200934729 九、發明說明 【發明所屬之技術領域】 ' 本發明關於一種用於純化元素氟的方法。 【先前技術】 . 元素氟可以用來將一或多個氟原子引入化合物中，例 如，藉由用氟原子取代氫原子或藉由加成到碳-碳雙鍵上 ^ 。另外，它在半導體生產中可應用作鈾刻劑，例如，基於 矽的半導體。它還可以用來作爲在半導體生產中使用的反 應器腔室的淨化氣體。眾所周知，在反應器腔室內，例如 ，在使用nf3或氫氟碳化物作爲蝕刻氣體之後，殘餘物可 能形成。這種殘餘物可以用元素氟去除。 尤其是用於半導體工業時，氟必須是高純度的。用於 純化氟的一方法描述於美國專利3,989,808中。KF和NiF2 的一混合物以3 :1的莫耳比製備，然後在一反應器中，將 φ 該混合物在約10 atm的壓力下與不純的氟以一分批的方 法接觸。將溫度緩慢提至500°C然後降低到250°C。在此過 程中形成K2NiF6。在幾個加熱和冷卻的循環以後，將溫度 提至225°C，並且將反應器抽真空。氣態雜質在抽真空過 程中被去除。加熱至5 00 °C時，該反應器的內容物釋放出 純化的氟。在氟的釋放終止後，剩餘的鎳鹽可再次與不純 的氟接觸，而該純化方法可以再次開始。 歐洲專利申請案1580163揭示一生產氟的方法，其中 具有一高的氧化程度的二元金屬氟化物或錯合的金屬氟化 -5- 200934729 物被加熱至1 5 0 °C和4 0 0 °C之間的溫度。該金屬化合物以尺 寸在1 .0到3.0 mm之間的細粒或小粒的形式使用。 【發明內容】 ' 本發明的一目的係提供一純化氟的方法，它允許元素 氟的純化以一快速並簡單的方式進行。藉由本發明的方法 達成了此目的和其他目的。 根據本發明用於製備純化的元素氟的方法包括一步驟 n ，其中將包括雜質的氟與固體氟化錳接觸，藉由使該氟通 過固體氟化錳上方和/或穿過固體氟化錳而使之與固體氟 化錳接觸。獲得了一雜質含量減少的氟並且它離開反應器 ;通常，在一段時間內供到該反應器中的氟的量大約對應 於在相同的一段時間內離開該反應器的氟的量。離開該反 應器的氟可被壓縮並儲存。使氟通過固體氟化錳上方和/200934729 IX. Description of the Invention [Technical Field to Which the Invention Is Ascribed] The present invention relates to a method for purifying elemental fluorine. [Prior Art] Elemental fluorine can be used to introduce one or more fluorine atoms into a compound, for example, by substituting a hydrogen atom with a fluorine atom or by addition to a carbon-carbon double bond. In addition, it can be used as an uranium engraving in semiconductor production, for example, germanium-based semiconductors. It can also be used as a purge gas for a reactor chamber used in semiconductor production. It is well known that residues may be formed in the reactor chamber, for example, after using nf3 or hydrofluorocarbon as an etching gas. This residue can be removed with elemental fluorine. Especially for the semiconductor industry, fluorine must be of high purity. A method for purifying fluorine is described in U.S. Patent 3,989,808. A mixture of KF and NiF2 was prepared at a molar ratio of 3:1, and then the mixture was contacted with impure fluorine in a batch process at a pressure of about 10 atm in a reactor. The temperature was slowly raised to 500 ° C and then lowered to 250 ° C. K2NiF6 is formed during this process. After several cycles of heating and cooling, the temperature was raised to 225 ° C and the reactor was evacuated. Gaseous impurities are removed during the vacuuming process. Upon heating to 500 °C, the contents of the reactor released purified fluorine. After the release of fluorine is terminated, the remaining nickel salt can be contacted again with impure fluorine, and the purification process can be started again. European Patent Application No. 1,580,163 discloses a process for the production of fluorine in which a binary metal fluoride having a high degree of oxidation or a miscible metal fluoride-5-200934729 is heated to 150 ° C and 400 ° The temperature between C. The metal compound is used in the form of fine particles or small particles having a size of between 1.0 and 3.0 mm. SUMMARY OF THE INVENTION An object of the present invention is to provide a method of purifying fluorine which allows the purification of elemental fluorine to be carried out in a quick and simple manner. This and other objects are achieved by the method of the present invention. The method for preparing purified elemental fluorine according to the present invention comprises