JPH01290724A - Method for refining molybdenum or tungsten - Google Patents
Method for refining molybdenum or tungstenInfo
- Publication number
- JPH01290724A JPH01290724A JP11829988A JP11829988A JPH01290724A JP H01290724 A JPH01290724 A JP H01290724A JP 11829988 A JP11829988 A JP 11829988A JP 11829988 A JP11829988 A JP 11829988A JP H01290724 A JPH01290724 A JP H01290724A
- Authority
- JP
- Japan
- Prior art keywords
- aqueous solution
- uranium
- molybdenum
- tungsten
- thorium
- 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.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 16
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 15
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 12
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims description 14
- 239000011733 molybdenum Substances 0.000 title claims description 14
- 239000010937 tungsten Substances 0.000 title claims description 10
- 238000007670 refining Methods 0.000 title description 2
- 229910052770 Uranium Inorganic materials 0.000 claims abstract description 25
- 229910052776 Thorium Inorganic materials 0.000 claims abstract description 23
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims abstract description 8
- 229940010552 ammonium molybdate Drugs 0.000 claims abstract description 8
- 235000018660 ammonium molybdate Nutrition 0.000 claims abstract description 8
- 239000011609 ammonium molybdate Substances 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- -1 pyridyl azo compound Chemical class 0.000 claims abstract description 7
- 239000004698 Polyethylene Substances 0.000 claims abstract 3
- 229920000573 polyethylene Polymers 0.000 claims abstract 3
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- CKQAOGOZKZJUGA-UHFFFAOYSA-N 1-nonyl-4-(4-nonylphenoxy)benzene Chemical compound C1=CC(CCCCCCCCC)=CC=C1OC1=CC=C(CCCCCCCCC)C=C1 CKQAOGOZKZJUGA-UHFFFAOYSA-N 0.000 claims description 4
- DNYWZCXLKNTFFI-UHFFFAOYSA-N uranium Chemical compound [U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U] DNYWZCXLKNTFFI-UHFFFAOYSA-N 0.000 claims 2
- 229910052742 iron Inorganic materials 0.000 abstract description 15
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 abstract description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract description 7
- 239000000693 micelle Substances 0.000 abstract description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002516 radical scavenger Substances 0.000 abstract description 6
- 238000010438 heat treatment Methods 0.000 abstract description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract description 2
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 abstract description 2
- 229910017604 nitric acid Inorganic materials 0.000 abstract description 2
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 abstract description 2
- 239000000654 additive Substances 0.000 abstract 1
- 230000000996 additive effect Effects 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 28
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 19
- 239000008346 aqueous phase Substances 0.000 description 12
- 238000000746 purification Methods 0.000 description 11
- 239000012071 phase Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 6
- HNVCXDAVEHOIBP-UHFFFAOYSA-N 2-[(5-bromopyridin-2-yl)diazenyl]-5-(diethylamino)phenol Chemical compound OC1=CC(N(CC)CC)=CC=C1N=NC1=CC=C(Br)C=N1 HNVCXDAVEHOIBP-UHFFFAOYSA-N 0.000 description 4
- MESJRHHDBDCQTH-UHFFFAOYSA-N 3-(dimethylamino)phenol Chemical compound CN(C)C1=CC=CC(O)=C1 MESJRHHDBDCQTH-UHFFFAOYSA-N 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000005191 phase separation Methods 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 4
- DZKDPOPGYFUOGI-UHFFFAOYSA-N tungsten(iv) oxide Chemical compound O=[W]=O DZKDPOPGYFUOGI-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- GSGDTSDELPUTKU-UHFFFAOYSA-N nonoxybenzene Chemical compound CCCCCCCCCOC1=CC=CC=C1 GSGDTSDELPUTKU-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 1
- HEUQJWXRYWVQNM-UHFFFAOYSA-N 5-(dimethylamino)-2-(1,3-thiazol-2-yldiazenyl)phenol Chemical compound OC1=CC(N(C)C)=CC=C1N=NC1=NC=CS1 HEUQJWXRYWVQNM-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- VVRQVWSVLMGPRN-UHFFFAOYSA-N oxotungsten Chemical class [W]=O VVRQVWSVLMGPRN-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明はＬＳＩゲート電極に用いられる、モリブデンま
たはタングステンの精製において、ウラン、トリウムを
それぞれｔ Ｉ）Ｉ）ｂ未満に除去すると共に、鉄を０
．１１）Ｈ未満に除去した簡便な精製方法に関する。Detailed Description of the Invention [Industrial Application Field] The present invention is used in the purification of molybdenum or tungsten used for LSI gate electrodes, in which uranium and thorium are removed to less than tI)I)b, respectively, and iron is removed. 0
．． 11) Concerning a simple purification method that removes less than H.
