200400095 玖、發明說明： 【發明所屬之技術領域】 本發明係關於一種金屬粉末之製造方法及製造裝置；特 別是關於一種可用於積層陶瓷電容器等之電子零件等上之 導電糊塡料、鈦材之接合材料、更且適合於觸媒等之各種用 途的鎮寺之金屬粉末之製造方法及製造裝置。 【先前技術】 鎳、銅等之金屬粉末係廣泛地被利用在電子材料及觸媒 等各種領域上，然而，近年來，特別是平均粒徑在1微米以 下之稱爲超微粉末的金屬粉末，更是可用以形成積層陶瓷電 容器之內部電極而受到囑目。自以往以來，銀、鈀、鉑、金 等之貴金屬粉末，或者鎳、鈷、鐵、鉬、鎢等之卑金屬粉末 係可用來做爲電子材料的導電糊，特別是做爲積層陶瓷電容 器之內部電極用。一般而言’積層陶瓷電容器係使介電體陶 瓷層與做爲內部電極使用的金屬層相互地重疊，介電體陶瓷 層的兩端係接續於內部電極之金屬層上而與外部電極形成 接續所構成。此處，構成介電體的材料，係可使用以鈦酸鋇、 鈦酸總、氧化銥等之筒介電率材料爲主成分之物。另一方 面’構成內部電極之金屬’雖然是可以使用前述之貴金屬粉 末或卑金屬粉末，然而因爲最近常要求較便宜的電子材料， 所以盛行利用後者之卑金屬粉末來開發積層陶瓷電容器，其 中特別是以鎳爲代表。 積層陶瓷電容器係藉由將鈦酸鋇等之介電體粉末與有 機黏合劑予以混合懸濁，並利用刮刀塗布法使成形爲片狀之 200400095 介電體而製做成生坯片；另一方面，將內部電極用之金屬粉 _ 末與有機溶劑、可塑劑、有機黏合劑等之有機化合物予以混 合而形成金屬粉末糊，再藉由網版印刷法印刷在前述之生坯 片上。將此等予以積層數百層，接著以100(TC以上燒成之， 最後將外部電極燒附在介電體陶瓷層之兩端上而得到積層 陶瓷電容器。 像上述這樣的積層陶瓷電容器之製造方法，在從金屬糊 將有機成分予以蒸發除去之工程、以及其後之燒結工程進行 ® 之際，金屬粉末會因爲膨脹、收縮而產生體積變化。也就是 說，因爲異於介電體及金屬粉末之物質會同時地燒結的原 故，所以在燒結過程中不可避免地會產生不同之因各種物質 之膨脹、收縮之體積變化而引起的燒結舉動；因此結果，就 必然會引起所謂的裂縫或剝離等之積層解離以及所謂的層 狀構造之破壞等之問題。 又且，隨著電容器之小型化、大容量化，因而就要求高 I 積層化、內部電極之薄層化或低電阻化等，所以做爲內部電 極使用的金屬粉末不用說粒徑就要在1微米以下了，更殷切 地期望粒徑在〇 · 5微米以下之超微粉。此時由於存在1微米 以上或2微米以上之粗粉，所以內部電極就變得難以薄層化 了，更且在電極表面上所產生的凹凸就成爲短路的原因了， 又且，結果就成爲積層解離的原因之一了。 在特開平1 0-21 931 3號公報中，曾揭示一種製造此種少 量的粗粉之金屬粉末的方法，其係具備使金屬接觸氯氣而連 200400095 續地產生金屬氯化物蒸氣之氯化工程，以及使在氯化工程中 . 所產生的金屬氯化物蒸氣接觸還原性氣體，以將金屬氯化物 連續地速原之還原工程。 上述之製造方法，係爲一種可以安定地、效率良好地製 造（特別是）1微米以下之鎳粉末的優良方法。然而，在所生 成的金屬粉末中另外含有1微米以上及2微米以上的粗粉， 因而期望一種經改善且可以控制此種粗粉之產生的製造方 法或裝置。 · 【發明內容】 【發明槪要】 從而’本發明之目的在於提供一種金屬粉末之製造方法 及製造裝置，其係一種使原料金屬與氯氣起反應而生成金屬 氯化物蒸氣’並使金屬氯化物蒸氣與氫氣起反應而製得金屬 粉末之方法，其中金屬粉末並無粗粉發生且粒徑安定，特別 是一種適合於平均粒徑在1微米以下之積層陶瓷電容器之 內部電極之金屬粉末。 · 本發明人等爲了達成上述之目的而反復地銳意檢討硏 究，結果發現在氯化爐中不反應的氯氣供給到還原爐中，將 因而使得反應溫度上昇，此即爲粗粉生成之原因。 本發明之金屬粉末之製造方法，即是一種基於上述認知發 現所完成的金屬粉末之製造方法，其係間斷或連續地將原料 金屬供給到氯化爐內’使原料金屬與氯氣在氯化爐內連續地 起反應而生成金屬氯化物蒸氣，並使金屬氯化物蒸氣與氫在 還原爐內連續地起反應而製得金屬粉末，其特徵在於：在該 200400095 金屬粉末之製造方法中，量稱於氯化反應中之氯化爐的重 量’並基於該量稱結果而控制原料金屬向氯化爐的供給情 況。 又且，本發明之金屬粉末之製造裝置，其特徵在於：備 有用以供給原料金屬之原料進料斗，及將從該原料進料斗供 給的原料金屬予以氯化之氯化爐，以及在該氯化爐所產生的 金屬氯化物蒸氣予以還原之還原爐；原料進料斗與氯化爐係 透過控制供給原料金屬之供給量用之閥而連通原料供給 鲁 管；氯化爐與還原爐係藉著將在氯化爐所發生的金屬氯化物 蒸氣輸送到還原爐之輸送管而連通；氯化爐係備有供給氯氣 至內部用之氯氣供給管；還原爐係備有將內部之金屬氯化物 蒸氣噴出之噴嘴，及將氫氣供給到內部用的氫氣供給管，以 及用以將被還原的金屬粉末予以冷卻之惰性氣體供給到內 部之冷卻氣體供給管；更且備有量稱氯化爐之全部重量之量 稱裝置，及基於該量稱裝置之量稱結果而控制原料金屬向氯 | 化爐的供給量之控制裝置。 依照本發明的話，因爲可基於量稱氯化爐全部重量之量 稱結果而控制原料金屬的供給量，所以能夠經常地塡充適量 的原料金屬到氯化爐中。因此，能夠使原料金屬與氯氣間之 反應達到均一化，而且可減低因未反應而被供給到還原爐的 氯氣。 本發明之金屬粉末，係爲一種可使用於積層陶瓷電容器 之內部電極的金屬，且爲銀、鈀、鈾、金等之貴金屬，或者 200400095 是鎳、鈷、鐵、鉬、鎢等之卑金屬。在彼等之中，卑金屬具 便宜之特點，因而較適宜，其中又以鎳比較理想。 就在本發明中所製造的金屬粉末之粒子性狀而言，並不 設於各別之用途而已，雖然並沒有特別地限定，但是在使用 於積層陶瓷電容器之內部電極的情況下，金屬粉末之平均粒 徑較宜是使用在0.1至0.5微米，更宜是0.1至1微米，特 佳是〇·1至0.5微米之範圍的微粒子。更且，金屬粉末之粒 子形狀，爲使燒結特性或陽散性向上提昇，因而以球狀較爲 理想。 本發明係一種以使原料金屬和氯氣在氯化爐內起反應而連 續地生成金屬氯化物蒸氣，並於還原爐內使此種金屬氯化物蒸 氣和氫氣起反應而連續地得到金屬粉末之方法（以下稱爲「氯化 還原法」）爲基礎之物。一般來說，藉由像這種氣相還原反應之 金屬粉末的製造過程，係使金屬氯化物蒸氣和氫氣接觸而瞬間 地生成金屬原子’金屬原子彼此間因衝突、凝集而生成超微粒 子’並進行成長。從而，依照還原爐內之金屬氯化物蒸氣的分 壓及溫度等之條件，可決定所生成的金屬粉末之粒徑。利用此 種氯化還原法，因爲產生對應於氯氣之供給量的量之金屬氯化 物蒸氣，藉由控制氯氣之供給量就可以控制向還原爐所供給之 金屬氯化物蒸氣的量。更且，金屬氯化物蒸氣因爲是由氯氣和 金屬間地反應所產生的，所以不同於利用固體金屬氯化物之加 熱蒸發而產生金屬氯化物蒸氣之方法，不光是可能將載送氣體 之使用量變少而已，依照製造條件而定不使用也是可能的。因 200400095 而，隨著載送氣體使用量之減低加熱能量也將跟著降低’所以 _ 能夠減低製造成本。 再者，藉由在以氯化反應所產生的金屬氯化物蒸氣中混合 惰性氣體，將可以控制於還原爐中之金屬氯化物蒸氣的分壓。 因此，藉著控制氯氣之供給量、或在還原爐所供給之金屬氯化 物蒸氣的分壓，就能夠控制金屬粉末之粒徑，並可以使金屬粉 末之粒徑安定化，同時能夠任意地設定粒徑。 如以上這樣的氯化還原法，係具有可得到安定的粒徑之金 ® 屬粉末的特點，又且能夠有效率地以低成本製造之優良特點。 然而，以氯化還原法連續地製造金屬粉末之際，在還原爐內之 氯化反應速度會有產生變化之情況。當在氯化反應速度產生變 化之情況下，因爲在氯化爐所產生的金屬氯化物蒸氣之產生量 就會變動，以致還原爐內之金屬氯化物之分壓產生變化，結果 所生成的金屬粉末之粒度就變得不安定，因而就有成爲得不到 預定理想的粒徑之金屬粉末的情形。特別是在製造積層陶瓷電 容器之內部電極用的鎳粉末時，在具有此種氯化反應速度變 ® 動的情況，就會有產生多量的1微米以上或2微米以上之粗 粉的情形。 例如，在製造鎳粉末之場合中，將數毫米之九粒狀原料鎳 塡充於氯化爐中，接著加熱至80(TC左右，然後連續地供給氯 氣及原料鎳使進行氯化反應。此時，原料鎳係經氯化而形成氯 化鎳蒸氣，因而在氯化爐內之原料鎳之塡充層就會減少。這個 時候’原料鎳塡充層若是沿著氯化爐之斷面定量地減少的話， -10- 200400095 則氯化反應速度就能保持一定。 然而，氯化爐內之原料鎳塡充層之溫度分布不均勻，又且 依照被供給到氯化爐之氯氣位置或原料鎳位置而定，在原料鎳 塡充層之中央或外周部之氯化有選擇地減少的情況。此種原料 鎳塡充層不均勻地減少持續時，就會產生貫穿該塡充層之某種 程度大小的間隙，因而一部分所供給的氯氣就不會與原料鎳接 觸，而與氯化鎳蒸氣同時直接地被供給到還原爐。此種未反應 的氯氣難免會被直接地供給到還原爐，此時在還原爐內之氯化 鎳蒸氣之分壓就會減少，同時由於氯氣係被提供於還原反應因 而使得鎳粉末之生成速度上昇，結果粗粉就會異常地增加。 本發明人等發現粗粉發生的最大原因是在像這種氯化反應 中未反應的氯氣流入還原爐所致。本來此種異常現象，雖然可 以連續地偵測從氯化爐產生的蒸氣及氣體組成並予以定量而得 知，然而因爲在本發明中氯氣及金屬氯化物之混合氣體，所以 其分離及定量會有困難。 因此，由於氯化反應速度係與氯化爐之重量的變化速度相 對應，因而監視氯化爐之重量的變化速度就可良好而適當地回 饋（feed back)控制氯化反應速度。氯化反應速度之控制手段， 在反應速度降低的情況下，因爲依照上述其主要的原因是由於 產生貫穿氯化爐內之原料金屬塡充層的間隙，以致未反應氯氣 流出所致，所以就有減少供給於氯化爐之氯氣量，或者限制從 氯化爐產生的金屬氯化物蒸氣之向還原爐的供給量等方法。然 而，此等方法全部都會降低金屬粉末之生產性，而且恐怕會因 200400095 還原爐內之反應不均勻而使得所生成的金屬粉末之粒度不安 定’所以較佳是使氯化爐內之原料金屬塡充層不形成間隙般地 將原料金屬供給到氯化爐。通常，就連續運轉而言，雖然原料 金屬是連續或間斷地供給到氯化爐，然而即使在此種情況中， 理想上仍是當偵測得知反應速度下降時，立即相對地增加原料 金屬之供給量。 又且，如以上所述之氯化爐，當使不與原料金屬接觸之未 反應的原來之氯氣流入還原爐時，氯化反應之反應速度就會急 Φ 劇地下降，而且就這樣放置時所生成的金屬粉末之粒度就會變 得不安定，因而必然會產生大量的粗粉。 是以，在本發明中乃監視氯化爐之重量的變化速度，並 確認變化速度急速降低之徵兆的時候，可以立刻地急速增加 原料金屬之供給量。例如，如第4圖所示，當檢出變化速度 急速降低之P時，迅速地以一次或複數次供給與間斷地乃至 連續地供給30分鐘相同的量或以上之原料金屬，然後，以 | 平常、或少量地減少而間斷地乃至連續地供給。藉由此種做 法，因爲可一舉地解消氯氣過多的情形，因而能夠減低未反 應的供給於還原爐之氯氣，並可得到粒度安定之金屬粉末， 尤其是能夠抑制粗粉之產生。 氯化爐之重量的量稱裝置，具體而言以負載測重計 (load cell)較佳，尤其是以可檢測隨時間變化之重量者最 佳。最後的反應速度係爲每單位時間所產生的金屬氯化物蒸 氣的重量，此種反應速度若是時常保持一定的話’則氯化反 -12- 200400095 應就安定，結果在還原爐內之反應也就安定’因而可得到粒 度安定的金屬粉末。 又且，如以上所述在連續或間斷地將原料金屬供給到氯 化爐的情況下，就貯存原料金屬之供給原料進料斗而言，其 重量也是藉由負載測重計來量稱。因此，從原料進料斗之重 量變化和氯化爐之重量變化就可以偵測並控制氯化反應之 反應速度。 在本發明之製造方法中較佳的態樣係如以下所述。 (1) 具備利用負載測重計量稱金屬鎳等原料金屬的 量稱裝置之原料進料斗，並形成供給於具備利用 負載測重計的量稱裝置之氯化爐的持有某種高 度之原料金屬塡充層。 (2) 然後加熱氯化爐使供給於氯化爐內的氯氣開始 氯化反應。 (3) 同時連續或間斷地供給原料金屬。 (4) 連續地檢測原料進料斗及氯化爐之重量變化所 引起的氯化反應之反應速度。 (5) 若發現反應速度變化，特別是降低時，則依照 使達到預定的反應速度般地增量供給原料金 屬。 、又且，在上述態樣中，較宜是量稱原料進料斗之重量與氯 化爐之重量，並偵測氯化反應之反應速度，進而連動並自動地 控制原料金屬之供給量，並控制反應速度而使得製造金屬粉末 200400095 之系統更進上一層樓。 利用本發明之裝置，藉由在還原爐之上游側上配置如以上 所述的氯化爐，並使氯化爐和還原爐直接連結，就可以同時且 連續地進行氯化反應和還原反應，因而能夠更有效率地製造金 屬粉末。另外，會產生對應於向氯化爐內之氯氣供給量的量之 金屬氯化物蒸氣，然而因爲氯化爐和還原爐係直接連結的原 故’因而利用控制氯氣之供給量就可以控制向還原爐供給之金 屬氯化物蒸氣的量。 又且，因爲藉由在氯化爐中設置惰性氣體供給管，就可以 將惰性氣體供給到氯化爐，因而就能夠控制在還原爐中之金屬 氯化物蒸氣之分壓。從而，藉著控制氯氣之供給量或者於還原 爐供給之金屬氯化物蒸氣的分壓，就能夠控制金屬粉末之粒徑 了。又且，由於具備有量稱氯化爐全部重量之量稱裝置，所以 能夠偵測得知氯化反應之反應速度的變化，並進而控制它以使 所得到的金屬粉末之粒度安定化，特別是能夠抑制粗粉之產 生。更且，也藉著具備測定關於原料進料斗之重量的量稱裝置， 因而能夠以較高精度控制反應速度。 以下，邊參照圖示邊詳細地說明關於本發明金屬粉末的製 造裝置之實施態樣。如第1圖所示之氯化反應係非常適合於氯 化爐5中進行。氯化爐5係藉以負載測重計9所支擦著。氯化 爐之上部係配置貯存並供給原料金屬3用的原料進料斗1，原 料進料斗1係透過中途裝有原料金屬4a、4b之原料金屬供給管 21而接續於氣化爐5之頂部。原料進料斗1係由負載測重計2 200400095 所支撐著；負載測重計2係接續於氯化爐之負載測重計9。 氯化爐5之上部係連接於氯氣供給管6，下部則與惰性供 給管8相連接。氯化爐5的周圍係配置加熱器7，氯化爐5之 下部係連接到金屬氯化物蒸氣輸送管1 2。氯化爐5爲縱長型、 橫臥型均沒有關係，然而爲使固體-氣體接觸反應均勻地進 行，則較宜是縱長型。又且，原料供給管2 1、氯氣供給管6及 惰性氣體供給管8之中間部，係爲如波紋管（be Mows)這樣具有 伸縮性及柔軟性之構造，因而得以正確地量稱原料進料斗1及 氯化爐5之重量。再者，於氯化爐5之底部係配置塡料1 1以構 成爐床。塡料1 1係以如石英玻璃等之小碎片所構成，可以使金 屬氯化物蒸氣及惰性氣體流通，而且能夠防止原料金屬落下。 氯氣係連接於流量計而連續地從氯氣供給管6導入。氯化 爐5及其他的組件較宜是石英玻璃製品。金屬氯化物蒸氣輸送 管12係接續於下述還原爐之上端表面處的金屬氯化物蒸氣噴 嘴1 4。 不論起始原料之原料金屬3的形態爲何均可以，然而依照 接觸效率、壓力損失上昇防止之觀點來看，較宜是粒徑爲約5 毫米至20毫米之粒狀、塊狀、板狀等等；又且，其純度較宜是 約99.5 %以上。在氯化爐5內之原料金屬塡充層10之高度，較 宜是依照氯氣供給速度、氯化爐溫度、連續運轉時間、原料金 屬3之形狀等，同時在可充分地變換金屬氯化物蒸氣之供給氯 氣的範圍而適當地設定。氯化爐5內之溫度’雖然若是原料金 屬之氯化溫度就可以’然而在金屬鎳的情況下’爲使反應充分 200400095 地進行宜是在800°C以上，而在鎳的熔點1 483°C以下，當考慮 反應速度及氯化爐5之耐久性時，則實用上較宜是在9〇(rc至 1100°C之範圍。 從氯氣供給管6連續地將氯氣供給到氯化爐5內，同時藉 由關閉原料供給閥而連續或間斷地從原料進料斗1供給原料金 屬。此時，原料金屬之供給量係利用負載測重計2加以量稱而 得。 在氯化爐所產生的金屬氯化物蒸氣，係照原樣藉著金屬氯 化物蒸氣輸送管彳2而輸送到還原爐，或者是依照情況，和以相 對於金屬氯化物蒸氣計爲1莫耳％至3 0莫耳％的從惰性供給管 而來之氮氣及氬氣等之惰性氣體混合，並將此種混合氣體輸送 至還原爐。