JPS63203730A - Production of high-purity metal bismuth - Google Patents
Production of high-purity metal bismuthInfo
- Publication number
- JPS63203730A JPS63203730A JP3454487A JP3454487A JPS63203730A JP S63203730 A JPS63203730 A JP S63203730A JP 3454487 A JP3454487 A JP 3454487A JP 3454487 A JP3454487 A JP 3454487A JP S63203730 A JPS63203730 A JP S63203730A
- Authority
- JP
- Japan
- Prior art keywords
- bismuth
- metal
- crude
- purity
- biocl
- 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
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 26
- 239000002184 metal Substances 0.000 title claims abstract description 26
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims description 28
- 229910052797 bismuth Inorganic materials 0.000 title claims description 25
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims abstract description 21
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 claims abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 229940073609 bismuth oxychloride Drugs 0.000 claims description 9
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 5
- 239000010453 quartz Substances 0.000 abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 239000012776 electronic material Substances 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 229910002804 graphite Inorganic materials 0.000 abstract description 2
- 239000010439 graphite Substances 0.000 abstract description 2
- 238000006460 hydrolysis reaction Methods 0.000 abstract 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract 1
- 239000000460 chlorine Substances 0.000 abstract 1
- 229910052801 chlorine Inorganic materials 0.000 abstract 1
- 230000007062 hydrolysis Effects 0.000 abstract 1
- 239000012535 impurity Substances 0.000 description 7
- 238000004821 distillation Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229910000416 bismuth oxide Inorganic materials 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000012223 aqueous fraction Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 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
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は粗金属ビスマスから純度９９．９９０９重量％
以上の高純度金属ビスマスを製造する方法に関するもの
である。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention is based on the invention, which is made from crude metal bismuth with a purity of 99.9909% by weight.
The present invention relates to a method for producing the above-mentioned high-purity metal bismuth.
電気光学効果、光伝導特性機能を持つＢ１１２ＳｉＯｚ
。B112SiOz with electro-optic effect and photoconductive properties
.
や、シンチレータ用材料のＢ１４Ｇｅ３０ｔ２、Ｂｉｔ
２Ｇｅ０２゜なとの酸化物結晶の原料として、できるだ
け高純度の酸化ビスマス（旧２０３）が必要であり、こ
の酸化ビスマスの原料となる金属ビスマス（Ｂｉ）の高
純度化が求められている。and scintillator material B14Ge30t2, Bit
As a raw material for oxide crystals such as 2Ge02°, bismuth oxide (formerly 203) of as high purity as possible is required, and there is a demand for high purity metal bismuth (Bi), which is the raw material for this bismuth oxide.
金属ビスマスは粗金属ビスマスの電解精製又は酸化ビス
マスの還元て得るのが一般的で、その純度はｆ１９．９
９重量％程度が限度であり、さらに純度を高めるため従
来はゾーン精ａ法が用いられている。この方法によれば
９９．９９９重量％程度の金属ビスマスを得ることがで
きるが、この方法てはコスト、量産なとの面から難点が
あり、また分配係数が１に近い元素や、１より大きい元
素については精製が困難で、さらに高純度のものを得る
ことができなかった。Bismuth metal is generally obtained by electrolytic refining of crude metal bismuth or reduction of bismuth oxide, and its purity is f19.9.
The limit is about 9% by weight, and in order to further increase the purity, the zone a method has conventionally been used. According to this method, metal bismuth of about 99.999% by weight can be obtained, but this method has disadvantages in terms of cost and mass production, and it also has problems with elements with distribution coefficients close to 1 or larger than 1. It was difficult to purify the elements, and it was not possible to obtain even higher purity ones.
〔発明が解決しようとする問題点ン
本発明の目的は、上記従来法の欠点を解消し、電子材料
等の原料に使用される純度９９．９９９９重量％以上の
高純度の金属ビスマススを収串良（、且つ低コストで得
ることができる高純度金属ビスマスの製造方法を提供す
ることにある。[Problems to be Solved by the Invention] The purpose of the present invention is to eliminate the drawbacks of the above-mentioned conventional methods and to efficiently collect bismuth metal with a purity of 99.9999% by weight or higher, which is used as a raw material for electronic materials, etc. (The object of the present invention is to provide a method for producing high-purity metal bismuth that can be obtained at low cost.)
この目的を達成するために本発明の方法は、粗金属ビス
マスを４５０〜７００℃で塩素ガスと反応させて粗三塩
化ビスマスを生成させ、該三塩化ビスマスを蒸留又は精
留して精製三塩化ビスマスを回収し、該精製三塩化ビス
マスを加水分解してオキシ塩化ビスマスとした後、該オ
キシ塩化ビスマスを７００〜９００℃の水素気流中で還
元するように構成したものである。To achieve this objective, the method of the present invention involves reacting crude metal bismuth with chlorine gas at 450-700°C to produce crude bismuth trichloride, and distilling or rectifying the bismuth trichloride to produce purified trichloride. It is configured to collect bismuth, hydrolyze the purified bismuth trichloride to produce bismuth oxychloride, and then reduce the bismuth oxychloride in a hydrogen stream at 700 to 900°C.
