JP5344170B2 - Tungsten recovery process - Google Patents
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- JP5344170B2 JP5344170B2 JP2009197667A JP2009197667A JP5344170B2 JP 5344170 B2 JP5344170 B2 JP 5344170B2 JP 2009197667 A JP2009197667 A JP 2009197667A JP 2009197667 A JP2009197667 A JP 2009197667A JP 5344170 B2 JP5344170 B2 JP 5344170B2
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims description 44
- 229910052721 tungsten Inorganic materials 0.000 title claims description 41
- 239000010937 tungsten Substances 0.000 title claims description 41
- 238000011084 recovery Methods 0.000 title description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 81
- 239000000377 silicon dioxide Substances 0.000 claims description 37
- 239000007788 liquid Substances 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 17
- 238000002386 leaching Methods 0.000 claims description 16
- 239000010802 sludge Substances 0.000 claims description 16
- 238000003672 processing method Methods 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 13
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 10
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 8
- 239000011575 calcium Substances 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 239000012670 alkaline solution Substances 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 5
- 239000005909 Kieselgur Substances 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 230000033444 hydroxylation Effects 0.000 claims 1
- 238000005805 hydroxylation reaction Methods 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
- 239000000047 product Substances 0.000 description 15
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 10
- 239000000920 calcium hydroxide Substances 0.000 description 10
- 235000011116 calcium hydroxide Nutrition 0.000 description 10
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 10
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 235000011121 sodium hydroxide Nutrition 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 3
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 3
- 229910001930 tungsten oxide Inorganic materials 0.000 description 3
- OMAWWKIPXLIPDE-UHFFFAOYSA-N (ethyldiselanyl)ethane Chemical compound CC[Se][Se]CC OMAWWKIPXLIPDE-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910009043 WC-Co Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- 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
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- Processing Of Solid Wastes (AREA)
- Manufacture And Refinement Of Metals (AREA)
Description
本発明は、タングステン含有スラッジからタングステン成分を効率よく回収する処理方法に関する。 The present invention relates to a processing method for efficiently recovering a tungsten component from a tungsten-containing sludge.
近年、電子材料や電極材料としてタングステン含有薄膜が用いられており、成膜用ターゲット原料として高純度タングステンの需要が高まっている。しかし、タングステン原料の資源は限られており、その安定な供給が問題になっている。一方、超硬合金は炭化タングステンなどを含有しており、超硬合金スクラップにはタングステンが含まれているので、このスクラップからタングステンを回収し、有効に利用することが求められている。 In recent years, tungsten-containing thin films have been used as electronic materials and electrode materials, and the demand for high-purity tungsten as a target material for film formation has increased. However, the resources of tungsten raw material are limited, and its stable supply is a problem. On the other hand, cemented carbide contains tungsten carbide and the like, and cemented carbide scrap contains tungsten. Therefore, it is required to recover tungsten from this scrap and use it effectively.
タングステンの回収方法として、従来、以下の方法が知られている。
（イ）超硬合金スクラップを酸化して粉砕し、この粉砕物に苛性ソーダ溶液を加えてタングステンを浸出させ、脱シリカ処理後、該溶液からタングステン酸カルシウムを沈殿させて回収する方法（非特許文献１）。
（ロ）超硬合金スクラップを不活性雰囲気下で亜鉛と混合し、８５０℃〜９５０℃に加熱して超硬合金スクラップに含まれているコバルトと亜鉛を合金化し、これを亜鉛の沸点以上に加熱して亜鉛を真空分離することによって炭化タングステン粉末とコバルト粉末の混合物（WC-Co）を回収する方法（亜鉛処理法）。
（ハ）超硬合金スクラップを１８００℃〜２３００℃に加熱して結合相(Co)中のガス化成分を発泡させてスポンジ状にし、これを粉砕して炭化タングステン粉末とコバルト粉末の混合物を回収する方法（高熱処理法）。
Conventionally, the following methods are known as a method for recovering tungsten.
(B) A method in which cemented carbide scrap is oxidized and pulverized, a caustic soda solution is added to the pulverized product to leach tungsten, and after desilicaization, calcium tungstate is precipitated from the solution and recovered (Non-Patent Document) 1).
