TWI428283B - Method of manufacturing manganese tetrafluoride - Google Patents
Method of manufacturing manganese tetrafluoride Download PDFInfo
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本發明係關於製備錳化合物的無機化學及方法，並更特別關於製備其鹵化產物的方法，即製備四氟化錳MnF4的方法。 The present invention relates to inorganic chemistry and methods for preparing manganese compounds, and more particularly to a method for preparing a halogenated product thereof, that is, a method for preparing manganese tetrafluoride MnF 4 .
在化學工業中使用四氟化錳作為強氧化劑及製造純氟的來源。關於四氟化錳，例如，已知製造氟的方法[***聯邦專利(Russian Federation Patent)2,221,739，分類C01B 7/20，公開日期：2004年4月1日]。該方法使用例如具有高氟含量之鹽類(六氟化鉀KF6和四氟化錳MnF4)及其它鹽類(如K3NiF7、K2NiF6和K2CuF6)與類似於彼等的化合物作為起始化合物。 Manganese tetrafluoride is used in the chemical industry as a strong oxidant and a source of pure fluorine. Regarding manganese tetrafluoride, for example, a method of producing fluorine is known [Russian Federation Patent 2,221,739, classification C01B 7/20, publication date: April 1, 2004]. The method uses, for example, salts having a high fluorine content (potassium hexafluoride KF 6 and manganese tetrafluoride MnF 4 ) and other salts (such as K 3 NiF 7 , K 2 NiF 6 and K 2 CuF 6 ) and similar These compounds are used as starting compounds.
也已知使用四氟化鋱作為氟化劑及進行MnF2之氟化作用的MnF4之製造方法，其係藉由冷凝在高溫(380-460℃)及在10-1至10-5托之壓力下所獲得的蒸氣產物[蘇聯發明者證書(Soviet Union Inventor Certificate)1,428,702，分類C01G 45/06，公開日期：1988年10月7日]。氟化劑的此一使用使得產物難以分離及招致成本增加。 A method of producing MnF 4 using ruthenium tetrafluoride as a fluorinating agent and fluorination of MnF 2 is also known, which is condensed at a high temperature (380-460 ° C) and at 10 -1 to 10 -5 Torr. The vapor product obtained under the pressure [Soviet Union Inventor Certificate 1,428,702, classification C01G 45/06, publication date: October 7, 1988]. This use of a fluorinating agent makes the product difficult to separate and incurs increased costs.
也有關於製造四氟化錳的方法的說明，包括自二氟化錳及三氟化錳的製造方法[Russian Journal of Inorganic Chemistry,Vol.43,No.4,1998,pp.465-469，Synthesis of Manganese Tetrafluoride at Atmospheric Pressure]。該 說明證明自三氟化錳的製造方法具有優點。該方法係在其內部具有冷卻設備之反應器中進行及在冷卻設備周圍形成固體產物。將約90至120公克量之片狀形式的起始物質(MnF3)放入在冷卻設備周圍的加熱區中。氟化作用發生在450-700℃之溫度及3.2-12.6公克/小時之氟進料速度下。就連續的氟化作用而言，已形成的產物以振動方法或使用圓柱型刮刀每5分鐘搖晃至收集器中，藉此獲得灰藍色四氟化錳粉末。 There are also descriptions of methods for producing manganese tetrafluoride, including methods for producing manganese difluoride and manganese trifluoride [Russian Journal of Inorganic Chemistry, Vol. 43, No. 4, 1998, pp. 465-469, Synthesis. Of Manganese Tetrafluoride at Atmospheric Pressure]. This description demonstrates the advantages of the method of producing manganese trifluoride. The process is carried out in a reactor having a cooling device inside thereof and forms a solid product around the cooling device. A starting material (MnF 3 ) in the form of a sheet of about 90 to 120 grams is placed in a heating zone around the cooling device. The fluorination occurs at a temperature of 450-700 ° C and a fluorine feed rate of 3.2-12.6 g/hr. For continuous fluorination, the formed product was shaken into the collector by a vibration method or using a cylindrical doctor blade every 5 minutes, thereby obtaining a gray-blue manganese tetrafluoride powder.
