TW201332891A - Recovery method for solid particle - Google Patents

Recovery method for solid particle Download PDF

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TW201332891A
TW201332891A TW101135139A TW101135139A TW201332891A TW 201332891 A TW201332891 A TW 201332891A TW 101135139 A TW101135139 A TW 101135139A TW 101135139 A TW101135139 A TW 101135139A TW 201332891 A TW201332891 A TW 201332891A
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sic
solid
liquid
particle diameter
carbon
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TWI458680B (en
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Yoshihiro Kubota
Tomoo Higuchi
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Shinetsu Chemical Co
Shinano Electric Refining Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D21/00—Separation of suspended solid particles from liquids by sedimentation
    • B01D21/01—Separation of suspended solid particles from liquids by sedimentation using flocculating agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D21/00—Separation of suspended solid particles from liquids by sedimentation
    • B01D21/26—Separation of sediment aided by centrifugal force or centripetal force
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/005—Separating solid material from the gas/liquid stream
    • B01J8/0055—Separating solid material from the gas/liquid stream using cyclones
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/90—Carbides
    • C01B32/914—Carbides of single elements
    • C01B32/956—Silicon carbide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/02—Silicon
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00—Treatment of sludge; Devices therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2215/00—Separating processes involving the treatment of liquids with adsorbents
    • B01D2215/02—Separating processes involving the treatment of liquids with adsorbents with moving adsorbents
    • B01D2215/029—Centrifuge-like arrangements
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Hydrology & Water Resources (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)
  • Separation Of Solids By Using Liquids Or Pneumatic Power (AREA)
  • Silicon Compounds (AREA)

Abstract

Provided is a method that is not only used to separate and recover solid particles having a bigger particle diameter from liquid containing solid particles of SiC or Si, but is also used to efficiently process solid-liquid separation for ultrafine solid particles having a particle diameter smaller than the solid particles to recover all the solid particles. A recovery method of the solid particles of SiC and/or Si includes: a first step, liquid containing solid particles of SiC and/or Si is processed by a centrifugal separation or/and a liquid cyclone to separate and recover solid particles having a larger particle diameter in the solid particles, and to discharge liquid in which solid particles having a smaller particle diameter are remained; a second step, an organic coagulant is added to the liquid discharged at the first step, such that the solid particles having a smaller particle diameter are coagulated, and liquid containing formed aggregate is processed by the centrifugal separation or filtration to recover the aggregate.

Description

固體粒子的回收方法 Method for recovering solid particles

本發明是有關於將在液體中含有的SiC或Si的固體微粒子從液體中分離回收的方法以及使所述回收的固體微粒子可以進行再利用的再生方法。 The present invention relates to a method for separating and recovering solid fine particles of SiC or Si contained in a liquid from a liquid, and a regeneration method for allowing the recovered solid fine particles to be reused.

近年，碳化矽粉(SiC粉)不僅使用於Si、水晶、SiC、GaAs、GaN等的單結晶或多結晶的基板、玻璃或陶瓷等的切割、研削或研磨，還作為SiC成形體的原料而被廣泛使用。所述SiC粉，通常用艾奇遜法(Acheson method)進行分批反應來加以製造。 In recent years, tantalum carbide powder (SiC powder) has been used not only for cutting, grinding, or polishing of single crystal or polycrystalline substrates such as Si, crystal, SiC, GaAs, or GaN, glass, ceramics, etc., but also as a raw material for SiC formed bodies. being widely used. The SiC powder is usually produced by a batch reaction using the Acheson method.

艾奇遜法是在大氣開放的U型爐中，在中心長方向上通以石墨電極，在所述電極的周圍，將數mm-數cm的矽砂以及碳的混合物以魚糕狀層疊，在石墨電極通以大電流加熱來進行SiC的製造。所述反應(SiO2+3C→SiC+CO)為吸熱反應，僅石墨電極為發熱體且為高溫狀態，因此電極周圍充分反應，主要生成高溫安定型結晶的αSiC。另一方面，遠離電極的部分未反應，或者大量生成用途比較有限的低溫安定型結晶的βSiC和αSiC的混合物等，反應不充分。反應後，將塊狀的堅硬固化的爐內物進行粗 粉碎，僅選擇需要的αSiC部分進一步進行微粉碎。剩餘的未反應物或βSiC和αSiC的混合物，作為不要物而再一次返回作為反應原料。經微粉碎的αSiC根據用途，藉由用水等進行濕式分級、或者用空氣或氮等進行乾式分級，而調整成符合所述用途的最適當的粒度或粒度分布。如此得到的SiC微粉被大量用作所述的切割、研削、研磨的研磨粒、研削材料，或SiC成形體的原料粉末。 The Acheson method is a graphite electrode in the U-shaped furnace in which the atmosphere is open, and a mixture of strontium sand and carbon of several mm to several cm is stacked in the shape of a fish cake around the electrode. The graphite electrode is heated by a large current to produce SiC. The reaction (SiO 2 +3C→SiC+CO) is an endothermic reaction, and only the graphite electrode is a heating element and is in a high temperature state, so that the electrode is sufficiently reacted to form a high-temperature stable crystal αSiC. On the other hand, the portion far from the electrode is not reacted, or a large amount of a mixture of βSiC and αSiC having a low-temperature stable crystal having a relatively limited use is generated, and the reaction is insufficient. After the reaction, the block-shaped hard-hardened furnace contents were coarsely pulverized, and only the required αSiC portion was selected and further finely pulverized. The remaining unreacted material or a mixture of βSiC and αSiC is returned as a raw material of the reaction as an unnecessary substance. The finely pulverized αSiC is adjusted to a most appropriate particle size or particle size distribution according to the use by wet classification with water or the like or dry classification with air or nitrogen or the like according to the use. The SiC fine powder thus obtained is used in a large amount as the raw material powder of the above-mentioned cut, ground, ground abrasive grain, grinding material, or SiC formed body.

在SiC微粉的製造中，根據使用目的或用途而要求最適當的平均粒徑或粒度分布，因此對所需粒度和不要粒度進行的分級步驟是不可缺少的。所述分級中，成本比較低的精密分級一般為水分級法，含有不需要的SiC微粉的水溶液會大量產生。同樣地，在乾式分級的場合也有不要的SiC微粉產生，它們的處理也成為問題。另外，對單結晶或多結晶的Si錠或成形物進行研削時，含有切屑Si微粒子的廢液會大量產生，所述處理也成為問題。 In the production of SiC fine powder, the most appropriate average particle diameter or particle size distribution is required depending on the purpose of use or use, and therefore the classification step for the desired particle size and the unnecessary particle size is indispensable. In the classification, the precision classification with a relatively low cost is generally a water classification method, and an aqueous solution containing an undesired SiC fine powder is produced in a large amount. Similarly, in the case of dry grading, unnecessary SiC fine powder is also produced, and their handling is also a problem. Further, when a single crystal or a polycrystalline Si ingot or a molded product is ground, a waste liquid containing chip Si fine particles is generated in a large amount, and the treatment also becomes a problem.

