JPH0446014A - Manufacture device for rare earth fluolide anhydride and its production - Google Patents
Manufacture device for rare earth fluolide anhydride and its productionInfo
- Publication number
- JPH0446014A JPH0446014A JP2150067A JP15006790A JPH0446014A JP H0446014 A JPH0446014 A JP H0446014A JP 2150067 A JP2150067 A JP 2150067A JP 15006790 A JP15006790 A JP 15006790A JP H0446014 A JPH0446014 A JP H0446014A
- Authority
- JP
- Japan
- Prior art keywords
- rare earth
- fluoride
- reaction
- volatile
- chamber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 44
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 150000002910 rare earth metals Chemical class 0.000 title claims description 11
- 150000008064 anhydrides Chemical class 0.000 title 1
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- -1 rare earth fluoride anhydride Chemical class 0.000 claims abstract description 29
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 19
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 17
- 239000012535 impurity Substances 0.000 claims abstract description 9
- 238000005070 sampling Methods 0.000 claims abstract description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 12
- LDDQLRUQCUTJBB-UHFFFAOYSA-O azanium;hydrofluoride Chemical compound [NH4+].F LDDQLRUQCUTJBB-UHFFFAOYSA-O 0.000 abstract description 8
- 238000003682 fluorination reaction Methods 0.000 abstract description 7
- 229910052759 nickel Inorganic materials 0.000 abstract description 6
- 229910052731 fluorine Inorganic materials 0.000 abstract description 4
- 239000011737 fluorine Substances 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- OEKDNFRQVZLFBZ-UHFFFAOYSA-K scandium fluoride Chemical compound F[Sc](F)F OEKDNFRQVZLFBZ-UHFFFAOYSA-K 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
- 229910001512 metal fluoride Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
皇１上豆且工立豆
本発明は、希土類酸化物のフッ素化の装置及びその製造
方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an apparatus for fluorinating rare earth oxides and a method for producing the same.
亘米皿韮皿
希土類金属を製造する際に、その出発原料として希土類
フッ化物がよく用いられる。その希土類フッ化物を製造
する代表的なものは、下記の通りである。When manufacturing rare earth metals, rare earth fluorides are often used as starting materials. Typical methods for producing rare earth fluorides are as follows.
ｌ） 希土類元素の塩の水溶液にフッ化水素酸を加え、
ゼラチン状の含水フッ化物を得る。乾燥後ＲＦ、・−Ｈ
，Ｏを得て脱水し、無水フッ化物を製造する方法。l) Adding hydrofluoric acid to an aqueous solution of a salt of a rare earth element,
A gelatinous hydrated fluoride is obtained. After drying RF, ・-H
, O is obtained and dehydrated to produce anhydrous fluoride.
２） 希土類酸化物に無水フッ化水素ガスによりフッ素
化し、無水フッ化物を製造する方法。2) A method of producing anhydrous fluoride by fluorinating rare earth oxides with anhydrous hydrogen fluoride gas.
３） 希土類酸化物にフッ化水素アンモニウムを添加し
て反応させ、希土類元素の無水フッ化物を製造する方法
。3) A method for producing anhydrous fluorides of rare earth elements by adding ammonium hydrogen fluoride to rare earth oxides and reacting them.
これらの方法で得られた希土類元素の無水フッ化物は不
純物として、酸化物およびフッ化酸化物を含んでいるた
め、さらに精製するためには、般的に融解塩法が用いら
れる。Since the anhydrous fluorides of rare earth elements obtained by these methods contain oxides and fluorinated oxides as impurities, the molten salt method is generally used for further purification.
が し と 点高純度な希
土類金属を得るためには、製造した希土類金属を、蒸留
精製法、ゾーン精製法等を用いることが必要とされてい
る。しかし、希土類金属製造用の出発原料である希土類
フッ化物中に、未反応の酸化物およびフッ化酸化物を含
んでいると、それを用いて希土類金属を製造した場合、
酸素が生成希土類金属中に不純物として残留する。However, in order to obtain highly pure rare earth metals, it is necessary to use a distillation refining method, a zone refining method, etc. for the manufactured rare earth metals. However, if the rare earth fluoride, which is the starting material for producing rare earth metals, contains unreacted oxides and fluorinated oxides, when rare earth metals are produced using it,
Oxygen remains as an impurity in the produced rare earth metal.
