JPS623084B2 - - Google Patents
Info
- Publication number
- JPS623084B2 JPS623084B2 JP3270380A JP3270380A JPS623084B2 JP S623084 B2 JPS623084 B2 JP S623084B2 JP 3270380 A JP3270380 A JP 3270380A JP 3270380 A JP3270380 A JP 3270380A JP S623084 B2 JPS623084 B2 JP S623084B2
- Authority
- JP
- Japan
- Prior art keywords
- selenium
- condenser
- distiller
- liquid
- storage tank
- 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.)
- Expired
Links
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 110
- 229910052711 selenium Inorganic materials 0.000 claims description 109
- 239000011669 selenium Substances 0.000 claims description 109
- 239000007788 liquid Substances 0.000 claims description 38
- 238000002844 melting Methods 0.000 claims description 35
- 230000008018 melting Effects 0.000 claims description 35
- 238000003860 storage Methods 0.000 claims description 22
- 238000005469 granulation Methods 0.000 claims description 21
- 230000003179 granulation Effects 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 9
- 238000004821 distillation Methods 0.000 claims description 8
- 238000000746 purification Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 5
- 238000007790 scraping Methods 0.000 claims description 3
- 238000004891 communication Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 description 11
- 239000012535 impurity Substances 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 238000009833 condensation Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 238000005292 vacuum distillation Methods 0.000 description 4
- 229910052797 bismuth Inorganic materials 0.000 description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 108091008695 photoreceptors Proteins 0.000 description 3
- 229910052714 tellurium Inorganic materials 0.000 description 3
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000011133 lead Substances 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 230000002411 adverse Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229940082569 selenite Drugs 0.000 description 1
- MCAHWIHFGHIESP-UHFFFAOYSA-L selenite(2-) Chemical compound [O-][Se]([O-])=O MCAHWIHFGHIESP-UHFFFAOYSA-L 0.000 description 1
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 description 1
- ZIJTYIRGFVHPHZ-UHFFFAOYSA-N selenium oxide(seo) Chemical class [Se]=O ZIJTYIRGFVHPHZ-UHFFFAOYSA-N 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Landscapes
- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
Description
【発明の詳細な説明】
本発明は、セレンの連続精製方法および装置に
関するものであり、特には粗セレン原料を真空蒸
留装置に連続的に供給しそして得られた蒸留セレ
ンを連続的に粒状化室内に滴下することにより高
純度粒状セレンを生成することから成るセレン連
続精製方法およびその実施に好適な装置に関する
ものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method and apparatus for continuous purification of selenium, and in particular to a method for continuously supplying crude selenium raw material to a vacuum distillation apparatus and continuously granulating the obtained distilled selenium. The present invention relates to a continuous selenium purification method comprising producing high-purity granular selenium by dropping it into a room, and an apparatus suitable for carrying out the method.
セレンは、ガラスや窯業分野での添加剤として
あるいは合金添加剤として、更には顔料の製造原
料および増感剤として古くから使用される他、セ
レン整流器および電子写真用感光体の光導電性素
子として広く使用されている。特に、電子写真技
術の普及と進歩に伴い、この分野での需要が増大
している。セレンを電子写真用感光体の分野に利
用する場合、特に酸素等の不純物が混入しない高
純度のセレンであることと、及び粒状物であるこ
とが必要である。粒状物である必要性は、粉末状
形態では蒸着作業時にセレン粉末が飛散しやすい
ためである。 Selenium has long been used as an additive or alloy additive in the glass and ceramic industries, as a raw material for pigment production and as a sensitizer, and as a selenium rectifier and photoconductive element for electrophotographic photoreceptors. Widely used. In particular, with the spread and progress of electrophotographic technology, demand in this field is increasing. When selenium is used in the field of electrophotographic photoreceptors, it is particularly important that the selenium be of high purity and not contaminated with impurities such as oxygen, and that it be in the form of granules. The reason why it is necessary to be a granular material is that in powder form, selenium powder tends to scatter during vapor deposition.
