3CC5893CC589
發明説明（ 經濟部中央標準局員工消費合作社印製 本發明係關於一種量測熔融浴上非金屬液態層電化學活 性之方法，其利用顯現活性部份之電化學元件之測量電池 和相對電極。此外，本發明關於一種用以量測電化學活性 之測量電池。 常常不僅需要在熔融浴中進行量測，亦需要在熔融浴上 之層中進行量測《例如，當麥/產鋼量測礦渣之氧電位^、 對於冶金方法過程之評估是ϋ的。亦可能卞要在鋁電解 期間量測.冰兔石溶融，以便能夠監控冶金方法。 — 從Radexrundschau 1"〇第236_243頁得知直接於礦渣中進 行乳量測。在此，係在«中排列一蘇嘍化，計測器。該 電化學元件係裝置—具相對電極之測量電 池和一電化學元 件。該電化學元件係從排列於參考材料中之參考電極以已 知方式製成。此參考材料再次由小型固體電解質管包圍。 例如’此類測量電池亦從歐洲專利第〇丨〇8 431號得知。其 係用以量測熔融浴中之氧活性，測量電池本身被保護，而 以保護蓋通過其上（例如礦逢）之層。 已知排列於熔融浴上熔融層中氧活性之直接量測，如礦 查或冰晶石，需要電化學元件正確放置於將量測之層中。 此層通常較薄（例如杓礦渣約〇至〖5公分），所以電化學元件 之分歧排列亦導致分歧之測量結果^因此測量電池之正確 排列常需要較高之能量和成本消耗，因爲不能夠輕易地量 測溶融洛表面之高度。因而定位需要探針較長之浸渍時間 ，所以’例如，能夠破壞該相對電極和測量鉛。 此外，得知分析礦渣之方法，其中採取礦渣樣品並在其 4- 本紙張尺度適用中國國家裸準（CNS) A4規格（210x297公釐） 太 ·裝-- .- (請先M讀背面之注項再填寫本頁) 訂 Λ冰 A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明（2 固化且部份於熔融後分析。 從技藝已知情況進行，本發明係基於提供一種量測電化 學活性之方法，其供應具最低可能消耗之正確量測結果。 此外，本發明係提供一種適當之電化學元件和用於這些量 測之測量電池。 根據本發明解決以上特徵化方法之任務，在於該測量電 池穿過非金屬液體層浸入熔融浴中，在於電化學元件之活 性部份通過被此層材料包園之非金屬液體層，在於此材料 係保持於電化學元件直到量測電化學活性後，且在於量測 係在將電化學元件浸入熔融浴中之熔融金屬後進行。已知 測量電池係爲至少一電化學元件和一相對電極之排列，相 對電極緊鄰電化學元件或達離其排列。相對電極能夠例如 固定於熔融容器壁或成爲此壁之部份。在此情況下，理所 當然相對電極本質上並非穿過非金屬液體層浸入熔融浴中 。以此方法，量測係於於一種幾乎不變之環境下進行。測 量電池之正確放置並不需要，因爲該熔融浴通常具有充分 之高度。熔融浴中溫度分布相當地較其上將量測活性之層 均相，所以溫度波動對於量測結果之影審相對於已知之量 測方法係被忽略。量測係在幾乎不變之環境下進行，所以 能夠得到可複製和/或可對照之量測結果。 爲了提高正確性和頃經證明有利之測量複製性，當將測 量電池之插入端通過非金屬液體層時，相對電極並非完全 被此層材料包圍，且/或此材料在量測前至少部份從相5電 極被移除，所以相對電極直接與熔融浴接觸。例如此能夠 -5- Γ裝------訂-----Λ冰 (請t閲讀背面之注意Ϋ項再填寫本頁) 本紙張尺度適用中國國家襟準（CNS ) A4規格（2丨0X297公釐）Description of the invention (printed by the Employees ’Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs) The present invention relates to a method for measuring the electrochemical activity of a non-metallic liquid layer on a molten bath, which utilizes a measurement cell and an opposite electrode of an electrochemical element showing an active part. In addition, the present invention relates to a measurement battery for measuring electrochemical activity. Often, not only the measurement in the molten bath, but also the measurement in the layer above the molten bath is required. The oxygen potential of the slag ^ is evaluated for the metallurgical process. It may also be measured during aluminum electrolysis. The ice rabbit stone is melted so that the metallurgical method can be monitored. — From Radexrundschau 1 " 〇 page 236_243 Milk measurement is carried out in the slag. Here, a Su-Hua, measuring device is arranged in «. The electrochemical element is a device-a measuring cell with an opposite electrode and an electrochemical element. The electrochemical element is arranged from The reference electrode in the reference material is made in a known manner. This reference material is again surrounded by a small solid electrolyte tube. For example, such a measuring cell It is known from European Patent No. 〇〇〇8 431. It is used to measure the oxygen activity in the molten bath, the battery itself is protected, and the protective cover passes through the layer above it (such as mine). The direct measurement of the oxygen activity in the molten layer on the molten bath, such as ore survey or cryolite, requires the electrochemical element to be placed correctly in the layer to be measured. This layer is usually thin (for example, dipper slag about 0 to 〖5 cm ), So the different arrangement of the electrochemical elements also leads to different measurement results ^ Therefore, measuring the correct arrangement of the battery often requires higher energy and cost consumption, because it is not easy to measure the height of the melted surface. Therefore, positioning requires a probe Long immersion time, so 'for example, it is possible to destroy the counter electrode and measure lead. In addition, the method of analyzing slag was learned, in which the slag sample was taken and the Chinese National Bare Standard (CNS) A4 specification was applied at its 4-paper scale (210x297mm) Too installed-.