JPS63203731A - Production of high-purity metal bismuth - Google Patents
Production of high-purity metal bismuthInfo
- Publication number
- JPS63203731A JPS63203731A JP62034547A JP3454787A JPS63203731A JP S63203731 A JPS63203731 A JP S63203731A JP 62034547 A JP62034547 A JP 62034547A JP 3454787 A JP3454787 A JP 3454787A JP S63203731 A JPS63203731 A JP S63203731A
- Authority
- JP
- Japan
- Prior art keywords
- bismuth
- hydrochloric acid
- soln
- purity
- bicl3
- 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 16
- 239000002184 metal Substances 0.000 title claims abstract description 16
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims description 20
- 229910052797 bismuth Inorganic materials 0.000 title claims description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 30
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims abstract description 25
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000009835 boiling Methods 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000004821 distillation Methods 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 10
- 229940073609 bismuth oxychloride Drugs 0.000 claims description 10
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 abstract description 6
- 239000012776 electronic material Substances 0.000 abstract description 2
- 238000001704 evaporation Methods 0.000 abstract description 2
- 238000007670 refining Methods 0.000 abstract description 2
- 238000000967 suction filtration Methods 0.000 abstract description 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 abstract 4
- 238000006460 hydrolysis reaction Methods 0.000 abstract 2
- 230000007062 hydrolysis Effects 0.000 abstract 1
- 238000009740 moulding (composite fabrication) Methods 0.000 abstract 1
- 239000012535 impurity Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-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
- 239000003153 chemical reaction reagent Substances 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
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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〕
本発明は粗酸化ビスマスから純度９９．９９８９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 crude bismuth oxide with a purity of 99.9989% 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っＢ１１２ＳｉＯｚ
。B112SiOz with electro-optic effect and photoconductive properties
.
や、シンチレータ用材料のＢ１４ＧｅｓＯｔ２、Ｂｉ
、、ＧｅＯ２゜なとの酸化物結晶の原料として、できる
だ客す高純度の酸化ビスマス（Ｂｉ１２：ｓ ）が必要
てあり、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。, scintillator materials B14GesOt2, Bi
As a raw material for oxide crystals such as GeO2°, bismuth oxide (Bi12:s) of as high purity as possible is required, and metal bismuth (Bi12:s), which is the raw material for this bismuth oxide, is required.
Bi) is required to be highly purified.
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
マスの還元で得るのが一般的で、その純度は９９．９９
重量％程度が限度であり、さらに純度を高めるため従来
はゾーン精製法が用いられている。この方法によれば０
Ｌ９９９１１量％程度の金属ビスマスを得ることができ
るが、この方法ではコスト、量産などの面から難点があ
り、また分配係敢が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 99.99.
The limit is about % by weight, and in order to further increase the purity, a zone purification method has conventionally been used. According to this method, 0
Although it is possible to obtain metallic bismuth with a concentration of about 99911% by mass, this method has drawbacks in terms of cost and mass production, and it is difficult to purify elements whose partition coefficient is close to 1 or larger than 1. Even higher purity could not be obtained.
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（、巨つ低コストで得
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。The purpose of the present invention is to eliminate the drawbacks of the conventional methods described above, and to obtain highly pure metal bismuth at a high purity (and extremely low cost) with a purity of 99.9999% by weight or more, which is used as a raw material for electronic materials, etc. The purpose of the present invention is to provide a method for producing high-purity metal bismuth.
この目的を達成するために本発明の方法は、粗酸化ビス
マスを濃塩酸で溶解し、残渣を濾別して三塩化ビスマス
水溶液を回収し、該三塩化ビスマス水溶液を蒸留器又は
精留器に入れて水分、塩酸及び低沸点物を蒸発させた後
、三塩化ビスマスの沸点近くの温度で蒸留して精製三塩
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 dissolving crude bismuth oxide in concentrated hydrochloric acid, filtering off the residue to recover a bismuth trichloride aqueous solution, and putting the bismuth trichloride aqueous solution into a distiller or rectifier. After evaporating water, hydrochloric acid, and low-boiling substances, distillation is performed at a temperature near the boiling point of bismuth trichloride to recover purified bismuth trichloride, and the purified bismuth trichloride is hydrolyzed to bismuth oxychloride. It is configured to reduce the bismuth oxychloride in a hydrogen stream at 700 to 900°C.
本発明では粗酸化ビスマスを１．１・５〜１．３当量の
濃塩酸（約３５％）で攪拌溶解し、チーゲル等を用いて
吸引濾過を行い、不溶解残渣を除いて三塩化ビスマス水
溶液を得る。In the present invention, crude bismuth oxide is stirred and dissolved in 1.1.5 to 1.3 equivalents of concentrated hydrochloric acid (approximately 35%), and suction filtration is performed using a Ziegel etc. to remove the undissolved residue and form a bismuth trichloride aqueous solution. get.
