200948478 六、發明說明： 【發明所屬之技術領域】 本案係關於新穎催化劑粉末，特別是用於製造奈米碳 管（CNTs =奈米碳管）。 5 【先前技術】 具有直徑為3至200奈米的奈米範圍之竣纖維（奈米 。 碳管）近來引起世人越來越多的興趣。這種具有石墨結構 © 之中空纖維係藉由低分子量碳化合物透過催化活性金屬或 金屬化合物在400至1100°C(較佳為450至700。〇下熱分解 10 而形成（CCVD程序=催化碳汽相沉積程序）。催化活性金屬 與氣體礙化合物（特別是低分子量碳氫化合物）在固定床 (粉末床）、移動式固定床或流體化床發生接觸。催化劑是以 煆燒型式在反應器中使用，在反應初期，催化劑的活性部 位由氧化物被還原到金屬。 15 奈米碳管與碳纖維的直徑基本上係藉由催化活性金屬 ❹ 顆粒的尺寸來決定。為了分離金屬顆粒，該顆粒尺寸應於 奈米範圍中，以及為了確保催化劑可以被處理，而將後者 施用於催化反應中不會被氫還原的催化惰性支樓材料（通 常是氧化物陶瓷）上，使得其形成催化活性金屬的表面範 2〇 圍，其中該催化活性金屬的尺寸決定該纖維的直徑。 CCVD程序的一缺點是：在反應過程中，由於逐漸形 成的纖維會妨礙氣體碳化合物接近催化活性範圍，而使催 化劑變成失活。每克催化劑的CNTs產率係取決於起始的 3 200948478 碳化合物、催化劑種類、 壓力、濃度等。 其結構和處理條件 例如：溫度、 1401763 B1出自精細分 5 10 15 鋁是將凝膠乾燥和研磨，並在研缽中：醋酸^和：氫氧化 :、鈦、_氧化物、氣氧化物與 ， 〇 :’還有催化活性金屬奶、^，"二= 樣地被描述。支撐材料與催化活性金 曹、:。物同 3〇:1。基於催化劑的重量，達成高達 、重置比為約 維產率。因此，催化劑必須以複雜：=== ?中移除。此外’就催化劑而言，如此多階:== =昂貴：亚且導致僅小比例的催化活性金4，以及因此小 的奈米碳管產率，其基於該催化劑。 WO 2006/050903也同樣揭露一用於催化劑的單一階段 的沈澱方法，其中支撐材料和活性金屬由各自的硝酸鹽= 溶液共沈澱。該WO文件的教示特別是關於催化活性:屬 級成物的最適化，其係為了達到基於所使用的催化劑之 CNTs的南產率’關於5到350倍催化劑重量的cnTs產率， 讀催化劑係使用可額外含有Mo的活性金屬組成物Mn_c〇 與作為支撐材料的MgO達成，其中該活性金屬組成物 Μη-Co係含有60 mol%的活性金屬和4〇 m〇1〇/(^支撐金 屬。因此，在大部份的應用中並不須要分離出催化劑。然 而，關於為了製造CNTs的所欲特性（可再生的催化活性和 〜致性的催化活性範圍尺寸），催化活性金屬與支樓材料的 20 5 ❹ 10 15 ❹ 200948478 共沈澱的控制是困難 母液的檢驗是昂貴的、此夕，自沈澱反應的含硝酸鹽之 再者，希望支撐杜該檢驗對環境理由是必須的。 粒範圍首先可以有料和包含催化活性金屬的催化劑顆 微米範園中之平均的流動，可供操作，亦即在至少幾 支撐材料和催化劑觀^尺寸，第二，希望在催化過程中， 圍或初始.繼圍會料，以於催化劑活性範 起始碳化合物可容2峻成即使在CNTs成長時，氣體 性金屬以氫氧化物、(_SS触）。切材科和純活 致過度燒結而防礙催二：沈灰二心後熱轉換為氧化物，導 其催化活性之催化活性=粒朋解’且包含之後不能表現 【發明内容】 本發明之目的是提佴一 克服先前技術缺點。^催化劑㈣單方法’其可 根=發明’催化活性金屬和 的沈澱在各別的位詈鉻疼 ^ 寸田對應合及 併前不需中間檢驗。這;…而上各別形成的沈澱懸浮液合 屬以-致的顆粒尺寸可"f制（特別的是)催化活性金 u e g A々入八i ，而產生一致直徑的奈米碳管， 粒。 77之支撐材料和催化活性金屬的初始顆 方法較佳由硫酸鹽系統開使進行，亦即，催 使用。使用氯始化合物被作為硫酸鹽水溶液 樣導致好的產物，而且關於廢水也不 5 20 200948478 =尤溶液(特別是氨和/或氫氧化鋼溶 和/或硫義的母離會形成-含有硫酸銨 -沈在有兩個區域的連接容器(joint ν_ι)中進 一個區則來混合含有催化活性金屬的鹽溶液和基液 (base S0luti0n)以及另—區域用來混合支撑材料鹽溶液和母 液或更進-步的基液。這可分別控制沈殿條件’例如：對 於，化活性金屬之沈殿和對於支撐材料之沈殿的pH、濃度 和溫度。此兩個區域各自有利地配備攪拌器。混合亦可藉 由（例如）將個別的反應溶液的切線(tangential)或逆流注入 到個別的反應區域進行。，催化活性金屬之沈殿的混合區 域，佳構成小於1/1⑽’特佳小於1/50G，以及大於1/3_ 的容器體積’ #有低於1分鐘之混合區域中相對較短的滯 留時間。 催化活性金屬的沈澱同樣可能在小型反應器中進行， 該小型反應器在主要反應器之前，且具有小於主要反應器 的1/100 ’較佳小於1/5〇〇的體積。在此，為了避免催化活 性金屬的沈澱產物彼此互相黏聚，而必須要快速轉送入主 要反應器。 s適的催化活性金屬是形成不穩定碳化物的金屬，特 =是Fe、Ni、Co、Cu、Mn、％和Zn和其混合物。在沈 澱後，這些金屬作為氫氧化物或氧氫氧化物存在。假使進 一步適當的藉由Mo以高達1〇mol%的量改質，特別偏好以 200948478 H到M莫耳比的WMn之混合物。 5 e 10 15 ❹ 域，以便在第；二鹽溶液被引入第-授掉器的區 ==量的驗性溶夜母 ===，’第一攪拌㈣區域= 區域中’高過飽和導致催化==.5。在第1拌器的 j度的晶核的自然產生。在第一授拌=== 能夠使催化活性金屬的氫氧化物的顆粒達到；要的 再者，氧或含氧的氣體，例如空氣，可以被注射入第 一攪拌器的區域而引起關於同時的氧化作用，例如：c〇2+ 至CoOOH或者Μη2+至Mn00H或Mn〇2。在此過程中^ 澱產物的顆粒尺寸可被以較精細顆粒之方向控制。 較佳用平均直徑為5到200奈米的催化活性金屬的氫 氧化物，特佳為10到1〇〇奈米。催化活性金屬在非常短二 間内實際上完全的沈澱與之後在與沈澱反應器之母液混 合’其中該氫氧化物的濃度被減至低於1/1〇〇，較佳低= 1/500,使得可得到具有窄的顆粒尺寸分布之催化活ς金屬 的氫氧化物。 支撐金屬鹽溶液被引入至第二攪拌器的區域並且在此 與鹼性母液混合，造成沈澱該支撐金屬的氫氧化物。取決 7 20 200948478 於所欲的支推金屬氣氧化物的尺寸，可額外將驗性溶液（如 同是在第一攪拌器的區域中，較佳為氨和/或氫氧化鈉溶液） 饋入以增強過飽和。此處通常8到11的PH為足夠的。支 撐材料的沈澱特佳在9到10.5的pH下進行。 較佳的支撐金屬為Mg、A卜Ca、Si、Ti、γ、Zr和其 混合物，其可藉由V、Mo和/或w的含量改質。較佳為. Mg或A1，特別是Mg ’更加具有高達10 mol%的Mo。 支撐金屬氫氧化物的沈澱條件被設定為使形成具有2❹ 10 至10倍催化活性金屬氫氧化物顆粒直徑的平均直徑之氫氧 化物顆粒。 催化活性金屬的鹽類係為支撐金屬的鹽類，較佳以0.2 至2(較佳為0.7至1.3)的莫耳比範圍引入反應器中，其係以 氧化物計算。 '200948478 VI. Description of the invention: [Technical field to which the invention pertains] This case relates to novel catalyst powders, particularly for the production of carbon nanotubes (CNTs = carbon nanotubes). 5 [Prior Art] Tantalum fibers (nanocarbon tubes) having a diameter of 3 to 200 nm have recently attracted increasing interest in the world. The hollow fiber having the graphite structure is formed by a low molecular weight carbon compound permeating a catalytically active metal or a metal compound at 400 to 1100 ° C (preferably 450 to 700. Thermal decomposition of the crucible 10) (CCVD program = catalytic carbon) Vapor phase deposition procedure). The catalytically active metal is contacted with a gas barrier compound (especially a low molecular weight hydrocarbon) in a fixed bed (powder bed), a mobile fixed bed or a fluidized bed. The catalyst is in a calcination type in the reactor. In the initial stage of the reaction, the active site of the catalyst is reduced from the oxide to the metal. The diameter of the carbon nanotubes and carbon fibers is basically determined by the size of the catalytically active metal ruthenium particles. The size should be in the nanometer range, and in order to ensure that the catalyst can be treated, the latter is applied to a catalytically inert building material (usually an oxide ceramic) which is not reduced by hydrogen in the catalytic reaction, so that it forms a catalytically active metal. The surface of the surface is 2, wherein the size of the catalytically active metal determines the diameter of the fiber. A disadvantage of the CCVD process During the reaction, the CNTs yield per gram of catalyst depends on the starting 3 200948478 carbon compound, catalyst type, pressure, due to the formation of fibers that hinder the gas carbon compound from approaching the catalytic activity range. , structure, etc. Its structure and processing conditions such as: temperature, 1401763 B1 from fine fraction 5 10 15 aluminum is the gel drying and grinding, and in the mortar: acetic acid and: hydroxide: titanium, _ oxide, Gas oxides, 〇: 'There is also a catalytically active metal milk, ^, " two = sample is described. Support material and catalytic activity Jin Cao,: the same as 3 〇: 1. Based on the weight of the catalyst, reach up to The reset ratio is the yaw yield. Therefore, the catalyst must be removed in a complex: === ? In addition, 'in terms of the catalyst, so many orders: == = expensive: sub- and resulting in only a small proportion of catalytic activity Gold 4, and thus small carbon nanotube yield, based on the catalyst. WO 2006/050903 also discloses a single stage precipitation process for catalysts in which the support material and the active metal are each from the respective nitrates. Salt = solution co-precipitation. The teachings of this WO document are particularly concerned with catalytic activity: optimization of genus grades