［従来の技術］
従来、ＬＳＩのゲート電極として多結晶Ｓｌが使用され
ていたが、ＬＳＩの高集積化に伴い、電極の抵抗による
信号伝搬遅延が問題となり、より抵抗の低い高融点金属
であるモリブデン、タングステンが使用されている。一
方、このモリブデン、タングステン中のウラン、トリウ
ム含有量が多いとソフトエラーの原因になることが知ら
れておりこれの簡便な精製方法の出現が期待されている
。[Prior art] Polycrystalline Sl has conventionally been used as gate electrodes in LSIs, but as LSIs become more highly integrated, signal propagation delays due to electrode resistance have become a problem, so a high melting point metal with lower resistance has been used. Molybdenum and tungsten are used. On the other hand, it is known that high contents of uranium and thorium in molybdenum and tungsten cause soft errors, and it is hoped that a simple purification method will emerge.
このため特にモリブデンからウラン、トリウムを除去す
る精製方法として結晶晶出法が提案されている（例えば
特開昭６０−６６４２５号公報、特開昭５９−２２６１
３号公報等）。For this reason, a crystallization method has been proposed as a purification method for removing uranium and thorium from molybdenum (for example, JP-A-60-66425, JP-A-59-2261).
Publication No. 3, etc.).
これらの方法はモリブデン酸アンモニウム水溶液を所定
の温度に加熱後、冷却してモリブデン酸アンモニウムを
晶析回収し、原料中のウラン、トリウムを晶析後の処理
母液中に残留せしめて分離するものである。この晶出し
た結晶を更にアンモニアに溶解し同様の操作を繰り返し
てウラン、トリウムの除去効果を上げていべものである
。These methods involve heating an aqueous ammonium molybdate solution to a predetermined temperature and then cooling it to crystallize and recover the ammonium molybdate, leaving the uranium and thorium in the raw materials in the treated mother liquor after crystallization and separating them. be. This crystallization is further dissolved in ammonia and the same operation is repeated to increase the effectiveness of removing uranium and thorium.
［発明が解決しようとする課題］
このような従来の結晶晶出法でモリブデンからウラン、
トリウムを１１）ｐｂ未満まで除去するには１回の操作
を行っただけでは不十分であり、数回の繰返し操作が必
要になる。そのため操作が極めて煩雑になり、作業性や
生産性が悪いというが課題を有し、またこのことはコス
ト面からも好ましいものではない。[Problem to be solved by the invention] Uranium,
One operation is not sufficient to remove thorium to less than 11) parts per billion, and several repeated operations are required. Therefore, the operation becomes extremely complicated, and there are problems in terms of workability and productivity, and this is also not desirable from a cost standpoint.
さらに、ＬＳＩゲート電極に用いられるモリブデンやタ
ングステンにおいては、鉄等の重金属の存在は、界面単
位を発生させたり、接合リークの原因となるため、これ
らの存在量を所定値以下、例えば０．１１）Ｉ）１１未
満に低減させる必要がある。Furthermore, in molybdenum and tungsten used in LSI gate electrodes, the presence of heavy metals such as iron may generate interface units or cause junction leakage, so the amount of these metals should be kept below a predetermined value, for example 0.11. ) I) It is necessary to reduce it to less than 11.
