JPH02248320A - Production of high purity bismuth oxide - Google Patents
Production of high purity bismuth oxideInfo
- Publication number
- JPH02248320A JPH02248320A JP6748289A JP6748289A JPH02248320A JP H02248320 A JPH02248320 A JP H02248320A JP 6748289 A JP6748289 A JP 6748289A JP 6748289 A JP6748289 A JP 6748289A JP H02248320 A JPH02248320 A JP H02248320A
- Authority
- JP
- Japan
- Prior art keywords
- nitric acid
- bismuth
- bismuth oxide
- bismuth nitrate
- dissolved
- 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
- 229910000416 bismuth oxide Inorganic materials 0.000 title claims description 27
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 title claims description 27
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 39
- 239000013078 crystal Substances 0.000 claims abstract description 15
- 239000002244 precipitate Substances 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 7
- 235000012501 ammonium carbonate Nutrition 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 18
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 10
- 239000001099 ammonium carbonate Substances 0.000 claims description 10
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 6
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 abstract description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 4
- 238000000746 purification Methods 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract description 2
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical compound [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 abstract 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 2
- 239000007788 liquid Substances 0.000 description 12
- 229910000014 Bismuth subcarbonate Inorganic materials 0.000 description 8
- FWIZHMQARNODNX-UHFFFAOYSA-L dibismuth;oxygen(2-);carbonate Chemical compound [O-2].[O-2].[Bi+3].[Bi+3].[O-]C([O-])=O FWIZHMQARNODNX-UHFFFAOYSA-L 0.000 description 8
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 7
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 229910052797 bismuth Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000002223 garnet Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G29/00—Compounds of bismuth
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は光通信や光計測で反射光を遮断するのに用いら
れる光アイソレーターのガーネット結晶やシンチレータ
−等に用いられるＢｉａＧｅＪ。やＢ１゜Ｇｅ０ｎ＊
（以下ＢＧＯ結晶と示す。）や電界電圧センサや磁界
センサ等に用いられるＢｉ＋＊５ｉＯｓ、。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to BiaGeJ used in garnet crystals and scintillators of optical isolators used to block reflected light in optical communication and optical measurement. YaB1゜Ge0n*
(hereinafter referred to as BGO crystal), Bi+*5iOs, which is used in electric field voltage sensors, magnetic field sensors, etc.
（以下ＢＳＯ結晶と示す。）に必要とされる高純度酸化
ビスマスの製造方法に関する。The present invention relates to a method for producing high-purity bismuth oxide required for (hereinafter referred to as BSO crystal).
［従来の技術］
従来よりＢＧＯ結晶やＢＳＯ結晶に用いられる高純度酸
化ビスマスは高純度金属ビスマスを硝酸に溶解し、得た
溶液をアンモニア水で中和してオキシ硝酸ビスマスを得
、これをか焼することにより製造されている。[Prior art] High-purity bismuth oxide conventionally used for BGO crystals and BSO crystals is obtained by dissolving high-purity metal bismuth in nitric acid, neutralizing the resulting solution with aqueous ammonia to obtain bismuth oxynitrate, and using this as a method. It is manufactured by baking.
しかし、上記従来法では原料とする金属ビスマスの純度
により得られる酸化ビスマスの純度が決ってしまうとい
う欠点があり、原料として高価な高純度ビスマスを使用
せざるを得ないという問題点があり、また、■式や０式
で示されるように金属ビスマスを硝酸で溶解する際に発
生するＮＯや８０２や０式で示されるようにオキシ硝酸
ビスマスをか焼する際に発生するＮ２Ｏ５は有害物質で
あり、装置の腐食や作業環境の悪化や公害の発生を防止
するためにこれら有害物を除害する設備が不可欠とぎれ
るという問題点がある。However, the conventional method described above has the disadvantage that the purity of bismuth oxide obtained is determined by the purity of bismuth metal used as a raw material, and there is a problem that expensive high-purity bismuth must be used as a raw material. NO, which is generated when bismuth metal is dissolved in nitric acid as shown in formulas ■ and 0, and N2O5, which is generated when bismuth oxynitrate is calcined as shown in formulas 802 and 0, are harmful substances. However, in order to prevent corrosion of equipment, deterioration of the working environment, and generation of pollution, there is a problem that equipment for eliminating these harmful substances must be discontinued.