作為所述溶液或廢液的處理，即便用離心分離機或過濾機將SiC或Si的微粒子回收並將其有效地利用，由於該狀態下超細微的粒子混在其中，因此極難進行完全的固液分離。作為工業廢棄物，通常進行焚燒處理，或者用大量的熱進行加熱乾燥後，將乾燥殘渣的SiC或Si回收，僅能作為經濟價值低的溶礦爐的脫氧劑而加以利用，或返回作為艾奇遜爐的原料而加以利用。將SiC以及Si的微粒子除去後的液體亦根據場合而進行蒸餾再利用，但是需要熱能高而不經濟。 As the treatment of the solution or the waste liquid, even if fine particles of SiC or Si are recovered by a centrifugal separator or a filter and are effectively utilized, since ultrafine particles are mixed therein in this state, it is extremely difficult to perform complete solidification. Liquid separation. As industrial waste, it is usually incinerated or heated and dried with a large amount of heat. After the SiC or Si of the dry residue is recovered, it can be used only as a deoxidizer for a low-concentration ore furnace, or returned as Ai The raw materials of the Qisen furnace are used. The liquid obtained by removing the fine particles of SiC and Si is also distilled and reused depending on the occasion, but it is required to have high heat energy and is not economical.

另外，將SiC作為遊離研磨粒，在漿狀下用線進行切割 的遊離研磨粒線鋸(wire saw)中，在水或油的溶劑中，將研削材料SiC的微粉和乙二醇、界面活性劑、防銹劑等種種添加材料加入，製作成漿，用於Si錠等的切割。若大量切割單結晶或多結晶Si，則所述漿從最適當的SiC的粒徑或粒度分布，由於磨耗、破裂、變形、細粒化而使粒度分布變寬、切割能力變差，同時切屑Si微粒子積蓄而使漿黏度上升，漿的循環使用會變得不可能，要與新的漿進行交換。在無法使用的漿廢液中，除水或油的溶劑以外，亦存在消耗並且細粒化的SiC、切屑Si或各種添加劑，由於排水汙染的問題，無法單純地加以廢棄。同樣地，藉由將金剛石粒進行固定而成的金剛石固定線鋸在製造晶圓以及薄片時產生的切屑Si微粒子也會含在漿廢液中，至今為止也難以再利用，其處理也成為問題。 In addition, SiC is used as a free abrasive grain and cut by wire in a slurry form. In a free abrasive wire saw, a fine powder of a grinding material SiC and a glycol, a surfactant, a rust preventive agent, and the like are added to a water or oil solvent to prepare a slurry for use in a slurry. Cutting of Si ingots and the like. If a large amount of single crystal or polycrystalline Si is cut, the slurry has a particle size distribution or a particle size distribution from the most suitable SiC, and the particle size distribution is broadened due to abrasion, cracking, deformation, fine granulation, and the cutting ability is deteriorated, while the chip is cut. The accumulation of Si particles increases the viscosity of the slurry, and the recycling of the slurry becomes impossible to exchange with the new slurry. In the slurry waste liquid which cannot be used, in addition to the solvent of water or oil, there are also SiC, chip Si or various additives which are consumed and finely granulated, and cannot be simply discarded due to the problem of drainage pollution. Similarly, the chip-fixed wire saw formed by fixing the diamond grains by the diamond-fixed wire saw is also contained in the slurry waste liquid when the wafer and the sheet are manufactured, and it is difficult to reuse it until now, and the processing thereof becomes a problem. .

這些線鋸漿廢液的SiC和Si的混合微粉，至今為止提出有不少回收、有效利用的方法，例如，於專利文獻1中，公開了一種碳化矽結晶體的製造方法，其於將研削泥中的金屬矽轉變為碳化矽時，加入必要量的碳，在非氧化條件下且1200℃以上進行加熱。另外，於專利文獻2中，公開了一種碳化矽的製造方法，其在廢矽汙泥中添加碳，將得到的混合物進行加熱。 The mixed fine powder of SiC and Si of these wire saw slurry waste liquids has been proposed so far, and many methods for recycling and effective use have been proposed. For example, Patent Document 1 discloses a method for producing a ruthenium carbide crystal body, which is used for grinding mud. When the metal ruthenium is converted into ruthenium carbide, a necessary amount of carbon is added, and heating is performed under non-oxidation conditions and at 1200 ° C or higher. Further, Patent Document 2 discloses a method for producing niobium carbide, which adds carbon to waste sludge and heats the obtained mixture.

這些方法為了將廢液中含有的細微的Si轉變為SiC，要在廢漿中添加必要量的碳，例如，石油焦碳(petroleum coke)或碳黑，然後進行加熱乾燥，或將所述廢漿進行離心分離或過濾，從而將得到的固體汙泥進行加熱，將切屑Si變為SiC(Si+C→SiC) 而回收利用。但是，這些方法中，由於超細微的粒子混雜在一起，實際上離心分離或過濾難以進行完全的固液分離，從而造成回收困難，超高速旋轉的高價的裝置或膨大的過濾面積會使成本變高，使實用化變得困難。現狀是可用離心分離機或液體旋風器僅將較大粒徑的粒子分離回收，進行再利用，但是含有殘留的超微粉的SiC或Si的殘液的固液分離困難，於該狀態下作為廢棄物。另外，即便於用加熱成本高的蒸餾法進行固液分離而再利用的場合，也由於超微粉的SiC以及Si過細，沒有利用價值，一般作為廢棄物來處理。 In order to convert the fine Si contained in the waste liquid into SiC, a necessary amount of carbon, for example, petroleum coke or carbon black, is added to the waste slurry, followed by heat drying, or the waste. The slurry is centrifuged or filtered to heat the obtained solid sludge to change the chip Si into SiC (Si+C→SiC) And recycling. However, in these methods, since ultrafine particles are mixed together, it is difficult to perform complete solid-liquid separation by centrifugation or filtration, which makes recovery difficult, and expensive equipment or expanded filtration area that rotates at a high speed causes cost. High, making practical use difficult. In the current state, only a large particle size particle can be separated and recovered by a centrifugal separator or a liquid cyclone, and reused. However, the solid-liquid separation of the residual liquid of SiC or Si containing residual ultrafine powder is difficult, and is discarded in this state. Things. In addition, even when it is used for solid-liquid separation by a distillation method with high heating cost, SiC and Si of ultrafine powder are too fine, and there is no use value, and it is generally treated as waste.

將溶液或廢液不進行固液分離而原封不動地進行加熱乾燥的方法需要大量的熱量而不經濟。即便暫時從廢漿中將SiC微粒子進行回收，在保持變形或細粒化的狀態下，無法用於線鋸等程度的用途。另外，與SiC微粒子一起回收的切屑Si微粒子因加熱而與碳反應，可新生成SiC，但是原本回收的Si由於是線鋸的切屑，超微粉且粒度分布廣，因此生成的SiC也為微粒子且粒度分布廣。與回收的SiC同樣地於要求所需的較大粒徑且狹窄的粒度分布的線鋸用等中是不適宜的低價值之物，由此期望改善。 The method in which the solution or the waste liquid is subjected to heat-liquid separation without solid-liquid separation requires a large amount of heat and is uneconomical. Even if the SiC fine particles are temporarily recovered from the waste slurry, they cannot be used for a wire saw or the like while being kept in a state of being deformed or finely granulated. In addition, the chip Si fine particles recovered together with the SiC fine particles react with carbon to form SiC, but the originally recovered Si is a chip of the wire saw, and has ultrafine particles and a wide particle size distribution, so that the generated SiC is also fine particles. Wide particle size distribution. In the same manner as the recovered SiC, it is an unsuitable low-value thing in a wire saw or the like which requires a large particle size and a narrow particle size distribution, and thus improvement is desired.