またフッ化アンモニウム等の余剰のフッ素が残留すると
、次工程の還元の時にＴａ等のルツボを腐食することが
ある。したがって、希土類酸化物をフッ素化する場合、
その反応の終点を決定し、かつ、生成した希土類元素フ
ッ化物に残留する揮発性反応生成物を除去する必要があ
る。Further, if excess fluorine such as ammonium fluoride remains, it may corrode the crucible of Ta or the like during the next step of reduction. Therefore, when fluorinating rare earth oxides,
It is necessary to determine the end point of the reaction and to remove volatile reaction products remaining in the produced rare earth element fluoride.
以上に鑑み本発明は、希土類酸化物のフッ素化の終点を
検出する方法及び希土類元素フッ化物中に残留する未反
応の反応、物質ならびに揮発性反応物を取り除く方法に
関するものである。In view of the above, the present invention relates to a method for detecting the end point of fluorination of rare earth oxides and a method for removing unreacted reactions, substances, and volatile reactants remaining in rare earth fluorides.
点を するための手 び
本発明者は、希土類元素をフッ素化する製造法において
、希土類フッ化物の生成の終点を揮発性反応生成物を測
定することにより決定する。さらにその後、生成した希
土類フッ化物中ならびに反応容器内に含まれる揮発性反
応生成物を真空排気することにより、不純物の少ない希
土類フッ化物を得ることを知見したものである。In a production method for fluorinating rare earth elements, the present inventor determines the end point of rare earth fluoride production by measuring volatile reaction products. Furthermore, it was discovered that by subsequently evacuating the volatile reaction products contained in the produced rare earth fluoride and the reaction vessel, a rare earth fluoride with less impurities could be obtained.
斯くして、本発明は、
１）希土類無水フッ化物の製造する装置において、反応
容器と該容器の中に希土類酸化物とフッ化原料とを反応
させる坩堝を配置し、反応容器上部に遮蔽板と、反応容
器に不活性ガスを導入する装置と、反応容器を真空にす
る真空装置と、真空装置の途中に排ガスサンプリング口
と排ガス中の凝縮物を除去する凝縮装置を有することを
特徴とする希土類無水フッ化物の製造装置。Thus, the present invention provides the following features: 1) In an apparatus for producing anhydrous rare earth fluoride, a reaction vessel and a crucible for reacting a rare earth oxide and a fluoride raw material are disposed in the vessel, and a shielding plate is provided above the reaction vessel. and a device for introducing an inert gas into the reaction container, a vacuum device for evacuating the reaction container, and an exhaust gas sampling port and a condensation device for removing condensate in the exhaust gas in the middle of the vacuum device. Rare earth anhydrous fluoride production equipment.
２）希土類酸化物をフッ素化する工程で、希土類フッ化
物の生成の終点を判定するために、揮発性反応生成物の
濃度を測定することにより希土類フッ化物の反応の終了
を決定することを特徴とする希土類無水フッ化物の製造
方法。2) In the process of fluorinating rare earth oxides, the end of the reaction of rare earth fluorides is determined by measuring the concentration of volatile reaction products in order to determine the end point of the production of rare earth fluorides. A method for producing rare earth anhydrous fluoride.
３）上記２）記載の工程で、希土類フッ化物を製造する
方法において、反応終了を決定した後、反応容器内なら
びに反応生成物及び希土類フッ化物に残留する揮発性反
応生成物、未反応のフッ化原料を真空排気することによ
り、不純物の少ない希土類フッ化物を得ることを特徴と
する希土類無水フッ化物の製造方法を提供するものであ
る。3) In the process described in 2) above, after determining the end of the reaction, the volatile reaction products remaining in the reaction vessel, the reaction product and the rare earth fluoride, and unreacted fluoride are removed. The present invention provides a method for producing anhydrous rare earth fluoride, which is characterized in that rare earth fluoride with few impurities is obtained by evacuating a chemical raw material.