有一種以氟氣之合成法獲得作為中間產物之MnF4的方法[蘇聯發明者證書1,432,001，分類C01G 45/06，公開編號：1,932,001]。其說明自三氟化錳MnF3製備MnF4的階段。將三氟化錳以工業氟在450-650℃之溫度下氟化，並將所得四氟化錳在70℃或更低之溫度下冷凝。當使用MnF4時，則根據下列反應方程式獲得氟氣：MnF4 → MnF3+1/2 F2 There is a method of obtaining MnF 4 as an intermediate product by synthesis of fluorine gas [Soviet Inventor Certificate 1, 432, 001, classification C01G 45/06, publication number: 1,932, 001]. This illustrates the stage of preparing MnF 4 from manganese trifluoride MnF 3 . The manganese trifluoride is fluorinated with industrial fluorine at a temperature of 450 to 650 ° C, and the obtained manganese tetrafluoride is condensed at a temperature of 70 ° C or lower. When MnF 4 is used, fluorine gas is obtained according to the following reaction equation: MnF 4 → MnF 3 + 1/2 F 2
上述的專利案說明獲得MnF4之製造方法，其係藉由使MnF3在450-650℃之溫度下在含有氟之氣流中交互作用，使MnF4昇華，並將其蒸氣在70℃或更低的溫度下冷凝。接著將因此獲得的四氟化錳加熱至70-300℃，以便可以獲得高純度的氟氣。該方法的缺點在於低轉成為MnF4，且需要複雜的設備用於加熱昇華及收集合成的MnF4。其另一個缺點在於必需進行的昇華及冷凝法使其 難以規劃為商業生產。 Patent cases described above to obtain a manufacturing method MnF 4, its lines by making MnF 3 deg.] C at a temperature of the gas stream containing 450-650 fluorine, in interaction, so that the sublimation MnF 4, deg.] C and a vapor or more at 70 Condensation at low temperatures. The manganese tetrafluoride thus obtained is then heated to 70-300 ° C so that high-purity fluorine gas can be obtained. A disadvantage of this method is the low turn become MnF 4, and requires a complicated apparatus for dye-sublimation and collection of synthetic MnF 4. Another disadvantage is that the sublimation and condensation methods that are necessary make it difficult to plan for commercial production.
吾等試圖以MnF2與氟氣反應且無需昇華MnF4而合成MnF4。但是，該嘗試係在使化合物熔融及玻化時結束。於是確定不可能以與過去一樣簡單的方法獲得MnF4。 Wudeng MnF 2 attempts to reaction with the fluorine gas and synthesized without sublimation MnF 4 MnF 4. However, this attempt ends when the compound is melted and vitrified. It was then determined that it was impossible to obtain MnF 4 in the same manner as in the past.
頃發現在該方法的運作期間，起始錳鹽的氟化作用係在其粒子表面上進行，並以燒結粒子而完成，該燒結阻礙氟穿透至粒子中。 It has been found that during operation of the process, the fluorination of the starting manganese salt is carried out on the surface of its particles and is accomplished by sintering the particles which hinder the penetration of fluorine into the particles.
吾等(本發明的發明者)已發現必需解決以確保鹽完全氟化的方式進行該方法的目的或使氟穿透至粒子儘可能深的內部的問題。以包括在反應下研磨任何起始化合物及固體粒子的方法達成本發明的目的。 We (the inventors of the present invention) have found that it is necessary to solve the problem of carrying out the method in such a manner as to ensure complete fluorination of the salt or to penetrate fluorine into the interior of the particle as deep as possible. The object of the invention is achieved by a process comprising milling any starting compound and solid particles under reaction.
根據本發明製造四氟化錳的方法，係以使錳化合物與氟化劑在250-350℃之溫度及1.0-10.0MPa之壓力下反應，使化合物氟化，同時不斷地或間斷地壓碎或研磨在反應中的起始化合物及錳化合物為特徵。 The method for producing manganese tetrafluoride according to the present invention is to react a manganese compound with a fluorinating agent at a temperature of 250 to 350 ° C and a pressure of 1.0 to 10.0 MPa to fluorinate the compound while continuously or intermittently crushing. Or the starting compound and the manganese compound which are ground in the reaction are characterized.
將反應中的起始化合物及錳化合物在反應器中不斷地或間斷地壓碎或研磨，而不用自反應器取出。 The starting compound and the manganese compound in the reaction are continuously or intermittently crushed or ground in the reactor without being taken out from the reactor.
將反應中的起始化合物及錳化合物在反應器中以球磨機或棒磨機不斷地或間斷地壓碎或研磨，而不用自反應器取出。 The starting compound and the manganese compound in the reaction are continuously or intermittently crushed or ground in a reactor by a ball mill or a rod mill without being taken out from the reactor.
使用選自MnF2、MnF2水合物、MnCl2、MnCO3及 MnO中的一或多種二價錳化合物作為起始化合物。 One or more divalent manganese compounds selected from the group consisting of MnF 2 , MnF 2 hydrate, MnCl 2 , MnCO 3 and MnO are used as starting compounds.
起始化合物以包含MnF2及/或其水合物較佳。 The starting compound preferably contains MnF 2 and/or a hydrate thereof.
氟化劑包含一或多種選自F2、ClF及ClF3之物質。 The fluorinating agent comprises one or more materials selected from the group consisting of F 2 , ClF and ClF 3 .
氟化劑以包含F2較佳。 The fluorinating agent is preferably contained in F 2 .
