201008874 六、發明說明： 【發明所屬之技術領域】 、本發明為關於用於太陽能電池原料的高純度發的製造 方法特關於將作為本方法的原料的四氯化《夕與辞， 分別以蒸氣狀態導人反紐，固崎出粒狀乃至粉綠的 石夕，將副產物氯化鋅電解後還原成辞並再利用，亦即 所謂氣相鋅彻㈣制高純度料製造方法。' 【先前技術】 ❹201008874 VI. Description of the Invention: [Technical Field to Be Invented by the Invention] The present invention relates to a method for producing a high-purity hair for use in a solar cell raw material, in particular, as a raw material for the method, tetrachlorination The state leads to the anti-news, and the solid-purity material is produced by the electrolysis of zinc chloride, which is a by-product of zinc sulphide (4). ' [Prior Art] ❹
南純度♦係作為半導體裝置时單結晶-鍵的原料冲 使用係藉由戶斤明西門子法（siemens pr〇cess)來製造。作 是，高純度矽作為今後巨大需求的太陽能電池用矽單結曰^ 或多結晶鑄錠的原料，由於西n子法成本高，為了製造伯 成本的高純度石夕’現在關於西門子法以外的各種製造方法 正在提案乃至開發中。 、 乂其中之一的鋅還原法，於西門子法尚未實用化之5〇多 年前曾-度使帛，之後1978至i980年在美國的Β·i ieThe southern purity ♦ is used as a semiconductor device in the case of a single crystal-bond raw material punching, which is manufactured by Siemens pr〇cess. As a raw material for high-purity lanthanum, a single-junction or a multi-crystalline ingot for solar cells, which is in great demand in the future, due to the high cost of the West N sub-method, in order to manufacture high-purity Various manufacturing methods are being proposed and even under development. One of the zinc reduction methods, which has not been put into practical use by the Siemens law more than 5 years ago, was once 度 帛, after 1978 to i980 in the United States Β·i ie
Columbus 研究所（Battelle Columbus Lab〇rat〇ry)，以低 成本化為目的，從，副產生的氣化鋅中藉由熔融鹽電解而回 收鋅和氯，組合再回收利用之步驟，實施了此方法。該方 法（以下稱為BCL法）的特徵為：使作為原料的四氯化石夕與 鋅’各自以蒸氣狀態導入錢應爐，固相析出粒狀乃至粉 末狀的矽，將副生的氯化鋅和未反應的四氯化矽以及鋅= 由凝聚器（condenser)而各自進行分離回收，將由四氯化石^ 和鋅以及氣化鋅的電解所得到的鋅在還原步騍中進行再利 320619 4 201008874 用。但是，反應爐及凝聚器中各物質的分離進行仍為不完 全而產生各種問題，之後沒有被實際應用。 之後，關於該BCL法，藉由設定還原反應溫度的範圍、 或使鋅蒸氣相對於導入之四氯化矽的莫耳比大於當量比 厂 等，而控制生成的矽的粒徑和粒形狀，以提高矽的收率為 ^目的，已有提出數個方案並申請專利（如：參照專利文獻1 至6) °然而，此等皆為在上述BCL法的範圍内，對於bcl ❹法中的門題點，亦即反應生成物的完全分離與完全回收以 及再^用之根本的解決方案則並沒有被提及。 彳之獻1]日本特開2003-34519號公報 [專利文獻2]日本特開2003— 95633號公報 [專利文獻3]日本特開2004- 18370號公報 H利文獻4]日本特開2004— 210594號公報 彳文獻5]日本特開2004—284935號公報 1之獻6]日本特開2006 — 290645號公報 0 【發明内容】 (發明欲解决的課題）. 離進解決虹法中反應爐及凝聚器中各物質的分 好的生產^而無法進行工業性實用化的問題點’能以良 收以及再利貧現紙法中反應生成物的完全分離與完全回 用，目的為提供可藉此而以低成本大量生產;^ 陽月b電池用古 工I八 _ 巧純度石夕的高純度矽的製造方法。 (解決课題的手段） 本毛明製造高純度矽的方法之特徵為：形成使具有加 5 320619 201008874 熱、保溫、冷卻機能的容器！以及容器2、與冷 能且在出口侧具有經由廢氣處理裝置而與外界氣體相連之 =部的容H3按照容器卜2、3的順序㈣結合之系統； 其中， 使容器卜2、3各自之溫度維持在91〇至13〇吖、刪 至400°c、代以下，同時從容器1的人口處，使高純度的 惰性氣體、四氯化魏體、以及鋅蒸氣在麵至聰胸 壓力下並維持四氯化賴化學當量比高於鋅的狀態，流向 容器1 ; 在容器1使石夕固相析出，在容器2使氣化辞液相凝聚 的同時並捕獲矽的微粒子，在容器3使剩餘之四氯化矽液 相凝聚並回收，而在系統内不包含從反應生成杨中分離鋅 的步驟。 因此’由於谷器1中之溫度範圍為91 〇至13 0 〇 t，故 沸點為907°C的鋅和沸點為58Ϊ的四氯化矽以氣相狀態瞬 φ 間100%反應，熔點為1414°C的矽則固相析出，堆積在容 器1的内面。之後，以四氯化矽的化學當量比大於鋅的狀 態下游入’鋅在還原反應中全部消耗，不再存在於容器丄 以後的系統中。因此’在系統内完全沒有必要進行從反應 生成物中分離鋅的步驟。而且’還原反應時如四氯化石夕的 當量比多，未反應而殘留的四氯化矽和還原生成的石夕發生 反應，會發生生成二氯化矽氣體的不均化反應，此反應在 1大氣壓下超過13.52C時’會急劇進行，容器.1的溫度若控 制在1300°C以下，可抑制該反應。容器2的溫度設定為3〇〇 320619 201008874 至400 C的範圍’ 5亥溫度在氯化辞的溶點別代以上、彿點 732 C以下’且在四氣切㈣點肌以上，故使氣化辞 •進f液相凝t且從氣相的四氯化石夕中分離的同_，可將在 谷胃1巾生成且與反應生成氣體-起被輸 送過來的一部分 ·-的石夕微粒子’以懸濁於溶融狀態的氣化辞之形式藉由容器 ' 2進行喊。由於通過容器2細氯切和惰性氣體係在 ，器3中維持在代以下，故將剩餘之四氣化石夕予以液相 ❾凝聚並回收’只將雜氣體經由廢氣處理裝置*釋放到外 衫部。 >將在容器2回收的氯化鋅與矽微粒子务自溶解及懸濁 於高純，的稀釋氯化鋅水溶液後，將石夕微粒子過滤、酸洗、 並用超高純度水洗淨後進行乾燥，回收餅（cake)狀的石夕。 作為濾、液的高濃度的氯化鋅水溶液在經調整濃度、pH、溫 度後’藉由使用銘板作為陰極、使用·職（不溶性電極）作 f陽極、使祕子交換膜作為_而進行電解，從而回收 ❹祕麟’將其做為讀切之還職而再彻。 (發明的效果） …根據本發明，在容器K還原反應器）回故鋅完全消耗 ，所生成之粒狀乃至海綿狀的⑪，在容器2(凝聚器）回收 虱化鋅和雜粒子，在容器3(凝㈣）时四氯化石夕，系 統=需要進行從反應生成物中分離鋅的步驟。且，由於 將谷，2所回收的氯化鋅和石夕微粒子溶解、懸濁於高純度 稀釋氯化鋅水溶液之後，過遽該氯化辞水溶液而回收石夕微 粒子，從作為濾液的濃氣化鋅水溶液藉由水溶液電解而回 320619 7 201008874 收鋅’故各分離（回收）步驟可容易實行且分離生成物可以 高純度狀態完全回收。因此’能以良好的生產性實現從BCL 法中將反應生成物完全分離與完全回收以及再利用，藉此 而使太陽能電池用尚純度矽的低成本量產成為可能。 【實施方式】 以下，有關本發明的高純度矽的製造方法的實施形 Ο Ο 態，參照附件圖面而進行説明。第丨圖表示本發明的高純 度矽的製造流程。 门、 二該製造流程，採用使具有加熱、保溫、冷卻機能的容 器1(還原反應器）以及容器2(凝聚器）和擁有冷卻機能且 在出口側具有經由廢氣處理裝置4而與外界氣體相連 口部的容器3(凝聚器）按照容器卜2、3的順序串聯^ 合的系統。並且，使容器卜2、3各自的溫度維持在^ =1300 C、30G至働。C、代以下的同時，從容器上入口 至度=氣:嗔氣)、四氣切氣體以及鋅蒸氣 ⑽hPa的壓力下並經常保持四氯化;^的化學 虽置比超過鋅3至1_左右的條件下，流向容Η予 性氣體的供給速声，氯化魏體、鋅蒸氣以及惰 容器3出口侧開2 奋^的入口部分的氣體流量而進行。 器2 八人針對4目對於鋅蒸氣使四氯切氣體的化學當旦 320619 8 201008874 . 比過剩的理由進行說明。容器1内部之溫度係藉由加熱保 溫裝置la以及冷卻裝置lb而維持在910至130(TC，該溫 度範圍係在鋅的沸點907°C、氣化鋅的沸點732°C以及四氣 ’ 化矽的沸點58°C以上、矽的熔點1414°C以下，此時的還原 . 反應如下所示。 還原反應 SiC14(gas)+2Zn(gas)~^Si(solid)+2ZnC12(gas) 從衆所周知的熱力學數據可知，在容器1的設定溫度 範圍910至1300°C中’在所有的溫區内，伴隨著放熱的還 ❹原反應幾乎瞬間100%進行。此時四氯化石夕的化學當量比 若為過剩，在1大氣壓下接近1300¾高溫時，會發生以下 之不均化反應（disproportionation)，生成的矽雖有一部 分變成二氯化矽’但在低溫區發生逆反應，最後會1〇〇% 轉換為石夕。 不均化反應 Si+SiC14—2SiC12 因此，在四氯化矽過剩的氣體流中進行反應時，所有 .鋅皆有效地被利用於使四氯化矽還原成矽，氣體流下游的 反應生成物中完全不含有鋅。所以，裝置内不需要鋅的分 離步驟。 . - 此情形，為了使鋅確實1〇()%發生反應，相對於鋅， 化矽化學當量比的過剩率最低也要3%。並且為了將 令器1、2、3的溫度以及整體壓力維持在穩定的目的範圍 内，此過剩率以較大為佳，但是因過剩的四氯化矽和生成 ，矽，生之不均化反應及其逆反應所生成的矽微粒子有變 夕的可迠性，同時會因生產設備系統内的四氯化矽循環量 9 320619 201008874 利用效率降低，故過剩率最大以 每署攸多種角度出發，以維持四氯化石夕的化學 ，胃另一3至謂％左右的狀態流向容器1為宜。 •就會急劇進=不均錢應在1大氣壓下超過i352〇c :反庳：、衰原盔’一虱化矽在向低溫的容器2移動時發生逆 的：粒气即使矽和四氯化矽。此時生成的矽為1微米左古 使回收也難以使用，所以有必要盡可能抑制該 办並仅姓* ss: 在I四氯化矽過剩的條件下，有 ,、’、、谷》1的溫度為比1352。0低的13〇(rc以下。 ^另二方面’本來就當量比而言若使鋅過剩，該不均化 反應就θ被抑制（參照專利文獻2)，但因 氣 和副生的氣化辞蒸氣以及-部分浮游的 〇 ===應&下游移動，即使在紙法亦會發生裝置内 者塞等的問題，有必要進行鋅、氯化鋅以及微粒砂的分離 f別是若麵氯鱗回收高純度鋅之枝巾採用易於運轉 ^理的水錢電解時，首先要_·鋅的蒸氣壓差進行 鋅的分離步驟’兩者的彿點分別為贿力和7耽，不 化鋅和四氯化石夕（彿點58。〇那樣在蒸氣壓上有決定矣 異’所以完全分離很困難。