[先前技術文獻] [Previous Technical Literature] [專利文獻] [Patent Literature]

[專利文獻1]特開平11-116227號公報 [Patent Document 1] JP-A-11-116227

[專利文獻2]特開2002-255532號公報 [Patent Document 2] JP-A-2002-255532

本發明是為了解決上述課題而成者，目的是提供一種不 僅從含有SiC或Si的固體微粒子的液體將較大粒徑的固體微粒子分離回收，也將粒徑比所述固體微粒子小的超細微的固體微粒子高效率地進行固液分離，將這些所有的固體微粒子回收的方法，以及一種將所述回收的固體微粒子中的Si轉化為SiC，同時將變形或細粒化而使用困難、且沒有利用價值的SiC作為可用於具有利用價值高的粒徑或粒度的線鋸、研光(lapping)、拋光(polishing)用等高附加價值的研削材料、研磨粒、研磨材料且有用的SiC而再生的方法。 The present invention has been made to solve the above problems, and the object is to provide a The solid fine particles having a large particle diameter are separated and recovered only from the liquid containing the solid fine particles of SiC or Si, and the ultrafine fine particles having a smaller particle diameter than the solid fine particles are efficiently and solid-liquid-separated, and all of these are a method for recovering solid microparticles, and a method for converting Si in the recovered solid microparticles into SiC while using deformation or fine granulation, which is difficult to use and has no use value, can be used for a particle having a high utilization value or Particle size sawing, lapping, polishing, and other high value-added grinding materials, abrasive grains, abrasive materials, and useful SiC for regeneration.

為了達成所述目的而成的專利申請範圍第1項所述的SiC及/或Si的固體微粒子回收方法是包括以下步驟的方法：第一步驟，將含有SiC及/或Si的固體微粒子的液體，用離心分離或/及液體旋風器將所述固體微粒子中的較大粒徑的固體微粒子分離回收，將較小粒徑的固體微粒子殘存的液體排出；以及第二步驟，向第一步驟排出的液體中添加有機凝結劑，將所述較小粒徑的固體微粒子凝結，將含有所形成的凝結體的液體進行離心分離或過濾而將所述凝結體回收。 The SiC and/or Si solid fine particle recovery method according to the first aspect of the patent application scope is a method comprising the following steps: the first step, a liquid containing solid particles of SiC and/or Si Separating and recovering the larger particle size solid particles in the solid fine particles by centrifugal separation or/and a liquid cyclone, and discharging the remaining liquid of the smaller particle size solid particles; and the second step, discharging to the first step An organic coagulant is added to the liquid to solidify the small-sized solid fine particles, and the liquid containing the formed coagulated body is centrifuged or filtered to recover the coagulated body.

申請專利範圍第2項所述的固體微粒子回收方法為如申請專利範圍第1項所述的方法，其中所述有機凝結劑為下述化學式(1)表示的陽離子性有機凝結劑， The method of claim 1, wherein the organic coagulant is a cationic organic coagulant represented by the following chemical formula (1),

(式中，R1為氫原子或甲基，R2為碳數1-10的烷基，X為從Cl、Br、以及F選出的任一個鹵化物，a為0-10的數，b為1-10的數，m最小為3的數)。 (wherein R 1 is a hydrogen atom or a methyl group, R 2 is an alkyl group having 1 to 10 carbon atoms, X is any halide selected from Cl, Br, and F, and a is a number of 0 to 10, b For a number of 1-10, m is a minimum of 3).

申請專利範圍第3項所述的固體微粒子回收方法為如申請專利範圍第1項或第2項所述的方法，其中相對於第一步驟排出的液體100重量份，將所述有機凝結劑設為0.01重量份-10重量份。 The method of claim 1, wherein the method of claim 1 is the method of claim 1, wherein the organic coagulant is set relative to 100 parts by weight of the liquid discharged in the first step. It is 0.01 parts by weight to 10 parts by weight.

申請專利範圍第4項所述的再生為有用的SiC的再生方法，其特徵在於：於藉由如申請專利範圍第1項所述的固體微粒子回收方法所回收的所述凝結體中，添加碳、或碳和氧化矽，在非氧化性環境下進行最低也為1800℃的加熱，使所述SiC的平均粒徑肥大化，或使所述Si轉化為SiC。 The method for regenerating SiC according to the fourth aspect of the invention is characterized in that carbon is added to the coagulum recovered by the solid particle recovery method according to claim 1 of the patent application. Or carbon and cerium oxide, which are heated at a minimum of 1800 ° C in a non-oxidizing environment to enlarge the average particle diameter of the SiC or convert the Si into SiC.

申請專利範圍第5項所述的再生為有用的SiC的再生方法為如申請專利範圍第4項所述的方法，其中與碳、或碳和氧化矽一起添加從B、B4C、以及B2O3中選出的任一種燒結助劑。 A method of regenerating a useful SiC according to claim 5, which is the method of claim 4, wherein B, B 4 C, and B are added together with carbon, or carbon and cerium oxide. Any one of the sintering aids selected from 2 O 3 .

根據本發明的SiC及/或Si的固體微粒子回收方法，可從含有SiC或Si的固體微粒子的液體中，高效率地將固液進行完 全分離，將它們的超微粉的固體微粒子回收。作為所述回收步驟，藉由進行第一步驟和第二步驟的2階段回收，可從含有粒度分布廣的種種的粒徑的固體微粒子的液體中，將較大粒徑的固體微粒子和較小粒徑的固體微粒子分開回收。所述經回收的固體微粒子中，較大粒徑的固體微粒子可以原封不動地再一次循環而使用，較小粒徑的固體微粒子可進行再生而使用。另外，根據所述固體微粒子回收方法，可分離成各微粒子的固體成分和完全透明的液體成分，因此，不汙染排水，排水汙染的問題不會發生。經固液分離的液體也可以再一次使用。 According to the solid particle recovery method of SiC and/or Si according to the present invention, the solid liquid can be efficiently discharged from a liquid containing solid particles of SiC or Si. Fully separated, the solid microparticles of their ultrafine powder are recovered. As the recovery step, by performing the two-stage recovery of the first step and the second step, solid particles having a larger particle diameter and smaller can be obtained from a liquid containing solid particles of various particle sizes having a wide particle size distribution. The solid particles of the particle size are separately recovered. Among the recovered solid fine particles, solid fine particles having a larger particle diameter can be used as they are once again circulated, and solid fine particles having a smaller particle size can be used for regeneration. Further, according to the solid fine particle recovery method, the solid component of each fine particle and the completely transparent liquid component can be separated, so that the problem of drainage pollution does not occur without contaminating the drainage. The solid-liquid separated liquid can also be used again.