（Ｂｉａ０３＋ ６ ＨＣＩ→２ ＢｉＣｌ３＋ ３
Ｂ２０ ）この溶解工程で濃塩酸は１．１５〜１．３当
量使用するのが好ましい、！、３当量以上だと蒸留又は
精留工程で水、塩酸などを除去するため過剰の塩酸は効
率的に良くないからである。また１、１５当量以下だと
酸化ビスマスの未溶解分が残ったり、溶解に長時間かか
る。(Bia03+ 6 HCI→2 BiCl3+ 3
B20) It is preferable to use 1.15 to 1.3 equivalents of concentrated hydrochloric acid in this dissolution step! This is because if the amount is 3 equivalents or more, water, hydrochloric acid, etc. are removed in the distillation or rectification process, so excess hydrochloric acid is not efficient. If the amount is less than 1.15 equivalents, undissolved bismuth oxide may remain or it will take a long time to dissolve.
この三塩化ビスマス水溶液を石英製の蒸留器、好ましく
は精留器を用い常圧で精製を行う、始めは１００〜ｌｌ
Ｏ℃で水、塩酸及び低沸点物を蒸発させ、温度が急激に
上昇し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℃になってから全還瀉させ、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８
０〜９０％を水留として回収する。This bismuth trichloride aqueous solution is purified at normal pressure using a quartz distiller, preferably a rectifier.
Water, hydrochloric acid and low-boiling substances are evaporated at 0°C, and the temperature rises rapidly until the top temperature of the distiller or rectifier reaches about 450°C, which is the boiling point of bismuth trichloride, and then the mixture is completely refluxed. Distillation is started after reaching an equilibrium state in the column, and 5 to 10% of the weight of bismuth trichloride is separated as the first distillation, and the subsequent fraction 8
0-90% 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 is more than 0%, the yield will be poor, which is not preferable, and the reason why the water distillation was limited to 80 to 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.
（８ｉＣ１ａ ＋ １１２０ →Ｂ１０Ｃ１＋
２ ＨＣＩ ）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。(8iC1a + 1120 →B10C1+
2 HCI) The reason why bismuth trichloride is hydrolyzed to produce bismuth oxychloride is because hydrogen reduction of bismuth trichloride as it is results in poor recovery.
得られたオキシ塩化ビスマスは洗浄乾燥後７００〜９０
０’ＩＣの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 drying.
Hydrogen reduction is performed in a hydrogen stream at 0'IC to obtain metal bismuth.
＜２ Ｂ１０Ｃ１＋ ３ ＋１２→２ Ｂｉ” ＋ ２
ＨＣＩ ＋ ２ Ｈａｄ）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
率が悪くなるからである。<2 B10C1+ 3 +12→2 Bi” + 2
HCI + 2 Had) High purity metal bismuth can be obtained by pickling the metal bismuth obtained here to remove surface oxides. The reason why the reduction temperature of bismuth oxychloride is set to 700 to 900°C is that below 700°C, the reduction rate is slow, and above 900°C, the recovery rate of bismuth metal becomes poor.
実施例１
不純物を含有した純度９９．８％の醸化ビスマスｔｏｏ
ｏ ｇを試薬１級の濃塩酸１．８ Ｈ中に入れて攪拌溶
解し、チーゲルを用いて吸引減退を行い不溶解ＩＦＩＩ
ｔｆｉを除いて三塩化ビスマス水溶液を得る。この三
塩化ビスマス水溶液を石英製の内容量２ヰの精留フラス
コに入れ、高さ６０口の充填式カラム精留器を用いて精
製を行った。始めは１００ Ｎ１１０℃で水、塩酸及び
低沸点物を蒸発させ、温度が急激に上昇して塔頂温度が
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７０分間本水壷回収した。Example 1 Brewed bismuth too with a purity of 99.8% containing impurities
0g in 1.8 H of concentrated hydrochloric acid of grade 1 reagent, stirred and dissolved, and reduced by suction using Ziegel to remove undissolved IFII.
A bismuth trichloride aqueous solution is obtained by removing tfi. This bismuth trichloride aqueous solution was placed in a rectifying flask made of quartz and having an internal capacity of 2 mm, and purified using a packed column rectifier with a height of 60 necks. Initially, water, hydrochloric acid, and low-boiling substances were evaporated at 100 N and 110°C, and after the temperature rose rapidly and the top temperature reached approximately 450°C, total reflux was performed for 10 minutes, and then the initial distillate was collected for 10 minutes. After that, the main water bottle was collected for 70 minutes.
得られた水留の三塩化ビスマスは９５０ｇであった。こ
の三塩化ビスマスを過剰の純水（５ＭΩ）中書と滴下し
、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７６０ｇのオキシ塩化ビスマスを得た。こ
れを高純度黒鉛ポートに入れ８００℃の水素気流中で３
時間水素還元を行い、１０％の硝酸で酸洗し金属ビスマ
ス ５４０ｇを得た。使用した原、料の分光分析結果及
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ａｔ’た比較のためゾーン請製法によって得
たものの不純物の含有量も併せて第１表に示す。The amount of bismuth trichloride in the resulting water distillate was 950 g. This bismuth trichloride was added dropwise with excess pure water (5 MΩ) to completely convert it into bismuth oxychloride, followed by Revalp washing and drying to obtain a dry weight of 760 g of bismuth oxychloride. This was placed in a high-purity graphite port and placed in a hydrogen stream at 800℃ for 3 hours.