並且鋅和氯化鋅的混合物中八 散混入微粒石夕的情況下，為了除去微粒石夕，要在辞的炫ς 42(TC以上之高溫熔融狀態過滤，或者將鋅不直接以辞的狀 態回收而是在鹽酸中溶解一次之後再進行過滤等，則 過多餘的步驟。結果反應生成物中含有鋅時，無法像本發 明那樣把微粒石夕作為製品、把氯化鋅作為電解用的水溶液 320619 10 201008874 •來進行簡易的回收。 氣體與鋅蒸氣在向容器1的供給速度的管理 . 上係藉由各自的蒸氣發生器5、6進行。 :=不_製的蒸發器6中投人液態四氯化 '、埶Sit的產生流速，一邊控制蒸發器所配備的電熱The Columbus Research Institute (Battelle Columbus Lab〇rat〇ry) has implemented this step by reducing the amount of zinc and chlorine recovered from molten zinc by submerged zinc oxide by a combination of recycling and utilization. method. This method (hereinafter referred to as BCL method) is characterized in that each of the silicon tetrachloride and zinc' as a raw material is introduced into a money furnace in a vapor state, and a granular or even powdery crucible is precipitated in a solid phase, and the by-product chlorination is carried out. Zinc and unreacted antimony tetrachloride and zinc = separated and recovered by a condenser, and zinc obtained by electrolysis of tetrachloride and zinc and zinc vapor is regenerated in a reduction step. 4 201008874 used. However, the separation of the substances in the reactor and the agglomerator is still incomplete and causes various problems, and has not been practically applied. Then, with respect to the BCL method, by setting the range of the reduction reaction temperature or by making the molar ratio of the zinc vapor to the introduced antimony tetrachloride larger than the equivalent ratio, the particle size and the particle shape of the produced crucible are controlled. In order to increase the yield of ruthenium, several proposals have been made and patents have been filed (for example, refer to Patent Documents 1 to 6). However, these are all within the scope of the above BCL method, and for the bcl method. The door problem, that is, the complete separation and complete recovery of the reaction product, and the fundamental solution for reuse are not mentioned. Japanese Laid-Open Patent Publication No. 2003-34519 [Patent Document 2] Japanese Laid-Open Patent Publication No. 2003-95633 (Patent Document 3) Japanese Laid-Open Patent Publication No. 2004- 18370, No. 4, Japanese Patent Application No. 2004-210594 Japanese Unexamined Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The problem of the good production of each substance in the device, and the inability to carry out industrial practical use, can be completely separated and completely reused in the process of good harvest and re-poor paper. And mass production at low cost; ^ Yang Yue b battery with the ancient work I eight _ smart purity Shi Xi high-purity 矽 manufacturing method. (Means for Solving the Problem) The method of producing high-purity lanthanum by Ben Maoming is characterized by forming a container having the heat, heat preservation and cooling function of adding 5 320619 201008874! And a system in which the container 2 has a capacity H3 on the outlet side and has a portion H3 connected to the outside air via the exhaust gas treatment device in accordance with the order (4) of the containers 2 and 3; wherein the containers 2 and 3 are respectively The temperature is maintained at 91 〇 to 13 〇吖, deleted to 400 ° C, below the generation, while high-purity inert gas, tetrachlorinated Wei, and zinc vapor are placed from the population of the container 1 to the chest pressure And maintaining the chemical equivalent ratio of the tetralazide lysate higher than the zinc, flowing to the container 1; in the container 1 to precipitate the solid phase of the stone, in the container 2 to make the gasification liquid phase agglomerate while capturing the fine particles of the crucible, in the container 3 The remaining liquid phase of ruthenium tetrachloride is coagulated and recovered, and the step of separating zinc from the reaction-formed poplar is not included in the system. Therefore, since the temperature range in the grain 1 is 91 〇 to 13 0 〇t, the zinc having a boiling point of 907 ° C and the cerium tetrachloride having a boiling point of 58 矽 are 100% reacted in a gas phase state, and the melting point is 1414. The °C solid phase precipitates and accumulates on the inner surface of the container 1. Thereafter, the chemical equivalent ratio of ruthenium tetrachloride is greater than that of zinc, and the zinc is completely consumed in the reduction reaction, and is no longer present in the system after the vessel 。. Therefore, there is absolutely no need to carry out the step of separating zinc from the reaction product in the system. Further, in the case of 'reduction reaction, such as the equivalent ratio of tetrachloride, the unreacted residual antimony tetrachloride and the regenerated yttrium react, and the heterogeneous reaction of the ruthenium dichloride gas occurs. When the pressure exceeds 13.52 C at 1 atm, it will proceed sharply, and if the temperature of the vessel 1. is controlled to be 1300 ° C or lower, the reaction can be suppressed. The temperature of the container 2 is set to 3〇〇320619 201008874 to the range of 400 C. The temperature of the 5 sea is above the melting point of the chlorination, below the 732 C of the Buddha's point, and above the muscle of the four gas cuts (four), so the gas is made.