因而，此種惰性氣體之供給行爲，就成爲控制金屬 粉末的粒度之因子。當混合的惰性氣體過剩時，姑且不論惰性 氣體消耗量多大，僅以能量損失論就不經濟。依照此種觀點來 看，以總壓力爲1 〇計，通過輸送管1 2之混合氣體中金屬氯化 物蒸氣的分壓，較佳爲0.5至1.0之範圍；特別是在製造一種 粒徑爲0.15微米至0.5微米之小粒徑的金屬粉末的情況下，較 爲理想的分壓爲0.6至0.9左右。從而，如以上所述的金屬氯 化物蒸氣生量係可以依照氯氣之供給量而任意地調整；又且， 金屬氯化物蒸氣之分壓也是能夠按照惰性氣體之供給量而任意 地調整。 在氯化爐5所產生的金屬氯化物蒸氣，係連續地被輸送至 還原爐1 3中。在還原爐之上端部係爲接續於金屬氯化物蒸氣輸 200400095 送管12的向下方突出之金屬氯化物蒸氣噴出噴嘴14(以下，簡 稱爲噴嘴1 4)。另外，在還原爐1 3之上端面係與氫氣供給管1 5 相連接，而還原爐1 3之下側部則接續於冷卻氣體供給管1 7。 又且，還原爐1 3之周圍係配置加熱器1 6。噴嘴1 4，如以下所 述’較宜是具有將從氯化爐5來到還原爐13內之金屬氯化物蒸 氣（包括含惰性氣體之情況）以較佳的流速噴出之功能。 當金屬氯化物蒸氣與氫氣進行還原反應之際，噴嘴14之前 端部開始形成類似LPG等氣體燃料之燃燒火焰，並向下方延燒 而形成反應焰1 8。投向還原爐1 3之氫氣供給量，金屬氯化物 蒸氣之化學當量，意即向氯化爐5供給的氯氣之化學當量的1 . 〇 至3.0倍左右，較宜是1_1至2_5倍左右，然而並沒有特別地限 定。但是，當供給過剩的氫氣時，就會有大量的氫氣流入還原 爐1 3內，以致就會擾亂從噴嘴1 4所噴出的金屬氯化物蒸氣噴 出流，即爲造成還原反應不均勻的原因，同時也會放出未消耗 的氣體，因而不經濟。再者，還原反應之溫度較宜是在反應充 分完成的溫度以上，當在製造鎳粉末之情況下，因爲所生成的 爲固體狀之鎳粉末時處理較容易的原故，則較宜是在鎳之熔點 以下，而且當考慮反應速度、還原爐1 3之耐久性、經濟性等時， 實用上較佳爲900°C至1100°C，然而並沒有特別地限定。 被導入如以上所述的氯化爐5中之氯氣，實質上之莫耳量 係與金屬氯化物蒸氣相同，其爲一種還原原料。從噴嘴1 4前端 所噴出之金屬氯化物蒸氣或金屬氯化物蒸氣-惰性氣體混合氣 體的氣體流，其線速度（金屬氯化物蒸氣及惰性氣體之總和（換算 200400095 成在還原溫度時之氣體供給量的計算値））在900°CS 11〇〇°C之 還原溫度時係設定爲約1公尺/秒至30公尺/秒，在製造如0·1 微米至0.3微米這樣之小粒徑的鎳粉末之情況下’則大約爲5 公尺/秒至25公尺/秒；又且在製造如〇·4微米至彳.〇微米這樣 之小粒徑的鎳粉末之情況下，則以大約爲1公尺/秒至1 5公尺/ 秒較適當。氫氣之在還原爐13內軸方向的線速度’宜是金屬氯 化物蒸氣之噴出速度（線速）之1/50至1/30左右，較宜是1/8 0 至1/250。從而，實質上靜止的氫氣氛圍氣中之金屬氯化物蒸 φ 氣，就會成爲從噴嘴1 4噴出的狀態。另外，氫氣供給管1 5之 出口方向較宜是不偏向火焰側。 利用本發明之製造方法，當增加投向氯化爐5之氯氣供給 流量時，在還原爐1 3所生成的金屬粉末1 9之粒徑就會變小， 相反的，減少氯氣供給流量時，粒徑就會變大。 更且，利用相對於如以上所述之氯化爐5出口附近的金屬 氯化物蒸氣所混合之性氣體，來調整金屬氯化物蒸氣之分壓， 具體而言，即藉此而使得在相對於金屬氯化物蒸氣計爲1莫耳 ® %至3 0莫耳％之範圍內混合，例如，分壓高時所生成的金屬粉 末之粒徑會變大，相反的，金屬氯化物蒸氣之分壓降低時所生 成的金屬粉末之粒徑變小。 如以上所述連續地在氯化爐5中進行氯化反應，並以所產 生的金屬氯化物蒸氣在還原爐13中製造金屬粉末之過程中，且 以負載測重計9連續地量稱氯化爐之重量而偵測得知其重量變 化。另一方面，也連續地以負載測重計2量稱原料進料斗彳之 -18- 200400095 重量變化’進而偵測得知供給於氯化爐5內之原料金屬3之重 量。從此種重量變化之時間曲線可得知氯化反應之反應速度。 最後’ K寸原料進料斗1之每卓位時間的重量變化與氯化爐5之 每單位時間的重量變化予以合倂，而得到在氯化爐5中所產生 的金屬氯化物蒸氣之每單位時間的重量，即爲氯化反應之反應 速度（金屬氯化物蒸氣產生量之重量/時間）。 在製造金屬粉末之中，係連續地監視此種反應速度，一旦 發現反應速度下降徵兆的情況，立即從原料進料斗1迅速地增 · 加金屬原料3之供給量，以使反應速度安定化。此時，因爲在 原料金屬塡充層10之上面變得不均勻的原故，因而理想上是一 邊供給原料金屬，一邊以目視確認使其上成爲平滑。再者，利 用分散控制系統等、並以負載測重計2及負載測重計9檢知重 量變化，且與原料金屬供給閥4 一起連動，理想上係設定成當 在發生反應速度下降微候的情況下，即開啓金屬供給閥4，並使 反應速度達到安定化适樣地供給原料金屬3。 在本發明之金屬粉末之製造方法中，亦可以設置有冷卻工 程。冷卻工程，如第1圖所示，可以是在還原爐1 3之噴嘴的相 對側的空間部分進行，或者，使用接續於還原爐出口之另外的 容器也可以。再者，在本發明所稱之冷卻，係指用以使在還原 反應所生成的氣流（含有鹽酸氣體）中金屬粒子之成長停止或受 抑制所進行的作業，具體而言，其意義係指一種使還原反應終 了時在1 000°C附近的氣流急劇地冷卻到400°c至800°c左右之 作業。 200400095 用以進行冷卻之較佳的具體實施例，例如其可以是如具有 將惰性氣體吹入從火焰前端到下方之空間部分的構造。具體而 言，藉由利用冷卻氣體供給管而吹入氮氣，而可以將氣流予以 冷卻。當進行防止金屬粉末1 9之凝集時，就能夠控制粒徑了。 冷卻氣體供給管，可以設置在1個處所，或者是設置在變化還 原爐1 3之上下方向位置的複數個處所，並可以任意地變更冷卻 條件，因而可以較佳精度而良好地進行粒徑之控制。 經由以上之工程，金屬粉末1 9、鹽酸氣體、及性氣體之混 # 合氣體被輸送至回收工程中，並在此從混合氣體中分離回收金 屬粉末1 9。分離回收，例如，較宜是袋式過濾器、水中捕集分 離裝置、油中捕集分離裝置、以及磁性分離裝置中之1種或2 種以上之組合，然而並沒有特別地限定。例如，在以袋式過濾 益捕集金屬粉末1 9之情況下’乃將於冷卻工程中所生成的金屬 粉末1 9、鹽酸氣體、及惰性氣體之混合氣體導入袋式過濾器中， 予以回收金屬粉末1 9，之後也可以再送至洗淨工程中。在使用 油中捕集分離之情況下，較宜是使用碳原子數爲1 0至1 8之正 ® 鏈烷烴或輕油者。在使用水中或油中捕集的情況下，於捕集液 中可以添加1〇ppm至10 00 ppm左右的聚氧伸烷基二醇、聚氧 丙二醇、或其衍生物（單烷基醚、單酯）、或者縮水山梨醇、縮水 山梨醇單醚等之界面活性劑、以苯并三唑或其衍生物爲代表之 金屬惰性劑之酚系、或胺系等之公知的氧化防止劑，此等之1 種或2種以上，同時具有防止金屬粉末粒子之凝集效果、以及 防銹效果。 如以上所述，在利用習用的氯化還原法而製造金屬粉末 -20- 200400095 之方法或製造裝置中，由於氯化爐內之原料金屬塡充層的不 均勻反應，而難免會發生未反應的氯氣流入還原爐，因而所 生成的金屬粉末之粒度就會變得不安定，以致就會產生特別 粗大的粒子。然而，利用本發明之製造方法及製造裝置，因 爲藉由量稱氯化爐之重量而得以安定地控制氯化反應之反 應速度，所以能夠防止未反應氯氣流入還原爐，結果就能夠 使得粒度達到定化，並製造沒有特別粗大粒子的金屬粉末。 更且，在習用的方法或習用的裝置中，如以上所述，因爲氯 化反應急劇地下降而不安定，所以反應速度上昇就變得不可 能，但是由於在本發明中反應速度係爲安定的，所以反應速 度上昇是可能的，結果就能夠使的金屬粉末之生產性向上提 昇。 【實施方式】 以下，藉由具體實施例詳細地說明本發明。 【實施例】 將1 5公斤的平均粒徑爲5毫米之原料鎳，從原料進料 斗塡充到如第1圖所示的金屬粉末之製造裝置中，使爐內氛 圍氣溫度成爲1 1 〇 〇 °C並以4 N升/分鐘的流量導入鹽酸氣 體，開始進行氯化反應。然後，從原料進料斗以0.5公斤原 料鎳分隔5分鐘間斷地將原料鎳供給到氯化爐5。將此種金 屬鎳予以氯化使產生氯化鎳蒸氣。 將氯氣供給量之1 〇%(莫耳比）的氮氣混入其中，將此種 氯化鎳蒸氣—氮氣混合氣體以2.3公尺/秒（1 〇 〇 〇它換算）之 流速從噴嘴14導入被加熱成1 000t之氛圍氣溫度的還原爐 中。同時，從還原爐1 3之頂部以7 N升/分鐘之流速供給氫 200400095 氣，以還原氯化鎳蒸氣。 同時連續地進行（達3 0小時）如以上所述的氯化反應和 還原反應，此時，原料進料斗1和氯化爐5之重量分別是由 負載測重計2及負載測重計9量稱，從此等重量變化而連續 地偵測得知在氯化爐內之氯化反應之反應速度。製造開始 後，因爲在2 5小時的時候發現反應速度有下降之徵兆’所 以每1次增加5公斤之從原料進料斗1而來的原料鎳供給 量，而使得反應速度安定化並繼續地製造。 含有於還原反應中所生成的鎳粉末之生成氣體，經於在 冷卻工程中與氮氣混合而被冷卻。接著，將由氮氣一鹽酸蒸 氣一鎳粉末所形成的混合氣體導入純水中，分離回收鎳粉 末。其次，以純水將所回收的鎳粉末予以洗淨，然後乾燥而 得到鎳粉末製品。所得到的鎳粉末之粒度分布係如第2圖所 示，又且SEM照片係示於第3A圖中。利用BET法測定的 平均粒徑爲〇·40微米，在有機溶劑中懸濁時之平均粒徑爲 1.50微米，又且，5微米以上之粗粉爲0%。就此處在有機 溶劑中懸濁時之平均粒徑及粒度分布而言，係使用雷射光繞 射法粒度測定機（庫爾特L S 2 3 0 :庫爾特公司製），將適當量 的金屬粉末懸濁於α -萜品醇中，再以超音波分散3分鐘， 以折射率1 · 8測定試樣，求得體積統計値之粒度分布。 【比較例】 除了不量稱原料進料斗1與氯化爐5之重量，且不控制 在氯化爐內之氯化反應之反應速度以外，均與實施例1同樣 -22- 200400095 地進行製造。所得到的鎳粉末之粒度分布係如第2圖所示， 又且S Ε Μ照片係示於第3 B圖中。利用B ET法測定的平均 粒徑爲〇 . 4 5微米，在有機溶劑中懸濁時之平均粒徑爲1 . 4 5 微米，又且，5微米以上之粗粉爲3.0 %。 在利用本發明之方法的實施例中所製造的鎳粉末之粒 度分布，依照第2圖所示，與在比較例中所製造的鎳粉末比 較起來，特別粗大的粗粉極其少，或者從第3圖之S Ε Μ照 片看來，在比較例所製造的鎳粉末中可見到多量的1微米以 上之粗粉，因此比較之下，可明白在實施例所製造的鎳粉末 中1微米以上之粗粉極少。 【發明效果】 如以上所述之說明，設若根據本發明金屬粉末之製造方 法及製造裝置的話，就可以有效率地製造符合積層陶瓷電容 器之內部電極等所要求的1微米以下之微細粒徑之鎳粉末 等之金屬粉末，更且能夠控制氯化反應之反應速度，結果就 可以達成製造出粒度均勻、而且無粗大粒子之金屬粉末的效 果了。 【圖式之簡單說明】 第1圖係爲顯示本發明實施態樣中金屬粉末之製造裝 置之構成的縱斷面圖。 第2圖所示者係爲在實施例及比較例中所的鎳粉末之 粒度分布。 第3 Α圖係爲在實施例中所製造的鎳粉末之S Ε Μ照片， 第3 Β圖係爲在比較例中所製造的鎳粉末之S ε Μ照片。 -2.3- 200400095 第4圖係爲顯示氯化爐中反應速度（氯化爐重量之變化 速度）的曲線圖。 【元件符號對照表】 5氯化爐 9負載測重計 1原料進料斗 2負載測重計 13還原爐 φ 3原料金屬200400095 发明 Description of the invention: [Technical field to which the invention belongs] The present invention relates to a method and a device for manufacturing a metal powder; in particular, it relates to a conductive paste and a titanium material that can be used on electronic parts, such as multilayer ceramic capacitors. The method and apparatus for manufacturing metal powders of Joji Temple which are suitable as bonding materials for various uses such as catalysts. [Prior art] Metal powders such as nickel and copper are widely used in various fields such as electronic materials and catalysts. However, in recent years, especially metal powders with an average particle size of 1 micrometer or less are called ultrafine powders. , And it can be used to form the internal electrodes of multilayer ceramic capacitors. Since the past, precious metal powders such as silver, palladium, platinum, and gold, or base metal powders such as nickel, cobalt, iron, molybdenum, and tungsten have been used as conductive pastes for electronic materials, especially as multilayer ceramic capacitors. For internal electrodes. Generally speaking, 'multilayer ceramic capacitors' are such that the dielectric ceramic layer and the metal layer used as the internal electrode overlap each other. Both ends of the dielectric ceramic layer are connected to the metal layer of the internal electrode to form a connection with the external electrode. Made up. Here, as the material constituting the dielectric body, a barrel dielectric material such as barium titanate, total titanate, iridium oxide, or the like can be used as a main component. On the other hand, although the metal constituting the internal electrode can use the aforementioned noble metal powder or base metal powder, recently, because cheaper electronic materials are often required, it is