Hydrogen reduction was carried out for a period of time, followed by pickling with 10% nitric acid to obtain 540 g of metal bismuth. The spectroscopic analysis results of the raw materials used and the content of impurities in the obtained high-purity metal bismuth are shown in Table 1.For comparison, the content of impurities in the product obtained by the zone contract manufacturing method is also shown. It is shown in Table 1.
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
．８４ｐｐｍであり、最終収率は６００２％であった。From this result, the total amount of impurities in high-purity metal bismuth is 0.
．． 84 ppm, and the final yield was 6002%.
実施例２
不純物を含有した実施例１とは異なる純度９９．９％の
酸化ビスマスを実施例１と同様に処理をした結果を同じ
く第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．［ｌｐｐｍであり、最終収率は６２
．０％であった。Example 2 Bismuth oxide with a purity of 99.9%, which is different from Example 1 and which contains impurities, was treated in the same manner as in Example 1. The results are also shown in Table 1. From these results, impurities in high purity metal bismuth were determined. The total is 0. [lppm, final yield is 62
．． It was 0%.
本発明によれば純度９９．９９９９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 99.9999% by weight or more can be stably produced.
また不純物含有量の多い粗酸化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 bismuth oxide containing a large amount of impurities is used, it is possible to obtain highly pure metallic bismuth by repeating the initial distillation, which has great industrial value.
Claims (1)
化ビスマス水溶液を回収し、該三塩化ビスマス水溶液を
蒸留器又は精留器に入れて水分、塩酸及び低沸点物を蒸
発させた後、三塩化ビスマスの沸点近くの温度で蒸留し
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 bismuth oxide is dissolved in concentrated hydrochloric acid, the residue is filtered to recover a bismuth trichloride aqueous solution, and the bismuth trichloride aqueous solution is put into a distiller or rectifier to evaporate water, hydrochloric acid, and low-boiling substances, and then Purified bismuth trichloride is recovered by distillation at a temperature close to the boiling point of bismuth trichloride, and the purified bismuth trichloride is hydrolyzed to bismuth oxychloride. The bismuth oxychloride is then heated in a hydrogen stream at 700 to 900°C. A method for producing high-purity metal bismuth, characterized by reducing it with
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62034547A JPS63203731A (en) | 1987-02-19 | 1987-02-19 | Production of high-purity metal bismuth |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62034547A JPS63203731A (en) | 1987-02-19 | 1987-02-19 | Production of high-purity metal bismuth |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63203731A true JPS63203731A (en) | 1988-08-23 |
Family
ID=12417335
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62034547A Pending JPS63203731A (en) | 1987-02-19 | 1987-02-19 | Production of high-purity metal bismuth |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63203731A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100816424B1 (en) | 2006-12-22 | 2008-03-25 | 인하대학교 산학협력단 | Photocatalyst having bismuthoxide-bismuthoxyhalide junction structure and preparation method thereof |
| JP2013139594A (en) * | 2011-12-28 | 2013-07-18 | Jx Nippon Mining & Metals Corp | Method for treating bismuth electrolytic slime |
| JP2013185214A (en) * | 2012-03-08 | 2013-09-19 | Jx Nippon Mining & Metals Corp | BISMUTH OR BISMUTH ALLOY HAVING SMALL AMOUNT OF α-RAY, AND METHOD FOR PRODUCING THE SAME |
| JP5903497B2 (en) * | 2012-11-02 | 2016-04-13 | Ｊｘ金属株式会社 | Method for producing low α-ray bismuth, low α-ray bismuth and bismuth alloy |
-
1987
- 1987-02-19 JP JP62034547A patent/JPS63203731A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100816424B1 (en) | 2006-12-22 | 2008-03-25 | 인하대학교 산학협력단 | Photocatalyst having bismuthoxide-bismuthoxyhalide junction structure and preparation method thereof |
| JP2013139594A (en) * | 2011-12-28 | 2013-07-18 | Jx Nippon Mining & Metals Corp | Method for treating bismuth electrolytic slime |
| JP2013185214A (en) * | 2012-03-08 | 2013-09-19 | Jx Nippon Mining & Metals Corp | BISMUTH OR BISMUTH ALLOY HAVING SMALL AMOUNT OF α-RAY, AND METHOD FOR PRODUCING THE SAME |
| JP5903497B2 (en) * | 2012-11-02 | 2016-04-13 | Ｊｘ金属株式会社 | Method for producing low α-ray bismuth, low α-ray bismuth and bismuth alloy |
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