in order to achieve a south yield of CNTs based on the catalyst used ' cnTs with 5 to 350 times catalyst weight The yield, the read catalyst is achieved by using an active metal composition Mn_c〇 additionally containing Mo with MgO as a support material, wherein the active metal composition Μη-Co contains 60 mol% of active metal and 4 〇m〇1〇 /(^ supports metal. Therefore, it is not necessary to separate the catalyst in most applications. However, regarding the desired properties (renewable catalytic activity and size of the catalytically active range) for the manufacture of CNTs, catalysis Active metal and branch material 20 5 ❹ 10 15 ❹ 200948478 Co-precipitation control is difficult to test the mother liquor is expensive, this evening, the nitrate-containing self-precipitation reaction, hope to support the test is environmental reasons necessary. The particle size can first be used to feed the average flow in the microparticle range of the catalyst comprising the catalytically active metal, which is operable, that is, at least a few support materials and catalysts, and secondly, in the catalytic process, Initially, it is expected that the carbon compound can be made into a carbon compound, and the gas metal can be hydroxide ((SS touch)) even when the CNTs grow. Excessive sintering of the cutting material and purely active and hindering the second: the heat is converted into an oxide after the two-hearted ash, and the catalytic activity of the catalytic activity is controlled to be granules and cannot be expressed after the inclusion. The aim is to overcome the shortcomings of the prior art. ^ Catalyst (4) Single method 'The root of it = the invention' The catalytically active metal and the precipitate are in the respective positions and the chromium is not required to be intermediately tested. This; and the separate precipitated suspensions formed by the particle size can be made to "specially" catalytically active gold ueg A into the eighti, resulting in a uniform diameter of the carbon nanotubes, grain. The initial support method of the support material and the catalytically active metal of 77 is preferably carried out by a sulfate system, i.e., for use. The use of a chlorine-based compound as a sulphate aqueous solution results in a good product, and also does not relate to wastewater. 5 20 200948478 = particularly solution (especially ammonia and/or oxidized steel and/or sulphur-derived parent-formation - containing sulphuric acid) The ammonium-sink is fed into a zone in a joint container (joint ν_ι) with two zones to mix the salt solution and the base fluid (base S0luti0n) containing the catalytically active metal and the other zone for mixing the support material salt solution and the mother liquor or A further step-by-step base fluid. This can be used to control the conditions of the chamber, for example: for the pH of the slab of the active metal and for the slab of the support material. The two