２８１ ÷１ｌＨＮＯ３雪 ２Ｂｉ（ＮＯ３）３ ＋
２８０ ＋ ４Ｈ２０■２１０ ＋ ０２−２ＮＯ２
■
２ＢｉＯＮＯ３富Ｂ１２Ｏ３＋ Ｎ２Ｏ５■［発明が解
決しようとする課題］
本発明の目的は上記問題点のない高純度酸化ビスマスの
製造方法の提供にある。281 ÷1lHNO3 Snow 2Bi(NO3)3 +
280 + 4H20■210 + 02-2NO2
■ 2BiONO3-rich B12O3+ N2O5 ■ [Problems to be Solved by the Invention] An object of the present invention is to provide a method for producing high-purity bismuth oxide free from the above-mentioned problems.
［課題を解決するための手段］
本発明者らは上記課題を解決するために種々検討した結
果、酸化ビスマスを硝酸に溶解する際には反応は０式で
進行し、ＮＯや８０２の発生は見られない事、酸化ビス
マスを溶解する硝酸の濃度を調整すると硝酸ビスマスの
溶解度の温度異存性が大きくなる事を見出し本発明に至
った。[Means for Solving the Problems] As a result of various studies to solve the above problems, the present inventors found that when bismuth oxide is dissolved in nitric acid, the reaction proceeds according to equation 0, and NO and 802 are generated. The present inventors have discovered that the temperature difference in solubility of bismuth nitrate increases when the concentration of nitric acid that dissolves bismuth oxide is adjusted.
Ｂｉ２Ｏ３＋ ６ＨＮＯ３婁２Ｂｉ０１０３）３４３１
１２０ ■すなわち、上記課題を解決するための
本発明の手段は酸化ビスマスを５０〜７５重量％の硝酸
を用いて４０〜８０’Ｃに加温しつつ溶解し、硝酸ビス
マス溶液とした後、該溶液を冷却し、硝酸ビスマスの結
晶を析出させ、分離して得た硝酸ビスマスの結晶を硝酸
に溶解して精製硝酸ビスマス溶液を得、該精製硝酸ビス
マス溶液に炭酸アンモニウムや炭酸水素アンモニウムを
加えてｐＨを５以上として沈殿を得、該沈殿を洗浄後３
００〜８００℃でか焼することを特徴とする高純度酸化
ビスマスの製造方法である。Bi2O3+ 6HNO3 2Bi0103) 3431
120 (1) That is, the means of the present invention for solving the above problem is to dissolve bismuth oxide using 50 to 75% by weight nitric acid while heating to 40 to 80'C to form a bismuth nitrate solution, and then The solution is cooled to precipitate bismuth nitrate crystals, and the separated bismuth nitrate crystals are dissolved in nitric acid to obtain a purified bismuth nitrate solution, and ammonium carbonate or ammonium hydrogen carbonate is added to the purified bismuth nitrate solution. The pH was adjusted to 5 or more to obtain a precipitate, and after washing the precipitate,
This is a method for producing high-purity bismuth oxide, characterized by calcination at 00 to 800°C.
［作用］
本発明において使用する硝酸の濃度は低くすぎても、高
すぎても酸化ビスマスの溶解量は少なく、かつ溶解度の
温度依存性も小さくなり、冷却により得られる精製硝酸
ビスマス結晶の量が少なく実用的ではない。また、硝酸
濃度をあまりに高（すると取扱が不便である。よって、
用いる硝酸の濃度は５０〜７５重量％とする事が必要で
あり、好ましくは５５〜６５重量％とすることが望まし
い。[Function] Even if the concentration of nitric acid used in the present invention is too low or too high, the amount of bismuth oxide dissolved is small, and the temperature dependence of solubility is also small, so that the amount of purified bismuth nitrate crystals obtained by cooling is reduced. It's not very practical. Also, if the nitric acid concentration is too high (which makes handling inconvenient,
The concentration of nitric acid used must be 50 to 75% by weight, preferably 55 to 65% by weight.