一般に、粒状の高純度セレンは、銅の電解精製
により得られたアノードスライムを焙焼して酸化
セレンとし、次いでこれを水に溶解して亜セレン
酸溶液とした後SO2ガスを吹込むことにより還元
し、得られたコークス状粗セレンを減圧または常
圧下で加熱して蒸発せしめ、生成蒸気を融点付近
まで冷却して液状セレンとなし、そして液状セレ
ンを純水中に滴下することにより製造されてい
る。これにより直径２〜３mmの粒状セレンが得ら
れている。しかしながら、この方法では、生成す
る粒状セレンが酸素、鉛等の不純物、水分を多量
に含みまた空気中の酸素の反応で各種セレン酸化
物（SeO2、SeO等）が混入する。これら不純物
は、一旦混入すると、通常の方法では分離し難
い。このような不純物の混入したままの状態の粒
状セレンから蒸着操作によつてセレン膜を作製す
ると、トラツプが出来る等の理由で光電記録特性
が著しく悪影響を受けることが認識されている。
このため、特定の不純物を逆に添加する方法（特
公昭42−19740号）が提唱されはしたが品質の管
理が難しく満足すべきものでない。別の方法とし
て、真空蒸留によつて得た液状セレンを減圧され
た密閉容器内に置いた容器内に注出して凝固させ
る方法が提案されている（特公昭54−16927号）。
しかし、この方法では生成される板状セレンを粉
砕することが必要とされ、また実験室的規模なら
ともかくも、工業的生産には適合しない。従つ
て、粒状の高純度セレンを酸素、鉛等の不純物や
水の影響を受けることなく工業的に製造しうる方
法の開発が待望されている。 Generally, granular high-purity selenium is produced by roasting anode slime obtained by electrolytic refining of copper to produce selenium oxide, then dissolving it in water to make a selenite solution, and then blowing SO 2 gas into it. The coke-like crude selenium obtained is evaporated by heating under reduced pressure or normal pressure, the generated vapor is cooled to around the melting point to form liquid selenium, and the liquid selenium is dropped into pure water. has been done. As a result, granular selenium with a diameter of 2 to 3 mm was obtained. However, in this method, the granular selenium produced contains a large amount of impurities such as oxygen and lead, and water, and various selenium oxides (SeO 2 , SeO, etc.) are mixed in due to reactions with oxygen in the air. Once these impurities are mixed in, they are difficult to separate by normal methods. It has been recognized that if a selenium film is produced by vapor deposition from granular selenium still contaminated with such impurities, the photoelectric recording properties will be significantly adversely affected due to the formation of traps and the like.
For this reason, a method (Japanese Patent Publication No. 42-19740) has been proposed in which specific impurities are added, but quality control is difficult and the method is not satisfactory. As another method, a method has been proposed in which liquid selenium obtained by vacuum distillation is poured into a container placed in a vacuum sealed container and solidified (Japanese Patent Publication No. 16927/1983).
However, this method requires pulverizing the plate-shaped selenium produced, and is not suitable for industrial production, although it may be used on a laboratory scale. Therefore, there is a long-awaited development of a method that can industrially produce granular high-purity selenium without being affected by impurities such as oxygen and lead, or water.
もう一つの従来の真空蒸留装置の問題点は、そ
れがセレンの品質面等の理由からバツチ方式が前
提となつていることであつた。このため、一定量
の粗セレンを蒸留操作毎に蒸留室内に装入し、そ
の都度蒸留室内の圧力管理を行わねばならないの
で、生産効率は悪くまた操作も煩雑であつた。こ
の点から、粗セレンから高純度粒状セレンへと一
貫して連続的に操業しうるセレン精製方法が要望
されている。 Another problem with conventional vacuum distillation equipment is that it is premised on a batch system for reasons such as the quality of selenium. Therefore, a certain amount of crude selenium must be charged into the distillation chamber for each distillation operation, and the pressure inside the distillation chamber must be controlled each time, resulting in poor production efficiency and complicated operations. From this point of view, there is a need for a selenium purification method that can be operated consistently and continuously from crude selenium to high-purity granular selenium.
以上のような斯界の現状に鑑み、本発明の目的
は、上記従来方法の欠点を解消し、特に電子写真
感光体用途に適した高純度粒状セレンを真空蒸留
方式により連続的に精製する方法および装置を提
供することである。 In view of the current state of the art as described above, an object of the present invention is to provide a method for continuously refining high-purity granular selenium by a vacuum distillation method, which eliminates the drawbacks of the above-mentioned conventional methods and is particularly suitable for use in electrophotographic photoreceptors. The purpose is to provide equipment.