以往的方法中，向液體中直接加入碳，不僅會使離心分離的量或過濾量増加，固液分離的負擔增大，效率變壞，而且碳為微粒子的場合時，如添加必要量的碳，就會形成油脂狀或圓球狀，使固液分離的操作完全不能進行，與此相比，本發明的固體微粒子回收方法是在第一步驟中，將較大粒徑的固體微粒子回收後，於第二步驟中，將較小粒徑的固體微粒子進行凝結，然後進行固液分離，所以具有超高速旋轉或膨大的過濾面積的那樣的高價的裝置的使用就變得不必要了，經濟且實用。 In the conventional method, the direct addition of carbon to the liquid not only increases the amount of centrifugal separation or the amount of filtration, but also increases the burden of solid-liquid separation, and the efficiency is deteriorated. When carbon is fine particles, if necessary, a necessary amount of carbon is added. The oily or spherical shape is formed, and the operation of solid-liquid separation is completely impossible. In contrast, the solid fine particle recovery method of the present invention recovers the solid particles having a larger particle diameter in the first step. In the second step, the solid particles having a smaller particle diameter are coagulated and then subjected to solid-liquid separation, so that the use of such a expensive device having a super-high-speed rotating or expanded filter area becomes unnecessary, and the economy is economical. And practical.

根據本發明的再生方法，於該等經回收的固體微粒子之中，可將較小粒徑的固體微粒子的Si轉化為SiC，將細微的SiC肥大化，從而再生為具有所需的粒徑以及粒度分布且利用價值高的粒子再生。 According to the regeneration method of the present invention, among the recovered solid fine particles, Si of a small particle diameter solid fine particle can be converted into SiC, and fine SiC is enlarged to be regenerated to have a desired particle diameter and Particle size distribution and regeneration with high value particles.

以下，對本發明的優選實施方式進行詳細說明，但是本發明的範圍不受該等形態的限定。 Hereinafter, preferred embodiments of the present invention will be described in detail, but the scope of the present invention is not limited by the embodiments.

本發明的SiC及/或Si的固體微粒子回收方法，是從以下的液體的懸濁液中，將至今為止難以利用而作為廢棄物的SiC微粒子、Si微粒子或它們的混合微粉經濟且效率良好地分離回收的方法：含有在SiC粉的製造時的分級步驟中作為副產物而生成的目標粒徑以下的不要的SiC微粒子的溶液；含有對單結晶或多結晶的Si錠或成形物進行研削時的切屑Si微粒子的廢液；將SiC作為遊離研磨粒，在漿狀態下，將單結晶或多結晶Si藉由用線進行切割的遊離研磨粒線鋸或將金剛石粒固定而成的金剛石固定線鋸來製造晶圓或薄片時產生的SiC微粒子或Si微粒子，含有該等SiC微粒子或Si微粒子的漿廢液等。 The SiC and/or Si solid fine particle recovery method of the present invention is economically and efficiently used as a waste SiC fine particle, Si fine particle or a mixed fine powder thereof from the following liquid suspensions. A method of separation and recovery: a solution containing unnecessary SiC fine particles having a target particle diameter or less generated as a by-product in a classification step in the production of SiC powder; and when a single crystal or a polycrystalline Si ingot or a molded product is subjected to grinding a waste liquid of the chip Si particles; a free abrasive grain saw with a single crystal or polycrystalline Si cut by a wire or a diamond fixed wire obtained by fixing the diamond particles in a slurry state using SiC as a free abrasive grain The SiC fine particles or Si fine particles generated when sawing a wafer or a sheet, and a slurry waste liquid containing the SiC fine particles or Si fine particles.

對本發明的固體微粒子回收方法中的各步驟進行詳細說明。 Each step in the solid fine particle recovery method of the present invention will be described in detail.

所述固體微粒子回收方法包括：第一步驟，從含有SiC或Si的固體微粒子液體中用離心分離或液體旋風器將固體微粒子中的較大粒徑的固體微粒子分離回收；以及第二步驟，向第一步驟排出的液體中添加有機凝結劑，將較小粒徑的固體微粒子凝 結，將含有所形成的凝結體的液體用離心分離機或過濾機進行固液分離，將凝結體回收。 The solid microparticle recovery method includes: a first step of separating and recovering larger particle size solid particles in the solid microparticles from a solid microparticle liquid containing SiC or Si by centrifugal separation or a liquid cyclone; and a second step, Adding an organic coagulant to the liquid discharged in the first step to condense solid particles of smaller particle size In the knot, the liquid containing the formed coagulated body is subjected to solid-liquid separation by a centrifugal separator or a filter to recover the coagulated body.

第一步驟中，將含有作為固體主成分的SiC或Si的固體微粒子的液體，用離心分離機或液體旋風器進行離心分離或分級，從而分離成固體微粒子中較大粒徑的固體微粒子或含有其的液體，與較小粒徑的固體微粒子殘存的液體。其中，將較大粒徑的固體微粒子回收，將較小粒徑的固體微粒子殘留的液體排出。 In the first step, a liquid containing solid fine particles of SiC or Si as a main component of the solid is centrifuged or classified by a centrifugal separator or a liquid cyclone to be separated into solid fine particles having a larger particle diameter or contained in the solid fine particles. Its liquid, a liquid remaining with solid particles of smaller particle size. Among them, the solid fine particles having a larger particle diameter are recovered, and the liquid remaining in the solid fine particles having a smaller particle diameter is discharged.

較大粒徑的固體微粒子，其平均粒徑為4 μm-15 μm為優選。所述固體微粒子由於粒徑比較大，因此可再一次循環使用。在此，粒子的平均粒徑為用雷射測定法(日機裝公司製MicrotracHRA)測定的平均徑。 The solid fine particles having a larger particle diameter preferably have an average particle diameter of from 4 μm to 15 μm. Since the solid fine particles are relatively large in particle diameter, they can be recycled again. Here, the average particle diameter of the particles is an average diameter measured by a laser measurement method (Microtrac HRA manufactured by Nikkiso Co., Ltd.).

作為將較大粒徑的固體微粒子進行離心分離的離心分離機，可以例舉Decanter bucket型離心過濾機等利用離心力為500 G-3000 G的固液分離機。作為將較大粒徑的固體微粒子進行分級而分離的液體旋風器，可列舉將含有粗細固體粒子的漿沿切線方向導入，藉由利用旋轉運動而成的離心力將粗粒子和細粒子分離者。粗粒子從下方作為濃厚漿排出，細粒子從上方作為稀釋漿排出。第一步驟藉由離心分離機或液體旋風器，可將作為固體成分的較大粒徑的固體微粒子分離，也可以將含有較大粒徑的固體微粒子的液體進行分離。 The centrifugal separator that centrifugally separates the solid fine particles having a large particle diameter may, for example, be a solid-liquid separator using a centrifuge force of 500 G to 3000 G, such as a Decanter bucket type centrifugal filter. A liquid cyclone that separates and separates solid fine particles having a large particle size is exemplified by introducing a slurry containing coarse and fine solid particles in a tangential direction, and separating the coarse particles and the fine particles by a centrifugal force by a rotational motion. The coarse particles are discharged as a thick slurry from below, and the fine particles are discharged as a diluted slurry from above. In the first step, a solid particle having a larger particle diameter as a solid component can be separated by a centrifugal separator or a liquid cyclone, or a liquid containing solid particles having a large particle diameter can be separated.