a step n in which fluorine comprising an impurity is contacted with solid manganese fluoride by passing the fluorine through the solid fluoride and/or through the solid manganese fluoride It is brought into contact with solid manganese fluoride. A fluorine having a reduced impurity content is obtained and it leaves the reactor; typically, the amount of fluorine supplied to the reactor over a period of time corresponds approximately to the amount of fluorine leaving the reactor over the same period of time. The fluorine leaving the reactor can be compressed and stored. Passing fluorine through the solid fluoride and/or
或穿過固體氟化錳以及從該反應器抽出純化的氟因此係一 連續的製程，而非一分批進行的製程。氟的連續通入當然 U 可以被中斷（如果希望的話），並且可以在任何中斷後繼 續進行。例如，如果氟化錳必須再生，可中斷氟在反應器 中的穿流。 本發明的方法適合於純化氟，該氟包含水、氟化氫、 氧氣和/或重金屬類，尤其是，氧氣和重金屬類，尤其是 鎢和砷。氟中雜質（例如以上提到的那些）的來源可以是 用來製備氟的原料中已經包含的雜質，例如，在作爲一氟 來源的氟化氫中（其中可能包含少量的砷化合物）、由處 -6 - 200934729 ，如上所 屬雜質類 ，或從腔 質。此外 砷化鎵） 鐘上方和 顆粒材料 床。在現 氟吸附並 的方法中 氟離開了 化錳反應 理而釋放 室溫的溫 更較佳地 等於或低 較佳地， Ξ 250 °C 和 理而導致的雜質、或者由於氟的特殊用途（例如 述，作爲蝕刻氣體或腔室清洗氣體。此處，重金 可能從反應器腔室壁的金屬中引入，例如鎳或鐵 一 室內所使用的反應物引入，例如鎢）而導致的雜 ，可去除鎵化合物（例如在半導體製造中使用的 〇 在該純化步驟中，將不純的氟通過固體氟化 ❾ /或穿過固體氟化锰。該固體氟化猛能夠例如以 (例如作爲一粉末）的形式安排爲固定床或流化 有技術中，不純的氟與氟化錳之間的接觸係以將 且隨後將其釋放的方式分批完成的，而在本發明 ，該接觸係連續進行。與氟化錳接觸後，純化的 與氟化錳接觸時所在的反應器。一部分氟與該氟 以形成氟化程度更高的氟化錳。它可以藉由熱處 〇 Φ 氟化錳和有待純化的氟之間的接觸係在高於 度下進行。較佳地，該溫度等於或大於°c。 ，該溫度等於或大於15(TC。一般而言，該溫度 於5 50°c。較佳地，該溫度等於或低於5 00°C。更 該溫度等於或低於450 °C。一高度較佳的範圍係 400°C之間。 在接觸期間氟和氟化錳之間的壓力係可變的。較佳地 ，它等於或大於1巴（絕對壓力）。更較佳地’它等於或 大於2巴（絕對壓力）。較佳地，它等於或低於1〇巴（ 200934729 絕對壓力）。 在一較佳的實施態樣中，術語“氟化錳”表示二氟化錳 、三氟化錳和四氟化錳以及兩種或所有化合物的任何混合 物。有可能使用二氟化錳、三氟化錳或四氟化錳作爲單一 二 化合物。在一較佳的實施態樣中，使用了二氟化錳或三氟 化錳。在與元素氟接觸期間，它被氧化，並且形成三氟化 錳和/或四氟化錳。在氟化錳與元素氟接觸期間經常形成 實質上包括三氟化錳和四氟化錳的多種混合物。 _ 氟化錳的粒子大小同樣是可變的。等於或大於0.1 μιη 至高達若干毫米（例如高達5 mm)的一尺寸是合適的。 較佳粒子大小等於或大於1 μιη。較佳粒子大小等於或小 於0.5 mm’尤其較佳等於或小於200 μιη。應理解，還可 能存在尺寸不夠大或過大的顆粒。較佳地，等於或小於 5 %的數目的顆粒小於上述下限尺寸，並且等於或小於5 % 的數目的顆粒大於上述上限尺寸。 在一較佳的實施態樣中，至少有兩個反應器交替使用 ❹ 。以這種方式，根據本發明的方法能以一連續的方式永久 地進行；假如只使用一反應器，當氟化錳必須再生時該連 續的方法必須不時地停止。假如使用兩個或更多的反應器 ，那麼一或多個反應器用於純化，而另一或其他的用於氟 化錳的再生。可以藉由將它加熱至高達550 °C而進行再生 ’例如在一惰性氣體流（例如氮氣）中。因此形成了三氟 化鐘。可替代地，消耗的氟化錳可以由新生的材料（二氟 化錳或三氟化錳或它們的混合物）所取代。 -8- 200934729 使用根據本發明的純化方法’可以減少在元素氟中的 水、氣化氣、氧氣或重金屬類以及其他雜質的含量’尤其 是氧氣含量和重金屬含量。在此假設氟化錳與這些雜質形 成了錳的氟氧化物、羥基氟化物或錳的金屬酸鹽。如果希 望的話，該純化處理可以重複直到達成所希望的純度。當 然，有待處理的不純的氟不得包含所有所述的雜質。僅包 括一或兩種所述雜質的不純的氟可以同樣地進行處理。通 過該氟化錳的純化氟就能用於需要純化的氟的那些目的。 與氟化錳反應以形成四氟化錳的氟可以藉由將四氟化錳加 熱到大約400°C而被釋放，並且然後即可在需要純化的氟 的反應中使用。 該方法是非常有利的，因爲它允許對元素氟進行一連 續的純化處理。 【實施方式】 φ 以下實例旨在進一步說明本發明而不對其進行限制。 實例 將一氟化鍤加入到由鎳、蒙乃爾合金（Monel)或其 他耐氟金屬製成的兩個反應器中。然後，將該溫度升到 350°C ’並且將包含一砷化合物的元素氟通過該二氟化錳 。與砷化合物的吸附同時，形成了三氟化錳以及隨後的四 氟化錳。離開反應器的純化氟可被壓縮和儲存以備隨後使 用。 -9- 200934729 爲了使第一反應器再生，停止通過第一反應器的氟氣 流，將第二反應器加熱並且使不純的元素氟通過該反應器 。第一反應器的內容物可以被棄置，或者可以藉由將其加 熱到高達500°C使其再生，選擇性地在其中通過氮氣。在 此，氟被分離出。 ❹ -10-Or passing through the solid manganese fluoride and withdrawing the purified fluorine from the reactor is therefore a continuous process rather than a batch process. The continuous passage of fluorine can of course be interrupted (if desired) and can be continued after any interruption. For example, if manganese fluoride must be regenerated, the flow of fluorine through the reactor can be interrupted. The process of the invention is suitable for the purification of fluorine, which comprises water, hydrogen fluoride, oxygen and/or heavy metals, especially oxygen and heavy metals, especially tungsten