化 • 进 进 液相 液相 液相 液相 液相 液相 液相 液相 液相 液相 液相 液相 液相 液相 液相 液相 液相 液相 液相 液相 液相 液相 液相 液相 液相 液相 液相 液相 液相 液相 液相 液相 液相 液相 液相 液相 液相 液相 液相 液相 液相 液相 液相 液相 液相'Shouting by container ' 2 in the form of gasification words suspended in a molten state. Since the fine chlorine cutting and the inert gas system of the container 2 are maintained in the lower portion of the device 3, the remaining four gas fossils are condensed and recovered in the liquid phase. Only the impurity gas is released to the outer shirt via the exhaust gas treatment device*. unit. > After the zinc chloride and the ruthenium particles recovered in the container 2 are self-dissolved and suspended in a high-purity diluted zinc chloride aqueous solution, the Shishi microparticles are filtered, pickled, and washed with ultra-high purity water. Dry and recycle the cake-like stone eve. After the adjusted concentration, pH, and temperature of the high-concentration zinc chloride aqueous solution of the filtrate and the liquid, the electrolysis is carried out by using the nameplate as the cathode, the use of the inactive electrode (insoluble electrode) as the f anode, and the secret exchange membrane as the _ In order to reclaim the secrets of the ❹ 麟 ' ' (Effects of the Invention) According to the present invention, in the vessel K, the reactor is reduced, the zinc is completely consumed, and the resulting granular or even spongy 11 is recovered in the vessel 2 (aggregator) to recover zinc oxide and impurities. In the case of the container 3 (condensation (4)), tetrachloride, the system = the step of separating zinc from the reaction product. In addition, after dissolving and suspending the zinc chloride and the diarrhea particles collected in the valley and the high-purity diluted zinc chloride aqueous solution, the chlorinated aqueous solution is recovered, and the shovel particles are recovered from the concentrated gas as the filtrate. The zinc aqueous solution is returned to 320619 7 201008874 by aqueous solution electrolysis. The separation (recovery) step can be easily carried out and the separated product can be completely recovered in a high purity state. Therefore, it is possible to achieve complete separation and complete recovery and reuse of the reaction product from the BCL method with good productivity, thereby enabling the solar cell to be mass-produced at a low cost. [Embodiment] Hereinafter, the embodiment of the method for producing high-purity germanium according to the present invention will be described with reference to the attached drawings. The figure is a diagram showing the manufacturing process of the high-purity germanium of the present invention. The second and second manufacturing processes employ a vessel 1 (reduction reactor) having a heating, holding, and cooling function and a vessel 2 (condenser) and have a cooling function and have an exhaust gas treatment device 4 connected to the outside air on the outlet side. The container 3 (aggregator) of the mouth is connected in series in the order of the containers 2 and 3. Further, the temperature of each of the containers 2 and 3 was maintained at ^ = 1300 C, 30 G to 働. C, at the same time, from the inlet of the vessel to the degree = gas: helium gas, four gas cut gas and zinc vapor (10) hPa under pressure and often maintain tetrachlorination; ^ chemical ratio is more than zinc 3 to 1_ Under the left and right conditions, the flow rate of the supply of the preservative gas is carried out, and the gas flow rate of the chlorinated Wei body, the zinc vapor, and the inlet portion of the outlet side of the inert container 3 is increased. Device 2 Eight people for the 4 mesh for zinc vapor to make the chemical of tetrachloro-cut gas to be 320619 8 201008874. The reason for the excess is explained. The temperature inside the vessel 1 is maintained at 910 to 130 (TC by the heating and holding device 1a and the cooling device 1b, which is in the temperature range of 907 ° C of zinc, 732 ° C of boiling point of zinc oxide, and four gas The boiling point of yttrium is 58 ° C or higher, and the melting point of yttrium is 1414 ° C or less. The reduction reaction at this time is as follows. Reduction reaction SiC14 (gas) + 2 Zn (gas) ~ ^ Si (solid) + 2ZnC12 (gas) The well-known thermodynamic data shows that in the temperature range of 910 to 1300 ° C of the vessel 1 'in all the temperature zones, the enthalpy reaction with the exotherm is almost instantaneously 100%. At this time, the chemistry of tetrachloride If the equivalence ratio is excessive, when the temperature is close to 1303⁄4 at 1 atm, the following disproportionation occurs, and although some of the generated ruthenium becomes ruthenium dichloride, but a reverse reaction occurs in the low temperature region, and finally 1 〇 〇% is converted to Shi Xi. Heterogeneous reaction Si+SiC14—2SiC12 Therefore, when the reaction is carried out in an excess gas stream of antimony tetrachloride, all zinc is effectively utilized to reduce ruthenium tetrachloride to ruthenium. The reaction product downstream of the gas stream is completely