第二步驟中，向第一步驟排出的液體即較小粒徑的固體微粒子殘存的液體中，添加有機凝結劑，將較小粒徑的固體微粒 子凝結而形成凝結體。將含有所述凝結體的液體用離心分離機或過濾機而固液分離成固體成分的凝結體和透明的液體成分，將凝結體回收。 In the second step, an organic coagulant is added to the liquid discharged from the first step, that is, the liquid remaining in the solid particles of smaller particle size, and the solid particles of smaller particle size are added. The child coagulates to form a coagulation body. The liquid containing the coagulated body is solid-liquid separated into a solid component coagulant and a transparent liquid component by a centrifugal separator or a filter, and the coagulated body is recovered.

作為有機凝結劑，例如可以例舉聚丙烯醯胺，聚乙烯胺，聚乙烯亞胺，各種的陽離子類的有機凝結劑等。特別是，下述化學式(1)中所示的陽離子性有機凝結劑效果良好。 Examples of the organic coagulant include polypropylene decylamine, polyvinylamine, polyethyleneimine, various cationic organic coagulants, and the like. In particular, the cationic organic coagulant shown in the following chemical formula (1) is effective.

式中，R1為氫原子或甲基，R1為氫原子或甲基，R2為碳數1-10的烷基，X為從Cl、Br、以及F選出的任一個鹵化物，a為0-10的數，b為1-10的數，m為3以上的數。 In the formula, R 1 is a hydrogen atom or a methyl group, R 1 is a hydrogen atom or a methyl group, R 2 is an alkyl group having 1 to 10 carbon atoms, and X is any halide selected from Cl, Br, and F, a The number is 0-10, b is a number of 1-10, and m is a number of 3 or more.

這些有機凝結劑與無機凝結劑不同，在後述的粒子的再生中，從Si微粒子轉化為SiC或SiC微粒子的肥大化時進行加熱分解而成為碳，因此該碳不像無機凝結劑那樣殘存而變為雜質，而成為再生中的反應原料的一部分，因此是適宜的。 Unlike the inorganic coagulant, in the regeneration of the particles described later, when the Si particles are converted into SiC or SiC fine particles, the particles are heated and decomposed to become carbon. Therefore, the carbon does not remain like the inorganic coagulant. It is an impurity and becomes a part of the reaction raw material in regeneration, and therefore it is suitable.

相對於第一步驟排出的液體100重量份，有機凝結劑的添加量為0.01重量份-10重量份。 The organic coagulant is added in an amount of from 0.01 part by weight to 10 parts by weight relative to 100 parts by weight of the liquid discharged in the first step.

第一步驟排出的液中殘存的較小粒徑的固體微粒子(0.1 μm-5 μm左右)凝結而回收的凝結體的平均粒徑，優選3 μm-15 μm。如比3 μm小，則效率良好地分離回收變困難。所述較小粒徑的固體微粒子具有破裂或變形，或者磨耗或細粒化，再利用困難，且沒有利用價值。由此，向回收的凝結體中添加碳、或碳和氧化矽，在1800℃以上進行加熱，藉此可從沒有利用價值的較小粒徑的固體微粒子，再生為利用價值高且具有較大粒徑，並且粒子的粒度分布狹窄的有用的SiC。 The average particle diameter of the coagulum recovered by coagulation of the smaller-sized solid fine particles (about 0.1 μm to 5 μm) remaining in the liquid discharged in the first step, preferably 3 μm - 15 Mm. If it is smaller than 3 μm, it is difficult to separate and recover efficiently. The smaller particle size solid microparticles have cracks or deformations, or are worn or finely granulated, are difficult to reuse, and have no utility value. Thereby, carbon, or carbon and cerium oxide are added to the recovered condensate, and heating is performed at 1800 ° C or higher, whereby the solid fine particles having a small particle diameter having no use value can be regenerated to have high utilization value and large Useful SiC having a particle size and a narrow particle size distribution of the particles.

本發明的再生為有用的SiC的再生方法為下述方法：向使較小粒徑的固體微粒子凝結回收而成的凝結體中，添加碳、或碳以及氧化矽，進一步根據需要而添加燒結助劑，之後在1800℃以上進行加熱反應，藉此使較小粒徑的固體微粒子中的SiC肥大化，另外使Si轉化為SiC，將這些固體微粒子再生。在此，所謂再生是指，細微化的SiC由於晶粒成長而肥大化，成為利用價值高的SiC，另外從Si新生成SiC，所述新生成的SiC由於晶粒成長而肥大化，形成利用價值高的SiC。該等再生的SiC優選為αSiC。 The method for regenerating SiC which is useful for regeneration in the present invention is a method of adding carbon, carbon, and cerium oxide to a coagulated body obtained by coagulating and collecting solid fine particles having a small particle diameter, and further adding sintering aid as needed. The agent is then subjected to a heating reaction at 1800 ° C or higher to thereby enlarge the SiC in the solid fine particles having a small particle diameter, and further convert Si into SiC to regenerate the solid fine particles. Here, the term "regeneration" refers to the fact that the fine SiC is enlarged by the grain growth, and the SiC is highly utilized, and SiC is newly formed from Si. The newly formed SiC is enlarged due to grain growth, and is formed and utilized. High value SiC. The regenerated SiC is preferably αSiC.

加熱反應的溫度若為1800℃以上的高溫，則使殘存的SiC或Si的反應物向αSiC結晶轉移，所以為優選，若未滿1800℃，則使反應物完全向SiC結晶轉移是困難的。 When the temperature of the heating reaction is a high temperature of 1800 ° C or higher, the residual SiC or Si reactant is transferred to the α SiC crystal. Therefore, if the temperature is less than 1800 ° C, it is difficult to completely transfer the reactant to the SiC crystal.

添加的碳作為形成SiC的反應原料的一部分而起作用，為使殘存的SiC肥大化的原料、新生成SiC的原料、使所述新生成SiC成長而肥大化的原料。進一步所述碳不僅僅為SiC的反應原料，還會作為容易反應的環境即反應的場所而起作用，對反應速度或生成的SiC的產率造成影響。因此，碳以粉末或粉體為優 選，所述粒徑以100 μm以下為優選。若粒徑太大，則反應速度變緩慢，同時生成的SiC的產率降低，所以不經濟。 The added carbon functions as a part of the reaction raw material for forming SiC, and is a raw material for making the remaining SiC rich, a raw material for newly forming SiC, and a raw material for growing the newly formed SiC to be enlarged. Further, the carbon acts not only as a reaction raw material of SiC, but also acts as a reaction-friendly environment, that is, a reaction site, and affects the reaction rate or the yield of SiC formed. Therefore, carbon is excellent in powder or powder. Optionally, the particle diameter is preferably 100 μm or less. If the particle diameter is too large, the reaction rate becomes slow, and at the same time, the yield of SiC formed is lowered, so that it is uneconomical.

碳的添加量因回收的凝結體的組成而變化。相對於凝結體中的Si的1.0莫耳，碳的添加量優選為1.0莫耳-1.5莫耳。 The amount of carbon added varies depending on the composition of the recovered coagulated body. The amount of carbon added is preferably 1.0 mole to 1.5 moles relative to 1.0 mole of Si in the condensate.

添加的氧化矽與所述的碳不同，對生成的SiC的產率幾乎沒有影響。但是，如所述粒徑過大，則反應速度變緩慢，因此不合適。氧化矽以粉末或粉體為優選，所述粒徑優選為200 μm以下。 The added cerium oxide is different from the carbon described, and has little effect on the yield of the produced SiC. However, if the particle diameter is too large, the reaction rate becomes slow, which is not suitable. The cerium oxide is preferably a powder or a powder, and the particle diameter is preferably 200 μm or less.