酸化ビスマスを硝酸に溶解すると溶解熱により液温が上
昇するが、通常溶解度を確保する」こほこの発熱のみで
は不十分であり、ヒーター等で加温する必要がある。し
かし、温度を高くしすぎると硝酸の蒸留が起きる等、取
扱上の危険性がますばかりか、装置材質とて安価なポリ
プロピレン等を用いることができなくなるので４０〜８
Ｇ’Ｃに加温する事が必要であり、好ましくは６０〜６
５゜Ｃに加温することが望ましい。また、加える硝酸の
量は少ないと未溶解の酸化ビスマスをろ過等により固液
分離せざるをえず、繁雑で、危険であるばかりか、固液
分離操作中に精製硝酸ビスマスが析出してくる恐れがあ
り、また加える硝酸の量が過剰であると溶液中の硝酸ビ
スマスの濃度を低下させ、経済性を損うことになるので
酸化ビスマスを完全に溶解することのできる量とするこ
とが望ましい。なお、酸化ビスマスを完全に溶解するた
めの量は溶解時の液温と硝酸濃度により異なるので事前
に採用する液温度と硝酸濃度とを決定し、必要硝酸量を
求めてお（ことが望ましい。この必要硝酸量は、例えば
、６１重量％硝酸を用いた場合、６５℃では前記０式で
計算される量の約１．１倍であり、ｓｏ’ｃでは約１．
９倍、４Ｇ”Ｃでは約２゜８倍である。なお、効率良く
溶解させるためには溶解速度を速くしすることが好まし
く、通常、計算量の１〜２割増しの硝酸量を過剰に加え
ることが望ましい。When bismuth oxide is dissolved in nitric acid, the temperature of the solution rises due to the heat of dissolution, but the heat generated here and there is usually not enough to ensure solubility, and it is necessary to heat it with a heater or the like. However, if the temperature is too high, it not only increases handling risks such as distillation of nitric acid, but also makes it impossible to use inexpensive equipment materials such as polypropylene.
It is necessary to heat to G'C, preferably 60 to 6
It is desirable to heat it to 5°C. Furthermore, if the amount of nitric acid added is small, undissolved bismuth oxide must be separated into solid and liquid by filtration, which is not only complicated and dangerous, but also causes purified bismuth nitrate to precipitate during the solid-liquid separation process. If the amount of nitric acid added is excessive, it will reduce the concentration of bismuth nitrate in the solution and impair economic efficiency, so it is desirable to use an amount that can completely dissolve bismuth oxide. . Note that the amount required to completely dissolve bismuth oxide varies depending on the liquid temperature and nitric acid concentration at the time of dissolution, so it is preferable to determine the liquid temperature and nitric acid concentration to be adopted in advance and calculate the required amount of nitric acid. For example, when using 61% by weight nitric acid, the required amount of nitric acid is about 1.1 times the amount calculated using the above formula 0 at 65°C, and about 1.
9 times, and about 2.8 times for 4G"C. In order to dissolve efficiently, it is preferable to increase the dissolution rate, and usually an excess amount of nitric acid is added, which is 1 to 20% more than the calculated amount. This is desirable.
４０〜８０℃に加温した硝酸ビスマス溶液を冷却すると
鉄、鉛、銀、ケイ素、ナトリウム、カルシウム、マグネ
シウム等の不純物は液中に残留し、溶解度を越えるビス
マス分が精製硝酸ビスマス結晶として析出する。この際
、どの程度まで液温を低下させるかは要求される精製硝
酸ビスマスの純度と経済性との兼合による。このように
して発生した精製硝酸ビスマス回収後の溶液は、得られ
る精製硝酸ビスマスの純度に影響を与えない限りにおい
て繰返して使用することが可能である。なお、得られた
精製硝酸ビスマスの純度が不十分である場合には精製硝
酸ビスマスを硝酸で加温し再溶解し冷却することにより
精製することができることは言うまでもない。When a bismuth nitrate solution heated to 40 to 80°C is cooled, impurities such as iron, lead, silver, silicon, sodium, calcium, and magnesium remain in the solution, and the bismuth content that exceeds the solubility precipitates as purified bismuth nitrate crystals. . At this time, the degree to which the liquid temperature is lowered depends on the balance between the required purity of purified bismuth nitrate and economical efficiency. The solution thus generated after recovering the purified bismuth nitrate can be used repeatedly as long as it does not affect the purity of the obtained purified bismuth nitrate. It goes without saying that if the purity of the purified bismuth nitrate obtained is insufficient, it can be purified by heating the purified bismuth nitrate with nitric acid, redissolving it, and cooling it.