(B) Cemented carbide scrap is mixed with zinc in an inert atmosphere and heated to 850 ° C. to 950 ° C. to alloy cobalt and zinc contained in the cemented carbide scrap, and this exceeds the boiling point of zinc. A method of recovering a mixture of tungsten carbide powder and cobalt powder (WC-Co) by heating and vacuum separating zinc (zinc treatment method).
(C) Cemented carbide scrap is heated to 1800 ° C to 2300 ° C to foam the gasified component in the binder phase (Co) to form a sponge, which is pulverized to recover a mixture of tungsten carbide powder and cobalt powder. Method (high heat treatment method).
超硬合金を含有する廃水スラッジに上記(イ)の処理方法を適用すると、該廃水スラッジに含まれる珪藻土のシリカ成分がアルカリ浸出の際にタングステン成分と共に溶出し、ｐＨ調整時にシリカ微粒子が析出してタングステンがこの沈殿に取込まれるので、タングステンの損失が多く、かつ濾過性に劣ると云う問題がある。また、上記廃水スラッジに上記(ロ)の亜鉛処理法を適用すると、シリカ成分を十分に除去できないので、WC-Co混合物にシリカ成分が混入し、回収物を再利用するのが難しくなる。また、上記(ハ)の高熱処理法は安価に処理できるが粗大なＷＣ粒子が混在し、しかもシリカ成分を除去できない。 When the above treatment method (a) is applied to wastewater sludge containing cemented carbide, the silica component of diatomaceous earth contained in the wastewater sludge is eluted together with the tungsten component during alkaline leaching, and silica fine particles are precipitated during pH adjustment. Since tungsten is taken into this precipitate, there is a problem that the loss of tungsten is large and the filterability is poor. Further, when the zinc treatment method (b) is applied to the wastewater sludge, the silica component cannot be sufficiently removed, so that the silica component is mixed into the WC-Co mixture, and it becomes difficult to reuse the recovered material. Moreover, although the high heat treatment method (c) can be processed at a low cost, coarse WC particles are mixed and the silica component cannot be removed.
本発明は、従来の処理方法における上記課題を解決したものであり、タングステンの損失が少なくシリカ成分を除去することができ、効率よくタングステンを回収することができる処理方法を提供する。 The present invention solves the above-mentioned problems in the conventional processing method, and provides a processing method that can remove the silica component with little loss of tungsten and efficiently recover tungsten.
〔１〕タングステン成分およびシリカ成分を含む原料混合物を酸化焙焼する工程、該酸化焙焼物にアルカリ溶液を加えてタングステン成分およびシリカ成分を浸出する工程、これを固液分離する工程、分離した浸出液に水酸化カルシウムを加えて液中のシリカ成分を沈澱化する工程、これを固液分離してタングステン成分の浸出液を得る工程を有し、該浸出液からタングステンを回収することを特徴とするタングステンの回収処理方法。
〔２〕原料混合物が超硬製品の製造工程から排出される炭化タングステン粉末および珪藻土を含んだスラッジである上記[１]に記載する処理方法。
〔３〕酸化焙焼温度が３００℃〜１１００℃である上記[１]〜上記[２]の何れかに記載する処理方法。
〔４〕酸化焙焼物のアルカリ浸出工程、浸出液中のシリカ成分の沈澱化工程において、液温が４０℃以上である上記[１]〜上記[３]の何れかに記載する処理方法。
〔５〕浸出液中のシリカ成分の沈澱化工程において、浸出液のｐＨが１３以上である上記[１]〜上記[４]の何れかに記載する処理方法。
〔６〕原料混合物が、タングステン成分およびシリカ成分と共にコバルト成分を含む超硬合金含有スラッジであり、酸化焙焼物のアルカリ浸出によってタングステン成分およびシリカ成分を浸出すると共に、コバルト成分を水酸化コバルトにし、固液分離して浸出液から分離する上記[１]〜上記[５]の何れかに記載する処理方法。
〔７〕上記[６]の処理方法において、酸化焙焼物のアルカリ浸出工程の液温が１４０℃以上である処理方法。
[1] A step of oxidizing and roasting a raw material mixture containing a tungsten component and a silica component, a step of adding an alkaline solution to the oxidized roasted product and leaching the tungsten component and the silica component, a step of separating the solid and liquid, and a separated leachate A step of precipitating the silica component in the liquid by adding calcium hydroxide to the mixture, and a step of obtaining a leaching solution of the tungsten component by solid-liquid separation thereof, and collecting tungsten from the leaching solution. Collection processing method.