在添加碳和氧化矽的場合時，與僅添加碳的場合同樣地一起成為使殘存的SiC肥大化的原料、新生成SiC的原料以及使所述新生成的SiC成長而肥大化的原料。 In the case where carbon and cerium oxide are added, together with the case where only carbon is added, a raw material for increasing the residual SiC, a raw material for newly forming SiC, and a raw material for growing and newly growing the newly formed SiC are obtained.

碳以及氧化矽的添加量因回收的凝結體的組成而變化。相對於凝結體中的SiC及/或Si的1.0莫耳，碳以及氧化矽的添加量優選為0.1莫耳-10莫耳。於未滿0.1莫耳的場合時，殘存的SiC的肥大化不充分，或者新生成的SiC的粒徑極微小，無法得到實用的SiC。另外，於10莫耳以上的場合時，相對於必要量而發生過剩，因此有必要在反應後將所述過剩部分除去，並且使粒徑所需以上地變得過大。所以優選碳以及氧化矽的混合比率為碳：氧化矽=3-4：1。 The amount of carbon and cerium oxide added varies depending on the composition of the recovered condensate. The amount of carbon and cerium oxide added is preferably from 0.1 mol to 10 mol with respect to 1.0 mol of SiC and/or Si in the condensate. When the thickness is less than 0.1 mol, the remaining SiC is insufficiently enlarged, or the newly formed SiC has a very small particle diameter, and practical SiC cannot be obtained. On the other hand, when it is 10 mol or more, it is excessive with respect to the required amount. Therefore, it is necessary to remove the excess portion after the reaction and to increase the particle size more than necessary. Therefore, it is preferred that the mixing ratio of carbon and cerium oxide is carbon: cerium oxide = 3-4:1.

根據需要，添加的燒結助劑為向凝結體至少添加碳、或一起混合碳以及氧化矽而添加。作為燒結助劑，可使用一般使用的SiC的燒結助劑，但是如從B、B4C、以及B2O3選出至少一種， 則燒結促進效果高，為優選。 The sintering aid added is added by adding at least carbon to the coagulum or by mixing carbon and cerium oxide as needed. As the sintering aid, a sintering aid for SiC which is generally used can be used. However, if at least one of B, B 4 C, and B 2 O 3 is selected, the sintering promotion effect is high, which is preferable.

以這些步驟再生回收的SiC，可以調整為符合其用途的最適的粒徑或粒度分布。例如，線鋸漿中的SiC和Si的混合微粉中，如過度使用至SiC的平均粒徑未滿1 μm，則切割速度會變慢，生產性變差，所以要與新的漿進行交換。另外，若平均粒徑為20 μm以上，會容易大量產生研削傷或切割損失，所以通常不用。因此，再生化的SiC的平均粒徑優選1 μm-20 μm。 The SiC recovered by these steps can be adjusted to an optimum particle size or particle size distribution in accordance with its use. For example, in the mixed fine powder of SiC and Si in the wire saw slurry, if the average particle diameter of SiC is excessively less than 1 μm, the cutting speed is slowed and the productivity is deteriorated, so that it is exchanged with a new slurry. Further, when the average particle diameter is 20 μm or more, it is easy to cause a large amount of grinding damage or cutting loss, so it is usually not used. Therefore, the average particle diameter of the regenerated SiC is preferably from 1 μm to 20 μm.

【實施例】 [Examples]

以下，對本發明的實施例進行詳細說明，但是本發明的範圍不受該等實施例的限定。 Hereinafter, the embodiments of the present invention will be described in detail, but the scope of the present invention is not limited by the embodiments.

(實施例1) (Example 1)

將艾奇遜法中製造的αSiC粉碎為平均粒徑18 μm後，藉由水分級分為粗與細。分為粗的αSiC再一次返回作為粉碎原料。 The αSiC produced in the Acheson method was pulverized to an average particle diameter of 18 μm, and then classified into coarse and fine by water classification. The crude αSiC is again returned as a pulverization material.

作為第一步驟，將分為平均粒徑10 μm以下的細之物的αSiC的水溶液用CMS公司製造的縱型固液分離裝置，以1000 G-2000 G進行離心分離，將2 μm以上的粒子的較大粒徑的固體微粒子分離、回收。 In the first step, an aqueous solution of αSiC classified into a fine material having an average particle diameter of 10 μm or less is subjected to centrifugal separation at 1000 G to 2000 G using a vertical solid-liquid separation device manufactured by CMS Co., Ltd., and particles of 2 μm or more are used. The larger particle size solid particles are separated and recovered.

作為第二步驟，向第一步驟排出的液體且富含未滿2 μm的微粒子的溶液中，相對於所述溶液100重量份，將聚乙烯亞胺凝結劑以1重量份進行添加，使溶液中的固體成分凝結。此後，將所述溶液用高強過濾器(excel filter)進行過濾。固液分離的微粉已凝結，因此過濾容易，且過濾速度快，過濾液沒有微粉的混 入，所以是透明的，回收的過濾液可以再循環使用。 As a second step, in the solution which is discharged to the liquid in the first step and rich in microparticles of less than 2 μm, the polyethyleneimine coagulant is added in an amount of 1 part by weight relative to 100 parts by weight of the solution to prepare a solution. The solid components in the mixture condense. Thereafter, the solution was filtered with an excel filter. The solid-liquid separation of the fine powder has condensed, so the filtration is easy, and the filtration speed is fast, and the filtrate is not mixed with the fine powder. In, so it is transparent, and the recovered filtrate can be recycled.

將回收的固體成分的凝結體進行乾燥，向所述乾燥固體成分400 Kg中，加入平均粒徑80 μm、比表面積393 m2/g的木碳粉48 Kg以及平均粒徑120 μm的二氧化矽粉70 Kg，進行良好的混合而作為再生中的反應原料。將其在溫度控制為1850℃的推式爐(pusher furnace)且Ar氣體的流通下，邊將放入容器的反應原料進行移動，邊進行加熱反應。得到的反應生成物完全為αSiC的結晶。進一步在大氣中，在750℃下將過剩的碳除去。其結果，平均粒徑未滿2 μm的至今為止不能使用的細部分的αSiC微粉肥大化(晶粒成長)而再生為平均粒徑9.5 μm的αSiC，回收成為有用的SiC粉。該SiC粉作為線鋸用的研磨粒而合適。 The aggregate of the recovered solid component was dried, and 48 kg of wood carbon powder having an average particle diameter of 80 μm, a specific surface area of 393 m 2 /g, and a dioxide having an average particle diameter of 120 μm were added to 400 Kg of the dry solid component. The powder was 70 Kg, and it was well mixed and used as a reaction raw material in regeneration. This was heated while reacting the reaction raw material placed in the vessel under a flow of Ar gas under a flow of a gas furnace controlled at 1,850 °C. The obtained reaction product was completely crystalline of αSiC. Further, excess carbon was removed at 750 ° C in the atmosphere. As a result, αSiC having an average particle diameter of 9.5 μm is regenerated into a fine SiC powder having an average particle diameter of less than 2 μm which has not been used until now, and is recovered as a useful SiC powder. This SiC powder is suitable as an abrasive grain for a wire saw.