精製硝酸ビスマスを溶解するのに必要とされる硝酸の量
は液温と濃度により異なるが、例えば、２０℃で１０重
量％の硝酸を用いれば、精製硝酸ビスマス １ ｋｇ当
り０．５４ ｋｇであり、２０ ＩＩ量％の硝酸を用い
れば０．７４ ｋｇであり、４０ ｆｆ１ｆｆｔ％硝酸
を用いれば１．７５ ｋｇとなる。しかし、あまりに高
濃度の硝酸を用いると中和時に必要とする炭酸塩の量が
おおくなり経済性が失われ、あまりに低くすると加水分
解によりオキシ炭酸ビスマスが生じるので、６〜１５重
量％の硝酸を使用することが好ましい。The amount of nitric acid required to dissolve purified bismuth nitrate varies depending on the liquid temperature and concentration, but for example, if 10% by weight nitric acid is used at 20°C, the amount is 0.54 kg per 1 kg of purified bismuth nitrate. , 20 II mass% nitric acid is used, the amount is 0.74 kg, and when 40 ff1fft% nitric acid is used, the amount is 1.75 kg. However, if too high a concentration of nitric acid is used, the amount of carbonate required during neutralization will be large and economical efficiency will be lost.If the concentration is too low, bismuth oxycarbonate will be produced by hydrolysis, so nitric acid of 6 to 15% by weight is used. It is preferable to use
塩基性炭酸塩が生成する反応は０式、０式で示されるが
、沈殿生成を完全とならしめるため、および得られた塩
基性炭酸塩に遊離の酸が付着し、乾燥工程で乾燥装置を
腐食しないようにするために液のｐＨを５以上にするこ
とが必要であり、好ましくは７以上とすることが望まし
い。The reaction that produces basic carbonate is shown in Equations 0 and 0, but in order to complete the precipitation, and to prevent free acid from adhering to the obtained basic carbonate, the drying equipment was removed during the drying process. In order to prevent corrosion, it is necessary to adjust the pH of the liquid to 5 or higher, preferably 7 or higher.
２Ｂｉ（ＮＯ３）３ ＋ ３（Ｎｌ（４）２ＣＯ３−Ｂ
ｉ２０２ＣＯ３＋ ６ＮＩＩ４ＮＯ３＋ ２ＣＯ２■２
ＢＩ（ＮＯ３）３ ＋ ６ＮＨ４■ＣＯ３−Ｂ１２０２
ＣＯ３＋ ６ＮＨ４ＮＯ３＋ ５ＣＯ２■中和に使用す
ることのできる炭酸塩としては炭酸アンモニウムや炭酸
水素アンモニウムであり、固体状のまま使用しても水溶
液として使用しても良い。また、アンモニア水に炭酸ガ
スを吹込むことにより作成した溶液を使用しても差し支
・えはない。生成するオキシ炭酸ビスマスは水難溶性の
塩であり、常法に従って固液分離し、洗浄する。2Bi(NO3)3 + 3(Nl(4)2CO3-B
i202CO3+ 6NII4NO3+ 2CO2■2
BI(NO3)3 + 6NH4■CO3-B1202
CO3+ 6NH4NO3+ 5CO2■ Carbonates that can be used for neutralization include ammonium carbonate and ammonium hydrogen carbonate, and they may be used in solid form or as an aqueous solution. There is also no harm in using a solution prepared by blowing carbon dioxide into aqueous ammonia. The bismuth oxycarbonate produced is a poorly water-soluble salt, and is separated into solid and liquid and washed according to a conventional method.
このようにして得たオキシ炭酸ビスマスは、必要であれ
ば乾燥した後にか焼するが、か焼温度があまりに低いと
分解せず、あまりに高いと生成する酸化ビスマス粒子が
互に融着し、塊状化すると共にか焼容器として用いるア
ルミナ等と反応し、汚染されるため３００〜８００℃と
することが必要である。なお、この温度範囲でか焼容器
として使用できる材質はアルミナ及びチタン等がある。The bismuth oxycarbonate thus obtained is dried and then calcined if necessary; however, if the calcination temperature is too low, it will not decompose, and if the calcination temperature is too high, the resulting bismuth oxide particles will fuse together and form lumps. It is necessary to keep the temperature at 300 to 800° C. because it reacts with alumina used as a calcination vessel and becomes contaminated. Note that materials that can be used as a calcination container in this temperature range include alumina and titanium.
オキシ炭酸ビスマス中に微量の硝酸アンモニウムが含ま
れていたとしても上記か焼により揮発除去されることは
言うまでもない。It goes without saying that even if a trace amount of ammonium nitrate is contained in bismuth oxycarbonate, it will be volatilized and removed by the above-mentioned calcination.