popular to use the latter base metal powder to develop multilayer ceramic capacitors. It is represented by nickel. Multilayer ceramic capacitors are prepared by mixing and suspending a dielectric powder such as barium titanate and an organic binder, and using a doctor blade coating method to form a 200400095 dielectric body into a green sheet; another On the one hand, metal powders for internal electrodes are mixed with organic compounds such as organic solvents, plasticizers, and organic binders to form metal powder pastes, which are then printed on the aforementioned green sheets by screen printing. These are laminated in hundreds of layers, then fired at 100 ° C or more, and finally external electrodes are fired on both ends of the dielectric ceramic layer to obtain a multilayer ceramic capacitor. Manufacturing of the multilayer ceramic capacitor as described above In the process of evaporation and removal of organic components from metal paste and subsequent sintering process ®, metal powders undergo volume changes due to expansion and contraction. That is, they are different from dielectrics and metals. The reason that the powder substance is sintered at the same time, so during the sintering process, different sintering behaviors caused by the volume change of the expansion and contraction of various substances will inevitably occur; therefore, the so-called cracks or peeling will inevitably be caused as a result. Problems such as dissociation of multilayers, destruction of so-called layered structures, etc. In addition, with the miniaturization and large capacity of capacitors, high I layering, thinning of internal electrodes, or low resistance are required. Therefore, it is needless to say that the metal powder used as the internal electrode has a particle size of less than 1 micron, and it is more eagerly expected that the particle size is 0.5 micron. Ultrafine powder below 1 meter. At this time, due to the existence of coarse powder above 1 micron or 2 micron, it is difficult to thin the internal electrode, and the unevenness on the electrode surface becomes the cause of the short circuit. Moreover, the result becomes one of the reasons for the dissociation of the layer. In Japanese Patent Application Laid-Open No. 10-21931 3, a method for manufacturing such a small amount of coarse metal powder has been disclosed, which is provided with metal in contact with chlorine gas. And even 200400095 chlorination projects that continuously produce metal chloride vapor, and used in chlorination projects. The generated metal chloride vapor is contacted with a reducing gas to continuously reduce the metal chloride to a reduction process. The above-mentioned manufacturing method is an excellent method for stably and efficiently manufacturing (especially) nickel powder below 1 micron. However, the produced metal powder additionally contains coarse powders of 1 micrometer or more and 2 micrometers or more. Therefore, an improved manufacturing method or apparatus capable of controlling the generation of such coarse powders is desired. · [Summary of the invention] [Summary of the invention] Therefore, the object of the present invention is to provide a method and a device for manufacturing a metal powder, which is a method for reacting a raw metal with chlorine gas to generate a metal chloride vapor, and to make the metal chloride A method for preparing metal powder by reacting steam with hydrogen, wherein the metal powder has no coarse powder and has a stable particle size, especially a metal powder suitable for an internal electrode of a multilayer ceramic capacitor having an average particle size of less than 1 micron. · The present inventors repeatedly and diligently conducted research in order to achieve the above-mentioned purpose, and as a result, it was found that the chlorine gas that does not react in the chlorination furnace is supplied to the reduction furnace, which will increase the reaction temperature, which is the reason for the formation of coarse powder. . The manufacturing method of the metal powder of the present invention is a manufacturing method of the metal powder based on the above-mentioned cognitive discovery. The method is to intermittently or continuously supply the raw metal into the chlorination furnace. The metal powder is continuously reacted to generate metal chloride vapor, and the metal chloride vapor and hydrogen are continuously reacted in a reduction furnace to obtain a metal powder. The metal powder is characterized in that in the method for manufacturing the 200400095 metal powder, the quantity is weighed. The weight of the chlorination furnace in the chlorination reaction is controlled based on the result of the weighing. Moreover, the metal powder manufacturing apparatus of the present invention is characterized by having a raw material feed hopper for supplying raw metal, a chlorination furnace for chlorinating the raw metal supplied from the raw material hopper, and Reduction furnace for reducing metal chloride vapor generated in chemical furnace; raw material feed hopper and chlorination furnace are connected to the raw material supply pipe through a valve that controls the supply amount of raw metal metal; chlorination furnace and reduction furnace are by The metal chloride vapor generated in the chlorination furnace is conveyed to the duct of the reduction furnace and communicated; the chlorination furnace is provided with a chlorine gas supply pipe for supplying chlorine gas to the interior; the reduction furnace is provided with the metal chloride vapor in the interior The spray nozzle, the hydrogen supply pipe for supplying hydrogen to the inside, and the cooling gas supply pipe for supplying the inert gas for cooling the reduced metal powder to the inside; moreover, all of the chlorination furnaces are provided in quantity. A weight weighing device and a control device that controls the amount of raw metal supplied to the chlorine furnace based on the weighing result of the weighing device. According to the present invention, since the supply amount of the raw metal can be controlled based on the weighing result based on the total weight of the chlorinating furnace, an appropriate amount of the raw metal can be constantly charged into the chlorinating furnace. Therefore, the reaction between the raw metal and the chlorine gas can be made uniform, and the chlorine gas supplied to the reduction furnace due to unreaction can be reduced. The metal powder of the present invention is a metal that can be used for the internal electrodes of a multilayer ceramic capacitor, and is a precious metal such as silver, palladium, uranium, gold, etc., or 200400095 is a base metal such as nickel, cobalt, iron, molybdenum, tungsten, etc. . Among them, base metals are more suitable because they are cheaper, and nickel is more preferred. The particle properties of the metal powder produced in the present invention are not limited to individual uses. Although not particularly limited, when used for internal electrodes of multilayer ceramic capacitors, The average particle size is preferably used at 0. 