將起始化合物在100-400℃之溫度下以具有露點為-40℃或更低的惰性氣體預處理。 The starting compound is pretreated at a temperature of from 100 to 400 ° C with an inert gas having a dew point of -40 ° C or lower.
本發明基本上的特徵如下：其係不依賴在高溫下的昇華作用，及冷卻和冷凝以氟化劑氟化錳化合物的產物，但是在250-350℃之溫度及1.0-10.0MPa之壓力下以其固體形式進行其氟化作用，同時不斷地或間斷地研磨起始化合物及反應產物。該方法係以在進行該方法之前或同時，以具有露點為-40℃或更低的惰性氣體(以-60℃或更低較佳)在100-400℃之溫度下(以150-350℃較佳)處理起始錳化合物為特徵。該方法係以在容納研磨裝置(例如，球磨機或棒磨機)之反應器中進行較佳。 The basic features of the present invention are as follows: it does not rely on the sublimation at high temperatures, and cools and condenses the product of the fluorinating agent fluorinated manganese compound, but at a temperature of 250-350 ° C and a pressure of 1.0-10.0 MPa. The fluorination is carried out in its solid form while continuously and intermittently grinding the starting compound and the reaction product. The method is carried out before or at the same time, with an inert gas having a dew point of -40 ° C or lower (preferably at -60 ° C or lower) at a temperature of 100-400 ° C (at 150-350 ° C) Preferably, the treatment of the starting manganese compound is characterized. The process is preferably carried out in a reactor containing a grinding device (e.g., a ball mill or a rod mill).
關於本發明，吾等將所欲的化合物之組成物以MnF4表示，但是因為該化合物通常部份包括自MnF2成為MnF4之中間產物及其二聚物，故將其通用組成物以MnFx(x=3.5-4)表示。 About the present invention, the desired compound Wudeng the composition of the object represented in MnF 4, but because the compound generally comprises from MnF portion 2 becomes intermediate and dimer MnF 4, the composition so it is common to MnF x (x=3.5-4) indicates.
根據本發明製備MnF4的方法，有可能使用市售取得的二價錳化合物如MnF2、MnCl2、MnCO3或MnO作為錳化合物。希望先使用MnF2，因為不需要移除陰離子，以 反應性的觀點而言，其次使用MnCO3。也允許使用錳化合物的水合物，但是有可能形成HF作為副產物。為了避免該情況，故有必要將其以具有露點為-40℃或更低的惰性氣體在150-350℃之溫度下處理。這樣有可能避免燒結產物的形成，並藉此改進轉化成為MnF4之速度及比率。甚至在使用無水MnF2時，例如希望在使用之前先將其乾燥，因為其包括少量水。 According to the method for producing MnF 4 of the present invention, it is possible to use a commercially available divalent manganese compound such as MnF 2 , MnCl 2 , MnCO 3 or MnO as a manganese compound. It is desirable to use MnF 2 first because there is no need to remove the anion, and from the viewpoint of reactivity, MnCO 3 is used next. It is also allowed to use a hydrate of a manganese compound, but it is possible to form HF as a by-product. In order to avoid this, it is necessary to treat it with an inert gas having a dew point of -40 ° C or lower at a temperature of 150 to 350 ° C. This makes it possible to avoid the formation of a sintered product and thereby improve the rate and ratio of conversion to MnF 4 . Even when anhydrous MnF 2 is used, it is for example desirable to dry it before use because it includes a small amount of water.
雖然對MnF2的純度沒有任何特殊的要求，但是雜質的過高百分比有可能阻礙氟化作用。例如，雖然認為90%或更高的純度令人滿意，但是更希望95%或更高的純度，且最理想的純度為97%或更高。氟化劑的純度也是一樣。雖然也沒有任何特殊的要求，但是例如在使用F2作為氟化劑時，則接受95%或更高的純度，更希望99%或更高的純度，且最理想的純度為99.9%或更高。 Although there is no particular requirement for the purity of MnF 2 , an excessive percentage of impurities may hinder fluorination. For example, although a purity of 90% or more is considered to be satisfactory, a purity of 95% or more is more desirable, and an optimum purity is 97% or more. The purity of the fluorinating agent is also the same. Although there is no special requirement, for example, when F 2 is used as the fluorinating agent, it is 95% or higher, more preferably 99% or higher, and the most desirable purity is 99.9% or more. high.
關於MnF2的粒徑，希望使用具有0.4毫米或更小的平均粒徑，更希望為100微米或更小的平均粒徑，且最希望為10微米或更小，考慮到：氟化效率係依據表面積而定，而且表面積相對於粒徑以反比例增加。 Regarding the particle diameter of MnF 2 , it is desirable to use an average particle diameter of 0.4 mm or less, more desirably an average particle diameter of 100 μm or less, and most desirably 10 μm or less, in consideration of: fluorination efficiency system Depending on the surface area, the surface area increases inversely with respect to the particle size.