の な
希土類酸化物の本明細書において希土類酸化物とは、Ｌ
ａ、 Ｃｅ、 Ｐｒ、 Ｎｄ５Ｙ、 Ｇｄ、 Ｔｂ％Ｌ
ｕ、 Ｓａ、 Ｄｙ。In this specification, the rare earth oxide refers to L
a, Ce, Pr, Nd5Y, Gd, Tb%L
u, Sa, Dy.
Ｈｏ、 Ｅｒの酸化物を指し、揮発性反応生成物とは、
ＮＨ，、ＨＦ、 ＮＨ４Ｆ、 ＮＨ４Ｆ−ＨＦ等を指す
ものである。Refers to the oxides of Ho and Er, and the volatile reaction products are:
It refers to NH,, HF, NH4F, NH4F-HF, etc.
フッ素化装置は、第１図に示すごとく、反応容器（１）
、電気炉（２）、凝縮器（３）、坩堝例えばカーボン坩
堝（５）、真空ポンプ（１１）、Ａｒ封入口（９）がら
士り一増吻六侶プ陵＼ヱ
揮発物質は、反応容器（１）、ニッケル製遮蔽板（８）
等に凝縮して付着して一部金属フッ化物となり、それが
坩堝（５）内に落下することにより不純物汚染源となる
。そのために坩堝（５）の上に足桁の付いた坩堝用Ｍ（
７）をして不純物が坩堝（５）の中に入らない様にする
必要があり、かつ揮発性反応生成物が抜ける構造とする
必要がある。その間孔部の大きさは揮発性反応生成物の
量及び蒸発速度により決定される。The fluorination apparatus consists of a reaction vessel (1) as shown in Figure 1.
, an electric furnace (2), a condenser (3), a crucible such as a carbon crucible (5), a vacuum pump (11), and an Ar sealing port (9). Container (1), nickel shielding plate (8)
Some of the metal fluoride condenses and adheres to the metal fluoride, and when it falls into the crucible (5), it becomes a source of impurity contamination. For this purpose, a crucible M (
7) to prevent impurities from entering the crucible (5), and a structure that allows volatile reaction products to escape. The size of the pores is determined by the amount of volatile reaction products and the rate of evaporation.
第１図に、希土類フッ化物の製造装置の例を示す。まず
反応容器（１）は、電気炉（２）内にセットされ、その
反応容器（１）内に上記の坩堝用Ｍ（７）の付いた坩堝
（５）を挿入する。坩堝（５）内には、予め、希土類酸
化物とフッ化原料例えば、フッ化アニモニウム及び又は
酸性フッ化アンモニウムとを混合する。FIG. 1 shows an example of an apparatus for producing rare earth fluorides. First, a reaction vessel (1) is set in an electric furnace (2), and a crucible (5) with the above-mentioned crucible M (7) is inserted into the reaction vessel (1). In the crucible (5), a rare earth oxide and a fluoride raw material such as ammonium fluoride and/or acidic ammonium fluoride are mixed in advance.
反応容器（１）の上端には、ニッケル製遮蔽板（８）の
付いた蓋がゴム製のＯリング等のシールを介して装着さ
れる。遮蔽板は、反応後生成したフッ化アンモニウムの
付着防止ならびに熱遮蔽のために飴ｊ＋ Ｘ ＝
／７’ｌ ｆ’；’； ｒＦ ｄｙ ３８／Ｆ’
ｌ 尊１．− １＋ Ａ −斜１ ｒＭ
／ Ｑ ’１反応容器内熱電対温度計（６）の取付口が
設けられている。この温度計は、予めセットされた坩堝
（５）の蓋の少し上にある位置にして、固定する。温度
計の上端は反応容器（１）の蓋にゴム製の○リング等の
シールを介して装着される。この反応で生成したフッ化
アンモニウム、フッ化水素アンモニウムは、１２０°Ｃ
以下、好ましくは０〜５０℃に保温された凝縮器（３）
で回収する。連結管（１３）内をその凝縮物で閉そくさ
れないために、Ａｒ等の不活性ガス又は乾燥空気をＡ、
ｒ封入口（９）から３〜１０ Ｑ ／ｍｉｎの流速で
流す。この時、反応容器内壁、反応容器の蓋、配管等に
、その凝縮物等を付着させないために１２０〜２００℃
に保温することが重要である。ここで保温とは、反応容
器（１）１．配管等を保温材で一定温度に保つことも包
括するものである。A lid with a nickel shielding plate (8) is attached to the upper end of the reaction vessel (1) via a seal such as a rubber O-ring. The shielding plate is made of candy j+
/7'l f';'; rF dy 38/F'
l Honored 1. - 1+ A - oblique 1 rM
/ Q'1 There is an installation port for the thermocouple thermometer (6) inside the reaction vessel. This thermometer is fixed at a position slightly above the preset lid of the crucible (5). The upper end of the thermometer is attached to the lid of the reaction vessel (1) via a seal such as a rubber circle. Ammonium fluoride and ammonium hydrogen fluoride produced in this reaction are heated at 120°C.