本発明の目的は、上記した従来の結晶晶出法に比較しモ
リブデンやタングステンの原料からウラン、トリウムの
存在量をｔ Ｉ）Ｉ）ｂ未満、鉄の存在量を０．１ ｐ
ｐｍ未満に精製することができる極めて簡便な精製方法
を提供することにある。The purpose of the present invention is to reduce the abundance of uranium and thorium from molybdenum and tungsten raw materials to less than tI)I)b, and to reduce the abundance of iron to 0.1 p, compared to the conventional crystallization method described above.
It is an object of the present invention to provide an extremely simple purification method capable of purifying to less than pm.
［課題を解決するための手段］
本発明の上記目的は、次に示す精製方法によって達成さ
れる。[Means for Solving the Problems] The above objects of the present invention are achieved by the following purification method.
すなわち本発明のモリブデンまたはタングステンの精製
方法は、モリブデンまたはタングステン中のウラン、ト
リウムの存在量がｉ ｐＩ）ｂ以上であるモリブデン酸
アンモニウム水溶液またはタングステン酸アンモニウム
水溶液に、ピリジルアゾ系化合物とポリエチレングリコ
ール−モノ−ノニルフェニルエーテルを添加することを
特徴とする。That is, the method for purifying molybdenum or tungsten of the present invention involves adding a pyridylazo compound and a polyethylene glycol monomer to an aqueous ammonium molybdate solution or an aqueous ammonium tungstate solution in which the amount of uranium and thorium in molybdenum or tungsten is i pI)b or more. -Characterized by adding nonylphenyl ether.
本発明の精製方法の出発原料として市販のモリブデンま
たはタングステンの酸化物を用いる。これらは金属分に
対してウラン、トリウムを各々 １１）ｐｂｂ以上一般
的には数１１１）ｂ〜数百ｐｐｂ存在する三酸化モリブ
デン、二酸化タングステンである。Commercially available molybdenum or tungsten oxides are used as starting materials for the purification method of the present invention. These are molybdenum trioxide and tungsten dioxide, which each contain 11) ppb or more of uranium and thorium, generally from several 111) b to several hundred ppb, based on the metal content.
また、鉄は、数９９１１１以上存在する。In addition, there are 99111 or more types of iron.
これを従来から良く知られている２５〜３０％のアンモ
ニア水で加熱溶解する。更に塩酸とアンモニア水を用い
てｐＨ８，０〜９．０の範囲に調整する。This is heated and dissolved with 25 to 30% ammonia water, which is well known in the art. Furthermore, the pH is adjusted to a range of 8.0 to 9.0 using hydrochloric acid and aqueous ammonia.
このモリブデン酸アンモニウム水溶液またはタングステ
ン酸アンモニウム水溶液に、ウラン、トリウム等の捕集
剤としてのピリジルアゾ系化合物を添加し、撹拌する。A pyridylazo compound as a scavenger for uranium, thorium, etc. is added to this aqueous ammonium molybdate solution or ammonium tungstate solution, and the mixture is stirred.
この捕集剤の添加量は、三酸化モリブデンまたは三酸化
タングステン１００重量部に対して、０．０００１〜１
．０重量部が望ましい。The amount of the scavenger added is 0.0001 to 1 to 100 parts by weight of molybdenum trioxide or tungsten trioxide.
．． 0 parts by weight is desirable.
捕集剤の添加量が０．０００１ｆｆｉｆｆｉ部未満では
、鉄の除去が不充分である。また、１．０重量部を超え
て添加した場合には、それ以上の添加効果が生じない。If the amount of scavenger added is less than 0.0001 ffiffi part, iron removal will be insufficient. Further, if it is added in an amount exceeding 1.0 parts by weight, no further effect will be produced.