(比較例1) (Comparative Example 1)

除了不添加有機凝結劑以外，以與實施例1同樣的條件、方法進行回收，結果微粉的SiC將濾布網眼堵塞，使固液分離變得困難。進一步，極少的流出的濾液混濁，濾液中含有超微粉的SiC，無法進行完全的固液分離。 The recovery was carried out under the same conditions and in the same manner as in Example 1 except that the organic coagulant was not added. As a result, the fine powder of SiC blocked the filter cloth mesh and made solid-liquid separation difficult. Further, very little outflowing filtrate was turbid, and SiC containing ultrafine powder in the filtrate could not perform complete solid-liquid separation.

(實施例2) (Example 2)

作為第一步驟，線鋸廢液(固態成分，αSiC：30重量%、Si：4.1重量%、Fe：0.9重量%；溶液成分，乙二醇+界面活性劑+水混合物65重量%)在CMS公司製造的縱型固液分離裝置中以1000 G-2000 G進行離心分離，將10 μm以上的較粗粒子的較大粒徑的固體微粒子分離回收。 As a first step, wire saw waste liquid (solid content, αSiC: 30% by weight, Si: 4.1% by weight, Fe: 0.9% by weight; solution component, ethylene glycol + surfactant + water mixture: 65% by weight) in CMS The vertical solid-liquid separation device manufactured by the company centrifuges at 1000 G-2000 G, and separates and collects solid particles of larger particle size of coarser particles of 10 μm or larger.

作為第二步驟，相對於第一步驟排出的液體100重量份，將下述化學式(1)表示的R1=甲基、R2=烷基、X=鹵化物、a=1、b=5、m=5的陽離子性有機凝結劑0.02重量份添加至第一步驟排出的液體中，使固體成分凝結後，用加壓過濾機以3 kg/cm2的壓力進行加壓過濾、固液分離。所述分離的濾液為透明的。所述濾液可以在線鋸裝置中進行再循環。 As a second step, R 1 = methyl group, R 2 = alkyl group, X = halide, a = 1, b = 5 represented by the following chemical formula (1) with respect to 100 parts by weight of the liquid discharged in the first step. 0.02 parts by weight of the cationic organic coagulant having m=5 was added to the liquid discharged in the first step, and after solid content was coagulated, pressure filtration and solid-liquid separation were carried out at a pressure of 3 kg/cm 2 using a pressure filter. . The separated filtrate is transparent. The filtrate can be recycled in a wire saw device.

將回收的固體成分的凝結體乾燥後，向所述乾燥固體成分350 kg中添加粉碎至平均粒徑為15 μm且比表面積為50 m2/g的焦碳76 kg、以及平均粒徑為50 μm的二氧化矽粉50 kg，進行混合，作為再生的反應原料。將其在1900℃的轉爐中且Ar氣體流通下進行加熱反應。得到的反應物生成物為100%的αSiC且平均粒徑為8 μm，這可與使用前的SiC研磨粒的平均粒徑8.5μm幾乎同樣地再生。另外，再生前的廢液中的SiC的平均粒徑為4 μm，相當耗損、變形。 After the coagulated solids of the recovered solid components were dried, pulverized to a dry solid content of 350 kg, 76 kg of coke having an average particle diameter of 15 μm and a specific surface area of 50 m 2 /g, and an average particle diameter of 50 were added. The μm cerium oxide powder is 50 kg and mixed to be used as a reaction raw material for regeneration. This was subjected to a heating reaction in a converter at 1900 ° C under a flow of Ar gas. The obtained reactant product was 100% αSiC and the average particle diameter was 8 μm, which was regenerated almost in the same manner as the average particle diameter of SiC abrasive grains before use of 8.5 μm. Further, the average particle diameter of SiC in the waste liquid before regeneration was 4 μm, which was considerable in loss and deformation.

(實施例2-1) (Example 2-1)

除了不添加二氧化矽粉以外，以與實施例2同樣的條件、方法進行再生、回收。經細粒化的SiC的粒徑沒有肥大化(晶粒成長)，幾乎原封不動地為平均粒徑6 μm，切屑的Si微粉和焦碳的反應中生成的新的SiC的平均粒徑為1 μm，且為顯示2個峰的廣的粒度分布。不適於線鋸等的程度的用途。 Regeneration and recovery were carried out under the same conditions and in the same manner as in Example 2 except that the cerium oxide powder was not added. The particle size of the finely granulated SiC is not enlarged (grain growth), and the average particle diameter is almost 6 μm as it is, and the average particle diameter of the new SiC formed in the reaction of the Si powder and coke of the chip is 1 Μm, and is a broad particle size distribution showing two peaks. It is not suitable for the purpose of wire saws and the like.

(實施例3) (Example 3)

作為第一步驟，將含有將單結晶Si錠經圓筒研削時的切屑 Si微粒子的廢液，用離心分離機以1000 G-2000 G進行離心分離，將2 μm以上的粒子的較大粒徑的固體微粒子進行分離回收。 As a first step, it will contain the chips when the single crystal Si ingot is ground through the cylinder. The waste liquid of the Si fine particles is centrifuged at 1000 G to 2000 G by a centrifugal separator, and solid fine particles having a larger particle diameter of 2 μm or more are separated and recovered.

作為第二步驟，相對於第一步驟排出的液體的分離後的殘液100重量份，將所述化學式(1)表示的R1=甲基、R2=烷基、X=鹵化物、a=8、b=9、m=20的陽離子性有機凝結劑7重量份添加進殘液，使微粉一次性凝結後，在離心分離機中，以500 G-1000 G進行離心分離，進行未滿2 μm的超微粒子的固液分離。由於超微粉凝結，固液為良好地分離，分離液為無色透明，可以原封不動地進行排放。 In the second step, R 1 = methyl group, R 2 = alkyl group, X = halide, a is represented by the chemical formula (1), relative to 100 parts by weight of the residual liquid after separation of the liquid discharged in the first step. 7 parts by weight of a cationic organic coagulant of =8, b=9, and m=20 is added to the raffinate, and the fine powder is once condensed, and then centrifuged at 500 G-1000 G in a centrifuge to be submerged. Solid-liquid separation of 2 μm ultrafine particles. Since the ultrafine powder is coagulated, the solid solution is well separated, and the separation liquid is colorless and transparent, and can be discharged as it is.

將回收的固體成分的凝結體乾燥，在其乾燥固體成分253 Kg(含有切屑、平均粒徑1.1 μm的Si微粒子25.3重量%、微量的胺類防銹劑)中，加入平均粒徑32 μm、比表面積695 m2/g的活性碳124 Kg和平均粒徑170 μm的石英粉25 Kg，良好地混合，作為再生的反應原料。將其與實施例1同樣地，在推式反應爐中溫度控制為1950℃，在Ar氣體的流通下，將放入容器的反應原料每40分在各區域邊移動，邊進行加熱反應。反應物生成物完全αSiC化。進一步在大氣中，在750℃下將過剩的碳除去。結果平均粒徑未滿1 μm的超微粉的Si切屑被回收作為平均粒徑7.5 μm的αSiC，進行有效資源化。所述回收的αSiC在研光(lap)研磨用研磨粒或SiC成形原料用為適宜的利用價值高者。 The aggregate of the recovered solid component was dried, and an average particle diameter of 32 μm was added to the dried solid component of 253 Kg (containing 25.3% by weight of the Si fine particles having an average particle diameter of 1.1 μm and a trace amount of the amine rust inhibitor). 124 Kg of activated carbon having a specific surface area of 695 m 2 /g and 25 Kg of quartz powder having an average particle diameter of 170 μm were well mixed as a reaction raw material for regeneration. In the same manner as in the first embodiment, the temperature was controlled to 1950 ° C in the push reactor, and the reaction was carried out while the reaction raw material placed in the container was moved around the respective regions for 40 minutes under the flow of the Ar gas. The reactant product was completely αSiCated. Further, excess carbon was removed at 750 ° C in the atmosphere. As a result, the Si chips of the ultrafine powder having an average particle diameter of less than 1 μm were recovered as αSiC having an average particle diameter of 7.5 μm, and were effectively resourced. The recovered αSiC is preferably used in polishing granules for polishing or SiC forming materials.