Hereinafter, a condenser (3) preferably kept at a temperature of 0 to 50°C
Collect it with. In order to prevent the inside of the connecting pipe (13) from being blocked by the condensate, an inert gas such as Ar or dry air is used.
Flow through the r sealing port (9) at a flow rate of 3 to 10 Q/min. At this time, in order to prevent the condensate from adhering to the inner wall of the reaction vessel, the lid of the reaction vessel, the piping, etc.
It is important to keep warm. Here, keeping warm means reaction vessel (1) 1. It also includes keeping piping etc. at a constant temperature with heat insulators.
流したＡｒ等の不活性ガス又は乾燥空気は出口からドラ
フトで吸引される。The flowed inert gas such as Ar or dry air is sucked in by a draft from the outlet.
第１図の装置に基づいて希土類フッ化物製造の操業例を
説明する。An example of operation for producing rare earth fluorides will be explained based on the apparatus shown in FIG.
先ず最初に、坩堝（５）の中に、希土類酸化物とフッ化
原料例えば、フッ化水素アンモニウムを十分に混合した
ものを所定量充填し、反応容器（１）の中に入れ、蓋例
えばカーボン製の蓋をする。そして、反応容器（１）に
ニッケル製遮蔽板（８）のついた蓋ならびにＡｒ封入口
（９）、反応容器内熱電対温度計（６）を取付けて密閉
状態とする。その後、反応容器（１）内を真空装置例え
ば、真空ポンプで十分排気する。真空排気は、坩堝（５
）内の充填物が、飛散しないように、除々に排気するこ
とが望ましい。First, a crucible (5) is filled with a predetermined amount of a sufficiently mixed mixture of a rare earth oxide and a fluoride raw material, such as ammonium hydrogen fluoride, and placed in a reaction vessel (1), with a lid such as carbon. Cover with a plastic lid. Then, a lid with a nickel shielding plate (8), an Ar sealing port (9), and a thermocouple thermometer inside the reaction container (6) are attached to the reaction container (1) to seal it. Thereafter, the inside of the reaction vessel (1) is sufficiently evacuated using a vacuum device, for example, a vacuum pump. Vacuum evacuation is performed using a crucible (5
) It is desirable to gradually exhaust the air to prevent the filling inside the container from scattering.
真空排気後、ＡｒガスをＡｒ封入口（９）より導入し、
３〜１Ｏｆｌ／ｍｉｎの流速で流す。After evacuation, Ar gas is introduced from the Ar sealing port (9),
Flow at a flow rate of 3-1 Ofl/min.
上記の準備が完了後、昇温を開始し、１５０℃×８〜１
０ｈｒ、 さらに３５０℃ｘｉｏ〜１５ｈｒ加熱して
希土類酸化物のフッ素化及び余剰不フッ素化の除去を行
う。この間、反応容器（１）、連続管（１３）は、保温
材またはリボンヒーターを巻いておきその反応容器（１
）ならびに連続管（１３）の表面温度が１３０〜２００
℃位にある様にして、凝縮物が付着しないようにしてＡ
ｒガス等のキャリアガスを介して凝縮器（３）で回収す
る。After completing the above preparations, start raising the temperature to 150℃ x 8-1
0 hr, and further heated at 350°C for 15 hr to fluorinate the rare earth oxide and remove excess non-fluorination. During this time, the reaction vessel (1) and the continuous tube (13) are wrapped with heat insulating material or a ribbon heater.