有必要指出常以商業為基準自MnCO3及HF合成，MnF2(MnCO3+2HF→MnF2+CO2+H2O)。建議使用以該方法所獲得的無水MnF2製造MnF4。其有可能減低生產成本。 It is necessary to point out that MnF 2 (MnCO 3 + 2HF → MnF 2 + CO 2 + H 2 O) is often synthesized from MnCO 3 and HF on a commercial basis. It is recommended to produce MnF 4 using anhydrous MnF 2 obtained by this method. It has the potential to reduce production costs.
例如，將考慮上列因素所獲得的MnF2放入反應容器中以初步乾燥。進行其乾燥處理以移除自MnF2製造法所殘留的結晶水及黏附於MnF2晶體表面的水。如下列所述 進行其乾燥。在低壓下加熱MnF2以移除其水。重複包括使壓力下降中斷-以具有露點為-40℃或更低的惰性氣體(例如He)沖洗及藉此使壓力上升-使壓力再下降的循環達到除水效率。雖然以重複循環次數改進除水百水比，但是通常要以5至10次才足以除水。雖然就該目的而言以100℃之溫度視為滿意，但是以300-400℃之溫度使乾燥更有效。 For example, MnF 2 obtained by considering the above factors is placed in a reaction vessel to be initially dried. The drying treatment was carried out to remove the crystal water remaining from the MnF 2 production method and the water adhered to the surface of the MnF 2 crystal. It was dried as described below. The MnF 2 is heated at a low pressure to remove its water. Repeating includes interrupting the pressure drop - flushing with an inert gas (e.g., He) having a dew point of -40 ° C or lower and thereby causing the pressure to rise - a cycle in which the pressure is again lowered to achieve water removal efficiency. Although the water removal ratio is improved by repeating the number of cycles, it is usually 5 to 10 times to remove water. Although it is considered satisfactory at a temperature of 100 ° C for this purpose, drying is more effective at a temperature of 300 to 400 ° C.
可以使用一或多種選自F2、ClF及ClF3之物質作為氟化劑(或氟化劑類)。其中以包括F2之氟化劑較佳。 One or more substances selected from the group consisting of F 2 , ClF and ClF 3 may be used as the fluorinating agent (or fluorinating agent). Among them, a fluorinating agent comprising F 2 is preferred.
關於本發明所述之錳價位，將氟化錳溶解在硝酸或氫氯酸水溶液中，以ICP(感應耦合電漿)光譜法分析錳，及以離子層析法分析氟，並計算在氟化錳中的錳對氟之比。 Regarding the manganese price in the present invention, the manganese fluoride is dissolved in a nitric acid or aqueous hydrochloric acid solution, the manganese is analyzed by ICP (Inductively Coupled Plasma) spectroscopy, and the fluorine is analyzed by ion chromatography, and the fluorination is calculated. The ratio of manganese to fluorine in manganese.
可以以上述操作進行MnF4的合成。如果將因此獲得的MnF4在鎳容器中加熱時，則可以獲得氟氣。在以氣相層析法及紅外線傅立葉(Fourier)變換分光法測量在氣體中的雜質量時，則確定氟純度為99.95%或更高。 The synthesis of MnF 4 can be carried out in the above operation. If the MnF 4 thus obtained is heated in a nickel vessel, fluorine gas can be obtained. When the amount of impurities in the gas was measured by gas chromatography and infrared Fourier transform spectroscopy, the purity of fluorine was determined to be 99.95% or more.
以參考下列實例更詳細說明本發明，但是，不應該將本發明解釋成受限於這些實例。 The invention is described in more detail with reference to the following examples, however, the invention should not be construed as being limited to the examples.
在露點受到控制的手套箱(6)中，將4500公克二氟化錳(MnF2)放入容納在測試裝置結構(圖1)中的反應器(4)之 淺盤(在圖2中的(5))上。 In the glove box (6) where the dew point is controlled, 4500 grams of manganese difluoride (MnF 2 ) is placed in the tray (4) of the reactor (4) contained in the test device structure (Fig. 1) (in Figure 2 (5)).
將反應器(4)抽空且供給氟氣，直到其具有2.0MPa之壓力P為止，並使反應器(4)保持在250℃之溫度T下，直到其壓力變固定為止。 The reactor (4) was evacuated and supplied with fluorine gas until it had a pressure P of 2.0 MPa, and the reactor (4) was maintained at a temperature T of 250 ° C until the pressure became fixed.
當其壓力P下降至小於1.0MPa時，則供給氟氣至反應器(4)，直到其壓力P上升至2.0MPa為止。 When the pressure P drops to less than 1.0 MPa, the fluorine gas is supplied to the reactor (4) until the pressure P thereof rises to 2.0 MPa.
當反應器(4)的壓力P穩定時，則認為反應完成。 When the pressure P of the reactor (4) is stabilized, the reaction is considered complete.