ここで用いられるピリジルアゾ系化合物としては、２−
（５−ブロモ−２−ピリジルアゾ）−５−ジエチルアミ
ノフェノール等のピリジルアゾ化合物、２−（２−チア
ゾリルアゾ）−５−ジメチルアミノフェノール等のチア
ゾリルアゾ化合物、エリオフロムブラックＴ等のナフチ
ルアゾ化合物等が例示される。The pyridylazo compounds used here include 2-
Examples include pyridylazo compounds such as (5-bromo-2-pyridylazo)-5-diethylaminophenol, thiazolyl azo compounds such as 2-(2-thiazolyl azo)-5-dimethylaminophenol, and naphthylazo compounds such as Eriofromblack T. .
次いで、この撹拌時に界面活性剤をさらに添加する。界
面活性剤として蒸気圧が低く、取り扱いに便利なポリエ
チレングリコール−モノ−、ノニルフェニルエーテルが
用いられる。このポリエチレングリコール−モノ−ノニ
ルフェニルエーテルは、二酸化モリブデンまたは二酸化
タングステン１００重量部に対して好ましくは０．０５
〜２００重量部を添加して曇点以上になるまで加熱する
。その温度は約８０℃である。上記の界面活性剤の添加
量が０．０５重量部未満では、ウラン、ｌ−リウム、鉄
の除去効果が不充分であり、かつ捕集剤から逆に汚染が
生じる。また、２００重量部を超えて添加した場合には
、それ以上の添加効果が生じない。Further surfactant is then added during this stirring. As the surfactant, polyethylene glycol mono- and nonylphenyl ether, which have a low vapor pressure and are convenient to handle, are used. This polyethylene glycol mono-nonylphenyl ether is preferably 0.05 parts by weight per 100 parts by weight of molybdenum dioxide or tungsten dioxide.
~200 parts by weight is added and heated until the cloud point is reached or higher. Its temperature is about 80°C. If the amount of the surfactant added is less than 0.05 part by weight, the removal effect of uranium, l-lium, and iron will be insufficient, and contamination will occur from the scavenger. Further, if it is added in an amount exceeding 200 parts by weight, no further effect will be produced.
この界面界面活性剤を添加して加熱することによって、
溶液中のミセルが脱水和して巨大ミセルを生成しミセル
相と水相に分離し、ウラン、トリウムおよび鉄は捕集剤
と共にミセル相中に取り込まれ、モリブデン酸アンモニ
ウム、タングステン酸アンモニウムの水溶液と分離する
ことができる。By adding this surfactant and heating,
The micelles in the solution are dehydrated to form giant micelles, which are separated into a micelle phase and an aqueous phase, and uranium, thorium, and iron are taken into the micelle phase together with a scavenger, and are mixed with an aqueous solution of ammonium molybdate and ammonium tungstate. Can be separated.
次にこの水溶液に硝酸を加えて酸濃度を５〜１０規定に
調整し、温度９０〜１００℃にするとモリブデン酸また
はタングステン酸の結晶が晶出する。これを従来から良
く知られた方法で乾燥、焼成、還元し金属モリブデンま
たは金属タングステンを得て加圧成形してターゲット材
料とする。Next, nitric acid is added to this aqueous solution to adjust the acid concentration to 5 to 10 normal, and when the temperature is raised to 90 to 100°C, crystals of molybdic acid or tungstic acid crystallize. This is dried, calcined, and reduced by a conventionally well-known method to obtain metallic molybdenum or metallic tungsten, which is then pressure-molded and used as a target material.
［発明の効果］
本発明の精製方法により、１回の操作で簡便、かつ効率
よくウラン、トリウムの存在量を１ ｐｐｂ未満に低減
することができ、半導体特性を損うとされている鉄も
０．１ ｐｐｍ未満に同時に精製し得るという効果を有
する。なお、本発明の精製方法を単独で用いるのみなら
ず、他の精製方法と組合せて用いてもよい。[Effects of the Invention] The refining method of the present invention can easily and efficiently reduce the amount of uranium and thorium to less than 1 ppb in a single operation, and can also reduce the amount of iron, which is said to impair semiconductor properties.