- (please read the notes on the back before filling in this page) Order Λ 冰 A7 B7 Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Invention Instructions (2 It is partly analyzed after melting. According to the situation known in the art, the present invention is based on providing a method for measuring electrochemical activity, which provides the correct measurement results with the lowest possible consumption. In addition, the present invention provides a suitable The electrochemical element and the measuring cell used for these measurements. The task of solving the above characterized method according to the present invention is that the measuring cell is immersed in the molten bath through the non-metallic liquid layer, and that the active part of the electrochemical element This layer of material contains a non-metallic liquid layer in that the material is held in the electrochemical element until the electrochemical activity is measured, and in that the measurement is performed after the electrochemical element is immersed in the molten metal in the molten bath. It is known The measuring cell is an arrangement of at least one electrochemical element and a counter electrode, and the counter electrode is arranged next to or away from the electrochemical element. The counter electrode can, for example, be fixed to or become part of the wall of the melting vessel. In this case, of course, the counter electrode is not essentially immersed in the molten bath through the non-metallic liquid layer. In this way, the measurement is carried out in an almost constant environment. It is not necessary to measure the correct placement of the battery, because the molten bath usually has a sufficient height. The temperature distribution in the molten bath is considerably more homogeneous than that of the layer on which the activity is measured, so the temperature fluctuations are neglected for the measurement results compared to known measurement methods. The measurement is carried out in an almost constant environment, so it is possible to obtain reproducible and / or comparable measurement results. In order to improve the accuracy and the proven reproducibility of the measurement, when the insertion end of the measurement cell is passed through the non-metallic liquid layer, the counter electrode is not completely surrounded by this layer of material, and / or this material is at least partially before measurement The electrode is removed from phase 5, so the opposite electrode is in direct contact with the molten bath. For example, this can be installed -5- Γ ----- ordered ----- Λ ice (please read the note Ϋ on the back and then fill out this page) This paper size is applicable to the Chinese National Standard (CNS) A4 specification ( 2 丨 0X297mm)
30&589 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（3 ) 在再測時發生。測定將量測之材料的氧活性較有利。位於 熔融浴非金屬層上之材料能夠例如成爲鐵熔融或鋁電解之 冰晶石。 解決測量電池量測具排列於支架之電化學元件之熔融浴 上非金屬層之電化學活性之任務，該電池含一具活性部份 之小型固體電解質管和一相對電極，在於該電化學元件和 相對電極係排列於熔融浴中，活性部份被將量測之非金屬 層包圍’且至少一部分相對電極與熔融浴直接接觸，即其 並非完全被將量測之非金屬層包团。相對電池直接接觸熔 融浴特別產生正確之量測結果。頃證明將活性部份製成電 化學元件之環形表面般對於正確之量測結果是有利的。相 對電極能夠在使用前以塗裝保護，例如硬紙板。當通過將 量測之層或進入熔融浴時破壞此保護塗裝，並避免將量測 之層黏附於相對電極。 以一種電絕緣材料塗裝小型固體電解質管之插入端較方 便’不塗裝插入端和耐火主體間之面積。例如以2 〇3或Mg〇 頃經證明是一種尤其適當之塗裝材料❶此一塗裝確保欲量 測層之材料黏附於電化學元件，所以電化學量測能夠在其 下之橡融浴中進行。本質上，欲量測之層材料能夠以不同 方式黏附於小型固體電解質管，例如以一種此材料用之適 當機械收集設備，形式爲以某距離包圍電化學元件之管。 插入端經以向耐火主體之方向最大6毫米塗裝較方便，尤 其該塗層爲約2.5毫米長。此外經證明電化學元件伸出耐火 主雜約9至13毫米，尤其是約11毫米。此一維度確保良好 -6- 本紙張尺度適用中國國家標準（CNS) M規格（2lGX297公兼） ------1T------f (請it·閲讀背面之注意事項再填寫本頁) A7 B7 經濟部中央標準局員工消費合作杜印製 五、發明説明（4 ) 黏附於將量測材料之電化學元件，亦確保此材料活性之可 信量測。此外，於電化學元件中排列熱力元件亦較方便， 因爲電化學活性亦受溫度影響，能夠考慮此可能之溫度波 動影響。 解決浸潰測量計測器量測具排列於支架和相對電極之電 化學元件之溶融浴上之非金屬液體層之電化學活性之任務 ’在於當浸入非金屬液髏廣時非耐火材料之保護層係排列 於相對電極上，且當浸入非金屬液體層時電化學元件不具 有保護層。相對電極之保護層避免當通過礦淹時，相對電 極被礦渣覆蓋。保護層溶於其下之熔融浴中，其例如燃燒 或熔融。除硬紙板外，能夠使用其它材料，例如一具低溶 點之金屬層，如銅。當相對電極未被礦渣復蓋時，礦渣能 夠黏附於電化學元件表面，且插入熔融浴中，因爲礦渣由 於缺乏保護蓋或類似直接方法而直接到達電化學元件。能 夠以保護層或保護蓋，如硬紙板，保護電化學元件免於在 運送期間等被破壞。在使用浸渍測董計測器前將保護蓋移 除，或者其在插入前由於輻射而燃燒。 