar structure.

すなわら、口の成型物は少なくとも２層、例えば、第１
図に示す通り、中心部１とぞの外周部２とを具えている
。この成型物は全体としては主としてＳｉＯ２とＣ（７
）混合物であるが、外周部２にＣを過剰に存在させ、そ
の内側の中心部１にＳｉＯ□を多く存在させる。この中
心部１や外周部２の８１０２やＣの割合を成型物全体の
５ｉ０２／Ｃの平均重量比とに関連させて示すと、中心
部１の５ｉ０２　／Ｃ重呈比が平均重量比より大きくし
、外周部２の５ｉＯ７／Ｃ＠Ｎｉ比が平均重量比より小
さい。That is, the mouth molding has at least two layers, e.g.
As shown in the figure, it has a central portion 1 and an outer peripheral portion 2. This molded product as a whole consists mainly of SiO2 and C(7
) A mixture in which an excessive amount of C is present in the outer peripheral part 2, and a large amount of SiO□ is present in the inner central part 1. When the proportions of 8102 and C in the center part 1 and the outer peripheral part 2 are shown in relation to the average weight ratio of 5i02/C of the entire molded product, the weight ratio of 5i02/C in the center part 1 is larger than the average weight ratio. However, the 5iO7/C@Ni ratio of the outer peripheral portion 2 is smaller than the average weight ratio.

まＩ：、５１０２の多い中心部１は第１図に示す如く必
ずしし成型物の中心に配置しなくとも良く、Ｃの多い外
周部２の内側であれば、いかなるところに配置すること
もできる。I: The center part 1 with many Cs does not necessarily need to be placed at the center of the molded product as shown in FIG. 1, but can be placed anywhere as long as it is inside the outer peripheral part 2 with many Cs. can.

この構成に係る原料成型物であると、生成反応の間にＳ
ｉＯが生成してもそれによるＳｉの飛散ｌｆ　ｔＪ：と
んとおさえられて金属Ｓ１、ＳｉＣ？７が生成できる。With a raw material molded product having this configuration, S during the production reaction
Even if iO is generated, Si scatters due to it lf tJ: Metal S1, SiC? 7 can be generated.

従来がら、原料とＣ等の還元剤を微粉砕して両名を良く
混合した後、これを塊成化し−Ｃ両名の反１．ｉ；を促
進させることが行なわれている。例えば、酸化鉱の１コ
−タリーキルン法による還元において、Ｃ粉を混合した
ベレットが使用されている。しがし、金属Ｓｉの製造に
おいては、単に３１０２とＣを微粉砕し、ベレットまた
はブリケラ１〜状にしたのみＣ−は十分満足されるＳｉ
の歩留りを得ることは回動である。Conventionally, the raw material and the reducing agent such as C are finely pulverized and the two are mixed well, and then this is agglomerated to form an anti-1. i; is being promoted. For example, in the reduction of oxide ores by the one-cotery kiln method, pellets mixed with C powder are used. However, in the production of metal Si, simply pulverizing 3102 and C into pellets or briquettes can produce Si that satisfies C-.
Obtaining a yield of is a rotation.

この点、本発明では単に粉状の８１０．とＣとを混合、
塊成化したものでなく、個々の１宛成化原料の外表面部
分には平均より多くのＣを配合し、逆に中心部分には平
均より多くの５１０２を配合（る。従って、この構造の
ものであると、内部で生成したガス状ＳｉＯが原料の内
部から外部へと拡散づる過程でＳｌまたはＳｉＣとして
捕えられ、原料がらのＳｉＯ放出聞を大巾）こ低下させ
る。In this regard, in the present invention, 810. and C mixed,
Rather than agglomerated materials, the outer surface portion of each 1-containing raw material contains more C than the average, and conversely, the center portion contains more 5102 than the average. Therefore, this structure If it is, the gaseous SiO generated inside is captured as Sl or SiC in the process of diffusing from the inside of the raw material to the outside, greatly reducing the SiO emission rate from the raw material.

この点について、以下に述べる実験にＪ二りその効果を
確認したところ、次の通りであった。Regarding this point, the effect was confirmed by J2 in the experiment described below, and the results were as follows.

まず、平均の原料となる８１０２粒子とＣＩａであるコ
ークス粒子を粉砕する。コークス中のＣは約８８％であ
るため、実際に原料の配合をｈ　’Ｊう場合はこの影響
を考慮するが、以下においては簡単のためＳｉＯ２．　
Ｃの両方とも純ａ１００％であるものとして配合量を示
す。実験は化学量論的に金１ｉ１ｓｉを生成・するたけ
の平均Ｃ配合量すなわちＳｉＯ２［３０ｇに対し、Ｃ２
４Ｑの割合（０％−２８，６％）で行なった。なＪ３、
塊成化にはタール系のバインダーを；へ加した。First, 8102 particles, which are the average raw material, and coke particles, which are CIa, are crushed. Since C in coke is approximately 88%, this effect will be taken into consideration when actually blending the raw materials, but for the sake of simplicity below, we will use SiO2.
The blending amounts are shown assuming that both C are 100% pure a. The experiment was conducted using the average C content of SiO2 [30 g, C2
It was conducted at a rate of 4Q (0%-28.6%). Na J3,
A tar-based binder was added for agglomeration.