(比較例2) (Comparative Example 2)

分別添加陰離子類凝結劑(丙烯醯胺丙烯酸蘇打共聚物)或 非離子類凝結劑(丙烯醯胺共聚物)來代替陽離子性有機凝結劑，除此以外，以與實施例3同樣的條件、方法進行回收。任何場合都不能良好地凝結，此後的離心分離或過濾中的固液的分離也不能順利進行，過濾液中固體成分大量流出。 Add an anionic coagulant (acrylamide acrylate soda copolymer) or The nonionic coagulant (acrylamide copolymer) was used in the same manner as in Example 3 except that the cationic organic coagulant was used instead. In any case, the coagulation cannot be performed well, and the separation of the solid and liquid in the subsequent centrifugation or filtration cannot be smoothly performed, and a large amount of solid components in the filtrate flow out.

(實施例4) (Example 4)

在加入至實施例3中的推式反應爐前的反應原料中，添加5重量%的B4C進行混合。此後的反應以及除碳也與實施例3在相同條件下進行。其結果，作為平均粒子徑為12 μm的αSiC而再生，作為線鋸用的研磨粒是有效的。 Into the reaction raw material before being added to the push reactor of Example 3, 5 wt% of B 4 C was added and mixed. The subsequent reaction and carbon removal were also carried out under the same conditions as in Example 3. As a result, it is regenerated as αSiC having an average particle diameter of 12 μm, and is effective as an abrasive grain for wire saw.

[產業上之可利用性] [Industrial availability]

本發明的SiC及/或Si的固體微粒子回收方法用作下述液體的處理：含有在SiC粉的製造中作為副產物而生成的目標粒徑以下的不要的SiC微粒子的溶液、含有Si錠或成形物研削時的切屑的Si微粒子的廢液、線鋸漿廢液等，將含有的細微的SiC或Si的固體成分和液體成分分離，進一步用於所述固體成分的各固體微粒子的回收。 The method for recovering solid microparticles of SiC and/or Si according to the present invention is used as a treatment for a liquid containing a Si ingot or a solution of unnecessary SiC fine particles having a target particle diameter or less which is produced as a by-product in the production of SiC powder. The waste liquid of the Si fine particles, the wire saw slurry waste liquid, and the like of the chips during the grinding of the molded product separate the solid component and the liquid component of the fine SiC or Si contained therein, and are further used for collecting the solid fine particles of the solid component.

藉由所述固體微粒子回收方法回收的各固體微粒子可從不要的粒徑的SiC微粒子、循環使用中消耗而變形或細微化的SiC微粒子、切屑Si微粒子，再生為具有符合用途的最適的粒徑或粒度分布的利用價值高的SiC。它們可以作為線鋸、研光、拋光用等的高附加價值的研削材料、研磨粒、研磨材料而被利用。 Each of the solid fine particles recovered by the solid fine particle recovery method can be regenerated from an SiC fine particle having an unnecessary particle diameter and SiC fine particles or chip Si fine particles which are decomposed or finely pulverized during recycling, and has an optimum particle diameter suitable for use. Or SiC with high utilization value of particle size distribution. They can be utilized as high value-added grinding materials, abrasive grains, and abrasive materials for wire sawing, polishing, polishing, and the like.

Claims (5)

一種SiC及/或Si的固體微粒子回收方法，包括：第一步驟，將含有SiC及/或Si的固體微粒子的液體，用離心分離或/及液體旋風器將所述固體微粒子中的較大粒徑的固體微粒子分離回收，將較小粒徑的固體微粒子殘存的液體排出；以及第二步驟，向第一步驟排出的液體中添加有機凝結劑，將所述較小粒徑的固體微粒子凝結，將含有所形成的凝結體的液體進行離心分離或過濾而將所述凝結體回收。 A method for recovering solid particles of SiC and/or Si, comprising: a first step of separating a liquid containing solid particles of SiC and/or Si into a larger particle of the solid particles by centrifugal separation or/and a liquid cyclone The solid microparticles of the diameter are separated and recovered, and the liquid remaining in the solid microparticles having a smaller particle diameter is discharged; and in the second step, an organic coagulant is added to the liquid discharged from the first step to coagulate the solid microparticles having a smaller particle diameter. The coagulated body is recovered by centrifuging or filtering the liquid containing the formed coagulated body. 如申請專利範圍第1項所述的固體微粒子回收方法，其中所述有機凝結劑為下述化學式(1)表示的陽離子性有機凝結劑， 式中，R1為氫原子或甲基，R2為碳數1-10的烷基，X為從Cl、Br以及F選出的任一個鹵化物，a為0-10的數，b為1-10的數，m最小為3的數。 The solid fine particle recovery method according to claim 1, wherein the organic coagulant is a cationic organic coagulant represented by the following chemical formula (1), Wherein R 1 is a hydrogen atom or a methyl group, R 2 is an alkyl group having 1 to 10 carbon atoms, X is any halide selected from Cl, Br and F, a is a number from 0 to 10, and b is 1 A number of -10, m is a minimum of 3. 如申請專利範圍第1項或第2項所述的固體微粒子回收方法，其中相對於第一步驟排出的液體100重量份，將所述有機凝結劑設為0.01重量份-10重量份。 The solid fine particle recovery method according to the first or second aspect of the invention, wherein the organic coagulant is set to be 0.01 part by weight to 10 parts by weight with respect to 100 parts by weight of the liquid discharged in the first step. 一種再生為有用的SiC的再生方法，其特徵在於：於藉由 如申請專利範圍第1項所述的固體微粒子回收方法所回收的所述凝結體中，添加碳、或碳和氧化矽，在非氧化性環境下進行最低也為1800℃的加熱，使所述SiC的平均粒徑肥大化，或使所述Si轉化為SiC。 A method for regenerating useful SiC, characterized by: The carbon or carbon and cerium oxide are added to the condensate recovered by the solid fine particle recovery method according to claim 1, and the heating is performed at a minimum of 1800 ° C in a non-oxidizing atmosphere. The average particle size of SiC is enlarged or converted into SiC. 如申請專利範圍第4項所述的再生為有用的SiC的再生方法，其中與碳、或碳和氧化矽一起添加從B、B4C以及B2O3中選出的任一種燒結助劑。 A method for regenerating a useful SiC as described in claim 4, wherein any one of the sintering aids selected from B, B 4 C, and B 2 O 3 is added together with carbon or carbon and lanthanum oxide.
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