本発明は、粗セレン溶融ステージと、蒸留−凝
縮ステージと、粒状化ステージとを蒸留−凝縮ス
テージが他の２つのステージより上方にあるよう
に設け、蒸留−凝縮ステージと溶融ステージとの
間および蒸留−凝縮ステージと粒状化ステージと
の間をそれぞれ上昇管および下降管によつて連通
することにより蒸留−凝縮ステージ減圧雰囲気を
他の２つのステージから該上昇管および下降管内
を流れる液状セレンによつて隔絶し、溶融ステー
ジおよび粒状化ステージには不活性ガスを封入す
ることを特徴とする。粒状化ステージにおいて
は、冷却回転ドラム上に液状セレンを滴下してそ
こに凝固せしめそして凝固したセレンをスクレー
パによつてかき取ることにより好適な粒状化が計
られる。 The present invention provides a crude selenium melting stage, a distillation-condensation stage, and a granulation stage such that the distillation-condensation stage is above the other two stages, and between the distillation-condensation stage and the melting stage. The distillation-condensation stage and the granulation stage are communicated by a riser and a downcomer, respectively, so that the vacuum atmosphere of the distillation-condensation stage is transferred from the other two stages by liquid selenium flowing in the riser and downcomer. The melting stage and the granulation stage are sealed with an inert gas. In the granulation stage, suitable granulation is achieved by dropping liquid selenium onto a cooled rotating drum, allowing it to solidify thereon, and scraping off the solidified selenium with a scraper.
斯くして、本発明は、粗セレン原料を不活性ガ
スを封入した溶解炉に連続的に供給し、溶融した
セレンを一定量づつ減圧された蒸留器内に上昇管
を経て吸引し、該蒸留器内で溶融セレンを蒸発せ
しめ、セレン蒸気を凝縮器において凝縮せしめ、
凝縮した液状セレンを下降管を経て不活性ガスを
封入した粒状化室に導き、該粒状化室内において
液状セレンを滴下しそして凝固せしめることから
成るセレンの連続真空精製方法を提供する。 Thus, in the present invention, crude selenium raw material is continuously supplied to a melting furnace filled with inert gas, and a fixed amount of molten selenium is sucked into a depressurized distillation vessel through a riser tube, and the distillation process is carried out by evaporate molten selenium in a vessel, condense selenium vapor in a condenser,
To provide a continuous vacuum purification method for selenium, which comprises guiding condensed liquid selenium through a downcomer to a granulation chamber filled with an inert gas, dropping liquid selenium in the granulation chamber, and solidifying the liquid selenium.
また上記の発明の具体的な態様の一つは、溶融
セレンを撹拌しながら蒸発せしめることである。 Further, one of the specific embodiments of the above invention is to evaporate molten selenium while stirring.
更に、本発明は、粗セレンを溶解するための溶
解炉であつて、粗セレンを連続的に供給するため
の供給機を備える溶解炉と該溶解炉の上方に設置
される蒸留器と、前記溶解炉と蒸留器とを繋ぎそ
して蒸留器内に一定の溶融セレン液面を維持する
に充分の寸法を有する上昇管と、前記蒸留器に隣
りあいそこに連通して設けられる凝縮器と、該蒸
留器および凝縮器を排気する排気系統と、前記凝
縮器において生成する液状セレンを受取るべく該
凝縮器の下方に配置される貯留槽と、該凝縮器の
底部と該貯留槽とを繋ぎ、該凝縮器から貯留槽へ
と液状セレンを連続的に流下させる下降管と、前
記貯留槽と連通する粒状化室であつて、該貯留槽
から滴下する液状セレンを冷却凝固させる回転冷
却ドラムおよび該ドラム上から凝固セレンをかき
落すためのスクレーパを収納しそしてかき落され
た粒状セレンを取出す為の出口を底部に備える粒
状化室とを包含するセレンの連続真空精製装置を
提供する。 Furthermore, the present invention provides a melting furnace for melting crude selenium, which comprises a feeder for continuously supplying crude selenium, a distiller installed above the melting furnace, and a distiller installed above the melting furnace. a riser pipe connecting the melting furnace and the distiller and having sufficient dimensions to maintain a constant molten selenium liquid level in the distiller; and a condenser provided adjacent to and in communication with the distiller; an exhaust system for evacuating the distiller and the condenser; a storage tank disposed below the condenser to receive liquid selenium produced in the condenser; connecting the bottom of the condenser to the storage tank; A downcomer pipe that allows liquid selenium to continuously flow down from a condenser to a storage tank, a granulation chamber that communicates with the storage tank, and a rotating cooling drum that cools and solidifies the liquid selenium dripping from the storage tank, and the drum. To provide a continuous vacuum purification device for selenium, which includes a granulation chamber housing a scraper for scraping off solidified selenium from above and having an outlet at the bottom for taking out the scraped off granular selenium.