［実施例−１］
液温６５℃で第１表に示した市販の酸化ビスマス２５６
ｇを試薬特級の濃硝酸（６１重量％）４００１に溶解し
た後、１５ ”Ｃに冷却し、硝酸ビスマス（旧（Ｎ０３
）３・５１（２０）の結晶を析出させ、遠心分離機を用
いて固液分離し、若干量の濃硝酸で洗浄し硝酸ビスマス
の結晶３０５ｇを得た。[Example-1] Commercially available bismuth oxide 256 shown in Table 1 at a liquid temperature of 65°C
g in reagent grade concentrated nitric acid (61% by weight) 4001, cooled to 15"C, and dissolved in bismuth nitrate (formerly N03
)3.51(20) was precipitated, solid-liquid separated using a centrifuge, and washed with a small amount of concentrated nitric acid to obtain 305 g of bismuth nitrate crystals.
（１）次いで、得た硝酸ビスマス結晶３５ ｇを試薬特
級の硝酸を水で希釈して得た２０重量％硝酸５０ ｉｔ
に溶解し、試薬特級のアンモニア水と炭酸ガスとで作成
したＮＨ３１８０ｇ／ｌ、 ＨＣＯ３−１９０ｇ／ｌ、
ＣＯ３−２７ｇ／ｌの溶液を用いてｐＨを７．７とし
た。生成した沈殿を吸引ろ過し洗浄した後乾燥し、１７
．３ ｇのオキシ炭酸ビスマスを得た。これをアルミナ
ボートに入れ５００℃で３時間か焼して高純度酸化ビス
マス（１） １５．６ ｇを得た。(1) Next, 50 liters of 20% by weight nitric acid obtained by diluting 35 g of the obtained bismuth nitrate crystals with reagent grade nitric acid with water.
NH3-180g/l, HCO3-190g/l, prepared with reagent-grade ammonia water and carbon dioxide gas.
The pH was brought to 7.7 using a solution of 27 g/l CO3. The generated precipitate was suction-filtered, washed, and then dried.
．． 3 g of bismuth oxycarbonate was obtained. This was placed in an alumina boat and calcined at 500°C for 3 hours to obtain 15.6 g of high purity bismuth oxide (1).
得た高純度酸化ビスマス（１）に含まれるの不純度を第
１表に示した。Table 1 shows the impurities contained in the obtained high purity bismuth oxide (1).
（２）次に前記硝酸ビスマス３５ ｇを試薬特級硝酸を
純水で希釈して得た１０重量％の硝酸６０１に溶解した
後、試薬特級の炭酸アンモニウム４０ｇを純水１２０
ｍｌに溶解して得た炭酸アンモニウム溶液を加えてｐＨ
を７．６に調整して沈殿を発生させた。この沈殿を固液
分離後洗浄し乾燥して１７．５ｇのオキシ炭酸ビスマス
を得た。これをチタンボートに入れ４５０℃で３時間か
焼して高純度酸化ビスマス（２） １５１１ ｇを得た
。得た高純度酸化ビスマス（２）に含まれるの不純度を
第１表に示した。(2) Next, 35 g of bismuth nitrate was dissolved in 10% by weight nitric acid 601 obtained by diluting reagent grade nitric acid with pure water, and then 40 g of reagent grade ammonium carbonate was dissolved in 120 g of pure water.
Add ammonium carbonate solution obtained by dissolving in ml and adjust the pH.
was adjusted to 7.6 to generate precipitation. This precipitate was separated into solid and liquid, washed and dried to obtain 17.5 g of bismuth oxycarbonate. This was placed in a titanium boat and calcined at 450°C for 3 hours to obtain 1511 g of high purity bismuth oxide (2). Table 1 shows the impurities contained in the obtained high purity bismuth oxide (2).
（３）次に前記硝酸ビスマス３５ ｇを試薬特級硝酸を
純水で希釈して得たｔｏ ｉｉ量％の硝酸６０ ｍｌに
溶解した後、試薬特級の炭酸水素アンモニウム５０ ｇ
を純水３００ ｍｌに溶解して得た炭酸水素アンモニウ
ム溶液を加えてｐｔｔを７，３に調整して沈殿を発生さ
せた。この沈殿を固液分離後洗浄し乾燥して１７．９ｇ
のオキシ炭酸ビスマスを得た。(3) Next, 35 g of the above bismuth nitrate was dissolved in 60 ml of TOII% nitric acid obtained by diluting reagent grade nitric acid with pure water, and then 50 g of reagent grade ammonium bicarbonate was dissolved.
An ammonium hydrogen carbonate solution obtained by dissolving the above in 300 ml of pure water was added to adjust the PTT to 7.3 to generate a precipitate. After solid-liquid separation, this precipitate was washed and dried to give 17.9g
of bismuth oxycarbonate was obtained.