It has the advantage that it can be simultaneously purified to less than 0.1 ppm. Note that the purification method of the present invention may not only be used alone, but also in combination with other purification methods.
［実施例］ 以下、実施例に基づき本発明を具体的に説明する。[Example] Hereinafter, the present invention will be specifically explained based on Examples.
実施例１
ウラン１１ ｐｐｂ、 ）リウム１３ ｐｐｂ、鉄９
ｐｐＩＩを含む三酸化モリブデン１ｇを３００ｄビー
カーに入れ、これに特級の２５％アンモニア水５ｄを加
え加熱溶解する。この溶液を室温まで放冷したのち蒸留
水１００Ｉｄ！を入れる。次に、塩酸とアンモニア水を
用イテｐＨ８，０〜９．０に調整する。続いて、２−（
５−ブロモ−２−ピリジルアゾ）−５−ジエチルアミノ
フェノール（０，０５％）１ｉｔｔを加えて撹拌し、ポ
リエチレングリコール−モノ−ノニルフェニルエーテル
０．３ｇを加えて約８０℃まで加温し、ミセル相と水相
とに相分離したのち、水相を取り出した。水相中のウラ
ン、トリウムの存在量は、共にｉ ｐｐｂ未満であり、
鉄の存在量は０．１ ｐｐ１１未満であった。Example 1 Uranium 11 ppb, ) Liumium 13 ppb, Iron 9
Put 1 g of molybdenum trioxide containing ppII into a 300 d beaker, add 5 d of special grade 25% ammonia water, and heat to dissolve. After cooling this solution to room temperature, 100 Id! of distilled water was added. Put in. Next, hydrochloric acid and aqueous ammonia are used to adjust the pH to 8.0 to 9.0. Next, 2-(
1 itt of 5-bromo-2-pyridylazo)-5-diethylaminophenol (0.05%) was added and stirred, and 0.3 g of polyethylene glycol mono-nonylphenyl ether was added and heated to about 80°C to form a micellar phase. After phase separation into an aqueous phase and an aqueous phase, the aqueous phase was taken out. The amounts of uranium and thorium in the aqueous phase are both less than i ppb,
The amount of iron present was less than 0.1 pp11.
実施例２〜３
ピリジルアゾ系化合物として、実施例１で用いた ２−
（５−ブロモ−２−ピリジルアゾ）−５−ジエチルアミ
ノフェノールに代えて、２−（２−チアゾリルアゾ）−
５−ジメチルアミノフェノール（実施例２）、エリオフ
ロムブラックＴ（実施例３）を同量用いた以外は実施例
１と同様に精製を行ない、ミセル相と水相とに相分離し
たのち、水相を取り出した。その結果、実施例２〜３の
いずれも、水相中のウラン、トリウムの存在量は、共に
１ ｐｐｂ未満であり、鉄の存在量はｏ、ｔ ｐｐｍ
未満であった。Examples 2-3 2- used in Example 1 as a pyridylazo compound
(5-bromo-2-pyridylazo)-5-diethylaminophenol, 2-(2-thiazolyl azo)-
Purification was carried out in the same manner as in Example 1, except that the same amounts of 5-dimethylaminophenol (Example 2) and Eriofromblack T (Example 3) were used, and after phase separation into a micelle phase and an aqueous phase, water I took out the phase. As a result, in all of Examples 2 to 3, the amounts of uranium and thorium in the aqueous phase were both less than 1 ppb, and the amount of iron was less than 1 ppm.