regions are each advantageously equipped with a stirrer. The tangential or countercurrent flow of the individual reaction solutions can be carried out, for example, by injection into individual reaction zones. The mixed region of the catalytically active metal is preferably less than 1/1 (10)', preferably less than 1/50 G, And container volume greater than 1/3_' has a relatively short residence time in the mixed zone of less than 1 minute. Precipitation of catalytically active metals may also be carried out in small reactors. The small reactor is in front of the main reactor and has a volume smaller than 1/100' of the main reactor, preferably less than 1/5 Torr. Here, in order to prevent the precipitated products of the catalytically active metal from sticking to each other, It must be quickly transferred to the main reactor. The appropriate catalytically active metal is a metal that forms unstable carbides, specifically Fe, Ni, Co, Cu, Mn, %, and Zn, and mixtures thereof. After precipitation, these metals It exists as a hydroxide or an oxyhydroxide. If it is further suitably modified by Mo in an amount of up to 1 〇 mol%, a mixture of WMn of 200948478 H to M molar ratio is particularly preferred. 5 e 10 15 ❹ Domain So that in the first; the two salt solution is introduced into the zone of the first-returner == the amount of the test solution of the night-in-law ===, 'the first agitation (four) zone = the zone 'high supersaturation leads to the catalysis ==.5. The natural generation of the nucleus of the j-degree of the first stirrer. In the first mixing ===, the particles of the hydroxide of the catalytically active metal can be reached; if necessary, oxygen or an oxygen-containing gas such as air, Can be injected into the area of the first agitator to cause simultaneous oxygen For example, c〇2+ to CoOOH or Μη2+ to Mn00H or Mn〇2. During this process, the particle size of the precipitated product can be controlled in the direction of finer particles. Preferably, the average diameter is 5 to 200 nm. a hydroxide of a catalytically active metal, particularly preferably 10 to 1 nanometer. The catalytically active metal is substantially completely precipitated in a very short two chambers and then mixed with a mother liquor of the precipitation reactor, wherein the hydroxide The concentration is reduced to less than 1/1 〇〇, preferably = 1/500, so that a hydroxide of a catalytically active ruthenium metal having a narrow particle size distribution can be obtained. The support metal salt solution is introduced to the second agitation. The area of the device and here mixed with the alkaline mother liquor causes precipitation of hydroxide of the supporting metal. Depending on the size of the desired metal oxide, it may be additionally fed into the test solution (as in the region of the first stirrer, preferably ammonia and/or sodium hydroxide solution). Enhanced supersaturation. Here, usually a pH of 8 to 11 is