在將反應器(4)抽空且餵入氮氣，直到其壓力達到周圍壓力之後，取出以氟氣處理之產物。 After the reactor (4) was evacuated and nitrogen was fed until the pressure reached the ambient pressure, the product treated with fluorine gas was taken out.
將產物稱重且根據增加的重量計算各反應產物的組成。 The product was weighed and the composition of each reaction product was calculated based on the increased weight.
接著將反應產物在切縫型研磨機(7)中研磨及放入反應器(4)中，其中重複如上述之氟化操作。以ICP及離子層析法分析最終產物之組成，並確定以重量為基準之組成。 The reaction product is then ground in a slitting mill (7) and placed in a reactor (4) in which the fluorination operation as described above is repeated. The composition of the final product was analyzed by ICP and ion chromatography, and the composition based on the weight was determined.
表1展示以上述參數為基準之試驗結果。 Table 1 shows the test results based on the above parameters.
根據實例，將起始原料及每一回試驗之後的反應產物各自以切縫型研磨機(7)研磨及間斷地施予氟氣處理。如果以上述的試驗編號表示每一次研磨時間，則其係在第1回之前(以切縫型研磨機(7)研磨起始原料)、在第1與第2回之間、在第2與第3回之間、在第3與第4回之間、及在第4回之後(研磨最終產物)。在第1與第2回之間沒有進行任何研磨之下進行根據第2回試驗的氟化處理時，則難以進行任何氟化作用，並未獲得任何MnF3.5，儘管花了長時間。 According to an example, the starting materials and the reaction products after each test are each ground by a slit type grinder (7) and intermittently subjected to fluorine gas treatment. If the polishing time is indicated by the test number described above, it is before the first pass (the starting material is ground by the slit grinder (7)), between the first and second passes, and between the first and the second. Between the third time, between the third and fourth times, and after the fourth time (grinding the final product). When the fluorination treatment according to the second round test was carried out without any grinding between the first and second passes, it was difficult to carry out any fluorination, and no MnF 3.5 was obtained, although it took a long time.
在露點受到控制的手套箱中，將2500公克二氟化錳(MnF2)裝入具有球磨機及容納在測試裝置結構(圖3)中的反應器(4)(在圖4中的(1))中。 In a glove box with a dew point controlled, 2500 grams of manganese difluoride (MnF 2 ) was charged into a reactor (4) having a ball mill and housed in a test device structure (Fig. 3) ((1) in Fig. 4 )in.
使反應器(4)保持不變，直到其具有250℃之恆溫T為止。將反應器(4)抽空且供給其氟氣，直到其具有2.0MPa之壓力P1為止，並將其關閉。將具有球磨機之反應器(4)旋轉以進行反應，同時將錳化合物在其中壓碎及研磨。 The reactor (4) was kept constant until it had a constant temperature T of 250 °C. The reactor (4) was evacuated and supplied with the fluorine gas until it has a far, and its closing pressure P of 2.0MPa. The reactor (4) having a ball mill is rotated to carry out the reaction while the manganese compound is crushed and ground therein.
當壓力的臨時檢查顯示壓力P2小於1.0MPa時，則將氟氣供給至反應器(4)，直到其壓力P1恢復為2.0MPa為止，並將其關閉。 When the temporary inspection of the pressure shows that the pressure P 2 is less than 1.0 MPa, the fluorine gas is supplied to the reactor (4) until its pressure P 1 returns to 2.0 MPa, and it is closed.
當反應器(4)的壓力P穩定時，則認為反應完成。 When the pressure P of the reactor (4) is stabilized, the reaction is considered complete.
在將反應器(4)抽空且餵入氮氣進料，直到其壓力達到周圍壓力之後，取出以氟氣處理之產物。 After the reactor (4) was evacuated and the nitrogen feed was fed until its pressure reached the ambient pressure, the product treated with fluorine gas was taken out.
將產物稱重，並根據增加的重量及以ICP和離子層析法的分析結果計算各反應產物的組成。 The product was weighed and the composition of each reaction product was calculated based on the increased weight and the analysis results by ICP and ion chromatography.
將試驗結果展示在表2中。 The test results are shown in Table 2.
表2也展示以改變作為參數的溫度T及壓力P(P1及P2)所獲得的結果。當在每一個實例中壓力檢查顯示壓力P2小於X MPa時，則將氟氣供給至反應器(4)，直到其壓力P1上升至Y MPa為止，並將其關閉，而其壓力範圍Y-X為1MPa。 Table 2 also shows the results obtained by changing the temperature T and the pressure P (P 1 and P 2 ) as parameters. When the pressure check shows that the pressure P 2 is less than X MPa in each of the examples, the fluorine gas is supplied to the reactor (4) until its pressure P 1 rises to Y MPa, and it is closed, and its pressure range YX It is 1 MPa.