and arsenic. The source of impurities in fluorine (such as those mentioned above) may be impurities already contained in the raw material for preparing fluorine, for example, in hydrogen fluoride as a source of fluorine (which may contain a small amount of arsenic compound), from 6 - 200934729, as above belong to the class of impurities, or from the cavity. In addition to gallium arsenide) above the clock and the bed of granular material. In the current fluorine adsorption method, the fluorine leaves the manganese reaction and the temperature at which the room temperature is released is more preferably equal to or lower, preferably Ξ 250 ° C and the resulting impurities, or due to the special use of fluorine ( For example, as an etching gas or a chamber cleaning gas. Here, heavy gold may be introduced from the metal of the reactor chamber wall, such as nickel or iron, which is introduced by a reactant used in a chamber, such as tungsten. Removal of gallium compounds (eg, ruthenium used in semiconductor fabrication, in the purification step, passing impure fluorine through solid ruthenium fluoride / or through solid manganese fluoride. The solid fluorination can be, for example, (for example, as a powder) The form is arranged in a fixed bed or fluidized technique. The contact between the impure fluorine and the manganese fluoride is done in batches in a manner that will subsequently be released, whereas in the present invention, the contact is continuously carried out. After contact with manganese fluoride, the purified reactor is in contact with the manganese fluoride. A part of fluorine and the fluorine form a higher degree of fluorination of manganese fluoride. It can be heated by 〇Φ manganese fluoride and remains to be treated The contact between the fluorine is carried out at an elevated temperature. Preferably, the temperature is equal to or greater than °c. The temperature is equal to or greater than 15 (TC. Generally, the temperature is at 5 50 ° C. Preferably, the temperature is equal to or lower than 500 ° C. The temperature is equal to or lower than 450 ° C. A highly preferred range is between 400 ° C. The pressure between fluorine and manganese fluoride during contact Preferably, it is equal to or greater than 1 bar (absolute pressure). More preferably, it is equal to or greater than 2 bar (absolute pressure). Preferably, it is equal to or lower than 1 bar (200934729) Absolute pressure. In a preferred embodiment, the term "manganese fluoride" means manganese difluoride, manganese trifluoride and manganese tetrafluoride, and any mixture of two or all of the compounds. It is possible to use difluoro. Manganese, manganese trifluoride or manganese tetrafluoride as a single di compound. In a preferred embodiment, manganese difluoride or manganese trifluoride is used. It is oxidized during contact with elemental fluorine. And forming manganese trifluoride and/or manganese tetrafluoride. It is often formed during the contact of manganese fluoride with elemental fluorine. The composition includes various mixtures of manganese trifluoride and manganese tetrafluoride. _ The particle size of manganese fluoride is also variable. A size equal to or greater than 0.1 μηη up to several millimeters (for example up to 5 mm) is suitable. Preferably, the