本発明では粗金属ビスマスを石英製の容器に入れ、容器
内を不活性ガスで充分置換した後塩素ガスを流し、金属
ビスマスを４５０〜７００℃、好マシくは５００〜６０
０℃で過剰の塩素ガスと反応させ三塩化ビスマスを生成
させる。In the present invention, crude metal bismuth is placed in a quartz container, and after sufficiently replacing the inside of the container with an inert gas, chlorine gas is passed through the container, and the metal bismuth is heated to a temperature of 450 to 700°C, preferably 500 to 600°C.
Bismuth trichloride is produced by reacting with excess chlorine gas at 0°C.
（２８ｉ＋ ３ ＣＩ２→２ＢｉＣ１３）塩素化での反
応温度を４５０〜７００℃とするのは４５０℃以下では
反応が遅＜、７００℃以上では反応が激しいため危険で
あるからである。好ましくは５００〜６００℃での反応
が穏やかであり最も好ましい、この三塩化ビスマスを回
収し、石英製の蒸留器、好ましくは精留器を用い常圧で
精製を行う。(28i+3CI2→2BiC13) The reaction temperature in chlorination is set at 450 to 700°C because below 450°C the reaction is slow and above 700°C the reaction is violent and dangerous. This bismuth trichloride, which is most preferable because the reaction is mild at 500 to 600° C., is recovered and purified at normal pressure using a quartz distiller, preferably a rectifier.
蒸留器又は精留器の塔頂温度が三塩化ビスマスの沸点で
ある約４５０℃になってから全還流させ、塔内を平衡状
態に到達させた後留出を開始し、三塩化ビスマス重量の
５〜ｌＯ％を初留として分離し、その後の留分８０〜９
０％を水留として回収する。When the top temperature of the distiller or rectifier reaches about 450°C, which is the boiling point of bismuth trichloride, total reflux is carried out, and after reaching an equilibrium state in the column, distillation is started, and the weight of bismuth trichloride is 5-10% is separated as the first distillate, and subsequent fractions 80-9
0% is recovered as water fraction.
蒸留又は精留で初留の量を三塩化ビスマス重量の５〜ｌ
Ｏ％とするのは低沸点物の混入を避けるためであり、１
０％以上とすると収率が悪くなるので好ましくない。ま
た水留を８０〜９０％に止めたのも高沸点物が混入しな
いようにしたためである。Distillation or rectification reduces the amount of initial distillation to 5 to 1 liters of bismuth trichloride weight.
The reason for setting O% is to avoid contamination with low boiling point substances, and 1
If it exceeds 0%, the yield will deteriorate, which is not preferable. Also, the reason why the water distillation was limited to 80-90% was to prevent high boiling point substances from being mixed in.
得られた精製三塩化ビスマスは過剰の純水（５ＭΩ以上
）中に滴下しオキシ塩化ビスマスとする。The obtained purified bismuth trichloride is dropped into excess pure water (5 MΩ or more) to obtain bismuth oxychloride.
（ＢｉＣ１３＋ １１２０→旧ＯＣ１＋２Ｈε１）三
塩化ビスマスを加水分解してオキシ塩化ビスマスとする
のは、三塩化ビスマスのままで水素還元を行うと回収率
が悪いためである。(BiC13+ 1120→old OC1+2Hε1) The reason why bismuth trichloride is hydrolyzed to bismuth oxychloride is that hydrogen reduction of bismuth trichloride as it is results in a poor recovery rate.
得られたオキシ塩化ビスマスは洗浄乾燃後７００〜９０
０℃で水素気流中で水素還元を行い金属ビスマスを得る
。The obtained bismuth oxychloride has a molecular weight of 700 to 90 after washing and dry combustion.
Metallic bismuth is obtained by hydrogen reduction in a hydrogen stream at 0°C.
（２旧ＯＣ１＋３Ｈａ→２ Ｂｉ’ ＋ ２ ＨＣＩ
＋ ２１ｈＯ）ここで得た金属ビスマスは酸洗して表面
酸化物を除去することにより高純度金属ビスマスを得る
ことができる。オキシ塩化ビスマスの還元温度を７００
〜９００℃としたのは、７００℃以下では還元速度が遅
＜、９００℃以上では金属ビスマスの回収率が悪（なる
からである。(2 old OC1+3Ha→2 Bi' + 2 HCI
+21hO) High purity metal bismuth can be obtained by pickling the metal bismuth obtained here to remove surface oxides. The reduction temperature of bismuth oxychloride is 700.
The reason for setting the temperature to 900°C is that below 700°C, the reduction rate is slow, and above 900°C, the recovery rate of metal bismuth is poor.