[2] The processing method according to the above [1], wherein the raw material mixture is a sludge containing tungsten carbide powder and diatomaceous earth discharged from the manufacturing process of the cemented carbide product.
[3] The processing method according to any one of [1] to [2] above, wherein the oxidation roasting temperature is 300 ° C to 1100 ° C.
[4] The processing method according to any one of [1] to [3] above, wherein the liquid temperature is 40 ° C. or higher in the alkali leaching step of the oxidized roasted product and the precipitation step of the silica component in the leachate.
[5] The processing method according to any one of [1] to [4], wherein the pH of the leachate is 13 or more in the precipitation step of the silica component in the leachate.
[6] The raw material mixture is a cemented carbide-containing sludge containing a cobalt component together with a tungsten component and a silica component. The tungsten component and the silica component are leached by alkali leaching of the oxidized roasted product, and the cobalt component is changed to cobalt hydroxide. The processing method according to any one of [1] to [5] above, wherein the liquid is separated from the leachate by solid-liquid separation.
[7] The processing method according to [6], wherein the liquid temperature in the alkaline leaching step of the oxidized roasted product is 140 ° C. or higher.
本発明の処理方法は、シリカ成分を含有する超硬合金スラッジについて、酸化焙焼物のアルカリ浸出液に消石灰〔Ca(OH)2〕を添加して液中のシリカ成分を沈澱化し、浸出液から容易に除去することができるので、シリカ成分を除去する際にタングステンの損失が殆どなく、従って効率よくタングステンを回収することができる。 In the treatment method of the present invention, for cemented carbide sludge containing a silica component, slaked lime [Ca (OH) 2 ] is added to the alkaline leachate of the oxidized roasted product to precipitate the silica component in the liquor, and easily from the leachate. Since it can be removed, there is almost no loss of tungsten when the silica component is removed, so that tungsten can be recovered efficiently.
さらに、シリカ成分の沈澱化工程後に固液分離して得られる浸出液はシリカ分を実質的に含まないタングステン酸アルカリ溶液（Na2WO4溶液等）であるので、これを酸化タングステンや炭化タングステンの製造原料として利用することができる。 Furthermore, since the leachate obtained by solid-liquid separation after the precipitation step of the silica component is an alkali tungstate solution (Na 2 WO 4 solution, etc.) substantially free of silica, It can be used as a raw material for production.
また、本発明の処理方法は、アルカリ浸出残渣および消石灰添加による沈澱物の濾過性が良く、酸化焙焼からNa2WO4溶液等を得るまでの処理が容易であるので、従来は有効にリサイクルされていない超硬合金スラッジを原料としてタングステンを回収することができる。 Further, the treatment method of the present invention has good filterability of precipitates due to the addition of alkali leaching residue and slaked lime, and the treatment from oxidation roasting to obtaining Na 2 WO 4 solution and the like is easy. Tungsten can be recovered from untreated cemented carbide sludge.
本発明の処理方法の概略を図１に示す。図示するように、本発明の処理方法は、タングステン成分（Ｗ成分）およびシリカ成分（SiO2成分）を含む原料混合物を酸化焙焼する工程、該酸化焙焼物にアルカリ溶液を加えてタングステン成分およびシリカ成分を浸出する工程、これを固液分離する工程、分離した浸出液に水酸化カルシウムを加えて液中のシリカ成分を沈澱化する工程、これを固液分離してタングステン成分の浸出液を得る工程を有し、該浸出液からタングステンを回収することを特徴とするタングステンの回収処理方法である。 An outline of the treatment method of the present invention is shown in FIG. As shown in the figure, the treatment method of the present invention includes a step of oxidizing and roasting a raw material mixture containing a tungsten component (W component) and a silica component (SiO 2 component), adding an alkaline solution to the oxidized roasted product, The step of leaching the silica component, the step of solid-liquid separation of this, the step of adding calcium hydroxide to the separated leachate to precipitate the silica component in the liquid, the step of solid-liquid separation to obtain the leachate of the tungsten component And recovering tungsten from the leaching solution.