It was less than
実施例４
ウラン１６ ｐｐｂ、 トリウム１１ ｐｐｂｓ鉄１
２ ｐｐａ＋を含む三酸化タングステン１ｇを３００ｄ
ビーカーに入れ、これに特級の２５％アンモニア水５ｄ
を加え加熱溶解する。この溶液を室温まで放冷したのち
蒸留水１ｏａＩｎｌを入れる。次に、塩酸とアンモニア
水を用いてｐＨ８，０〜９．０に調整する。続いて、２
−（５−ブロモ−２−ピリジルアゾ）−５−ジエチルア
ミノフェノール（０，０５％） ｌｄを加えて撹拌し
ポリエチレングリコール−モノ−ノニルフェニルエーテ
ル０．３ｇを加えて、約８０℃まで加温し、ミセル柑と
水相とに相分離したのち、水相を取り出した。水相には
ウラン、トリウムの存在量は、共に １１）ｌｌｂ未満
であり、鉄の存在量はは０．１９９１１未満であった。Example 4 Uranium 16 ppb, Thorium 11 ppbs Iron 1
2 1g of tungsten trioxide containing ppa+ is 300d
Place in a beaker and add 5 d of special grade 25% ammonia water.
Add and heat to dissolve. After this solution was allowed to cool to room temperature, 1 oaInl of distilled water was added. Next, the pH is adjusted to 8.0 to 9.0 using hydrochloric acid and aqueous ammonia. Next, 2
-(5-bromo-2-pyridylazo)-5-diethylaminophenol (0.05%) ld was added and stirred, 0.3 g of polyethylene glycol mono-nonylphenyl ether was added, and the mixture was heated to about 80°C. After phase separation into micellar and aqueous phases, the aqueous phase was taken out. In the aqueous phase, the amounts of uranium and thorium were both less than 11) lb, and the amount of iron was less than 0.19911.
実施例５〜６
ピリジルアゾ系化合物として、実施例４で用いた ２−
（５−ブロモ−２−ピリジルアゾ）−５−ジエチルアミ
ノフェノールに代えて、２−（２−チアゾリルアゾ）−
５−ジメチルアミノフェノール（実施例５）、エリオフ
ロムブラックＴ（実施例６）を同量用いた以外は実施例
４と同様に精製を行ない、ミセル相と水相とに相分離し
たのち、水相を取り出した。その結果、実施例５〜６の
いずれも、水相中のウラン、トリウムの存在量は、共に
ｉ ｐＩ）ｂ未満であり、鉄の存在量は０．１１）Ｉ
）Ｉｎ未満であった。Examples 5-6 2- used in Example 4 as a pyridylazo compound
(5-bromo-2-pyridylazo)-5-diethylaminophenol, 2-(2-thiazolyl azo)-
Purification was carried out in the same manner as in Example 4, except that the same amounts of 5-dimethylaminophenol (Example 5) and Eriofromblack T (Example 6) were used. After phase separation into a micelle phase and an aqueous phase, water I took out the phase. As a result, in all of Examples 5 to 6, the abundances of uranium and thorium in the aqueous phase were both less than i pI)b, and the abundance of iron was 0.11)I
) In.
特許出願人 三井金属鉱業株式会社 代理人 弁理士 伊 東 辰 雄 代理人 弁理士 伊 東 哲 也Patent applicant: Mitsui Metal Mining Co., Ltd. Agent: Patent Attorney Tatsuo Ito Agent: Patent Attorney Tetsuya Ito
Claims (1)
ｂ以上であるモリブデン酸アンモニウム水溶液に、ピリ
ジルアゾ系化合物とポリエチレングリコール−モノ−ノ
ニルフェニルエーテルを添加することを特徴とするモリ
ブデンの精製方法。 ２、タングステン中のウラン、トリウムの存在量が１ｐ
ｐｂ以上であるタングステン酸アンモニウム水溶液に、
ピリジルアゾ系化合物とポリエチレングリコール−モノ
−ノニルフェニルエーテルを添加することを特徴とする
モリブデンの精製方法。[Claims] 1. The amount of uranium and thorium in molybdenum is 1pp.