実施例１
不純物を含有した純度９９．９９％の金属ビスマス１０
００ｇを石英ボートにのせ石英管内に入れ、管内を充分
窒素ガスで置換した後塩素ガス５００ｃｃ／分を通じ、
８００℃で７時間反応させて三塩化ビスマス１４８０ｇ
を得た。この三塩化ビス、マスを石英製の内容ａ Ｉ
ＥＸの精留フラスコに入れ、高さ８０ｃａの充填式カラ
ム精留器の塔頂温度が約４５０℃になってから１０分間
全還流を行い、次いで１０分間初留を回収し、以後２時
間水留を回収した。得られた水留の三塩化ビスマスは１
１２℃１ｇであった。この三塩化ビスマスを過剰の純水
（５ＭΩ）中に滴下し、完全にオキシ塩化ビスマスにし
てレバルプ洗浄、乾燥を行って乾量９０２ｇのオキシ塩
化ビスマスを得た。これを高純度黒鉛ボート（こ入れ８
００℃の水素気液中で３時間水素還元を行い、１０％の
硝酸で酸洗し金属ビスマス ６３５ｇを得た。使用した
原料及び得られた高純度金属ビスマス中の不純物の含有
量を第１表に示す、市た比較のためゾーン精製法によっ
て得たものの不純物の含有量も併せて第１表に示す。Example 1 99.99% pure metal bismuth 10 containing impurities
00g was placed on a quartz boat and put into a quartz tube, and after the inside of the tube was sufficiently replaced with nitrogen gas, chlorine gas was passed through at 500cc/min.
1480g of bismuth trichloride after reacting at 800℃ for 7 hours
I got it. This bistrichloride mass is made of quartz content a I
After the top temperature of a packed column rectifier with a height of 80 ca reached approximately 450°C, total reflux was performed for 10 minutes, the initial distillate was collected for 10 minutes, and water was then heated for 2 hours. The residue was collected. Bismuth trichloride of the obtained water distillate is 1
It was 1g at 12°C. This bismuth trichloride was dropped into excess pure water (5 MΩ) to completely convert it into bismuth oxychloride, and was washed and dried to obtain 902 g of dry bismuth oxychloride. Add this to a high-purity graphite boat.
Hydrogen reduction was performed in a hydrogen gas liquid at 00°C for 3 hours, and pickling was performed with 10% nitric acid to obtain 635 g of metal bismuth. Table 1 shows the raw materials used and the content of impurities in the high-purity bismuth metal obtained. Table 1 also shows the content of impurities in the material obtained by the zone refining method for comparison.
この結果から高純度金属ビスマス中の不純物の合計は０
．７８ρｐｍであり、最終収率は８３．５％であった。From this result, the total amount of impurities in high-purity metal bismuth is 0.
．． The final yield was 83.5%.
実施例２
不純物を゛含有した純度９９．９％の金属ビスマスを実
施例１と同様に処理をした結果を同じ＜１１！１表に示
す、この結果から高純度金属ビスマス中の不純物の合計
は０．４０ρｐ−であり、最終収率は８１．０％であっ
た。Example 2 The results of treating 99.9% pure metal bismuth containing impurities in the same manner as in Example 1 are shown in the same <11!1 table. From this result, the total impurities in high purity metal bismuth are The final yield was 81.0%.
本発明によれば純度９９．９１３９９重量％以上の高純
度金属ビスマスを安定して製造することができる。According to the present invention, high purity metallic bismuth having a purity of 99.91399% by weight or more can be stably produced.
また不純物含有量の多い粗金属ビスマスを用いた場合に
も、当初の蒸留を繰り返すことにより高純度の金属ビス
マスを得ることが可能であり、その工業的価値は大なる
ものがある。Furthermore, even when crude metal bismuth containing a large amount of impurities is used, it is possible to obtain highly pure metal bismuth by repeating the initial distillation, which has great industrial value.
Claims (1)
せて粗三塩化ビスマスを生成させ、該三塩化ビスマスを
蒸留又は精留して精製三塩化ビスマスを回収し、該精製
三塩化ビスマスを加水分解してオキシ塩化ビスマスとし
た後、該オキシ塩化ビスマスを７００〜９００℃の水素
気流中で還元することを特徴とする高純度金属ビスマス
の製造方法。Crude metal bismuth is reacted with chlorine gas at 450 to 700°C to produce crude bismuth trichloride, the bismuth trichloride is distilled or rectified to recover purified bismuth trichloride, and the purified bismuth trichloride is hydrolyzed. A method for producing high-purity metal bismuth, which comprises reducing the bismuth oxychloride in a hydrogen stream at 700 to 900°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3454487A JPS63203730A (en) | 1987-02-19 | 1987-02-19 | Production of high-purity metal bismuth |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3454487A JPS63203730A (en) | 1987-02-19 | 1987-02-19 | Production of high-purity metal bismuth |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63203730A true JPS63203730A (en) | 1988-08-23 |
Family
ID=12417244
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3454487A Pending JPS63203730A (en) | 1987-02-19 | 1987-02-19 | Production of high-purity metal bismuth |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63203730A (en) |
-
1987
- 1987-02-19 JP JP3454487A patent/JPS63203730A/en active Pending
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