使具有球磨機之反應器始終維持旋轉，除了在供給氟及在檢查其狀態時(包括壓力)之外。從表2所示的結果明白較高的溫度及較高的壓力傾向引起較高的氟化程度。也發現比所謂以MnF3.7表示的組成物更高的氟化程度逐漸較不可能發生。 The reactor with the ball mill is always kept rotating, except when supplying fluorine and checking its state (including pressure). From the results shown in Table 2, it is understood that a higher temperature and a higher pressure tend to cause a higher degree of fluorination. It has also been found that a higher degree of fluorination than the so-called composition represented by MnF 3.7 is gradually less likely to occur.
在露點受到控制的手套箱中，將2500公克氟化錳單水合物(MnF2．H2O)裝入具有球磨機及容納在測試裝置結構(圖3)中的反應器(4)(在圖4中的(1))中。 In a glove box with a dew point controlled, 2500 grams of manganese fluoride monohydrate (MnF 2 .H 2 O) was charged into a reactor (4) with a ball mill and housed in the test device structure (Fig. 3) In (1) of 4).
將反應器(4)抽空且供給氟氣，直到其具有6.0MPa之壓力P1為止，並將其關閉。使具有球磨機之反應器旋轉以進行反應，同時將錳化合物在其中壓碎及研磨，並將加熱器啟動，以保持反應器(4)，直到其具有300℃之恆溫T為止。 The reactor (4) was evacuated and fluorine gas is supplied, having up until 1, and its closing pressure P of 6.0MPa. The reactor having the ball mill was rotated to carry out the reaction while the manganese compound was crushed and ground therein, and the heater was started to maintain the reactor (4) until it had a constant temperature T of 300 °C.
當壓力的臨時檢查顯示壓力P2小於5.0MPa時，則將氟氣供給至反應器(4)，直到其壓力P1恢復為6.0MPa為止，並將其關閉。 When the temporary inspection of the pressure shows that the pressure P 2 is less than 5.0 MPa, the fluorine gas is supplied to the reactor (4) until its pressure P 1 returns to 6.0 MPa, and it is closed.
當反應器(4)的壓力P穩定時，則認為反應完成。 When the pressure P of the reactor (4) is stabilized, the reaction is considered complete.
在將反應器(4)抽空且餵入氮氣，直到其壓力達到周圍壓力之後，取出以氟氣處理之產物。 After the reactor (4) was evacuated and nitrogen was fed until the pressure reached the ambient pressure, the product treated with fluorine gas was taken out.
將產物稱重，並根據增加的重量及以ICP和離子層析法的分析結果計算各反應產物的組成。 The product was weighed and the composition of each reaction product was calculated based on the increased weight and the analysis results by ICP and ion chromatography.
也使用不同的起始原料進行試驗，並將結果全部展示 在表3中。 Also experiment with different starting materials and show the results In Table 3.
當在每一個實例中壓力檢查顯示壓力P2小於X MPa時，則將氟氣供給至反應器(4)，直到其壓力P1上升至Y MPa為止，並將其關閉，而其壓力範圍Y-X為1MPa。 When the pressure check shows that the pressure P 2 is less than X MPa in each of the examples, the fluorine gas is supplied to the reactor (4) until its pressure P 1 rises to Y MPa, and it is closed, and its pressure range YX It is 1 MPa.
在露點受到控制的手套箱中，將2500公克二氟化錳(MnF2)裝入具有球磨機及容納在測試裝置結構(圖3)中的反應器(4)(在圖4中的(1))中。 In a glove box with a dew point controlled, 2500 grams of manganese difluoride (MnF 2 ) was charged into a reactor (4) having a ball mill and housed in a test device structure (Fig. 3) ((1) in Fig. 4 )in.
保持反應器(4)，直到其具有300℃之恆溫T為止。將反應器(4)抽空且供給三氟化氯ClF3，直到其具有2.0MPa之壓力P1為止，並將其關閉。將具有球磨機之反應器旋轉以進行反應，同時將錳化合物在其中壓碎及研磨。 The reactor (4) was held until it had a constant temperature T of 300 °C. The reactor (4) was evacuated and supplied with chlorine trifluoride ClF 3 until it had a pressure P 1 of 2.0 MPa, and it was turned off. The reactor having the ball mill is rotated to carry out the reaction while the manganese compound is crushed and ground therein.
當壓力的臨時檢查顯示壓力P2小於1.0MPa時，則將三氟化氯供給至反應器(4)，直到其壓力P1恢復為2.0 MPa為止，並將其關閉。 When the temporary inspection of the pressure showed that the pressure P 2 was less than 1.0 MPa, chlorine trifluoride was supplied to the reactor (4) until its pressure P 1 returned to 2.0 MPa, and it was closed.
當反應器(4)的壓力P穩定時，則認為反應完成。 When the pressure P of the reactor (4) is stabilized, the reaction is considered complete.