sufficient. The precipitation of the support material is particularly preferably carried out at a pH of from 9 to 10.5. Preferred supporting metals are Mg, A, Ca, Si, Ti, γ, Zr and mixtures thereof which can be modified by the contents of V, Mo and/or w. Preferably, Mg or A1, especially Mg', has up to 10 mol% of Mo. The precipitation conditions of the supporting metal hydroxide are set so as to form hydroxide particles having an average diameter of 2 ❹ 10 to 10 times the diameter of the catalytically active metal hydroxide particles. The salt of the catalytically active metal is a metal-supporting salt, preferably introduced into the reactor at a molar ratio of 0.2 to 2 (preferably 0.7 to 1.3), which is calculated as an oxide. '
當各自的氫氧化物沈澱之後，所得到的懸浮液要進-步擾摔#又時間’以致於發生氫氧化物顆粒的黏聚作用 這段時間可延長G.5到1M、時，較佳1到3小時。在⑹ 時間裡’ ^佳地最初不同的氫氧化物顆粒變成彼此依附 以致於顯著地支撐材料的初始顆粒與活性材料的顆粒在^ 們表 鬼而升> 成多孔的黏聚物(aggi〇merate)。這產j 顯著球狀黏輯粒，其巾該麟齡具有高達80微米，! 仏為2到50微米’特佳為低於2()微米之平均黏聚物直徑 球狀的黏聚物顆粒具有>5%體積比的孔隙度，較佳為〉1〇( 體積比’且特佳為>2〇%體積比。 $ 20 200948478 所得到的黏聚物包含支撐初始顆粒和催化活性初始顆 粒，該黏聚物係自母液中被分離出來，清洗直到中性，以 及乾燥以及在空氣中350到500°C下鍛燒。 乾燥後的鍛燒也可以在進行催化處理之前進行，在之 5 前或者是作為活化期的一部份。 ' 在絕大多數情形中，經鍛燒的催化劑並不須要研磨。 " 圖1係圖表示地顯示反應器1適合用於以較佳的連續 ® 方式進行本發明之方法。該反應器具有裝設兩個攪拌器3 和4,並且在對應的混合區域中有攪拌器對容器内的液體施 10 加切剪作用的一反應容器2。沈澱催化活性金屬的攪拌器區 域係藉由一垂直方向開啟的圓筒型金屬護罩5保護。於較 佳的實例中，在攪拌器3周圍的小體積攪拌區域，活性金 屬硫酸鹽水溶液經由線路6饋入，以及氳氧化鈉溶液和/或 氨水溶液經由線路7饋入。在主要攪拌器4的區域，支撐 15 金屬硫酸鹽經由線路8饋入，而且假使合適，氫氧化鈉溶 © 液和/或氨溶液可經由線路9饋入。再者，用來控制老化和 控制沈澱在攪拌器區域中氫氧化物黏聚程序的稀釋水可經 由線路10饋入。沈澱懸浮液可經由線路11在適當位置取 出，例如：在容器2的底部。 20 圖2係圖表示地顯示一反應容器具有第三攪拌器12和 一用於支撐金屬之更分離沉澱的護罩13 ;除此之外，與圖 1相同之參照數字表示相同的元件。 可藉由本身已知的方法自母液分離出顆粒，例如藉由 9 200948478 沈積去、旋風器、旋轉分離器或藉由過濾。 本發明的催化劑粉末可用於製造奈米碳管和/或碳纖 維。 以下用製造包含鉛/猛活性金屬和鎮/銘支樓金屬的催 化劑顆粒之實例來說明本發明。 【貫施方式】 實例1至7 : 10 15 使用如圖1所示的反應器。此實驗室反應器具有10公 升的液體體積。攪拌器區域3具有20毫升的體積。對應到 圖1，參照數字之物流（stream)6至1〇，於室溫下以表1指 的置和/農度被引導入。這些物流被重量地(gravimetrically) 調控。在每個情形中，在已建立穩態條件之後，固體經超 過3小時的自母液過濾出’在過濾器上清洗直到中性，於 15〇C下乾燥’且在空氣中於42〇t>c鍛燒。 催化劑顆粒的平均直徑經光學測量為35至4〇微米。 表面被許多催化活性金屬的小氧化物顆粒覆蓋的 點聚支撐顆粒所組成。 中的粉末的活性測試如下：取〇·5公克每一個情形 中的石某Γ粉末置於已推入炼接石英管(fUSed Silica tube) 管形爐中rea Μ之薄層’㈣接石英管被放置在一 以_連接㈣管線。當沖洗氣㈣續流動， 接石英管^的減和帆體積比的氬氣之混合物沖洗炼 雜慢加酿63(rC，這會造絲化活性金屬的氧 20 200948478 化物顆粒被還原為金屬。由於催化活性初始顆粒之體積的 減少’壓力會產生於黏聚物内且造成黏聚物的崩解。6〇分 鐘後，50%的沖洗氣體接著被乙烯(ethene/ethylene)置換。77 表1: 物流 7 β $ - 1Λ 實例 C〇S〇4 Maso^ NdOH ms〇4 益>1念【合0占)E、 顧3 * v 1 0 2 ' 1.2 1,35. 0*13 AsW CLS 320 82 43 1?2 • 149 2 1/h 0, 2 * 1,2 CL 94 0*13 0,9 1 g/1 120 L20 €Q 43 172 X33 * 3 1 l/h 0. 2S -。 1.2 0.35 o.z 1 丨9 A 120 120 31 1 172 74 4 l/h 0. 2 1,2 0,2 0.13 1.2 g/i 120 1 120 21 105 ： 113 117 5 l/h 0 ‘ 2 1*2 _ 0-科 oas ...140 I 1Ϊ5 25 163 5g,S 107 £ l/h 0. 3 1 1,2 . 0,32 oas imm 120 | 120 22S | ·」 77 1 l/h 0, 2 1,2€ 0.4 0.13 0.3 ^ * - 120 iao 31 -1 214 112 10 * 〇 15 20 25 30 12 0分鐘後，產生之產物會在沖洗氣體之後再次慢慢冷 卻’取出石英船’並且測量含有奈米碳管和催化劑粉末的 產物重量。結果顯示於表2中。 11 35 200948478 表2:After the respective hydroxides are precipitated, the resulting suspension is subjected to step-by-step smashing, and time is so that the occurrence of the cohesive action of the hydroxide particles can be extended by G. 5 to 1 M, preferably. 