) and the surface temperature of the continuous pipe (13) is 130 to 200
℃ to prevent condensate from adhering to A.
It is recovered in a condenser (3) via a carrier gas such as r gas.
この反応の終点は、サンプリング口（１２）より吸引し
て揮発性反応生成物のうちＮＨ，の濃度を間断的あるい
は連続的に測定して０．１％以下になった濃度とする。The end point of this reaction is defined as the concentration of NH, among the volatile reaction products, which is measured intermittently or continuously by suctioning through the sampling port (12) and becomes 0.1% or less.
その後、Ａｒガスを止めて真空ポンプ（１１）で排気を
２〜５時間行い、反応生成物である希土類フッ化物中に
含まれる揮発性反応生成物ならびに未反応のフッ化水素
アンモニウムを追い出しドラフトで吸引する。この際に
、真空ポンプと凝縮器（３）の間にトラップ（１４）を
置き、真空ポンプ（１１）を保護しておく必要がある。After that, the Ar gas is stopped and exhaust is performed using a vacuum pump (11) for 2 to 5 hours to drive out the volatile reaction products contained in the rare earth fluoride as well as unreacted ammonium hydrogen fluoride, using a draft. Suction. At this time, it is necessary to place a trap (14) between the vacuum pump and the condenser (3) to protect the vacuum pump (11).
この電気炉（７）は、電気炉制御用熱電対温度計（４）
で、反応容器（１）内の温度を制御した。This electric furnace (7) is equipped with a thermocouple thermometer (4) for electric furnace control.
The temperature inside the reaction vessel (1) was controlled.
スＵＬＩＩ
第１図の装置を用いて、酸化スカンジウムをフッ素化し
てフッ化スカンジウムを製造する場合の実施例を示す。An example will be shown in which scandium fluoride is produced by fluorinating scandium oxide using the apparatus shown in FIG.
カーボン坩堝（５）の中に酸化スカンジウムと理論量よ
り１０％過剰の酸性フッ化水素アンモニウムを添加し、
フッ素樹脂系の撹伴棒を用いて手早く混合する。その後
このカーボン坩堝（５）をステンレス類の反応容器（１
）の中に装入して足桁のついたカーボン坩堝用蓋（７）
を、その上に載せた。そして反応容器の上部に、反応後
生成したフッ化アンモニウムの付着防止ならびに熱遮蔽
を行うために設けたニッケル製遮蔽板（８）の付いた蓋
をした。Adding scandium oxide and acidic ammonium hydrogen fluoride in excess of the theoretical amount by 10% into a carbon crucible (5),
Mix quickly using a fluororesin stirring rod. Thereafter, this carbon crucible (5) was placed in a stainless steel reaction vessel (1).
) Carbon crucible lid with foot beams (7)
was placed on top of it. Then, a lid with a nickel shielding plate (8) provided for preventing the adhesion of ammonium fluoride produced after the reaction and for heat shielding was placed on the top of the reaction vessel.
前操作として真空ポンプで反応容器（１）ならびに凝縮
器（３）（コンテツサー）内を排気したのち停止し、反
応容器（１）にＡｒを充填する。As a pre-operation, the reaction vessel (1) and the condenser (3) are evacuated using a vacuum pump, and then stopped, and the reaction vessel (1) is filled with Ar.
その後加熱を開始し、１３０〜１８０℃で１０〜１５時
間、約３５０℃で１０〜１５時間反応させる。 この反
応中、生成する揮発性反応生成物を追い出すためにＡｒ
を５Ｑ／ｍｉｎを流入させて、その揮発性反応生成物を
排出させドラフトで吸引させた。Thereafter, heating is started and the reaction is carried out at 130-180°C for 10-15 hours and at about 350°C for 10-15 hours. During this reaction, Ar is used to drive out the volatile reaction products generated.
was injected at a rate of 5 Q/min, and the volatile reaction products were discharged and suctioned by a draft.