在將反應器(4)抽空且餵入氮氣，直到其壓力達到周圍壓力之後，取出以氟氣處理之產物。 After the reactor (4) was evacuated and nitrogen was fed until the pressure reached the ambient pressure, the product treated with fluorine gas was taken out.
將產物稱重，並根據增加的重量及以ICP和離子層析法的分析結果計算各反應產物的組成。 The product was weighed and the composition of each reaction product was calculated based on the increased weight and the analysis results by ICP and ion chromatography.
將試驗結果展示在表4中。 The test results are shown in Table 4.
表4也展示將氟化劑改變成氟化氯ClF所獲得的結果。當在每一個實例中壓力檢查顯示壓力P2小於X MPa時，則將氟化劑供給至反應器(4)，直到其壓力P1上升至Y MPa為止，並將其關閉，而其壓力範圍Y-X為1MPa。 Table 4 also shows the results obtained by changing the fluorinating agent to fluorinated chlorine ClF. When the pressure check shows that the pressure P 2 is less than X MPa in each of the examples, the fluorinating agent is supplied to the reactor (4) until its pressure P 1 rises to Y MPa, and it is closed, and its pressure range YX is 1 MPa.
考慮以氟置換包括氯之中間產物，且產物的氯含量是氟的約1%或更少。 It is contemplated to replace the intermediate product including chlorine with fluorine, and the chlorine content of the product is about 1% or less of fluorine.
在氟化處理之前，先將起始原料在100-400℃之溫度 下在具有露點為-40℃或更低的惰性氣體中預處理，以具有更低的結晶水含量，以便在加熱最終產物(MnF4)後可以獲得具有較低HF含量之氟。 Prior to the fluorination treatment, the starting material is pretreated at a temperature of 100-400 ° C in an inert gas having a dew point of -40 ° C or lower to have a lower crystallization water content in order to heat the final product. Fluorine having a lower HF content can be obtained after (MnF 4 ).
在露點受到控制的手套箱中，將各自具有不同水含量的2500公克二氟化錳(MnF2．nH2O)裝入具有球磨機及容納在測試裝置結構(圖3)中的反應器(4)(在圖4中的(1))中。 In a glove box with a dew point controlled, 2500 grams of manganese difluoride (MnF 2 .nH 2 O) each having a different water content was charged into a reactor having a ball mill and housed in a test device structure (Fig. 3) (4) ) ((1) in Fig. 4).
將反應器(4)抽空且同時供給具有露點為-40℃或更低的惰性氣體，反應器(4)的內溫T保持在100-400℃，藉此獲得具有不同水含量之起始原料(MnF2．xH2O)。 The reactor (4) is evacuated and simultaneously supplied with an inert gas having a dew point of -40 ° C or lower, and the internal temperature T of the reactor (4) is maintained at 100 to 400 ° C, thereby obtaining starting materials having different water contents. (MnF 2 .xH 2 O).
保持反應器(4)，直到其具有300℃之恆溫T為止。將反應器(4)抽空且供給氟氣，直到其具有6.0MPa之壓力P1為止，並將其關閉。將具有球磨機之反應器旋轉以進行反應，同時將錳化合物在其中壓碎及研磨。 The reactor (4) was held until it had a constant temperature T of 300 °C. The reactor (4) was evacuated and fluorine gas is supplied, having up until 1, and its closing pressure P of 6.0MPa. The reactor having the ball mill is rotated to carry out the reaction while the manganese compound is crushed and ground therein.
當壓力的臨時檢查顯示壓力P2小於5.0MPa時，則將氟氣供給至反應器(4)，直到其壓力P1恢復為6.0MPa為止，並將其關閉。 When the temporary inspection of the pressure shows that the pressure P 2 is less than 5.0 MPa, the fluorine gas is supplied to the reactor (4) until its pressure P 1 returns to 6.0 MPa, and it is closed.
當反應器(4)的壓力P穩定時，則認為反應完成。 When the pressure P of the reactor (4) is stabilized, the reaction is considered complete.
在將反應器(4)抽空且餵入氮氣，直到其壓力達到周圍壓力之後，取出以氟氣處理之產物。 After the reactor (4) was evacuated and nitrogen was fed until the pressure reached the ambient pressure, the product treated with fluorine gas was taken out.
將產物稱重，並根據增加的重量及分析結果計算各反應產物的組成。 The product was weighed and the composition of each reaction product was calculated based on the increased weight and analysis results.
接著將上述方法所獲得及具有通式MnF3.86或具有較高的氟含量的欲測試之450±5公克之各物質在如圖1所示 之分解反應器(10)中在加熱下分解。 Next, each of the substances obtained by the above method and having a formula of MnF 3.86 or having a high fluorine content of 450 ± 5 g to be tested was decomposed under heating in a decomposition reactor (10) as shown in FIG.