〔原料混合物〕
Ｗ成分およびSiO2成分を含む原料混合物としては、超硬製品の製造工程から排出される超硬合金を含むスラッジなどが用いられる。超硬合金を含むスラッジには炭化タングステン（WC）や結合材成分のコバルト（Co）が含まれている。また、その廃水スラッジには濾過性を高めるために珪藻土が添加されており、珪藻土のシリカ成分が含まれている。
[Raw material mixture]
As the raw material mixture containing the W component and the SiO 2 component, sludge containing cemented carbide discharged from the production process of the cemented carbide product is used. Sludge containing cemented carbide contains tungsten carbide (WC) and the binder component cobalt (Co). In addition, diatomaceous earth is added to the wastewater sludge in order to improve filterability, and the silica component of diatomaceous earth is included.
〔酸化焙焼工程〕
上記原料混合物を大気下（酸化雰囲気）で焙焼する。原料混合物を酸化焙焼することによって、付着している有機物が分解して除去される。また、次式[１]に示すように、原料混合物に含まれている炭化タングステンは酸化して三酸化タングステン（WO3）になり、炭素は炭酸ガスになって系外に出る。また、コバルトが含有されている場合には、コバルトはタングステンの一部と化合してタングステン酸コバルト（CoWO4）になる。酸化焙焼物にはこれらの三酸化タングステン、タングステン酸コバルト、および上記シリカが含まれている。一般に上記廃水スラッジを酸化焙焼すると、焙焼物には概ねWO3が２５〜３５wt％、CoWO4が１５〜２０wt％、SiO2が２５〜５０wt％含まれている。
[Oxidation roasting process]
The raw material mixture is roasted in the air (oxidizing atmosphere). By oxidizing and baking the raw material mixture, the adhering organic substances are decomposed and removed. Further, as shown in the following formula [1], tungsten carbide contained in the raw material mixture is oxidized to tungsten trioxide (WO 3 ), and carbon becomes carbon dioxide gas and goes out of the system. When cobalt is contained, cobalt is combined with a part of tungsten to be cobalt tungstate (CoWO 4 ). The oxidized roasted product contains these tungsten trioxide, cobalt tungstate, and the silica. In general, oxidation roasting the waste sludge, approximately WO 3 is 25～35Wt% in roasting thereof, CoWO 4 is 15~20wt%, SiO 2 is contained 25-50%.
WC + 5/2O2 → WO3 + CO2 … [１]
WC + Co + 3O2 → CoWO4 + CO2 … [２]
WC + 5 / 2O 2 → WO 3 + CO 2 … [1]
WC + Co + 3O 2 → CoWO 4 + CO 2 … [2]
酸化焙焼の焙焼温度は３００℃〜１１００℃が適当であり、６００℃〜９００℃が好ましい。焙焼温度が３００℃より低いとタングステンの酸化に長時間を必要とし、一方、１１００℃より高くても酸化時間はあまり変わらず加熱コストが嵩む。 The roasting temperature for oxidation roasting is suitably 300 ° C to 1100 ° C, preferably 600 ° C to 900 ° C. If the roasting temperature is lower than 300 ° C., it takes a long time to oxidize tungsten. On the other hand, if it is higher than 1100 ° C., the oxidation time does not change so much and the heating cost increases.
〔アルカリ浸出工程〕
酸化焙焼物を解砕し、アルカリ溶液を添加してタングステン成分を溶出させる。アルカリ溶液としては水酸化ナトリウム溶液などを用いることができる。アルカリ溶液の添加量は焙焼物に含まれるタングステン成分を溶出させるのに十分な量が好ましい。アルカリ浸出の液温は、CoWO4が含まれていない場合には４０℃以上でよく、CoWO4が含まれている場合にはその分解を促すために１４０℃以上が好ましい。
[Alkaline leaching process]
The oxidized roast is crushed and an alkaline solution is added to elute the tungsten component. As the alkaline solution, a sodium hydroxide solution or the like can be used. The addition amount of the alkaline solution is preferably an amount sufficient to elute the tungsten component contained in the baked product. The liquid temperature of the alkali leaching may in case 40 ° C. or more does not contain CoWO 4, if it contains CoWO 4 is preferably at least 140 ° C. to promote its degradation.