また上記の発明の具体的な態様の一つとして、
蒸留器に撹拌装置が設置される。 In addition, as one of the specific embodiments of the above invention,
A stirring device is installed in the distiller.
図面を参照して本発明の具体例について説明す
る。第１図において参照番号１は溶解炉を表す。
溶解炉は粗セレンを溶解するため300℃水準に昇
温しうる電熱その他の加熱器を備えている。溶解
炉１は密閉式とし、その上端にはホツパ３内に供
給された粗セレン原料を一定量づつ溶解炉に連続
的に供給するためのスクリユーフイーダ等の供給
機が接続されている。溶解中、湯面上部の空間に
窒素あるいは、アルゴン等の不活性ガスを封入す
るための導管７が炉内上部に通じることによつて
酸素の混入を極力防止することができる。溶解炉
１の底には蓄積した不純物を適宜の弁を介して定
期的に抜出す為の抜出口９が装備されている。溶
解炉において溶融したセレンは通常、鉛、酸素、
鉄、テルル、銅、ビスマス等の不純物を含んでい
る。 Specific examples of the present invention will be described with reference to the drawings. In FIG. 1, reference number 1 represents a melting furnace.
The melting furnace is equipped with electric and other heaters that can raise the temperature to 300℃ to melt crude selenium. The melting furnace 1 is of a closed type, and a feeder such as a screw feeder is connected to the upper end of the melting furnace 1 to continuously feed a fixed amount of the crude selenium raw material supplied into the hopper 3 to the melting furnace. During melting, a conduit 7 for sealing nitrogen or an inert gas such as argon into the space above the melt surface is connected to the upper part of the furnace, thereby making it possible to prevent oxygen from entering as much as possible. The bottom of the melting furnace 1 is equipped with an extraction port 9 for periodically extracting accumulated impurities through a suitable valve. Melted selenium in a melting furnace usually contains lead, oxygen,
Contains impurities such as iron, tellurium, copper, and bismuth.
溶解炉１において溶融した液状セレンは上昇管
１０を経て蒸留器１２に導入される。上昇管１０
の周囲には電熱その他の加熱コイルが配設されて
いる。蒸留器内部は１トール以下の負圧下にあ
る。上昇管１０の長さ、即ち蒸留器底と溶解炉出
口との間の高さは、溶解炉から連続的に液状セレ
ンが負圧下の蒸留器内に吸上げられそして蒸留器
内に適度な液面を維持しうるように選定される。
従つて、溶解炉内の雰囲気圧力、蒸留器内の圧力
および両者を繋ぐ液状セレン柱の静圧ヘツドが蒸
留器内での液状セレンの水準を決定する。蒸留器
外部には液状セレンを蒸発せしめるべく加熱装置
が具備されている。蒸留器内部は減圧状態にもよ
るが350℃前後に維持され、従つて上昇管を通し
て350℃前後に維持されて蒸留器内に昇流する液
状セレンは瞬時的にそして連続的に蒸発せしめら
れる。また、蒸留器内に設けた撹拌機によつて撹
拌しつゝ加熱することにより、原料セレン液の対
流運動が促進され器内原料温度がより均一化する
ことによつて局部温度上昇による突払現象を防止
し、セレンよりも沸点の高い不純分の飛散による
不純物混入がさけられ、高純度のセレンが得られ
ることとなる。 Liquid selenium melted in the melting furnace 1 is introduced into the distiller 12 via the riser 10. rising pipe 10
Electric or other heating coils are arranged around the . The inside of the distiller is under negative pressure of less than 1 Torr. The length of the riser pipe 10, that is, the height between the bottom of the still and the outlet of the melting furnace, is such that liquid selenium is continuously drawn up from the melting furnace into the still under negative pressure, and a suitable amount of liquid is stored in the still. It is selected so that the surface can be maintained.