頃證明從硬紙板製成保護層，且整個相對電極表面較佳 在支架外側以保護層覆蓋較有利。此外，電化學元件伸出 支架約9至13毫米較方便。在一種浸溃測量計測器有利之 具體實施例中，支架具有一種硬紙板管，於其插入端從耐 火材料排列測量頭，包圍電化學元件之相對電極至少部份 爲環形，例如，在於其穿過如金屬試管般之測量頭，且其 伸出其前方《此外，相對電極之觸點和電化學元件之觸點 f ·裝 訂 冰 (請t閲讀背面之注$項再填寫本頁)30 & 589 Printed by the employee consumer cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 V. Description of the invention (3) occurred during the retest. It is advantageous to determine the oxygen activity of the material to be measured. The material on the non-metallic layer of the molten bath can, for example, become cryolite for iron melting or aluminum electrolysis. Solve the task of measuring the electrochemical activity of the non-metallic layer arranged on the molten bath of the electrochemical element of the bracket of the battery measuring tool. The battery contains a small solid electrolyte tube with an active part and a counter electrode, which lies in the electrochemical element Arranged in the molten bath with the counter electrode, the active part is surrounded by the measured non-metallic layer and at least a part of the counter electrode is in direct contact with the molten bath, ie it is not completely surrounded by the non-metallic layer to be measured. Direct contact with the melt bath relative to the battery produces particularly accurate measurement results. It has proved that making the active part into an annular surface of an electrochemical element is advantageous for correct measurement results. The counter electrode can be protected by painting before use, such as cardboard. When passing the measured layer or entering the molten bath, the protective coating is destroyed and the measured layer is prevented from adhering to the counter electrode. It is more convenient to coat the insertion end of the small solid electrolyte tube with an electrically insulating material without painting the area between the insertion end and the refractory body. For example, 2 〇3 or Mg〇 has been proved to be a particularly suitable coating material ❶ this coating ensures that the material of the layer to be measured is adhered to the electrochemical element, so the electrochemical measurement can be under the rubber melt bath In progress. In essence, the layer material to be measured can adhere to the small solid electrolyte tube in different ways, such as a suitable mechanical collection device for this material, in the form of a tube surrounding the electrochemical element at a certain distance. It is convenient to apply a maximum of 6 mm to the refractory body at the insertion end, especially the coating is about 2.5 mm long. In addition, it has been shown that the electrochemical element protrudes from the main refractory by about 9 to 13 mm, especially about 11 mm. This dimension guarantees good -6- This paper scale is applicable to the Chinese National Standard (CNS) M specifications (2lGX297 public and public) ------ 1T ------ f (please read the notes on the back and then fill in (This page) A7 B7 Printed by the consumer cooperation of the Central Bureau of Standards of the Ministry of Economic Affairs. 5. Description of the invention (4) Adhered to the electrochemical element that will measure the material, and also ensure the reliable measurement of the activity of this material. In addition, it is more convenient to arrange thermal elements in the electrochemical element, because the electrochemical activity is also affected by temperature, and this possible temperature fluctuation can be considered. Solve the task of the electrochemical activity of the non-metallic liquid layer arranged on the melting bath of the electrochemical element of the bracket and the counter electrode of the immersion measuring instrument measuring tool is to protect the non-refractory material when immersed in the non-metallic liquid It is arranged on the opposite electrode, and the electrochemical element does not have a protective