1 to 3 hours. In (6) time, the initial different hydroxide particles become attached to each other so as to significantly support the initial particles of the material and the particles of the active material in the form of agglomerated > Merate). This produces a significant spheroidal viscous granule, which has a spheroidal age of up to 80 microns, and a spheroidal viscous particle of 2 to 50 micrometers. The porosity having a volume ratio of > 5% is preferably >1 〇 (volume ratio 'and particularly preferably > 2 〇% by volume. $ 20 200948478 The obtained viscous polymer contains support initial particles and initial activity of catalytic activity Granules, which are separated from the mother liquor, washed until neutral, and dried and calcined at 350 to 500 ° C in air. The calcination after drying can also be carried out before the catalytic treatment. 5 before or as part of the activation period. 'In most cases, the calcined catalyst does not need to be ground. " Figure 1 is a diagram showing that the reactor 1 is suitable for better continuous The method of the present invention is carried out in a manner of 6. The reactor has two agitators 3 and 4, and in a corresponding mixing zone, a stirrer is used to apply a shearing action to the liquid in the vessel. The region of the agitator of the catalytically active metal is in a vertical direction The cylindrical metal shroud 5 is protected. In a preferred embodiment, the active metal sulfate aqueous solution is fed via line 6 in a small volume agitation zone around the agitator 3, and a sodium niobate solution and/or an aqueous ammonia solution. Feeded via line 7. In the region of the main agitator 4, the support 15 metal sulphate is fed via line 8, and if appropriate, the sodium hydroxide solution and/or the ammonia solution can be fed via line 9. Again, The dilution water used to control aging and control the precipitation of the hydroxide in the agitator zone can be fed via line 10. The precipitation suspension can be removed via line 11 in place, for example at the bottom of vessel 2. 2 is a diagram showing a reaction vessel having a third agitator 12 and a shroud 13 for supporting a more separated precipitate of the metal; the same reference numerals as in Fig. 1 denote the same elements. The method known per se separates the particles from the mother liquor, for example by means of 9 200948478 deposition, cyclones, rotary separators or by filtration. The catalyst powder of the invention can be used for the production of carbon nanotubes and/or Fibers The following description is made by way of an example of the production of catalyst particles comprising a lead/laminant active metal and a town/mound metal. [Examples] Examples 1 to 7: 10 15 A reactor as shown in Fig. 1 was used. This laboratory reactor has a liquid volume of 10 liters. The agitator zone 3 has a volume of 20 ml. Corresponding