A method for purifying molybdenum, which comprises adding a pyridylazo compound and polyethylene glycol-mono-nonylphenyl ether to an aqueous ammonium molybdate solution having a concentration of at least b. 2. The amount of uranium and thorium in tungsten is 1p
In an ammonium tungstate aqueous solution having a PB or higher,
A method for purifying molybdenum, which comprises adding a pyridylazo compound and polyethylene glycol mono-nonylphenyl ether.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63118299A JP2691414B2 (en) | 1988-05-17 | 1988-05-17 | Purification method of molybdenum or tungsten |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63118299A JP2691414B2 (en) | 1988-05-17 | 1988-05-17 | Purification method of molybdenum or tungsten |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01290724A true JPH01290724A (en) | 1989-11-22 |
| JP2691414B2 JP2691414B2 (en) | 1997-12-17 |
Family
ID=14733239
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63118299A Expired - Lifetime JP2691414B2 (en) | 1988-05-17 | 1988-05-17 | Purification method of molybdenum or tungsten |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2691414B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104282888A (en) * | 2013-07-10 | 2015-01-14 | 国家纳米科学中心 | Molybdenum trioxide serving as lithium ion battery cathode material and preparation method of molybdenum trioxide |
| CN111893326A (en) * | 2020-08-03 | 2020-11-06 | 中南大学 | Method for extracting tungsten by two-step acid decomposition method |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101938280B1 (en) | 2016-11-28 | 2019-01-15 | 엔에이티엠 주식회사 | Recycling method of tungsten scrap having metal coating layer |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5487622A (en) * | 1977-12-26 | 1979-07-12 | Power Reactor & Nuclear Fuel Dev Corp | Uranium trapping method |
| JPS54150311A (en) * | 1978-05-18 | 1979-11-26 | Kuraray Co Ltd | Extracting method for uranium from acidic aqueous solution |
| JPS59226133A (en) * | 1983-04-26 | 1984-12-19 | Mitsubishi Metal Corp | Method for refining molybdenum |
| JPS6066425A (en) * | 1983-09-22 | 1985-04-16 | Nippon Telegr & Teleph Corp <Ntt> | High-purity molybdenum target and high-purity molybdenum silicide target for lsi electrode and manufacture thereof |
| JPS61197423A (en) * | 1985-02-25 | 1986-09-01 | ジ−・テイ−・イ−・プロダクツ・コ−ポレイシヨン | Collection of tungsten from ammoniacal solution |
-
1988
- 1988-05-17 JP JP63118299A patent/JP2691414B2/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5487622A (en) * | 1977-12-26 | 1979-07-12 | Power Reactor & Nuclear Fuel Dev Corp | Uranium trapping method |
| JPS54150311A (en) * | 1978-05-18 | 1979-11-26 | Kuraray Co Ltd | Extracting method for uranium from acidic aqueous solution |
| JPS59226133A (en) * | 1983-04-26 | 1984-12-19 | Mitsubishi Metal Corp | Method for refining molybdenum |
| JPS6066425A (en) * | 1983-09-22 | 1985-04-16 | Nippon Telegr & Teleph Corp <Ntt> | High-purity molybdenum target and high-purity molybdenum silicide target for lsi electrode and manufacture thereof |
| JPS61197423A (en) * | 1985-02-25 | 1986-09-01 | ジ−・テイ−・イ−・プロダクツ・コ−ポレイシヨン | Collection of tungsten from ammoniacal solution |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104282888A (en) * | 2013-07-10 | 2015-01-14 | 国家纳米科学中心 | Molybdenum trioxide serving as lithium ion battery cathode material and preparation method of molybdenum trioxide |
| CN111893326A (en) * | 2020-08-03 | 2020-11-06 | 中南大学 | Method for extracting tungsten by two-step acid decomposition method |
| CN111893326B (en) * | 2020-08-03 | 2021-07-20 | 中南大学 | Method for extracting tungsten by two-step acid decomposition method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2691414B2 (en) | 1997-12-17 |
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