Therefore, the atmospheric pressure in the melting furnace, the pressure in the distiller, and the static pressure head of the liquid selenium column connecting the two determine the level of liquid selenium in the distiller. A heating device is provided outside the distiller to evaporate the liquid selenium. The inside of the distiller is maintained at around 350°C depending on the reduced pressure state, and therefore the liquid selenium flowing up into the distiller is maintained at around 350°C through the riser pipe and evaporated instantaneously and continuously. In addition, by stirring and heating with a stirrer installed in the distiller, convection movement of the raw selenium solution is promoted, and the temperature of the raw material in the distiller becomes more uniform, thereby eliminating the sudden rise in local temperature. This phenomenon is prevented, impurity contamination due to the scattering of impurities having a boiling point higher than that of selenium is avoided, and highly pure selenium can be obtained.
セレン蒸気は、隣接する凝縮器１４に、衝突
板、金網あるいは多孔板のようなミスト除去装置
１３を通して流入する。凝縮器１４内にはその上
部に複数の内部水冷されるバツフルプレート１６
が設けられており、セレン蒸気はこれらとの接触
に際して沸点以下に冷却されて、液体となり凝縮
器の底に流下しそしてそこに溜まる。凝縮器の頂
端近くには適当な真空ポンプに接続される排気口
１５が取付けられ、蒸留器および凝縮器内部を所
定の負圧にまで排気している。 Selenium vapor enters the adjacent condenser 14 through a mist removal device 13 such as an impingement plate, wire mesh or perforated plate. Inside the condenser 14, there are a plurality of internally water-cooled buttful plates 16 on the top thereof.
are provided, and upon contact with these, the selenium vapor is cooled below its boiling point and becomes a liquid which flows to the bottom of the condenser and collects there. An exhaust port 15 connected to a suitable vacuum pump is installed near the top of the condenser to evacuate the interior of the distiller and condenser to a predetermined negative pressure.
凝縮器の底部に溜まつた液状セレンは下降管２
０を経て貯留槽２１内に連続的に抜出される。下
降管２０の寸法は後述する貯留槽２０の上方の雰
囲気圧力と凝縮器１４内部の負圧との圧力差の下
で液状セレンの連続抜出しを可能とするよう選定
されねばならない。貯留槽２１の出口はそこに溜
まつた液状セレンが出口から溢流して滴下してい
くように滴下口２４を形成する。下降管および貯
留槽とも液状セレンを300℃の水準に維持しうる
よう適当な加温設備を備えている。 Liquid selenium accumulated at the bottom of the condenser is transferred to downcomer pipe 2.
0 and is continuously extracted into the storage tank 21. The dimensions of the downcomer pipe 20 must be selected to allow continuous withdrawal of liquid selenium under the pressure difference between the atmospheric pressure above the reservoir 20 and the negative pressure inside the condenser 14, which will be described below. The outlet of the storage tank 21 is formed with a dripping port 24 so that the liquid selenium accumulated there overflows from the outlet and drips. Both the downcomer and the storage tank are equipped with appropriate heating equipment to maintain liquid selenium at a level of 300°C.
貯留槽２１の滴下口２４は貯留槽の巾全面に多
数の細孔（ノズル）を有し、粒状化室２６上方に
開いている。粒状化室２６はケーシング３２によ
つて画成されそしてケーシング３２は貯留槽２１
の壁に密封着されている。滴下口２４から滴下す
る液状セレン滴２５は本具体例においては冷却さ
れた回転ドラム２７上に滴下して冷却凝固せしめ
られそしてスクレーパ２８によつてドラム周囲か
ら掻落される。スクレーパによつて掻落された粒
状の高純度セレンはケーシング３２の逆円錐状底
部に粒状化室底部４０によつて示されるように収
集されそして取出口３０を通して適宜回収され
る。また粒状化室内および貯留槽の湯面上部空間
にアルゴン、窒素等の不活性ガスを封入するため
不活性ガス導入口がケーシング３２あるいは貯留
槽２１のいずれかあるいは両方に設けられると、
さらに酸素含有量の少ない高純度セレンが得られ
る。図面においては２つの導入管路２３および２
９を示してある。貯留槽の上部空間に不活性ガス
を導入する場合、液状セレンの冷却を避けるため
導入前に加温器２２を通すことが好ましい。 The dripping port 24 of the storage tank 21 has a large number of pores (nozzles) over the entire width of the storage tank, and is open above the granulation chamber 26 . The granulation chamber 26 is defined by a casing 32 and the casing 32 is connected to the reservoir 21
is sealed to the wall. In this embodiment, the liquid selenium droplets 25 dripping from the dripping port 24 are dropped onto the cooled rotating drum 27, cooled and solidified, and then scraped off from around the drum by the scraper 28. The granular high-purity selenium scraped off by the scraper is collected at the inverted conical bottom of the casing 32, as shown by the granulation chamber bottom 40, and is appropriately recovered through the outlet 30. Furthermore, if an inert gas inlet is provided in either or both of the casing 32 and the storage tank 21 in order to fill the granulation chamber and the space above the hot water surface of the storage tank with an inert gas such as argon or nitrogen,
Furthermore, high purity selenium with low oxygen content can be obtained. In the drawing two inlet lines 23 and 2
9 is shown. When introducing an inert gas into the upper space of the storage tank, it is preferable to pass the inert gas through a warmer 22 before introduction in order to avoid cooling the liquid selenium.