layer when immersed in the non-metallic liquid layer. The protective layer of the counter electrode prevents the counter electrode from being covered by slag when flooding through the mine. The protective layer dissolves in the molten bath below it, for example burning or melting. In addition to cardboard, other materials can be used, such as a metal layer with a low melting point, such as copper. When the counter electrode is not covered by slag, the slag can adhere to the surface of the electrochemical element and be inserted into the molten bath because the slag directly reaches the electrochemical element due to the lack of a protective cover or similar direct method. A protective layer or cover, such as cardboard, can be used to protect the electrochemical element from damage during transportation, etc. Remove the protective cover before using the immersion tester gauge, or it will burn due to radiation before insertion. It has been proved that the protective layer is made of cardboard, and the entire opposite electrode surface is preferably covered with the protective layer on the outside of the support. In addition, it is convenient for the electrochemical element to extend out of the holder by about 9 to 13 mm. In an advantageous embodiment of the dip measuring instrument, the holder has a cardboard tube, the measuring head is arranged from the refractory material at its insertion end, and the opposing electrode surrounding the electrochemical element is at least partially ring-shaped, for example, in Pass the measuring head like a metal test tube, and it protrudes in front of it "In addition, the contact of the counter electrode and the contact of the electrochemical element f · Binding ice (please read the note $ item on the back and fill in this page)
3CG589 經濟部中央榡準局員工消费合作衽印製 A7 B7 五、發明説明（5 ) 係位於支架内部較方便。這些觸點係連接於已知方法中之 測量和評估電器。 本發明係根據此解決任務，在於使用具排列於支架中之 電化學元件之測量電池，並具相對電極，以在熔融浴上之 非金屬液體層中進行熔融浴中材料之電化學活性量測。 一種本發明之具體實施例係利用以下附圈詳述。附圈表 示： 圖1 一種測量電池之説明具體實施例，其具根據本發明之 化學元件之測量電池， 圈2 一種具未塗裝小型電解質管（直徑5毫米）之具體實施 例， 圈3 一種具未塗裝薄小型電解質管（直徑3毫米）之具體實 施例，其中該小管未伸出相對電極， 圖4 一種其中活性部份爲電化學元件環形表面之具體實施 例， 圖5 一種插入熔融容器之測量元件，其裝礦渣黏附於電化 學元件，相對電極部份熔去並被礦渣覆蓋。 根據圈1 ’測量電池具有一電化學元件，其以膝合劑2排 列於支架中。支架在測量電池插入端伸出耐火材料3，例如 模造砂’與其連接，從硬紙板管4製成。電極5從連接測量 電器之電化學元件伸出。相對電極係從金屬管製成，其包 圍電極5並從測量電池插入端之支架的耐火材料3伸出。此 伸出部份被一層紙板包圓，其未示於附圈中，且其避免材 料黏附，而測量電池插入端伸入熔融浴上之非金屬液體層 ir------^ L (請先閱讀背面之注意事項再填寫本頁)3CG589 Printed by the Consumers Cooperation Cooperation Bureau of the Central Bureau of Economics of the Ministry of Economic Affairs A7 B7 V. Description of invention (5) It is more convenient to locate inside the bracket. These contacts are connected to measurement and evaluation appliances in known methods. The present invention is based on this problem-solving task by using a measuring cell with electrochemical elements arranged in a holder and having an opposite electrode to measure the electrochemical activity of materials in the molten bath in a non-metallic liquid layer on the molten bath . A specific embodiment of the present invention is described in detail using the following enclosed circle. The attached circle indicates: Fig. 1 A specific embodiment of a measuring cell with a measuring cell according to the present invention, circle 2 A specific embodiment with an uncoated small electrolyte tube (diameter 5 mm), circle 3 A specific embodiment with an uncoated thin small electrolyte tube (3 mm in diameter), where the small tube does not protrude from the counter electrode, Figure 4 A specific embodiment in which the active part is the annular surface of the electrochemical element, Figure 5 An insertion melt The measuring element of the container, which contains slag, adheres to the electrochemical element, and the opposite electrode part melts away and is covered by the slag. According to the circle 1 ', the measuring cell has an electrochemical element, which is arranged in the holder with a