塊成原料はほぼ球形のベレン１〜であり、Ｃ；農度の異
なる内、外２重層で構成づる。低温で塊成化したペレッ
トは一旦９００’Ｃまで昇温する口とにより焼成し、焼
成ペレットを第２図に示すＳｉの収率測定実験装置の誘
導加熱型の電気炉内で、２０００“Ｃまで冒温し、その
後、２０００”Ｃに保持して反応を完結させ、ペレット
をか外に取出し、ごの重量と分析値よりＳｉの収率を計
算する。The raw material for agglomeration is approximately spherical belene 1~, which is composed of two layers, C: inner and outer layers with different agricultural degrees. The pellets agglomerated at a low temperature are fired by raising the temperature to 900'C, and the fired pellets are heated to 2000'C in an induction heating electric furnace of the Si yield measurement experimental apparatus shown in Figure 2. After that, the pellet was heated to 2000"C to complete the reaction. The pellet was taken out, and the yield of Si was calculated from the weight of the pellet and the analytical value.

なお、第２図で３はスペーサ（ＳｉＣ板）、３ａはシリ
カヂ１−ブ、３ｂは誘導コイル、４は黒鉛るつは、５は
支持台、６はのぞき窓、７は排ガス管、８はミラー、９
は光高温計、１０は塊成化原料の試トｌを示１゜ 内外の苦の重量割合を一定とし、内外に配分するＣの割
合を変化させて、実験を行なった。In Fig. 2, 3 is a spacer (SiC plate), 3a is a silica die, 3b is an induction coil, 4 is a graphite tube, 5 is a support stand, 6 is a peephole, 7 is an exhaust gas pipe, and 8 is an induction coil. mirror, 9
Reference numeral 10 indicates an optical pyrometer, and 10 indicates a trial of the agglomerated raw material. 1° Experiments were conducted by keeping the weight proportions of the inner and outer parts constant and varying the proportion of C distributed between the inner and outer parts.

第１表に内層と外層の重量圧を４０　：　６０としたと
きの内、外層へのＣの分配率と＄１収率の関係を示づ。Table 1 shows the relationship between the distribution ratio of C to the outer layer and the $1 yield when the weight pressure of the inner layer and the outer layer is 40:60.

この試験結果から本発明の効果は明らかである。The effects of the present invention are clear from this test result.

第１表 なお、上記のところで本発明は市販ならひに現在製造さ
れるＳｉＯ２粉末全てに適用できるが、本発明はなるべ
く高純度、例えば、９８％以上のものを原料とするとき
に、その効果は〜跨発揮でき、とくに、９９％台、更に
は、９９．９９９％やそれ以上の高純度の８１０２粉末
にも適用でさ、更に、ＣＲとしてはＣを含むものは何れ
の固体にも適用で・きるが、高純度の黒鉛、ツノ−ボン
ブラック等も適用できる。Table 1 As mentioned above, the present invention can be applied to all currently produced SiO2 powders if they are commercially available. It can be applied to 8102 powder with a purity of 99% or even 99.999% or higher.Furthermore, as CR, it can be applied to any solid containing C. However, high purity graphite, horn bomb black, etc. can also be used.

実　　施　　例 次に、実施例を示すと、次の通りである。Example Next, examples are as follows.

まず、第３図に示す小型の抵抗加熱式反応炉を用いて、
ＳｌおよびＳｉＣ製造実験を行なった。First, using a small resistance heating reactor shown in Figure 3,
Sl and SiC production experiments were conducted.

この反応炉において符号１２は電極１３は黒鉛発熱体、
１４は鉄皮、１５はシリカるつぼ、１６は断熱材、１７
は・５、た、１８はス料の塊成化原石を承り。また、Ｓ
ｉ製造の場合（こ１．Ｌ装入ＪるＳｉＯ２とＣの重量比
をＣ４Ｏ：２４ニ、ＳｉＣ製ｉ１　（７）場合ニｔ、！
５ｉ０２トｃ（７）’１ｆｆｉ比を６０　：　３６に固
定し、その上で各々につき外周部と中心部のＣ吊を変化
させて３種の塊成化原石１．２．３をつくった。In this reactor, reference numeral 12 indicates an electrode 13 which is a graphite heating element;
14 is the iron skin, 15 is the silica crucible, 16 is the insulation material, 17
Ha・5, Ta, 18 received agglomerated raw stone of steel. Also, S
In the case of i manufacturing (this 1.L charge, the weight ratio of SiO2 and C is C4O:24, and if SiC is made in i1 (7), !
5i02tc(7)'1ffi ratio was fixed at 60:36, and three types of agglomerated fossilized raw stones 1.2.3 were made by changing the C-hangs of the outer periphery and center.