酸化焙焼物に含まれるWO3は、次式[３]に示すように、水酸化ナトリウムと反応してタングステン酸ナトリウム（Na2WO4）になり、液中に溶出する。また、酸化焙焼物に含まれるCoWO4は、次式[４]に示すように、水酸化ナトリウムと反応してタングステン酸ナトリウム（Na2WO4）と水酸化コバルト（Co(OH)2）を生成する。また、酸化焙焼物に含まれるシリカ(SiO2)は水酸化ナトリウムと反応して珪酸ナトリウム（Na2SiO3）を生成し、液中に溶出する。 WO 3 contained in the oxidized roasted product reacts with sodium hydroxide to become sodium tungstate (Na 2 WO 4 ) as shown in the following formula [3], and is eluted in the liquid. Further, CoWO 4 contained in the oxidized roasted product reacts with sodium hydroxide to form sodium tungstate (Na 2 WO 4 ) and cobalt hydroxide (Co (OH) 2 ) as shown in the following formula [4]. Generate. Silica (SiO 2 ) contained in the oxidized roasted product reacts with sodium hydroxide to produce sodium silicate (Na 2 SiO 3 ), which is eluted in the liquid.
WO3 + 2NaOH → Na2WO4 + H2O … [３]
CoWO4 + 2NaOH → Na2WO4 + Co(OH)2 … [４]
WO 3 + 2NaOH → Na 2 WO 4 + H 2 O… [3]
CoWO 4 + 2NaOH → Na 2 WO 4 + Co (OH) 2 … [4]
〔固液分離工程〕
上記アルカリ浸出物を固液分離して、固形分の水酸化コバルトを分離し、タングステン酸ナトリウムとシリカを液中に含む浸出液を回収する。
[Solid-liquid separation process]
The alkaline leachate is subjected to solid-liquid separation to separate solid cobalt hydroxide, and a leachate containing sodium tungstate and silica in the liquid is recovered.
〔シリカ沈澱化工程〕
上記固液分離した浸出液に消石灰(Ca(OH)2)を添加する。消石灰は液中のシリカと反応して、CaO・SiO2・H2Oを生成する。この生成した酸化カルシウムとシリカの混合物は濾過性が良いので、容易に濾過して浸出液から分離することができる。タングステン酸ナトリウムは消石灰と反応せずに液中に残る。
[Silica precipitation step]
Slaked lime (Ca (OH) 2 ) is added to the leachate obtained by solid-liquid separation. Slaked lime reacts with silica in the liquid to produce CaO · SiO 2 · H 2 O. Since the resulting mixture of calcium oxide and silica has good filterability, it can be easily filtered and separated from the leachate. Sodium tungstate remains in the liquid without reacting with slaked lime.
上記沈澱化工程において、浸出液はｐＨ１３以上の強アルカリ性が好ましい。また、液温は室温以上が適当であり、上記沈澱物の生成を速めるには４０℃以上が好ましい。消石灰の添加量は液中のシリカ量に対して当量であれば良い。 In the precipitation step, the leachate is preferably strongly alkaline with a pH of 13 or higher. The liquid temperature is suitably room temperature or higher, and preferably 40 ° C. or higher for speeding up the formation of the precipitate. The amount of slaked lime added may be equivalent to the amount of silica in the liquid.
〔固液分離工程〕
消石灰を添加した浸出液を濾過してカルシウムおよびシリカを含む上記混合沈殿物を分離する。この濾液はシリカを実質的に含まないタングステン酸ナトリウム溶液であるので、これをタングステン回収の原料液として用いることができる。
[Solid-liquid separation process]
The leachate added with slaked lime is filtered to separate the mixed precipitate containing calcium and silica. Since this filtrate is a sodium tungstate solution substantially free of silica, it can be used as a raw material liquid for tungsten recovery.