上述した冷却回転ドラムの使用以外にも、滴下
中のセレンを凝固するよう粒状化室の下半部を冷
却したり、粒状化室内に滴下行路に沿つて冷却ト
ンネルを設置することによつて粒状化は実現され
うる。更には、室内に導入する不活性ガスをあら
かじめ冷却し、落下中のセレン滴に向けて吹きつ
けるようにしてもよい。その他、従来から使用さ
れている幾つかの粉末製造方式を利用することが
できる。例えば、第２図に示すように、貯留槽２
１の底に注出口４１を形成しそこから液状セレン
を注出しそしてその周囲から口４２を通して不活
性ガスを噴射して液状セレンの流れを分断するこ
とによつても粒状のセレンが得られる。 In addition to the use of the cooling rotating drum described above, it is possible to cool the lower half of the granulation chamber to solidify the selenium being dropped, or to install a cooling tunnel along the dripping path in the granulation chamber to cool the granules. can be realized. Furthermore, the inert gas introduced into the room may be cooled in advance and blown toward the falling selenium droplets. In addition, several conventionally used powder manufacturing methods can be used. For example, as shown in FIG.
Granular selenium can also be obtained by forming a spout 41 at the bottom of the spout 1, pouring out liquid selenium therefrom, and injecting inert gas from around the spout 41 through the spout 42 to interrupt the flow of the liquid selenium.
また、セレンは、無定形セレン、単斜セレン等
の同素体を有し、特定の用途によつては特定の形
態のセレンを要求されることがある。セレンの結
晶形態を左右する主なる因子の一つは冷却速度で
あり、そのため貯留槽の加熱温度、冷却回転ドラ
ムの冷却温度、滴下口からドラムまでの落下距離
の制御により冷却速度を変えることができる。こ
の理由のため、回転ドラムを垂直方向に可動の構
成としておくのが好都合である。 Furthermore, selenium has allotropes such as amorphous selenium and monoclinic selenium, and a specific form of selenium may be required depending on the specific application. One of the main factors that influences the crystal form of selenium is the cooling rate, and therefore the cooling rate can be changed by controlling the heating temperature of the storage tank, the cooling temperature of the cooling rotary drum, and the falling distance from the drip opening to the drum. can. For this reason, it is advantageous to have a vertically movable configuration for the rotating drum.
図面に示した構成において、溶融セレンあるい
はセレン蒸気と接触する設備内壁面はアルミニウ
ム製とするかもしくはアルミニウムでコーテイン
グしておくことが好ましい。アルミニウムはセレ
ンと固溶体を形成せず、従つて生成されるセレン
が汚染されない。また、装置の外周面には保温の
ため適当な断熱材を設けることが好ましい。 In the configuration shown in the drawings, the inner wall surface of the equipment that comes into contact with molten selenium or selenium vapor is preferably made of aluminum or coated with aluminum. Aluminum does not form a solid solution with selenium, so the selenium produced is not contaminated. Further, it is preferable to provide a suitable heat insulating material on the outer peripheral surface of the device for heat retention.