free of Therefore, there is no need for a separation step of zinc in the device. - In this case, in order to make zinc react 1% (%), the excess ratio of chemical equivalent ratio of bismuth to zinc is 3% at least. The temperature of the vessels 1, 2, and 3 and the overall pressure are maintained within a stable range of interest. This excess ratio is preferably larger, but due to excess ruthenium tetrachloride and formation, enthalpy, heterogeneous reaction and its reverse reaction. The generated bismuth microparticles have a variable enthalpy, and the utilization efficiency of ruthenium tetrachloride circulating in the production equipment system is reduced to 9 320619 201008874. Therefore, the excess rate is maximum at each angle to maintain tetrachloroethylene. The chemical of fossil eve, the other 3 to the state of the stomach flows to the container 1 is appropriate. • It will be sharply entered = the uneven money should exceed i352〇c at 1 atmosphere: 庳:, 衰 头盔 头盔 '一虱The phlegm is reversed when moving to the low temperature container 2: the granule gas is ruthenium and ruthenium tetrachloride. The ruthenium generated at this time is 1 micron, and the recovery is difficult to use, so it is necessary to suppress this as much as possible. Surname* ss: excess in I tetrachloride Under the condition, there are,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, It is suppressed (see Patent Document 2). However, due to the gasification of the gas and the by-products, and the partial floating of the 〇=== should be moved downstream, even in the paper method, problems such as plugging in the device may occur. It is necessary to carry out the separation of zinc, zinc chloride and fine sand. If the surface of the high-purity zinc is recycled, it is easy to operate and the water is electrolyzed. Separation step 'both points of the Buddha are bribes and 7 耽, not zinc and tetrachloride 夕 (Buddha 58). In the case of enthalpy, the vapor pressure is determined to be different. Therefore, it is difficult to completely separate. In the case where the mixture of zinc and zinc chloride is mixed into the granules, in order to remove the granules, it is necessary to filter in the high-temperature molten state of TC or higher, or to directly smear the zinc. In the case where the solution is dissolved once in hydrochloric acid and then filtered, the excess step is passed. As a result, when zinc is contained in the reaction product, it is not possible to use the powder as a product and the zinc chloride as an aqueous solution for electrolysis. 320619 10 201008874 • Simple recovery. The management of the supply rate of gas and zinc vapor to the vessel 1 is carried out by the respective steam generators 5 and 6. The ============================= The flow rate of liquid tetrachlorinated ', 埶Sit', while controlling the electric heat provided by the evaporator
Q 電力，藉此而可控制其供給速度。將固體或 9〇7^、的鋅投人石英玻璃製的蒸發器5，加熱至接近沸點 熱如㈣控鋅的液面高度一面控制蒸發器所配備的電 '、、、器的輸出電力，藉此而可控制供給速度。Q power, by which the supply speed can be controlled. The solid or 9锌7, zinc is thrown into the evaporator 5 made of quartz glass, and heated to a boiling point close to the boiling point, such as the liquid level of the (4) zinc control, to control the output power of the electric device, the device, and the device. Thereby, the supply speed can be controlled.
有關容器1的内部溫度，以下管理=的 I ::::生的氣化辞全部在蒸氣狀態下向下 點高的91，r=T溫度要維一 的運艟^ 另一方面，本發明採用的在常壓附近 Ο 間=產^13饥後所生成的石夕與剩餘的四氯化石夕之 防止此情況，應’向容器2的方向排出。為了 l3〇〇°c以下彳夕各盗1的出口附近的溫度必須被管理在 因逆反應而再I二3化反應在13机以下的低溫區會 態心，但在n 3 H匕石夕。該砍會以微粒子狀 °c，藉由後述方法/ 封谷器1内的溫度超過1352 狀態回收_。 盗2中也可完全捕獲並以高純度 反應熱，氣相麵反料放減應，若不除去 之同時，六哭〗 c左右的溫度開始反應，在反應進行 、谷rol内部溫度也會上升到 1300°C以上。因此， 11 320619 201008874 H维持容器1的溫度在9iG至刪。C，將容器1的前段 、(上游側）裝人具有加熱、保溫功能的電爐la _，將後段（下 :裝人藉由空冷或者冷媒等而具有冷卻機能的構造體 1 b中。 .· 容器1所回收的矽通常為高純度的粒狀乃至海綿狀， •取出時可能會產生微量的梦微粉、或混人0. ^以下之不 純物微粒子’為去除不純物微粒子，從容器！取出後以藉 ❹由弱魏，超純水洗淨並騎乾料宜。 # 關於容器2(凝聚器）’其目的為凝聚氯化鋅而 二成為液相狀態，同時以在氯化鋅熔液中懸濁之狀態捕 # ’于游的矽微粒子，然後分離剩餘的四氯化矽氣體和惰性 3的流動。為此，配置在容器2 τ部的氯化鋅液體接受 〇Ρ刀的溫度，必須要在732至283。(：之間。同時，為了降Regarding the internal temperature of the container 1, the following management = I::: raw gasification words are all in the vapor state, the point is 91, r=T temperature is required to maintain one. On the other hand, the present invention The use of the stone in the vicinity of the normal pressure = the production of ^13 after the hunger and the remaining tetrachloride stone to prevent this, should be 'discharged in the direction of the container 2. In order to maintain the temperature near the exit of each thief 1 below l3 〇〇 °c, it is necessary to manage the temperature in the low temperature zone below 13 machines due to the reverse reaction, but at n 3 H. The cut is in the form of fine particles °c, which is recovered by the method described later / the temperature inside the rice sealer 1 exceeds 1352. The Pirate 2 can also completely capture and react with high-purity heat, and the gas phase should be reduced. If it is not removed, the temperature around the six cries will start to react. When the reaction proceeds, the temperature inside the valley rol will rise. Up to 1300 ° C. Therefore, 