酸化スカンジウムと酸性フッ化水素アンモニウムの反応
の終点を判断するために約３５０℃で温度保持開始後、
サンプリング口（１２）より揮発物（ＮＨ，）を検知管
で適宜測定するかもしくは赤外線ＮＨ，濃度計により連
続測定し、ＮＨ，濃度が〈０．１％になったところを反
応の終点とした。その後、Ａｒガスを停止し、真空ポン
プ（１１）で２〜４時間排気させて生成したフッ化スカ
ンジウムの表面及び内部にある揮発物を吸引除去した。After starting to maintain the temperature at about 350°C to determine the end point of the reaction between scandium oxide and acidic ammonium hydrogen fluoride,
Volatile matter (NH,) was appropriately measured from the sampling port (12) with a detection tube or continuously measured with an infrared NH, concentration meter, and the end point of the reaction was defined as the point where the NH concentration reached <0.1%. . Thereafter, the Ar gas was stopped, and the vacuum pump (11) was used to evacuate for 2 to 4 hours, and the volatile substances present on the surface and inside of the generated scandium fluoride were removed by suction.
そして真空ポンプ（１１）を停止後、Ａｒを再び５Ｑ
／ｍｉｎを流入させて冷却後取り出した。取り出したフ
ッ化スカンジウムは、ポーラスなものであり、そこに含
まれる全ＮＨ，量はｌｏｏｐｐｍ以下であった。 また
フッ化スカンジウムとしてのフッ素以外のフッ素も１１
００ｐｐ以下であった。Then, after stopping the vacuum pump (11), the Ar was turned on again at 5Q.
/min, and after cooling, it was taken out. The scandium fluoride taken out was porous, and the total amount of NH contained therein was less than looppm. Fluorine other than fluorine as scandium fluoride is also 11
00pp or less.
且豆五羞呈
（１）本発明によって希土類酸化物のフッ化反応の終点
が明らかになり、生成した希土類フッ化物中の酸素濃度
を小さくできる。またフッ化反応の終点が判明すること
により、不純物としての酸化物、フッ化酸化物が少なく
なり、さらに精製する必要がなくなる利点がある。(1) According to the present invention, the end point of the fluorination reaction of rare earth oxides is clarified, and the oxygen concentration in the produced rare earth fluoride can be reduced. Furthermore, by determining the end point of the fluorination reaction, there is an advantage that the amount of oxides and fluorinated oxides as impurities is reduced, and there is no need for further purification.
（２）本発明によって生成した希土類フッ化物の表面及
び中に含まれる揮発性反応生成物ならびに未反応のフッ
化水素アンモニウムが除去ができ、次工程で用いられる
容器の損傷を小さくできる利点がある。(2) Volatile reaction products and unreacted ammonium hydrogen fluoride contained on and in the rare earth fluoride produced by the present invention can be removed, which has the advantage of minimizing damage to the container used in the next step. .