前記した溶解炉１において溶解されるセレン量
は、上昇管および下降管が常に液状セレンで充填
されまた蒸留器および凝縮器内に一定の液状セレ
ンが維持されうるように配慮せねばならない。こ
うすることによつて、蒸留器−凝縮器の負圧雰囲
気は溶解炉および粒状化室と完全に隔離され、安
定した蒸留および凝縮操作が確保される。また、
何らかの理由で、操業を中断した場合、上昇管お
よび蒸留器内の液状セレンは溶解炉内にそして凝
縮器および下降管内の液状セレンは貯留槽にそれ
ぞれ収容される。従つて、溶解炉および貯留槽の
容量はそれを収容するに充分の大きさとすべきで
ある。 The amount of selenium melted in the above-mentioned melting furnace 1 must be taken into consideration so that the riser pipe and the downcomer pipe are always filled with liquid selenium and a constant level of liquid selenium can be maintained in the distiller and condenser. By doing so, the negative pressure atmosphere of the distiller-condenser is completely isolated from the melting furnace and the granulation chamber, ensuring stable distillation and condensation operations. Also,
If the operation is interrupted for any reason, the liquid selenium in the riser and still is stored in the melting furnace, and the liquid selenium in the condenser and downcomer is stored in a storage tank. Therefore, the capacity of the melting furnace and storage tank should be large enough to accommodate it.
実施例
第１図に示したのと同様の試験装置を使用し
て、30ppmの鉛、50ppmの酸素、10ppmの鉄、
3ppmのテルル、5ppmの銅および3ppmのビスマ
スを含有する粗セレンを、33Kg／時間の割合で溶
解炉に装入した。装入物は−３mmの粒状のものと
した。溶解炉において350℃に加熱した。上昇管
は25mm直径×2.4ｍ長さのものを使用した。蒸留
器および凝縮器は１トール以下に減圧しそして蒸
留器は350℃に加熱した。凝縮器バツフルプレー
トは水冷により250℃に保つた。下降管は上昇管
と同寸のものを使用した。冷却回転ドラムは30cm
径×40cm巾のものを30rpmの回転速度において使
用した。長期にわたつて連続した操業が実施で
き、得られた粒状のセレン製品の鉛含量は
0.5ppmであり、その他の酸素、鉄、テルル、銅
およびビスマスはいずれも0.5ppm以下であり、
きわめて高純度のものであつた。上記設備におい
ては、内壁面はすべてアルミニウム製とした。ま
た、不活性ガスとしては窒素を使用した。EXAMPLE Using a test apparatus similar to that shown in Figure 1, 30 ppm lead, 50 ppm oxygen, 10 ppm iron,
Crude selenium containing 3 ppm tellurium, 5 ppm copper and 3 ppm bismuth was charged to the melting furnace at a rate of 33 Kg/hour. The charge was -3 mm granules. It was heated to 350°C in a melting furnace. The riser used was 25 mm in diameter and 2.4 m in length. The distiller and condenser were vacuumed to less than 1 Torr and the still was heated to 350°C. The condenser full plate was kept at 250°C by water cooling. The downcomer pipe was the same size as the riser pipe. Cooling rotating drum is 30cm
A diameter x 40 cm width was used at a rotation speed of 30 rpm. Continuous operation can be carried out over a long period of time, and the lead content of the obtained granular selenium products is
0.5ppm, and other oxygen, iron, tellurium, copper and bismuth are all 0.5ppm or less,
It was of extremely high purity. In the above equipment, all inner walls were made of aluminum. Further, nitrogen was used as an inert gas.
第１図は本発明を実施するための装置の概略図
でありそして第２図は粒状化室の別の実施例を示
す。
１：溶解炉、５：給送機、３：ホツパ、１０：
上昇管、１２：蒸留器、１４：凝縮器、１３：ミ
スト除去装置、１６：バツフルプレート、２０：
下降管、２１：貯留槽、２４：滴下口、２６：粒
状化室、３２：ケーシング、２７：冷却回転ドラ
ム、２８：スクレーパ、３０：取出口。
FIG. 1 is a schematic diagram of an apparatus for carrying out the invention, and FIG. 2 shows an alternative embodiment of the granulation chamber. 1: Melting furnace, 5: Feeder, 3: Hopper, 10:
rising pipe, 12: distiller, 14: condenser, 13: mist removal device, 16: baffle plate, 20:
Downpipe, 21: Storage tank, 24: Dripping port, 26: Granulation chamber, 32: Casing, 27: Cooling rotating drum, 28: Scraper, 30: Output port.