これをチタンボートに入れｓｏｏ”ｃで３時間か焼して
高純度酸化ビスマス（３） １６．１ ｇを得た。This was placed in a titanium boat and calcined for 3 hours at soo'c to obtain 16.1 g of high purity bismuth oxide (3).
得た高純度酸化ビスマス（３）に含まれるの不純度を第
１表に示した。Table 1 shows the impurities contained in the obtained high purity bismuth oxide (3).
第１表より本発明の方法によれば市販の酸化ビスマスよ
り容易に高純度酸化ビスマスが得られていることがわか
る。From Table 1, it can be seen that according to the method of the present invention, higher purity bismuth oxide can be obtained more easily than commercially available bismuth oxide.
［発明の効果］
本発明の方法では原料として酸化ビスマスを使用し、中
和剤として炭酸ソーダ等を用いてオキシ炭酸ビスマスを
得、これをか焼するために有害な窒素酸化物の発生がな
いばかりか、本発明の方法自体に精製効果があるために
不純な原料でも使用できることとなる。[Effect of the invention] In the method of the present invention, bismuth oxide is used as a raw material, and bismuth oxycarbonate is obtained using soda carbonate or the like as a neutralizing agent. Since this is calcined, no harmful nitrogen oxides are generated. Moreover, since the method of the present invention itself has a purification effect, even impure raw materials can be used.
Claims (1)
〜８０℃に加温しつつ溶解し、硝酸ビスマス溶液とした
後、該溶液を冷却し、硝酸ビスマスの結晶を析出させ、
分離して得た硝酸ビスマスの結晶を硝酸に溶解して精製
硝酸ビスマス溶液を得、該精製硝酸ビスマス溶液に炭酸
アンモニウムや炭酸水素アンモニウムを加えてｐＨ５以
上として沈殿を得、該沈殿を洗浄後３００〜８００℃で
か焼することを特徴とする高純度酸化ビスマスの製造方
法。40% bismuth oxide using 50-75% by weight nitric acid
After dissolving while heating to ~80°C to form a bismuth nitrate solution, the solution is cooled to precipitate bismuth nitrate crystals,
The bismuth nitrate crystals obtained by separation are dissolved in nitric acid to obtain a purified bismuth nitrate solution, ammonium carbonate or ammonium hydrogen carbonate is added to the purified bismuth nitrate solution to adjust the pH to 5 or higher to obtain a precipitate, and the precipitate is washed for 300 min. A method for producing high purity bismuth oxide, characterized by calcination at ~800°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6748289A JPH02248320A (en) | 1989-03-22 | 1989-03-22 | Production of high purity bismuth oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6748289A JPH02248320A (en) | 1989-03-22 | 1989-03-22 | Production of high purity bismuth oxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02248320A true JPH02248320A (en) | 1990-10-04 |
Family
ID=13346239
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6748289A Pending JPH02248320A (en) | 1989-03-22 | 1989-03-22 | Production of high purity bismuth oxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02248320A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007175600A (en) * | 2005-12-27 | 2007-07-12 | Mitsubishi Rayon Co Ltd | Method for manufacturing oxide catalyst |
| CN102275945A (en) * | 2011-07-06 | 2011-12-14 | 陕西科技大学 | Method for preparing scintillation bismuth silicon oxide powder |
| CN102275943A (en) * | 2011-07-06 | 2011-12-14 | 陕西科技大学 | Method of preparing bismuth silicate powder with molten-salt growth method |
| CN107268086A (en) * | 2016-04-06 | 2017-10-20 | 中国科学院上海硅酸盐研究所 | A kind of method for improving Bismuth silicate scintillation crystal near ultraviolet band transmitance |
-
1989
- 1989-03-22 JP JP6748289A patent/JPH02248320A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007175600A (en) * | 2005-12-27 | 2007-07-12 | Mitsubishi Rayon Co Ltd | Method for manufacturing oxide catalyst |
| CN102275945A (en) * | 2011-07-06 | 2011-12-14 | 陕西科技大学 | Method for preparing scintillation bismuth silicon oxide powder |
| CN102275943A (en) * | 2011-07-06 | 2011-12-14 | 陕西科技大学 | Method of preparing bismuth silicate powder with molten-salt growth method |
| CN107268086A (en) * | 2016-04-06 | 2017-10-20 | 中国科学院上海硅酸盐研究所 | A kind of method for improving Bismuth silicate scintillation crystal near ultraviolet band transmitance |
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