11 320619 201008874 H maintains the temperature of the container 1 at 9iG to delete. C. The front stage and the (upstream side) of the container 1 are equipped with an electric furnace la _ having a heating and heat insulating function, and the rear stage (bottom: a structure 1b having a cooling function by air cooling or a refrigerant, etc.). The cockroaches recovered in the container 1 are usually in the form of high-purity granules or even sponges. • A small amount of dream micro-powder may be generated when it is taken out, or a mixture of impurities of less than 0. ^ below is used to remove impurities, and the container is removed from the container! It is recommended to wash it by weak Wei, ultrapure water and ride dry material. # About container 2 (aggregator)' The purpose is to agglomerate zinc chloride and become liquid phase, while hanging in zinc chloride melt The state of turbidity captures the particles of the sputum, and then separates the remaining ruthenium tetrachloride gas and the flow of inert 3. For this reason, the temperature of the zinc chloride liquid disposed in the τ portion of the vessel 2 is required to receive the trowel. In 732 to 283. (: between. At the same time, in order to descend
低從容哭9抓丨」 叮两j IT 玄：°° 2排出的四氯化矽氣體以及惰性氣體中的氯化鋅 分壓，必須盡可能地降低溫度。因此，為了將氯化 參。◦ 2氣的刀壓至少降到在1 hPa以下，溫度必須控制在4 〇 〇 f =下，最好是使氯化鋅能夠不凝固的30(TC為宜。為此， _ 的下。卩係裝入300至400°C的具有加熱保溫功能的 電爐2a中。 一方面，容器2的上部（上游侧)係裝入 者冷媒笪 ^ ^ 、聲而具備冷卻機能的構造體2b中’可將從容器丨排 91〇至130(Tc的反應生成物降溫至3〇〇至4〇〇。〇。再 庐微息令，2通向容器3的出口部分，藉由固相析出而捕 又七里的氯化鋅的蒸氣之同時，為了使容器3的冷卻機能 320619 12 201008874 •更有效地發揮，以設置亦可使四氯化魏體與 度冷卻至⑽t：以下（最料7〇。〇的氯化辞的凝汽^ • (trap)2c 為宜。 • 之後，容'器3(凝聚器）將未反應的剩餘四氯化矽予以 .·液化’從情性氣體中分離回收。為此，四氣化矽的蒸氣屋 …至少要在100 hPa以下，容器3的溫度必須在〇它以下， 又以零下1(TC以下為宜。 ❹、H明另—徵為：將容器2所捕獲的氯化辞和石夕 微粒子各自轉、㈣於高純度_氯化鋅水溶液後，將 石夕微粒子過遽、洗淨、乾燥後回收餅狀石夕，從該遽液之濃 氯化鋅水洛液藉由水溶液電解而回收鋅，以鋅作為四氣化 矽的還原劑進行再利用。 、、從氯化鋅的水溶液電解槽7，將鋅回收後變稀的電解 液^至氯化鋅溶解槽8，調整至指定的氯化辞濃度，再度 〜°至電解祷7。該稀釋氯化鋅水溶液係被使用於容器2 ❸、'、氯化鋅的’谷解。容器2的氣化鋅經過冷卻、固化步驟後 ，至/合解槽8,此溶解液經由過濾分離矽微粒子後，進行 氯化鋅/辰度、PH、溫度等調整後，作為水溶液電解槽7 電解液使用。. 電解槽7係藉由使用鋁板作為陰極、使用DSE(不溶性 電極）作為陽極、使用離子交換膜作為隔膜來進行電解，從 、回，鋅。此時’氣化辞水溶液使用的水若使用半導體用 中^南’屯度水，就能得到純度5N(nine，意指純度百分率 9」的個數，例如5N的純度即表示99. 999%，以下同 13 320619 201008874 義）以上的高純度辞’將其蒸德後可作為四氣化 需的純度6N(nine)的鋅蒸氣而進行再利用 遇2所 同時發生賴氣，可麵水後液化细收，作氯^解 鹽酸、其他工業製品的原料利用。 巧四亂化石夕' 採用法，之後提出的專利申請的方法幾乎皆 嘁孤電解法作為氯化鋅的電解方法。鋏 鹽電解法和水溶液電解法相比，理論上電解槽忒力= Ο Ο t降Ϊ雇左右的可能性，但必須在糊至6GrC的高溫 進仃處理。為此，副线氣的㈣上雜度以及裝置材 質有混入不純物的危險，向電解槽循環供給電解液以及從 電解槽回收、保管㈣鋅等在附帶設備的溫度維持上需要 ，外的熱能源’且由於電解的穩定運轉較難而有I置工作 率低下的問題’和使用1齡以下之水溶㈣水溶液電解 、遜色的夕。因此，作為以高純度狀態穩定回收鋅的方 ^係以水/谷液電解方法為較佳。本發明中，最大的優點 疋因還原反應生成物中沒有殘留未反應的鋅，所以可用高 純水溶解的方法很容易地回收水溶液電解使用的氯化鋅。 其次’容器2所捕獲的矽微粒子，因通常為-1〇至〇. i 以111的粒子，過濾時需要使用孔徑在0.1# m以下的樹脂系 過澹器。因從氯化鋅水溶液過濾出的矽微粒子表面附著有 不純物氯化鋅，使用高純度的弱鹽酸水溶液洗淨後，再藉 由超高純度水洗淨並乾燥後，即可得到餅狀的高純度石夕。 藉此’加上容器1捕獲的粒狀乃至海綿狀的矽，從原料四 氣化石夕中的矽可以95%以上的收率回收高純度矽。 14 320619 201008874 根據上述本發明的方法，能得到幾乎不含游離微粉的 间純度矽，而若需求游離微粉之產生為少且更大更細密的 、塊狀矽打，藉由將依據本發明所獲得的矽予以衝壓成型為 .10至200mm左右的塊狀，在真空或減壓氬氣環境下，在13〇〇 ••至1400X：進行熱處S，即可得到目的產品。該情況下的衝 麼成型甩的模具’必須選用氮化石夕等機械強度強且不污染 矽的材料。再者，熱處理用的容器必須選用高純度碳化矽 等高溫下也不會污染石夕的耐熱材料。如果熱處理溫度上升 到石夕的炼融溫度以上，則、溶融、固化後，需要粉碎，也會 成為污染的原因。因此，熱處理溫度為比發的熔點稱低的 1300 至 14〇〇。〇為宜。 、最後，作為太陽能電池用高純度矽至少要有6N(nine) 以上的純度，按照本發明的方法，在反應生成物的完全分 離^中，即使有污染防止機能.，也不能_其具備精製 ，此。所以，依據本發明的方法製造純度⑽以丨此）以上的 ❹间=度料’原料四氯化石夕氣體、還原劑辞蒸氣、以及同 時抓通的惰性氣體，不論任-者都要求6N(nine)以上的純 度。 再者’若四氯化發中含有三氯石夕烧、二氯石夕烧等石夕氫 化物時’混合氣體中的發氫化物在本發明容器丄的設定溫 園内’皆以鋅蒸氣還原而析出石夕，變成氯化鋅蒸氣和 '狀~以只要使用料合氣體純度在6N以上，都可以適 用於本發明的方法。值是，相對於鋅，原料氣體的化學當 量的過剩率’必須疋相對應於使用之混合氣體的化學當量 15 320619 201008874 者。 四氯化矽氣體中矽氫化物的濃度超過10%時，為確保 • 由鋅還原而副生且從容器3的開口部和惰性氣體一起向外 * 界排出的氳氣的安全性，需要在放出口附近以大量的空氣 . 稀釋。如此，將四氯化矽與矽氫化物的混合氣體作為原料 使用，亦即意指可以將本發明的方法與大量副生同樣混合 氣體的西門子法組合從而用來製造多晶矽。 本發明在實施上必須滿足上述條件。有關其他條件， ® 只要在滿足上述條件的範圍内，可以適當進行選擇。例如， 可選擇容器1係作為立式圓塔狀而捕獲下部所析出之矽的 構造、或是以作為橫式的圓形管狀而使内部全體矽析出的 構造。 例如容器2亦可製成分為2個區域的構造，該2個區 域係主要冷卻高溫的反應生成物的部分、以及將凝聚的氯 化鋅以液態或固態存留的部分。使用的容器、器具的材料 q 以及與容器相連的配管的材料，這些部分的具備對所接觸 的溫度以及氛圍氣體物質的财熱性、耐腐钱性的材料，最 好選用已經在其他領域實用化的值得信賴的材料。例如， 已經作為半導體材料的熱處理用而被一般性使用的石英玻 璃和碳化砍，作為一般耐熱、耐腐钱材料使用的氮化石夕或 Inconel(註冊商標）以及鎳，甚至一般耐酸、耐腐蝕樹脂使 用的Teflon(註冊商標）、聚丙烯、氯乙烯等的材料，在本 發明實施時都可以使用。 然後，針對本發明的實施例進行說明。 16 320619 201008874 (實施例l) 容器1係内徑300mm、長度2500mm的碳化石夕管， • 與之相連接的容器2上部為内徑100mm、高度l5〇〇mm 的碳化矽管，下部為内徑700mm、深度l〇〇〇mm的錄容 / 器，與容器2下部相連接的容器3係使用不銹鋼製的凝聚 • 器，在容器3設置經由廢氣處理裴置4而與外界相連的開 口部。容器1和2配備有加熱、保溫用的電熱加熱器1&和 ❹輸送部分空氣的空冷機構lb。在容器3設置可冷卻至零下 l〇°C以下的冷卻器3a 〇 器1、2、3的 之後將預熱至 溫度分別設定爲9i〇t：、30(TC、零下2〇t：， 將串聯接續容器1、2、3的系統全體以純度6N(nine) 以上的氬氣置換後，將該氬氣以投入時流量5L/分的速 度由容器1向容器3的方向流動的同時，容器1、2、3的 ，40〇 c且純度爲6N(n.ine)以上的四氯化矽氣體和預熱至 約910 C且純度6N為（nine)以上的鋅蒸氣，維持四氯化矽 ❾對鋅的當量比在多出5至15%的狀態，分別將該四氯化石夕 和鋅以平均166.5g/分和平均U6 4g/分的速度由容器Low calm and crying 9 grabs 丨 j two j IT Xuan: ° ° 2 discharge of antimony tetrachloride gas and zinc chloride in the inert gas partial pressure, must be as low as possible. Therefore, in order to chlorinate the ginseng. The pressure of the ◦ 2 gas is reduced to at least 1 hPa, and the temperature must be controlled at 4 〇〇 f =, preferably 30 (TC is suitable for the zinc chloride to not solidify. For this, _ the lower. 卩It is placed in an electric furnace 2a having a heating and heat retaining function of 300 to 400 ° C. On the one hand, the upper portion (upstream side) of the container 2 is a structure 2b in which the refrigerant is charged and the cooling function is provided. From the container 〇 91 〇 to 130 (Tc reaction product is cooled to 3 〇〇 to 4 〇〇. 