第１図は、本発明の一態様である希土類フッ化物の製造
装置の一例の正面図である。
１：反応容器
２：電気炉
３：凝縮器
４：電気炉制御用熱電対温度計
５＝坩堝
６：反応容器内熱電対温度計
７コ坩堝用蓋
８：ニッケル製遮蔽板
９：Ａｒ封入口
ｌＯ：充填物
１１：真空ポンプ
１２：サンプリング口
１３：連続管
１４ニドラツプFIG. 1 is a front view of an example of an apparatus for producing rare earth fluoride, which is one embodiment of the present invention. 1: Reaction vessel 2: Electric furnace 3: Condenser 4: Electric furnace control thermocouple thermometer 5 = Crucible 6: Thermocouple thermometer inside reaction vessel 7 Crucible lid 8: Nickel shielding plate 9: Ar sealing port lO: Filling 11: Vacuum pump 12: Sampling port 13: Continuous tube 14 Nidrap
Claims (1)
容器と該容器の中に希土類酸化物とフッ化原料とを反応
させる坩堝を配置し、反応容器上部に遮蔽板と、反応容
器に不活性ガスを導入する装置と、反応容器を真空にす
る真空装置と、真空装置の途中に排ガスサンプリング口
と排ガス中の揮発物を除去する凝縮装置を有することを
特徴とする希土類無水フッ化物の製造装置。 ２）希土類酸化物をフッ素化する工程で、希土類フッ化
物の生成の終点を判定するために、揮発性反応生成物の
濃度を測定することにより希土類フッ化物の反応の終了
を決定することを特徴とする希土類無水フッ化物の製造
方法。 ３）特許請求の範囲第２項記載の工程で、希土類フッ化
物を製造する方法において、反応終了を決定した後、反
応容器内ならびに反応生成物及び希土類フッ化物に残留
する揮発性反応生成物、未反応のフッ化原料を真空排気
することにより、不純物の少ない希土類フッ化物を得る
ことを特徴とする希土類無水フッ化物の製造方法。[Scope of Claims] 1) An apparatus for producing rare earth anhydrous fluoride, which includes a reaction vessel, a crucible for reacting a rare earth oxide and a fluoride raw material disposed in the vessel, a shielding plate above the reaction vessel, A rare earth anhydride characterized by having a device for introducing an inert gas into a reaction container, a vacuum device for evacuating the reaction container, and an exhaust gas sampling port and a condensation device for removing volatile matter in the exhaust gas in the middle of the vacuum device. Fluoride production equipment. 2) In the process of fluorinating rare earth oxides, the end of the reaction of rare earth fluorides is determined by measuring the concentration of volatile reaction products in order to determine the end point of the production of rare earth fluorides. A method for producing rare earth anhydrous fluoride. 3) In the method for producing rare earth fluoride in the process described in claim 2, after determining the end of the reaction, volatile reaction products remaining in the reaction vessel and in the reaction product and rare earth fluoride; A method for producing an anhydrous rare earth fluoride, characterized in that a rare earth fluoride with few impurities is obtained by evacuating unreacted fluoride raw materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2150067A JPH0446014A (en) | 1990-06-11 | 1990-06-11 | Manufacture device for rare earth fluolide anhydride and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2150067A JPH0446014A (en) | 1990-06-11 | 1990-06-11 | Manufacture device for rare earth fluolide anhydride and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0446014A true JPH0446014A (en) | 1992-02-17 |
Family
ID=15488796
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2150067A Pending JPH0446014A (en) | 1990-06-11 | 1990-06-11 | Manufacture device for rare earth fluolide anhydride and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0446014A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012067061A1 (en) * | 2010-11-19 | 2012-05-24 | Jx日鉱日石金属株式会社 | Production method for high-purity lanthanum, high-purity lanthanum, sputtering target composed of high-purity lanthanum, and metal gate film containing high-purity lanthanum as main component |
| CN103922381A (en) * | 2013-10-09 | 2014-07-16 | 赣州虔东稀土集团股份有限公司 | Rare earth fluoride and its production method |
-
1990
- 1990-06-11 JP JP2150067A patent/JPH0446014A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012067061A1 (en) * | 2010-11-19 | 2012-05-24 | Jx日鉱日石金属株式会社 | Production method for high-purity lanthanum, high-purity lanthanum, sputtering target composed of high-purity lanthanum, and metal gate film containing high-purity lanthanum as main component |
| CN103221560A (en) * | 2010-11-19 | 2013-07-24 | 吉坤日矿日石金属株式会社 | Production method for high-purity lanthanum, high-purity lanthanum, sputtering target composed of high-purity lanthanum, and metal gate film containing high-purity lanthanum as main component |
| JP5497913B2 (en) * | 2010-11-19 | 2014-05-21 | Ｊｘ日鉱日石金属株式会社 | Method for producing high purity lanthanum |
| US9234257B2 (en) | 2010-11-19 | 2016-01-12 | Jx Nippon Mining & Metals Corporation | Production method for high-purity lanthanum, high-purity lanthanum, sputtering target composed of high-purity lanthanum, and metal gate film containing high-purity lanthanum as main component |
| CN103922381A (en) * | 2013-10-09 | 2014-07-16 | 赣州虔东稀土集团股份有限公司 | Rare earth fluoride and its production method |
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