to Figure 1, reference numeral stream 6 to 1 〇, at room temperature, is indicated by Table 1. /Farming is introduced. These streams are gravimetrically regulated. In each case, after steady state conditions have been established, the solids are filtered out of the mother liquor for more than 3 hours 'cleaning on the filter until neutral , dried at 15 ° C and calcined in air at 42 °t > c. The average diameter of the catalyst particles is optically measured to be 35 to 4 Å. The surface is composed of a plurality of point-supporting particles covered by small oxide particles of a catalytically active metal. The activity test of the powder in the following is as follows: take 〇·5 g Each case of Shimiao powder placed in a thin layer of rea 已 that has been pushed into a fUSed Silica tube tube furnace (4) connected to a quartz tube It is placed in a _connected (four) pipeline. When the flushing gas (4) continues to flow, the quartz tube is reduced by the sum of the sail volume ratio of the argon mixture. The mixture is slowly mixed with 63 (rC, which will regenerate the active metal oxygen 20 200948478. The chemical particles are reduced to metal. The reduction in the volume of the catalytically active primary particles 'pressure is generated in the binder and causes disintegration of the binder. After 6 minutes, 50% of the flushing gas is subsequently replaced by ethylene (ethene/ethylene). 77 Table 1: Logistics 7 β $ - 1Λ Example C〇S〇4 Maso^ NdOH ms〇4 益>1念[合0占)E, Gu 3 * v 1 0 2 ' 1.2 1,35. 0*13 AsW CLS 320 82 43 1?2 • 149 2 1/h 0, 2 * 1,2 CL 94 0*13 0,9 1 g/1 120 L20 €Q 43 172 X33 * 3 1 l/h 0. 2S -. 1.2 0.35 oz 1 丨9 A 120 120 31 1 172 74 4 l/h 0. 2 1,2 0,2 0.13 1.2 g/i 120 1 120 21 105 : 113 117 5 l/h 0 ' 2 1*2 _ 0-科oas ...140 I 1Ϊ5 25 163 5g,S 107 £ l/h 0. 3 1 1,2 . 0,32 oas imm 120 | 120 22S | ·" 77 1 l/h 0, 2 1, 2€ 0.4 0.13 0.3 ^ * - 120 iao 31 -1 214 112 10 * 〇15 20 25 30 12 After 0 minutes, the resulting product will slowly cool again after flushing the gas 'take out the quartz ship' and measure the carbon containing The product weight of the tube and catalyst powder. The results are shown in Table 2. 11 35 200948478 Table 2:
5 【圖式簡單說明】 圖1係圖表示地顯示反應器1適合用於以較佳的連 方式進行本發明之方法。 - ίο 15 20 圖2係圖表示地顯示—反應容器具有第三攪拌器12和❹ 一用於支撐金屬之更分離沉殿的護罩13 【主要元件符號說明】 1 反應器 2 反應容器 3 攪拌器 4 攪拌器 5圓筒型金屬護罩 6 線路，物流 7 線路，物流 8 線路，物流 9 線路，物流 〇 10線路，物流 11線路 12第三攪拌器 13護罩 12 255 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a diagram showing that the reactor 1 is suitable for carrying out the method of the present invention in a preferred connection. - ίο 15 20 Figure 2 is a diagram showing that the reaction vessel has a third agitator 12 and a hood 13 for supporting the metal separation chamber. [Main component symbol description] 1 Reactor 2 Reaction vessel 3 Stirring 4 agitator 5 cylindrical metal shield 6 line, logistics 7 line, logistics 8 line, logistics 9 line, logistics 〇 10 line, logistics 11 line 12 third agitator 13 shield 12 25