〇. 庐 庐 令 令 , , , , , , , , , , , 容器 容器 容器 容器 容器 容器 容器 容器 容器 容器 容器 容器 容器 容器 容器 容器 容器At the same time as the vapor of zinc chloride in the seven-mile, in order to make the cooling function of the container 3 320619 12 201008874 • more effective, the setting can also cool the tetrachloride body and the degree to (10) t: below (maximum 7 〇. The chlorination of the condensate ^ • (trap) 2c is appropriate. • Afterwards, the vessel 3 (aggregator) treats the unreacted remaining ruthenium tetrachloride. Liquefaction is separated and recovered from the inert gas. Therefore, the steam house of the four gasification ... ... must be at least 100 hPa, the temperature of the container 3 must be below it, and the temperature is below zero (TC It is advisable to use ❹, H 明, another--: the chlorination and the Shixi granules captured in the container 2 are respectively transferred, and (4) after the high-purity ZnCl solution, the shi shi granules are smashed, washed and dried. After recovering the cake-like stone, the zinc is recovered from the concentrated zinc chloride water solution of the mash by aqueous solution electrolysis, and the zinc is reused as a reducing agent for the four gasified ruthenium. In the tank 7, the electrolyte which has been thinned by zinc is removed to the zinc chloride dissolution tank 8, and adjusted to the specified concentration of the chlorination, again ~ ° to the electrolysis. 7. The diluted zinc chloride aqueous solution is used in the container 2 ❸, ', and the solution of zinc chloride. After the cooling and solidification steps of the vaporized zinc in the container 2 are carried out to the solution tank 8, the solution is separated into fine particles by filtration, and then zinc chloride/tin, After adjusting the pH, temperature, etc., it is used as an electrolyte solution in the aqueous solution electrolytic cell 7. The electrolytic cell 7 is electrolyzed by using an aluminum plate as a cathode, DSE (insoluble electrode) as an anode, and an ion exchange membrane as a separator. , zinc. At this time, 'gasification water used in aqueous solution By using a medium-sized water for semiconductors, a purity of 5N (nine, meaning a purity percentage of 9) can be obtained. For example, the purity of 5N means 99.999%, the same as 13320619 201008874. Purity word 'after steaming, it can be reused as zinc gas of 6N (nine) purity required for four gasification. When it is used, it can be lysed at the same time. It can be liquefied after surface water, and it can be used as chlorine, hydrochloric acid, and others. The use of raw materials for industrial products. The method of applying the patent application method is almost the same as the electrolytic method of zinc chloride. The bismuth salt electrolysis method is compared with the aqueous solution electrolysis method.忒力 = Ο Ο t The possibility of squatting around, but it must be treated at a high temperature of 6GrC. For this reason, the (4) upper heterogeneity of the sub-line gas and the material of the device may be mixed with impurities. The electrolyte is circulated and supplied to the electrolytic cell, and the electrolyte is recovered and stored from the electrolytic cell. (4) Zinc is required for temperature maintenance of the attached equipment, and external thermal energy is required. 'And the problem of low I-operating rate due to stable operation of electrolysis' and the use of water-soluble (four) aqueous solution of 1st and younger ages, and inferior color. Therefore, it is preferable to use a water/glutle liquid electrolysis method as a method for stably recovering zinc in a high purity state. In the present invention, the greatest advantage is that since unreacted zinc remains in the reduction reaction product, zinc chloride used for electrolytic solution electrolysis can be easily recovered by a method of dissolving in high-purity water. Next, the fine particles trapped in the container 2 are usually -1 to 〇. i. For the particles of 111, a resin-based filter having a pore diameter of 0.1 m or less is required for filtration. The surface of the niobium microparticles filtered from the zinc chloride aqueous solution is adhered with the impurity zinc chloride, washed with a high-purity weak hydrochloric acid aqueous solution, and then washed with ultra-high purity water and dried to obtain a cake-like height. Purity Shi Xi. By adding the granules or the sponge-like cockroaches captured by the container 1, the high-purity lanthanum can be recovered in a yield of 95% or more from the cerium in the raw material of the four gas fossils. 