1 to 0. 5 microns, more preferably 0. 1 to 1 micron, particularly preferably 0.1 to 0. Particles in the 5 micron range. Furthermore, the shape of the particles of the metal powder is preferably spherical in order to improve the sintering properties or anionic properties. The invention relates to a method for continuously generating metal chloride vapor by reacting raw metal and chlorine gas in a chlorination furnace, and reacting such metal chloride vapor and hydrogen in a reduction furnace to continuously obtain metal powder. (Hereinafter referred to as "chlorination reduction method"). Generally speaking, the metal powder is produced by a gas-phase reduction reaction such as metal chloride vapor and hydrogen in an instant, and metal atoms are formed instantaneously. "Metal atoms generate ultrafine particles due to collisions and agglomeration." For growth. Therefore, the particle diameter of the metal powder to be produced can be determined in accordance with conditions such as the partial pressure of the metal chloride vapor in the reduction furnace and the temperature. With this chlorination reduction method, since metal chloride vapor is generated in an amount corresponding to the supply amount of chlorine gas, the amount of metal chloride vapor supplied to the reduction furnace can be controlled by controlling the supply amount of chlorine gas. Moreover, because metal chloride vapor is generated by the reaction between chlorine gas and metal, it is different from the method of generating metal chloride vapor by heating and evaporation of solid metal chloride, and it is not only possible to change the amount of carrier gas used. Only a few, it is possible not to use depending on the manufacturing conditions. Since 200400095, as the amount of carrier gas used decreases, the heating energy will also decrease ', so it can reduce manufacturing costs. Furthermore, by mixing an inert gas with the metal chloride vapor generated by the chlorination reaction, the partial pressure of the metal chloride vapor in the reduction furnace can be controlled. Therefore, by controlling the amount of chlorine gas supplied or the partial pressure of the metal chloride vapor supplied in the reduction furnace, the particle diameter of the metal powder can be controlled, and the particle diameter of the metal powder can be stabilized and arbitrarily set. Particle size. The chlorination reduction method as described above has the characteristics of being able to obtain gold ® metal powder with a stable particle size, and it can be manufactured efficiently at low cost. However, when the metal powder is continuously produced by the chlorination reduction method, the chlorination reaction rate in the reduction furnace may be changed. When the chlorination reaction speed changes, the amount of metal chloride vapor produced in the chlorination furnace will change, so that the partial pressure of the metal chloride in the reduction furnace will change, resulting in the formation of metal. The particle size of the powder becomes unstable, so that it may become a metal powder with a predetermined ideal particle size. In particular, when manufacturing nickel powder for internal electrodes of multilayer ceramic capacitors, when such a chlorination reaction rate is changed, a large amount of coarse powder of 1 micrometer or more or 2 micrometers or more may be generated. For example, in the case of manufacturing nickel powder, a few millimeters of granular raw material nickel rhenium is charged in a chlorination furnace, and then heated to about 80 ° C, and then chlorine gas and raw material nickel are continuously supplied to perform a chlorination reaction. At this time, the raw material nickel is chlorinated to form nickel chloride vapor, so the amount of nickel coating in the chlorination furnace will be reduced. At this time, if the raw material nickel coating is quantified along the section of the chlorination furnace If the temperature decreases, -10- 200400095 will keep the chlorination reaction rate constant. However, the temperature distribution of the raw material nickel coating in the chlorination furnace is uneven, and it depends on the location or raw material of the chlorine gas supplied to the chlorination furnace. Depending on the position of nickel, chlorination may be selectively reduced in the center or peripheral portion of the raw nickel coating. When the non-uniform reduction of this raw nickel coating is sustained, a certain amount of penetration will occur through the coating. This kind of gap is large, so part of the supplied chlorine gas will not contact the raw nickel, and will be directly supplied to the reduction furnace simultaneously with nickel chloride vapor. Such unreacted chlorine gas will inevitably be directly supplied to the reduction furnace. ,this The partial pressure of nickel chloride vapor in the reduction furnace will decrease, and at the same time, the generation rate of nickel powder will increase due to the chlorine gas being supplied to the reduction reaction, resulting in an abnormal increase in coarse powder. The present inventors found that coarse powder The biggest cause is that unreacted chlorine gas flows into the reduction furnace during this chlorination reaction. Originally, this abnormal phenomenon can be obtained by continuously detecting and quantifying the composition of steam and gas generated from the chlorination furnace. However, since the mixed gas of chlorine gas and metal chloride is difficult to separate and quantify in the present invention, since the chlorination reaction speed corresponds to the rate of change of the weight of the chlorination furnace, the chlorination is monitored. The rate of change in the weight of the furnace can be used to control the chlorination reaction rate in a good and appropriate way. When the reaction rate is reduced, the main reason for the above is that it is caused by the penetration. The gap between the raw material metal filling layer in the chlorination furnace is caused by the unreacted chlorine gas flowing out, so the supply to the chlorination furnace is reduced. Gas volume, or limiting the supply of metal chloride vapor from the chlorination furnace to the reduction furnace. However, all of these methods will reduce the