更に、比較例として従来例の粒状のＳｉＯ２とコークス
の混合物から成る塊成化原石を用意した。これら塊成化
原料（焼成後のもの）を第３図に示づ反応炉に装入し、
一定時間一定電力を通電した後、反応炉を冷却し、生成
物中の金属Ｓ１生成ｍあるいはＳｉＣ生成量を求めた。Further, as a comparative example, an agglomerated ore made of a mixture of granular SiO2 and coke of a conventional example was prepared. These agglomerated raw materials (after firing) are charged into the reactor shown in Fig. 3,
After applying constant electric power for a certain period of time, the reactor was cooled, and the amount of metal S1 produced (m) or SiC produced in the product was determined.

この結果は、従来例の粒状の８１０２とコークス混合′
勿の場合の生成量を１００としたときの相対舶で金属Ｓ
１あるいはＳｉＣの生成量を示づと、第２表 第２表から明らかなように、従来の卯月より本発明に係
るものの方が、収量が増し−Ｃおり、本発明による原料
の優位性が明らかとなった。。This result shows that the conventional example of granular 8102 and coke mixture'
Metal S in the relative ship when the production amount in the case of course is 100
1 or SiC production, as is clear from Table 2, the yield of the raw material according to the present invention is higher than that of the conventional Uzuki, indicating the superiority of the raw material according to the present invention. It became clear. .

〈発明の効果ン 本発明は、主として５１０２とＣの混合物がら成る成望
慟であるが、外周部とその内側の中心部とがＣ含有量が
相違する諾状構造物であり、しがも、外周部に過剰のＣ
が含まれる。従って、金属Ｓ１や５ｉＣ７７の製造反応
時に土として中心部からＳｉＯが生成−づるが、このＳ
ｉＯは飛散せず（こ外周部（こより固定され、Ｓ１収率
は大巾に向」−シ、Ｓ１製造時の霜力原中位が低下−づ
る。とくに、高価な高ｆ沌度の３１０２粉末を用いると
きは、Ｓｉ収率の大巾の向上によりその効果は一隔助長
される。<Effects of the Invention> The present invention is a composite structure mainly composed of a mixture of 5102 and C, but it is a composite structure in which the outer peripheral part and the inner center part have different C contents. , excessive C on the outer periphery
is included. Therefore, during the manufacturing reaction of metal S1 and 5iC77, SiO is produced from the center as soil, but this S
iO does not scatter (it is fixed from the outer periphery), and the S1 yield increases significantly, and the medium frost force during S1 production decreases. When powder is used, the effect is further enhanced due to the significant improvement in Si yield.

【図面の簡単な説明】[Brief explanation of drawings]

第１図は本発明の一つの実施例に係る原石成型物の断面
図、第２図はＳｌの収率測定実験装置の一例の配置図、
第３図は本発明に係るものと比較例とを用いて金属Ｓ１
あるいはＳｉＣを製造し、その際の効果を求めた実験装
置の一例の配置図である。 符号１・・・・・中心部　　　　２・・・・・・外周部
３・・・・・ＳｉＣ板（スペーサー暑 ３ａ・・・・・・シリカヂ］−ブ ３１）・・・・・・誘導コイル　　４・・・・・・黒鉛
るつ【−［５・・・・・・支持台　　　　６・・・・・
・のぞき窓７・・・・・・排ガス管　　　８・・・・・
ミラー９・・・・・・光高温計 １０・・・・・・試料（塊成化原料） １２・・・・・・電極　　　　　１３・・・・黒鉛発熱
体１４・・・・・鉄皮FIG. 1 is a cross-sectional view of a molded raw stone according to one embodiment of the present invention, and FIG. 2 is a layout diagram of an example of an experimental device for measuring the yield of Sl.
FIG. 3 shows the metal S1 using the one according to the present invention and the comparative example.
Alternatively, it is a layout diagram of an example of an experimental device for manufacturing SiC and determining the effects at that time. Code 1... Center part 2... Outer circumference part 3... SiC plate (spacer heat 3a... Silicaji]-bu 31)... Induction coil 4...Graphite melt [-[5...Support stand 6...
・Peep window 7...Exhaust gas pipe 8...
Mirror 9... Optical pyrometer 10... Sample (agglomeration raw material) 12... Electrode 13... Graphite heating element 14... Iron shell

Claims (1)

【特許請求の範囲】[Claims] 主としてＳｉＯ＿２とＣとの混合物から成る成型物であ
って、この成型物の平均のＳｉＯ＿２／Ｃの重量比に対
し、中心部のＳｉＯ＿２／Ｃの重量比を大きくかつ外周
部のＳｉＯ＿２／Ｃの重量比を小さく構成して成ること
を特徴とするＳｉＣあるいは金属Ｓｉ製造用原料成型物
。A molded product mainly consisting of a mixture of SiO_2 and C, in which the weight ratio of SiO_2/C in the center is larger than the average weight ratio of SiO_2/C in the molded product, and the weight of SiO_2/C in the outer periphery is increased. A raw material molded product for producing SiC or metal Si, characterized in that it is configured with a small ratio.