將欲測試的各物質加熱至380℃之溫度T，以達成最高程度的氟分解。 Each substance to be tested was heated to a temperature T of 380 ° C to achieve the highest degree of fluorine decomposition.
將欲測試的各物質分解所產生的氟氣收集在絕對壓力273毫米汞柱下以液態氮冷卻之容器中。 The fluorine gas generated by decomposition of each substance to be tested was collected in a container cooled by liquid nitrogen at an absolute pressure of 273 mmHg.
在將容器加熱至周圍溫度之後，在加熱下藉由分解所獲得的氟氣，其HF含量以FT-IR分析。 After heating the vessel to ambient temperature, the HF content of the fluorine gas obtained by decomposition under heating was analyzed by FT-IR.
將結果展示在表5中。 The results are shown in Table 5.
表5確認具有較低水含量之起始原料得到產生具有較低氟化氫(HF)含量之氟的最終產物。 Table 5 confirms that the starting materials having a lower water content result in a final product that produces fluorine having a lower hydrogen fluoride (HF) content.
圖1： figure 1:
1‧‧‧接收器 1‧‧‧ Receiver
2‧‧‧壓縮器 2‧‧‧Compressor
3‧‧‧歧管 3‧‧‧Management
4‧‧‧反應器 4‧‧‧Reactor
5‧‧‧電熱器 5‧‧‧Electric heater
6‧‧‧手套箱 6‧‧‧Gift box
7‧‧‧切縫型研磨機 7‧‧‧Scratch Grinder
8‧‧‧真空泵 8‧‧‧Vacuum pump
9‧‧‧電熱器 9‧‧‧Electric heater
10‧‧‧反應器-熱壓器 10‧‧‧Reactor-heat exchanger
圖2： figure 2:
1‧‧‧熱電偶 1‧‧‧ thermocouple
2‧‧‧電熱器 2‧‧‧Electric heater
3‧‧‧反應器 3‧‧‧Reactor
4‧‧‧密封凸緣 4‧‧‧ Sealing flange
5‧‧‧淺盤 5‧‧‧Shallow
6‧‧‧氣體、初產物及最終產物的輸入-輸出之管接頭 6‧‧‧Inlet-out fittings for gases, primary products and final products
圖3： image 3:
1‧‧‧接收器 1‧‧‧ Receiver
2‧‧‧壓縮器 2‧‧‧Compressor
3‧‧‧歧管 3‧‧‧Management
4‧‧‧具有球磨機之反應器 4‧‧‧Reactor with ball mill
5‧‧‧電熱器 5‧‧‧Electric heater
6‧‧‧馬達 6‧‧‧Motor
7‧‧‧真空泵 7‧‧‧vacuum pump
‧‧‧閥 ‧‧‧valve
圖4： Figure 4:
1‧‧‧反應器 1‧‧‧reactor
2‧‧‧熱電偶 2‧‧‧ thermocouple
3‧‧‧密封凸緣 3‧‧‧ sealing flange
4‧‧‧氣體、初產物及最終產物的輸入-輸出之管接頭 4‧‧‧Inlet-out fittings for gases, primary products and final products
5‧‧‧球磨機 5‧‧‧Ball mill
6‧‧‧電熱器 6‧‧‧Electric heater
7‧‧‧軸(供啟動旋轉) 7‧‧‧Axis (for starting rotation)
圖1係展示使用批次式反應器之測試裝置的示意圖。 Figure 1 is a schematic diagram showing a test apparatus using a batch reactor.
圖2係展示在圖1之測試裝置中的批次式反應器之放大圖示。 Figure 2 is an enlarged illustration of the batch reactor shown in the test apparatus of Figure 1.
圖3係展示使用具有球磨機的反應器之測試裝置的示意圖。 Figure 3 is a schematic diagram showing a test apparatus using a reactor having a ball mill.
圖4係展示在圖3之測試裝置中具有球磨機的反應器之放大圖示。 Figure 4 is an enlarged illustration of a reactor having a ball mill in the test apparatus of Figure 3.
1‧‧‧接收器 1‧‧‧ Receiver
2‧‧‧壓縮器 2‧‧‧Compressor
3‧‧‧ 歧管 3‧‧‧ Manifold
4‧‧‧反應器 4‧‧‧Reactor
5‧‧‧電熱器 5‧‧‧Electric heater
6‧‧‧手套箱 6‧‧‧Gift box
7‧‧‧切縫型研磨機 7‧‧‧Scratch Grinder
8‧‧‧真空泵 8‧‧‧Vacuum pump
9‧‧‧電熱器 9‧‧‧Electric heater
10‧‧‧反應器-熱壓器 10‧‧‧Reactor-heat exchanger
P‧‧‧壓力錶 P‧‧‧ pressure gauge
T‧‧‧熱電偶 T‧‧‧ thermocouple
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