〔Na2WO4溶液の処理工程〕
回収したタングステン酸ナトリウム（Na2WO4）溶液を用い、タングステン酸アンモニウム〔(NH4)2WO4〕を経て酸化タングステン粉（ＷＯ3粉）を製造し、あるいは該酸化タングステンの水素還元によってタングステン粉を製造し、これを炭化処理して炭化タングステン粉（WC粉）を製造することができる。
[Na 2 WO 4 solution treatment process]
The recovered sodium tungstate (Na 2 WO 4 ) solution is used to produce tungsten oxide powder (WO 3 powder) via ammonium tungstate [(NH 4 ) 2 WO 4 ], or tungsten is reduced by hydrogen reduction of the tungsten oxide. Powder can be manufactured and this can be carbonized to produce tungsten carbide powder (WC powder).
具体的には、例えば、Na2WO4溶液にカルシウム源を添加してタングステン酸カルシウム（CaWO4）沈殿を生成させ、これを回収し、酸分解してタングステン酸（H2WO4）を製造し、これをアンモニアに溶解してタングステン酸アンモニウム〔(NH4)2WO4〕溶液とし、この溶液からパラタングステン酸アンモニウム〔5(NH4)2O・12WO3・5H2O〕を晶析させる。これを焼成して酸化タングステン粉とした後に水素還元してタングステン粉（Ｗ粉）を得ることができ、さらに炭化処理して炭化タングステン粉（WC粉）を得ることができる。 Specifically, for example, a calcium source is added to a Na 2 WO 4 solution to form a calcium tungstate (CaWO 4 ) precipitate, which is recovered and acid decomposed to produce tungstic acid (H 2 WO 4 ). This was dissolved in ammonia to obtain an ammonium tungstate [(NH 4 ) 2 WO 4 ] solution, and ammonium paratungstate [5 (NH 4 ) 2 O · 12WO 3 · 5H 2 O] was crystallized from this solution. Let This can be fired to obtain tungsten oxide powder, which can then be hydrogen reduced to obtain tungsten powder (W powder), and further carbonized to obtain tungsten carbide powder (WC powder).
本発明の実施例を以下に示す。
〔実施例１〕
タングステン(Ｗ)４５wt％、クリストバライトを主成分とするシリコン(Si)１４wt％を含有するスラッジ１kgを、大気中にて７００℃で２時間焙焼した。この焙焼物を濃度１６０ｇ/Ｌの苛性ソーダ溶液５Ｌに混合し、８０℃で２時間浸漬した。このスラリーを濾過し、固形分として残る水酸化コバルトを分離した。次に、この固液分離した濾洗液７Ｌに消石灰３７１ｇを加え、室温下で２０時間反応させ、生成した沈澱を濾過して分離し、濾液としてＷ濃度３９ｇ/Ｌ、Ｓｉ濃度０.１３ｇ/Lのタングステン酸ナトリウム溶液８.２Ｌを得た。Ｗの回収率は７１％であり、Ｓｉ濃度はパラタングステン酸アンモニウムを製造するうえで問題のないレベルであった。
Examples of the present invention are shown below.
[Example 1]
1 kg of sludge containing 45 wt% tungsten (W) and 14 wt% silicon (Si) containing cristobalite as a main component was roasted at 700 ° C. for 2 hours in the air. This roasted product was mixed with 5 L of caustic soda solution having a concentration of 160 g / L and immersed at 80 ° C. for 2 hours. This slurry was filtered to separate the remaining cobalt hydroxide as a solid content. Next, 371 g of slaked lime is added to 7 L of the filtered washing liquid separated into solid and liquid and reacted at room temperature for 20 hours, and the formed precipitate is separated by filtration. As a filtrate, W concentration 39 g / L, Si concentration 0.13 g / 8.2 L of sodium tungstate solution was obtained. The W recovery was 71%, and the Si concentration was at a level causing no problem in producing ammonium paratungstate.
〔実施例２〜４〕
表１に示すスラッジを用い、表１に示す条件の他は実施例１と同様にして、タングステン酸ナトリウム溶液を得た。この結果を表１に示した。
[Examples 2 to 4]
Using the sludge shown in Table 1, a sodium tungstate solution was obtained in the same manner as in Example 1 except for the conditions shown in Table 1. The results are shown in Table 1.
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