knee mixture 2. The bracket protrudes from the refractory material 3 at the insertion end of the measuring cell, for example, molded sand ', and is made from a cardboard tube 4. The electrode 5 protrudes from the electrochemical element connected to the measuring appliance. The counter electrode is made of a metal tube, which surrounds the electrode 5 and extends from the refractory material 3 of the holder of the measuring cell insertion end. This protruding part is rounded by a layer of cardboard, which is not shown in the attached ring, and it avoids the material from sticking, and the non-metallic liquid layer ir ------ ^ L (Please please (Read the notes on the back before filling this page)
經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（6 ) 。電化學元件1之小型固體電解質管7在其插入端經塗裝— 種電絕緣材料8。此層相當地來自MgO，然而其亦能夠來 自八丨2〇3或另一絕緣材料。該層的5〇毫米厚；其亦能夠稍 厚。該塗層向耐火主體方向2.5毫米長。介於該面積之間， 該電絕緣材料8排列於小型電解質管和埋入小型固雄電解質 管7之耐火材料上’存在約11毫米長之未塗裝面積，所謂 電化學元件1之活性部份。 關於量測，測量電池係插入鋼熔融上之礦渣層。在此， 電化學元件1被礦渣包圍，所以礦渣亦插入鋼熔融中。電化 學元件1之面積中鋼熔融之溫度平衡迅速達到，量測液雅礦 渣層之氧活性。排列於相對電極6之紙板1 〇通過礦渣層避 免礦；查黏附於相對電極6。著手於此時，測量時相對電極6 直接與鋼熔融接觸。 在電化學元件1上面不使用電絕緣材料8，亦能夠使用其 它材料，其導致礦渣黏附於電化學元件1。電化學元件j， 其從膠合劑2伸出約9至1 3毫米，尤其是1 1毫米，能更例如 被小型管包園，例如外面被硬紙板1 〇保護之電極6，建立 一種如圈2和3所示之環面積。在此，硬紙板1〇不需形成— 種蓋’其包園相對電極6全部表面，但其亦能夠排列於相對 電極6開口部份之外面，例如利用膠帶。圈4表示一種測量 電池，其中活性部份係電化學元件之環形表面9。在圖5中 ，電化學元件之排列示於熔融浴中，礦渣黏附於活性部份 ，而相對電極已部份溶去並被礦澄部份塗裝。 ---------^ ·裝------訂-----Λ缽 (請4?聞讀背面之注f項再填寫本頁〕 -9-A7 B7 printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs V. Invention Instructions (6). The small solid electrolyte tube 7 of the electrochemical element 1 is coated with an electrically insulating material 8 at its insertion end. This layer is quite derived from MgO, however it can also come from Ba203 or another insulating material. This layer is 50 mm thick; it can also be slightly thicker. The coating is 2.5 mm long towards the refractory body. Between this area, the electrically insulating material 8 is arranged on the small electrolyte tube and the refractory material embedded in the small solid male electrolyte tube 7 'There is an uncoated area of about 11 mm long, the so-called active part of the electrochemical element 1 Copies. Regarding the measurement, the measurement cell is inserted into the slag layer on the molten steel. Here, the electrochemical element 1 is surrounded by slag, so the slag is also inserted into the molten steel. The temperature balance of the molten steel in the area of the electrochemical element 1 is quickly reached, and the oxygen activity of the liquid slag layer is measured. The cardboard 10 arranged on the opposite electrode 6 avoids ore through the slag layer; it is adhered to the opposite electrode 6. Starting at this time, the counter electrode 6 is directly in molten contact with steel during measurement. No electrical insulating material 8 is used on the electrochemical element 1, but other materials can also be used, which causes slag to adhere to the electrochemical element 1. The electrochemical element j, which protrudes from the adhesive 2 by about 9 to 13 mm, especially 11 mm, can be more rounded by a small tube, such as an electrode 6 protected by a cardboard 10 on the outside, creating a ring Ring area shown in 2 and 3. Here, the cardboard 10 does not need to form a kind of cover which covers the entire surface of the opposing electrode 6, but it can also be arranged on the outer surface of the opening of the opposing electrode 6, for example, using an adhesive tape. Circle 4 represents a measuring cell in which the active part is the annular surface 9 of the electrochemical element. In Figure 5, the arrangement of the electrochemical elements is shown in the molten bath, the slag adheres to the active part, and the counter electrode has been partially dissolved and coated by the ore part. --------- ^ · Installation ------ order ----- Λ bowl (Please 4? Read the note f on the back and fill in this page) -9-