productivity of the metal powder, and it is likely that the reaction in the reduction furnace will be uneven due to the 200400095 The particle size of the generated metal powder is unstable. Therefore, it is preferable to supply the raw metal to the chlorination furnace without forming a gap between the raw metal filling layer in the chlorination furnace. Generally, for continuous operation, although The raw metal is continuously or intermittently supplied to the chlorination furnace, but even in this case, ideally, when the reaction speed is detected to decrease, the supply of the raw metal is relatively increased immediately and relatively. Also, as above In the chlorination furnace, when the unreacted original chlorine gas not in contact with the raw metal is flowed into the reduction furnace, the reaction speed of the chlorination reaction sharply decreases, and the metal powder generated when it is left standing as it is The particle size will become unstable, and a large amount of coarse powder will inevitably be produced. Therefore, in the present invention, when the rate of change in the weight of the chlorination furnace is monitored and the signs of a rapid decrease in the rate of change are confirmed, the supply amount of the raw metal can be increased rapidly immediately. For example, as shown in FIG. 4, when P, whose rate of change is rapidly decreasing, is detected, one or more times of supply of the same amount or more of the raw metal as intermittently or even continuously for 30 minutes is quickly provided, and then, Usually, or a small amount, intermittently and even continuously. With this method, since the situation of excessive chlorine gas can be eliminated in one fell swoop, the unreacted chlorine gas supplied to the reduction furnace can be reduced, and the metal powder with stable particle size can be obtained, and especially the generation of coarse powder can be suppressed. A weighing device for the weight of the chlorination furnace is preferable, specifically, a load cell, and particularly a device capable of detecting a change in weight over time. The final reaction rate is the weight of the metal chloride vapor produced per unit time. If this reaction rate is constantly maintained, then the chlorination trans-12- 200400095 should be stable, and the reaction in the reduction furnace is also the result. Stable 'can thus obtain stable metal powder. When the raw metal is continuously or intermittently supplied to the chlorination furnace as described above, the weight of the raw material feed hopper that stores the raw metal is also measured by a load cell. Therefore, the reaction speed of the chlorination reaction can be detected and controlled from the change in the weight of the raw material feed hopper and the change in the weight of the chlorination furnace. The preferable aspect in the manufacturing method of this invention is as follows. (1) A raw material feed hopper equipped with a weighing device for weighing raw metals such as metallic nickel by a load cell, and forming a certain level of raw material supplied to a chlorination furnace equipped with a weighing device using a load cell Metal filling layer. (2) The chlorination furnace is then heated so that the chlorine gas supplied to the chlorination furnace starts a chlorination reaction. (3) Simultaneous or intermittent supply of raw metal. (4) Continuously detect the reaction rate of the chlorination reaction caused by the weight change of the raw material feed hopper and the chlorination furnace. (5) If a change in the reaction rate is observed, particularly when the reaction rate is decreased, the raw material metal is supplied in increments such that the predetermined reaction rate is reached. In addition, in the above aspect, it is more appropriate to weigh the weight of the raw material feed hopper and the weight of the chlorination furnace, and detect the reaction speed of the chlorination reaction, and then link and automatically control the supply of raw metal, and Controlling the reaction speed makes the system for making metal powder 200400095 even better. With the device of the present invention, by arranging the chlorination furnace as described above on the upstream side of the reduction furnace and directly connecting the chlorination furnace and the reduction furnace, the chlorination reaction and the reduction reaction can be performed simultaneously and continuously. Therefore, metal powder can be manufactured more efficiently. In addition, metal chloride vapor is generated in an amount corresponding to the amount of chlorine gas supplied to the chlorination furnace. However, because the chlorination furnace and the reduction furnace are directly connected, it is possible to control the supply of chlorine gas to the reduction furnace. The amount of metal chloride vapor supplied. In addition, since the inert gas supply pipe is provided in the chlorination furnace, the inert gas can be supplied to the chlorination furnace, so the partial pressure of the metal chloride vapor in the reduction furnace can be controlled. Therefore, by controlling the amount of chlorine gas supplied or the partial pressure of the metal chloride vapor supplied from the reduction furnace, the particle size of the metal powder can be controlled. In addition, since a weighing device is provided to weigh the entire weight of the chlorination furnace, it can detect the change in the reaction rate of the chlorination reaction, and then control it to stabilize the particle size of the obtained metal powder, especially It can suppress the generation of coarse powder. Furthermore, since a weighing device for measuring the weight of the raw material feed hopper is provided, the reaction speed can be controlled with high accuracy. Hereinafter, embodiments of the apparatus for manufacturing a metal powder according to the present invention will be described in detail with reference to the drawings. The chlorination reaction system shown in Fig. 1 is very suitable for carrying out in the chlorination furnace 5. The chlorination furnace 5 was rubbed by 9 load scales. The upper part of the chlorination furnace is provided with a raw material hopper 1 for storing and supplying the raw metal 3. The raw material hopper 1 is connected to the top of the gasification furnace 5 through a raw metal supply pipe 21 containing the raw metals 4a and 4b halfway. The raw material hopper 1 is supported by a load tester 2 200400095; the load tester 2 is a load tester 9 connected to the chlorination furnace. The upper part of the chlorination furnace 5 is connected to the chlorine gas supply pipe 6, and the lower part is connected to the inert supply pipe 8. A