14 320619 201008874 According to the method of the invention described above, it is possible to obtain an intermediate purity enthalpy which contains almost no free micropowder, and if it is required to produce less fine and more fine, lumpy beating, by means of the present invention The obtained crucible is stamped and formed into a block shape of about .10 to 200 mm, and in a vacuum or reduced pressure argon atmosphere, at a heat point S of 13 〇〇•• to 1400X, the desired product can be obtained. In this case, the mold for forming the ruthenium must be made of a material such as nitriding stone which is mechanically strong and does not contaminate ruthenium. Further, the container for heat treatment must be made of a high-purity carbonized crucible or the like which does not contaminate the stone-like heat-resistant material at a high temperature. If the heat treatment temperature rises above the melting temperature of Shixi, it will need to be pulverized after being melted or solidified, which may cause contamination. Therefore, the heat treatment temperature is 1300 to 14 Å lower than the melting point of the hair. It is appropriate. Finally, the high-purity lanthanum for solar cells must have a purity of at least 6 N (nine) or more. According to the method of the present invention, even if there is a pollution prevention function in the complete separation of the reaction product, it cannot be refined. ,this. Therefore, according to the method of the present invention, the purity (10) is more than 丨 度 度 度 原料 原料 原料 原料 原料 原料 原料 原料 原料 原料 原料 原料 原料 原料 原料 原料 原料 原料 原料 原料 原料 原料 原料 原料 原料 原料 原料 原料 四 四 四 四 四 四 四 四 四 四 四Nine) above the purity. Furthermore, 'if the tetrachlorinated hair contains the lithium hydride such as smectite or chlorite, the hydride in the mixed gas is reduced by zinc vapor in the set temperature of the container of the present invention. On the other hand, it is possible to apply the method of the present invention to the zinc chloride vapor and the "form" as long as the purity of the used gas is 6N or more. The value is that, with respect to zinc, the excess ratio of the chemical quantity of the material gas must be 疋 corresponding to the chemical equivalent of the mixed gas used 15 320619 201008874. When the concentration of ruthenium hydride in the ruthenium tetrachloride gas exceeds 10%, it is necessary to ensure the safety of helium gas which is produced by the reduction of zinc and is discharged from the opening of the container 3 and the inert gas together. Drain the outlet with plenty of air. Dilute. Thus, the use of a mixed gas of ruthenium tetrachloride and ruthenium hydride as a raw material means that the method of the present invention can be combined with a Siemens method of mixing a large amount of by-products to produce polycrystalline germanium. The present invention must meet the above conditions in its implementation. For other conditions, ® can be appropriately selected as long as the above conditions are met. For example, the container 1 can be selected as a vertical circular tower shape to capture the structure in which the lower portion is deposited, or a structure in which the entire inner portion is decanted as a horizontal circular tube. For example, the container 2 may have a structure divided into two regions, a portion that mainly cools the high-temperature reaction product, and a portion that retains the aggregated zinc chloride in a liquid or solid state. The container used, the material q of the appliance, and the material of the piping connected to the container, and the materials having the heat and the rot-resistant property of the temperature and the gaseous substance to be contacted are preferably used in other fields. Trustworthy material. For example, quartz glass and carbonized chopping, which have been generally used as heat treatment for semiconductor materials, are used as a general heat-resistant and anti-corrosive material, or are inconel (registered trademark) and nickel, and even general acid-resistant and corrosion-resistant resins. A material such as Teflon (registered trademark), polypropylene, or vinyl chloride to be used can be used in the practice of the present invention. Next, an embodiment of the present invention will be described. 16 320619 201008874 (Example 1) The container 1 is a carbonized stone tube having an inner diameter of 300 mm and a length of 2,500 mm, and the upper portion of the container 2 connected thereto is a carbonized tantalum tube having an inner diameter of 100 mm and a height of l5 mm, and the lower portion is inner. A container having a diameter of 700 mm and a depth of 10 mm, and a container 3 connected to the lower portion of the container 2 are made of a stainless steel agglomerator, and the container 3 is provided with an opening connected to the outside via the exhaust gas treatment device 4. . The containers 1 and 2 are equipped with an electric heater 1& for heating and heat preservation, and an air-cooling mechanism 1b for transporting a part of the air. After the container 3 is provided with the coolers 3a, which can be cooled to below 〇°C, the heaters 3a, 2, 3 are preheated to a temperature of 9i〇t:, 30 (TC, minus 2〇t:, The entire system in which the containers 1, 2, and 3 are connected in series is replaced with argon gas having a purity of 6 N or more, and then the argon gas flows from the container 1 in the direction of the container 3 at a flow rate of 5 L/min. 1, 2, 3, 40 〇c and a purity of 6N (n.ine) or more of ruthenium tetrachloride gas and zinc vapor preheated to about 910 C and having a purity of 6N or more, maintaining ruthenium tetrachloride The equivalent ratio of bismuth to zinc is in the state of 5 to 15% more, and the ferrocene and zinc are respectively taken from the container at an average rate of 166.5 g/min and an average U6 4 g/min.