Claims (1)
融したセレンを一定量づつ減圧された蒸留器内に
上昇管を経て吸引し、該蒸留器内で溶融セレンを
蒸発せしめ、セレン蒸気を凝縮器において凝縮せ
しめ、凝縮した液状セレンを下降管を経て粒状化
室内において液状セレンを滴下しそして凝固せし
めることから成るセレンの連続真空精製方法。 ２ 溶融セレンを撹拌しながら蒸発せしめる特許
請求の範囲第１項記載の方法。 ３ 粗セレン原料を溶解するための溶解炉であつ
て、粗セレン原料を連続的に供給するための供給
機を備える溶解炉と、該溶解炉の上方に設置され
る蒸留器と、前記溶解炉と蒸留器とを繋ぎそして
蒸留器内に一定の溶融セレン液面を維持する上昇
管と、前記蒸留器に隣りあいそこに連通して設け
られる凝縮器と、該蒸留器および凝縮器を排気す
る排気系統と、前記凝縮器において生成する液状
セレンを受取るべく該凝縮器の下方に配置される
貯留槽と、該凝縮器の底部と該貯留槽とを繋ぎ、
該凝縮器から貯留槽へと液状セレンを連続的に流
下させる下降管と、前記貯留槽と連通する粒状化
室であつて、該貯留槽から滴下する液状セレンを
冷却凝固させる回転冷却ドラムおよび該ドラム上
から凝固セレンをかき落すためのスクレーパを収
納しそしてかき落された粒状セレンを取出す為の
出口を底部に備える粒状化室とを包含するセレン
の連続真空精製装置。 ４ 蒸留器に撹拌装置が設けられることを特徴と
する特許請求の範囲第３項記載の装置。[Claims] 1. A crude selenium raw material is continuously supplied to a melting furnace, a fixed amount of molten selenium is sucked into a depressurized distillation vessel through a riser pipe, and the molten selenium is evaporated in the distillation vessel. A continuous vacuum purification method for selenium, which comprises condensing selenium vapor in a condenser, dropping the condensed liquid selenium through a downcomer into a granulation chamber, and solidifying the liquid selenium. 2. The method according to claim 1, wherein molten selenium is evaporated while stirring. 3. A melting furnace for melting crude selenium raw material, which is equipped with a feeder for continuously supplying the crude selenium raw material, a distiller installed above the melting furnace, and a melting furnace for melting the raw selenium raw material. a riser pipe that connects the distiller and the distiller and maintains a constant molten selenium liquid level in the distiller; a condenser that is provided adjacent to and in communication with the distiller; and a condenser that exhausts the distiller and the condenser. connecting an exhaust system, a storage tank disposed below the condenser to receive liquid selenium produced in the condenser, and a bottom of the condenser and the storage tank;
a downcomer pipe that allows liquid selenium to continuously flow down from the condenser to the storage tank; a granulation chamber that communicates with the storage tank; a rotating cooling drum that cools and solidifies the liquid selenium dripping from the storage tank; A continuous vacuum purification apparatus for selenium, comprising a granulation chamber housing a scraper for scraping solidified selenium from a drum and having an outlet at the bottom for taking out scraped granular selenium. 4. The device according to claim 3, characterized in that the distiller is provided with a stirring device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3270380A JPS56129604A (en) | 1980-03-17 | 1980-03-17 | Method and apparatus for continuously vacuum purifying selenium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3270380A JPS56129604A (en) | 1980-03-17 | 1980-03-17 | Method and apparatus for continuously vacuum purifying selenium |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS56129604A JPS56129604A (en) | 1981-10-09 |
| JPS623084B2 true JPS623084B2 (en) | 1987-01-23 |
Family
ID=12366201
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3270380A Granted JPS56129604A (en) | 1980-03-17 | 1980-03-17 | Method and apparatus for continuously vacuum purifying selenium |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS56129604A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4957909B2 (en) * | 2007-12-25 | 2012-06-20 | 三菱マテリアル株式会社 | Selenium distillation method and distillation apparatus |
| CN106927433B (en) * | 2017-04-18 | 2020-04-17 | 昆明鼎邦科技股份有限公司 | Crude selenium slag wet material vacuum melting equipment |
-
1980
- 1980-03-17 JP JP3270380A patent/JPS56129604A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS56129604A (en) | 1981-10-09 |
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