heater 7 is arranged around the chlorination furnace 5, and a lower portion of the chlorination furnace 5 is connected to a metal chloride vapor transfer pipe 12. It does not matter whether the chlorination furnace 5 is a vertical type or a horizontal type. However, in order to make the solid-gas contact reaction proceed uniformly, the vertical type is preferable. In addition, the intermediate portions of the raw material supply pipe 21, the chlorine gas supply pipe 6, and the inert gas supply pipe 8 are of a structure having flexibility and flexibility such as a bellows (be Mows), so that the raw material feed can be accurately weighed. Weight of hopper 1 and chlorination furnace 5. Furthermore, the bottom 11 of the chlorination furnace 5 is provided with an aggregate 11 to constitute a hearth. The material 11 is composed of small pieces such as quartz glass, which can circulate metal chloride vapor and inert gas, and can prevent the raw metal from falling. The chlorine gas is connected to the flow meter and is continuously introduced from the chlorine gas supply pipe 6. The chlorination furnace 5 and other components are preferably quartz glass products. The metal chloride vapor transfer pipe 12 is connected to a metal chloride vapor nozzle 14 at the upper end surface of the reduction furnace described below. Regardless of the form of the starting metal 3 as the starting material, it is possible, but from the viewpoints of contact efficiency and prevention of pressure loss rise, it is more preferable to use granular, lumpy, plate-like particles having a particle diameter of about 5 mm to 20 mm. Etc .; Also, its purity is preferably about 99. 5% or more. The height of the raw material metal filling layer 10 in the chlorination furnace 5 is preferably based on the supply rate of chlorine gas, the temperature of the chlorination furnace, the continuous operation time, the shape of the raw metal 3, etc., and at the same time, the metal chloride vapor can be sufficiently changed. The range of the supplied chlorine gas is appropriately set. The temperature in the chlorination furnace 5 'is possible if it is the chlorination temperature of the raw metal. However, in the case of metallic nickel', it is preferable to perform the reaction at a temperature of 200400095 or higher, and the melting point of nickel is 1 483 ° Below C, when considering the reaction rate and the durability of the chlorination furnace 5, it is practically preferable to be in the range of 90 ° C to 1100 ° C. Chlorine gas is continuously supplied from the chlorine gas supply pipe 6 to the chlorination furnace 5. At the same time, the raw metal is continuously or intermittently supplied from the raw material hopper 1 by closing the raw material supply valve. At this time, the amount of raw metal supplied is measured by using a load cell 2. The metal chloride vapor is transported to the reduction furnace through the metal chloride vapor conveying pipe 彳 2 as it is, or, as the case may be, from 1 mole% to 30 mole% relative to the metal chloride vapor. The inert gas such as nitrogen and argon from the inert supply tube is mixed and sent to the reduction furnace. Therefore, the supply behavior of this inert gas becomes a factor controlling the particle size of the metal powder. When Mixed inertia When there is excess gas, no matter how much the inert gas is consumed, it is not economical to use only energy loss theory. From this point of view, based on the total pressure of 10, the metal chloride vapor in the mixed gas passing through the pipe 12 is Partial pressure, preferably 0. 5 to 1. 0 range; especially in the manufacture of a particle size of 0. 15 microns to 0. In the case of metal powders with a small particle size of 5 microns, the ideal partial pressure is 0. 6 to 0. 9 or so. Therefore, the metal chloride vapor generation amount as described above can be arbitrarily adjusted in accordance with the supply amount of chlorine gas, and the partial pressure of the metal chloride vapor can also be arbitrarily adjusted in accordance with the supply amount of the inert gas. The metal chloride vapor generated in the chlorination furnace 5 is continuously transferred to the reduction furnace 13. The upper end portion of the reduction furnace is a metal chloride vapor ejection nozzle 14 (hereinafter, simply referred to as a nozzle 14) that is continuous with the metal chloride vapor delivery pipe 200400095, and projects downward from the delivery pipe 12. In addition, the upper end surface of the reduction furnace 13 is connected to the hydrogen supply pipe 15, and the lower side of the reduction furnace 13 is connected to the cooling gas supply pipe 17. In addition, a heater 16 is arranged around the reduction furnace 13. The nozzles 14, as described below, are more preferable to have the function of ejecting the metal chloride vapor (including the case containing an inert gas) from the chlorination furnace 5 to the reduction furnace 13 at a better flow rate. When the metal chloride vapor and hydrogen undergo a reduction reaction, the front end of the nozzle 14 starts to form a combustion flame similar to a gas fuel such as LPG, and is burned downward to form a reaction flame 18. The amount of hydrogen supplied to the reduction furnace 13 is the chemical equivalent of the metal chloride vapor, which means 1 of the chemical equivalent of the chlorine gas supplied to the chlorination furnace 5. 〇 to 3. It is about 0 times, preferably about 1_1 to 2_5 times, but it is not particularly limited. However, when an excessive amount of hydrogen is supplied, a large amount of hydrogen flows into the reduction furnace 13 so that the metal chloride vapor jet stream from the nozzle 14 is disturbed, which is the cause of the non-uniform reduction reaction. It also emits unconsumed gas, which is uneconomical. Furthermore, the temperature of the reduction reaction is preferably higher than the temperature at which the reaction is fully completed. In the case of producing nickel powder, it is more convenient to handle the nickel powder because it is easier to handle when the solid nickel powder is produced. The melting point is equal to or lower than the melting point, and in consideration of the reaction rate, the durability, economical efficiency, and the like of the reduction furnace 13, it is practically preferably 900 ° C. to 1100 ° C., but it is not particularly limited. The chlorine gas introduced into the chlorination furnace 5 as described above has substantially the same molar amount as the metal chloride vapor, which is a reducing raw material. The gas velocity of the metal chloride vapor or metal chloride vapor-inert gas mixed gas ejected from the front end