2、氯化鋅濃 到一部分為海綿狀的粒狀石夕24kg， 2 m以下的微粒發的氣化鋅290kg。 各自溶解及懸濁於ρίί 2 320619 17 201008874 度為10g/L的高純度氯化鋅水溶液後，用聚丙烯過濾器 過濾分離微粒矽，用2當量濃度的高純度鹽酸洗淨後，再 ' 用超高純度水洗淨，用Teflon(註冊商標）過濾器過濾，然 後直接在90°C以下進行減壓乾燥，得到4. 8Kg的餅狀石夕。 . 藉由以上步驟得到的矽的純度，可確認皆在6N(nine)以上。 (實施例2) 實施例1中，將分離微粒矽後的一部分氯化鋅水溶液 ❹調整至氯化鋅濃度200g/L、PH3、溫度30°C，然後使用 鋁作為陰極板、使用DSE作為陽極（不溶性陽極）、使用離 子父換膜作為隔膜來進行水溶液電解，其結果是已確認到 投入電解的氯化鋅中含有的鋅的95%以上能以5N(nine) 以上的純度回收，將其以9071以上蒸餾，純度成為 6N(nine)以上、 (實施例3) 將實施例1中得到的粒狀、海綿狀以及餅狀的矽，用 ❹氮化矽的模具衝壓成直徑i〇〇mm，半球型，在碳化矽容器 中’ 〇· 1 kPa以下的高純度氬氣氛圍下，在14001進行2 小時熱處理的結果，得到完全不含有游離微粉且純度幾乎 達至】7N(nine)的直徑i〇〇mm的半球狀石夕塊。 (實施例4) 使用四氯化矽氣體中含有約的三氯矽烷的純度 (nine)的混合氣體為原料氣體，相對於鋅以當量比維持 剩於混合氣體5至15% ’按照混合氣體平均164. 2 g 刀、鋅平均114· 5 §/分的速度供給，其他用與實施例1 320619 18 201008874 _ 同樣方法進行反應10小時後，容器1與容器2各得到12 kg 和2. 5 kg的高純度石夕。純度都在6N(nine)以上。 • 至此說明了本發明的一種實施方式，本發明不僅限於 • 上述實施方式，也可說在其技術性思想範圍内以各種不同 , 方式來實施。 " (產業上利用的可能性） 本發明係根本性地改善至今還沒有實用化的使四氯化 矽和鋅各自以蒸氣狀態導入反應爐並固相析出粒狀乃至粉 ® 末狀的矽，且使副生氯化鋅藉由電解而還原為鋅以再次利 用，亦即所謂依據氣相法的鋅還原法（BCL法）的缺陷，而 可在工業上實用化。藉此，可以低成本生產6N(nine)等級 的太陽能電池用高純度矽。 【圖式簡單說明】 第1圖為本發明的一種實施方式的步驟流程圖。 【主要元件符號說明】 1 還原反應器（容器1) la 加熱、保溫裝置 lb 冷卻裝置 2 凝聚器（容器2) 2 a 加熱、保溫裝置（電爐） 2b 具備冷卻機能的構造體 2c 凝汽閥 3 凝聚器（容器3) 3a 冷凍機 4 廢氣處理裝置 5 辞蒸發器 6 四氯化矽蒸發器 7 水溶液電解槽 8 溶解槽 19 3206192. The zinc chloride is concentrated to a part of a spongy granular granule of 24 kg, and 290 kg of vaporized zinc is emitted from particles of 2 m or less. After dissolving and suspending in a high-purity zinc chloride aqueous solution of 10 g/L at ρίί 2 320619 17 201008874, the fine particles were separated by filtration using a polypropylene filter, washed with 2 equivalents of high-purity hydrochloric acid, and then used. The ultra-high-purity water was washed, and it was filtered with a Teflon (registered trademark) filter, and then dried under reduced pressure at 90 ° C or less to obtain a cake of 4. 8 Kg. The purity of the ruthenium obtained by the above steps can be confirmed to be above 6N (nine). (Example 2) In Example 1, a part of the zinc chloride aqueous solution after the separation of the fine particles was adjusted to a zinc chloride concentration of 200 g/L, a pH of 3, and a temperature of 30 ° C, and then aluminum was used as a cathode plate and DSE was used as an anode. (Insoluble anode), and the use of the ion-replacement membrane as a separator to perform aqueous solution electrolysis. As a result, it was confirmed that 95% or more of the zinc contained in the zinc chloride to be electrolyzed can be recovered in a purity of 5 N or more. The mixture was distilled at a temperature of 9071 or higher, and the purity was 6 N or more. (Example 3) The granules, the sponge-like shape, and the cake-like enamel obtained in Example 1 were punched into a diameter i〇〇mm by a mold of tantalum nitride tantalum. , hemispherical type, in a high-purity argon atmosphere of 〇·1 kPa or less in a tantalum carbide container, the heat treatment at 14001 for 2 hours yields a diameter that is completely free of free fine powder and has a purity of almost 7N (nine). I〇〇mm hemispherical stone block. (Example 4) A mixed gas containing a purity of about trichloromethane in a hafnium tetrachloride gas is used as a raw material gas, and an excess ratio of zinc is maintained in an equivalence ratio of 5 to 15% of the mixed gas. 164. 2 。 。 164 164 164 164 164 164 164 164 164 164 164 164 164 164 164 164 164 164 164 164 164 164 164 164 164 164 164 164 164 164 164 164 164 164 164 164 164 164 High purity Shi Xi. The purity is above 6N (nine). An embodiment of the present invention has been described so far, and the present invention is not limited to the above-described embodiments, and can be implemented in various ways within the scope of the technical idea. " (Probability of Industrial Utilization) The present invention fundamentally improves the enthalpy of introducing cerium tetrachloride and zinc into a reaction furnace in a vapor state and solid-phase precipitation of granules or powders at the end of the powder. Further, the by-produced zinc chloride is reduced to zinc by electrolysis for reuse, that is, a defect of the zinc reduction method (BCL method) by the vapor phase method, and can be industrially put to practical use. Thereby, high-purity germanium for solar cells of 6N (nine) grade can be produced at low cost. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a flow chart showing the steps of an embodiment of the present invention. [Description of main component symbols] 1 Reduction reactor (container 1) la Heating, holding device lb Cooling device 2 Coagulator (container 2) 2 a Heating and holding device (electric furnace) 2b Structure with cooling function 2c Steam trap 3 Coagulator (container 3) 3a Freezer 4 Exhaust gas treatment unit 5 Evaporator 6 Helium tetrachloride evaporator 7 Aqueous solution tank 8 Dissolution tank 19 320619