particle size is equal to or greater than 1 μηη. The preferred particle size is equal to or less than 0.5 mm', particularly preferably equal to or less than 200 μηη. It should be understood that particles of insufficient or large size may also be present. Preferably, equal to or The number of particles less than 5% is less than the above lower limit size, and the number of particles equal to or less than 5% is larger than the above upper limit size. In a preferred embodiment, at least two reactors alternately use ❹. In this way, the process according to the invention can be carried out permanently in a continuous manner; if only one reactor is used, the continuous process must be stopped from time to time when the manganese fluoride has to be regenerated. If two or more reactors are used, one or more reactors are used for purification and the other or others are used for regeneration of manganese fluoride. Regeneration can be carried out by heating it up to 550 ° C, for example in an inert gas stream (e.g., nitrogen). Thus a trifluoride clock is formed. Alternatively, the consumed manganese fluoride can be replaced by a nascent material (manganese difluoride or manganese trifluoride or a mixture thereof). -8- 200934729 The use of the purification method according to the present invention can reduce the contents of water, gasification gas, oxygen or heavy metals and other impurities in elemental fluorine, especially oxygen content and heavy metal content. It is assumed here that manganese fluoride and these impurities form a metal oxide of oxyfluoride, hydroxy fluoride or manganese of manganese. If desired, the purification process can be repeated until the desired purity is achieved. Of course, the impure fluorine to be treated must not contain all of the impurities mentioned. Impure fluorine comprising only one or two of said impurities can be treated similarly. The purified fluorine by the manganese fluoride can be used for those purposes requiring purification of fluorine. Fluorine which reacts with manganese fluoride to form manganese tetrafluoride can be released by heating manganese tetrafluoride to about 400 ° C, and then can be used in the reaction requiring fluorine to be purified. This method is very advantageous because it allows for a continuous purification of the elemental fluorine. [Embodiment] φ The following examples are intended to further illustrate the invention without limiting it. EXAMPLES Neodymium fluoride was added to two reactors made of nickel, Monel or other fluorine-resistant metal. Then, the temperature was raised to 350 ° C ' and elemental fluorine containing an arsenic compound was passed through the manganese difluoride. Simultaneously with the adsorption of the arsenic compound, manganese trifluoride and subsequent manganese tetrafluoride are formed. The purified fluorine leaving the reactor can be compressed and stored for later use. -9- 200934729 In order to regenerate the first reactor, the flow of fluorine gas through the first reactor is stopped, the second reactor is heated and impure elemental fluorine is passed through the reactor. The contents of the first reactor may be disposed of, or may be regenerated by heating it up to 500 ° C, optionally passing nitrogen through it. Here, fluorine is separated. ❹ -10-