of the nozzle 14 is the linear velocity (the sum of the metal chloride vapor and the inert gas (200400095 is converted into the gas supply at the reduction temperature). Calculation of the amount 値)) at 900 ° CS 1 100 ° C reduction temperature is set to about 1 m / sec to 30 m / sec, such as in the manufacture of 0.1 m to 0. In the case of nickel powder with a small particle diameter of 3 microns, it is about 5 m / s to 25 m / s; and in the manufacture of such as 0.4 m to 彳. In the case of a nickel powder having a small particle diameter of 0 micron, it is more suitable to be about 1 m / s to 15 m / s. The linear velocity of the hydrogen gas in the axial direction of the reduction furnace 13 is preferably about 1/50 to 1/30 of the metal chloride vapor ejection speed (linear velocity), and more preferably 1/8 0 to 1/250. Therefore, the metal chloride in the substantially still hydrogen atmosphere vaporizes the φ gas, and the gas is discharged from the nozzle 14. The outlet direction of the hydrogen supply pipe 15 is preferably not biased toward the flame side. According to the manufacturing method of the present invention, when the flow rate of the chlorine gas fed to the chlorination furnace 5 is increased, the particle size of the metal powder 19 generated in the reduction furnace 13 becomes smaller. On the contrary, when the flow rate of the chlorine gas is decreased, the particle size is reduced. The diameter will become larger. Further, the partial pressure of the metal chloride vapor is adjusted by using a sexual gas mixed with the metal chloride vapor near the outlet of the chlorination furnace 5 as described above, specifically, by this, the relative Metal chloride vapor is mixed within the range of 1 Moore ®% to 30 Molar%. For example, the particle size of the metal powder generated when the partial pressure is high will increase. Conversely, the partial pressure of metal chloride vapor The particle diameter of the metal powder produced when it decreases is small. The chlorination reaction is continuously performed in the chlorination furnace 5 as described above, and the metal powder is produced in the reduction furnace 13 by using the generated metal chloride vapor. The weight of the furnace is detected to detect its weight change. On the other hand, the weight change of the raw material feed hopper -18-200400095 was also continuously weighed with the load weight gauge 2 to detect the weight of the raw metal 3 supplied to the chlorination furnace 5. From the time curve of such a weight change, the reaction rate of the chlorination reaction can be known. Finally, the weight change per bit time of the K inch raw material feed hopper 1 and the weight change per unit time of the chlorination furnace 5 are combined to obtain per unit of metal chloride vapor generated in the chlorination furnace 5. The weight of time is the reaction rate of the chlorination reaction (weight / time of the amount of metal chloride vapor generated). In the production of metal powder, such a reaction rate is continuously monitored, and once signs of a decrease in the reaction rate are detected, the supply amount of the metal raw material 3 is rapidly increased from the raw material hopper 1 to stabilize the reaction rate. At this time, since the upper surface of the raw material metal filling layer 10 becomes uneven, it is desirable to visually confirm that the upper surface is smoothed while the raw metal is being supplied. Furthermore, by using a distributed control system, etc., and detecting the change in weight with the load cell 2 and the load cell 9 and interlocking with the raw metal supply valve 4, it is ideally set to wait for a while when the reaction speed drops. In this case, the metal supply valve 4 is opened, and the reaction speed is stabilized to supply the raw metal 3 in an appropriate manner. In the method for producing a metal powder of the present invention, a cooling process may be provided. The cooling process may be performed in the space on the opposite side of the nozzle of the reduction furnace 13 as shown in Fig. 1, or another container connected to the outlet of the reduction furnace may be used. The term "cooling" as used in the present invention refers to an operation performed to stop or suppress the growth of metal particles in a gas stream (containing hydrochloric acid gas) generated by a reduction reaction. Specifically, the meaning means An operation for rapidly cooling the air flow near 1000 ° C to about 400 ° c to 800 ° c at the end of the reduction reaction. 200400095 A preferred embodiment for cooling is, for example, a structure in which an inert gas is blown into a space portion from the front end of the flame to the lower portion. Specifically, the gas stream can be cooled by blowing nitrogen gas through a cooling gas supply pipe. When the agglomeration of the metal powder 19 is prevented, the particle size can be controlled. The cooling gas supply pipe can be installed in one place or a plurality of places in positions above and below the changing reduction furnace 13 and the cooling conditions can be arbitrarily changed, so that the particle size can be performed with good accuracy and good quality. control. Through the above process, the metal powder 19, the hydrochloric acid gas, and the mixed gas of mixed gas are transported to the recovery project, and the metal powder 19 is separated and recovered from the mixed gas. The separation and recovery are, for example, one or a combination of two or more of a bag filter, a water-capture separation device, an oil-capture separation device, and a magnetic separation device. However, it is not particularly limited. For example, in the case of trapping metal powder 19 with a bag filter, 'the mixed gas of metal powder 19, hydrochloric acid gas, and inert gas generated in the cooling process is introduced into a bag filter and recovered. The metal powder 19 can also be sent to the cleaning process afterwards. In the case of trapping and separation in oil, it is more preferable to use n-paraffin or light oil with 10 to 18 carbon atoms. In the case of trapping in water or oil, a polyoxyalkylene glycol, polyoxypropylene glycol, or a derivative thereof (monoalkyl ether, (Monoester), or surfactants such as glycidyl sorbitol, glycidyl monoether, etc., metal inerts such as benzotriazole or its derivatives, phenol-based or amine-based known oxidation inhibitors, One or two or more of these have both an effect of preventing aggregation of metal powder particles and an effect of preventing rust. As described above, in the method or manufacturing device for manufacturing metal powder-20-200400095 by the conventional chlorination reduction method, the non-reaction will inevitably occur due to the non-uniform reaction of the raw material metal filling layer in the chlorination furnace. The chlorine gas flows into the reduction furnace, so the particle size of the resulting metal powder becomes unstable, so that particularly coarse particles will be produced. However, with the manufacturing method and manufacturing apparatus of the present invention, the reaction rate of the chlorination reaction can be stably controlled by measuring the weight of the chlorination furnace, so that unreacted chlorine gas can be prevented from flowing into the reduction furnace, and as a result, the particle size can be achieved. It is standardized and a metal powder is produced without particularly coarse particles. Furthermore, in the conventional method or the conventional device, as described above, since the chlorination reaction drastically decreases and becomes unstable, it becomes impossible to increase the reaction rate. However, in the present invention, the reaction rate is stable. It is possible to increase the reaction speed, and as a result, the productivity of the metal powder can be increased. [Embodiment] Hereinafter, the present invention will be described in detail through specific examples. [Example] 15 kg of raw material nickel having an average particle diameter of 5 mm was charged from a raw material feed hopper into a metal powder manufacturing apparatus as shown in FIG. 1 so that the temperature of the atmosphere in the furnace became 1 1 〇 0 ° C, hydrochloric acid gas was introduced at a flow rate of 4 N liters / minute, and the chlorination reaction was started. Then, from the raw material hopper to 0. Five kilograms of raw nickel were supplied to the chlorination furnace 5 intermittently for 5 minutes. This metal nickel is chlorinated to produce nickel chloride vapor. 10% (mole ratio) of nitrogen gas is mixed into the chlorine gas supply, and this nickel chloride vapor-nitrogen mixed gas is 2. A flow rate of 3 m / s (equivalent to 1,000) is introduced from the nozzle 14 into a reduction furnace heated to an atmospheric temperature of 1,000 t. At the same time, hydrogen 200400095 gas was supplied from the top of the reduction furnace 13 at a flow rate of 7 N liters / minute to reduce the nickel chloride vapor. Simultaneously (up to 30 hours) the chlorination reaction and reduction reaction as described above are performed continuously. At this time, the weights of the raw material feed hopper 1 and the chlorination furnace 5 are respectively determined by the load cell 2 and the load cell 9 Weighing scales, from these weight changes, the reaction rate of the chlorination reaction in the chlorination furnace is continuously detected. After the start of production, because the reaction rate showed signs of decline at 25 hours, the raw material nickel supply from the raw material hopper 1 was increased by 5 kg per time, so that the reaction rate was stabilized and production continued. . The generated gas containing the nickel powder generated in the reduction reaction is cooled by being mixed with nitrogen in a cooling process. Next, a mixed gas formed by nitrogen-hydrochloric acid vapor-nickel powder was introduced into pure water, and the nickel powder was separated and recovered. Next, the recovered nickel powder was washed with pure water and then dried to obtain a nickel powder product. The particle size distribution of the obtained nickel powder is shown in Fig. 2 and the SEM photograph is shown in Fig. 3A. The average particle diameter measured by the BET method was 0.40 μm, and the average particle diameter when suspended in an organic solvent was 1. 50 micrometers, and coarse powder of 5 micrometers or more is 0%. The average particle size and particle size distribution when suspended in an organic solvent here are determined by using a laser diffraction particle size analyzer (Kurt Co. LS 2 3 0: Coulter Co., Ltd.) The powder was suspended in α-terpineol, and then dispersed by ultrasonic for 3 minutes, and the sample was measured at a refractive index of 1 · 8 to obtain a particle size distribution of volume statistics. [Comparative Example] Except that the weights of the raw material feed hopper 1 and the chlorination furnace 5 were not weighed, and the reaction rate of the chlorination reaction in the chlorination furnace was not controlled, they were manufactured in the same manner as in Example 1-22-200400095 . The particle size distribution of the obtained nickel powder is shown in FIG. 2, and the S EM photograph is shown in FIG. 3B. The average particle size measured by the B ET method was 0. 4 5 microns, the average particle size when suspended in organic solvents is 1. 4 5 microns, and coarse powder over 5 microns is 3. 0%. According to the particle size distribution of the nickel powder produced in the example using the method of the present invention, as shown in FIG. 2, compared with the nickel powder produced in the comparative example, particularly coarse coarse powder is extremely small, or In the photograph of S EM in FIG. 3, a large amount of coarse powder of 1 micrometer or more can be seen in the nickel powder produced in the comparative example. Therefore, by comparison, it can be understood that the nickel powder produced in the example is 1 micrometer or more. There are very few coarse meals. [Effects of the Invention] As described above, if the method and apparatus for manufacturing the metal powder according to the present invention are used, it is possible to efficiently manufacture a fine particle size of 1 micrometer or less that meets the requirements of internal electrodes and the like of a multilayer ceramic capacitor. Metal powders such as nickel powder can control the reaction rate of the chlorination reaction. As a result, the effect of producing metal powder with uniform particle size and no coarse particles can be achieved. [Brief description of the drawings] FIG. 1 is a longitudinal sectional view showing the structure of a metal powder manufacturing apparatus in an embodiment of the present invention. Figure 2 shows the particle size distribution of the nickel powders used in the examples and comparative examples. Figure 3A is a photograph of S EM of the nickel powder manufactured in the example, and Figure 3B is a photograph of S ε M of the nickel powder manufactured in the comparative example. -2. 3- 200400095 Figure 4 is a graph showing the reaction rate (the rate of change in the weight of the chlorination furnace) in the chlorination furnace. [Comparison Table of Component Symbols] 5 Chlorination Furnace 9 Load Gauge 1 Raw Material Feed Hopper 2 Load Gauge 13 Reduction Furnace φ 3 Raw Metal
-24--twenty four-