JP2003305432A - Method for recovering mercury from waste - Google Patents
Method for recovering mercury from wasteInfo
- Publication number
- JP2003305432A JP2003305432A JP2002111763A JP2002111763A JP2003305432A JP 2003305432 A JP2003305432 A JP 2003305432A JP 2002111763 A JP2002111763 A JP 2002111763A JP 2002111763 A JP2002111763 A JP 2002111763A JP 2003305432 A JP2003305432 A JP 2003305432A
- Authority
- JP
- Japan
- Prior art keywords
- mercury
- waste
- complex
- sulfur
- recovering
- 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
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 229910052753 mercury Inorganic materials 0.000 title claims abstract description 110
- 239000002699 waste material Substances 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 21
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 25
- 239000011733 molybdenum Substances 0.000 claims abstract description 25
- 239000000243 solution Substances 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- 239000003638 chemical reducing agent Substances 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 6
- 238000011084 recovery Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- -1 Sulfide ions Chemical class 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 208000030527 Minamata disease Diseases 0.000 description 1
- 208000009507 Nervous System Mercury Poisoning Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000010169 landfilling Methods 0.000 description 1
- 229910001338 liquidmetal Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- QXKXDIKCIPXUPL-UHFFFAOYSA-N sulfanylidenemercury Chemical compound [Hg]=S QXKXDIKCIPXUPL-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- 231100000925 very toxic Toxicity 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/52—Mechanical processing of waste for the recovery of materials, e.g. crushing, shredding, separation or disassembly
Landscapes
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Treating Waste Gases (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、廃棄物の水銀回収
方法に関し、特に、還元により水銀を分離して取り出す
とともに、水銀に強い親和性を示す化合物で水銀を捕獲
することにより、例えば、蛍光管等の廃棄物に含まれる
水銀を除去して回収し、かつ水銀を除去した廃棄物を有
効に再利用することができる廃棄物の水銀回収方法に関
するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for recovering mercury from wastes, and more particularly, by separating and extracting mercury by reduction and capturing mercury with a compound having a strong affinity for mercury, for example, fluorescence The present invention relates to a method for recovering mercury from waste, which enables mercury contained in waste such as pipes to be removed and recovered and the waste from which mercury has been removed to be effectively reused.
【０００２】[0002]
【従来の技術】蛍光管は、白熱灯に比べて少ない電気量
でより明るい光が得られることから、家庭用や事業用を
問わず広く使用されており、国内における蛍光管の生産
量は、年間約４億５千万本に達している。この場合、蛍
光管には、１本につき十数ミリグラムを越える水銀が使
用されていることから、少なく見積もっても年間数トン
の水銀が使用されていることになる。そこで、問題は古
くなった蛍光管の処理であり、毎年、生産量にほぼ相当
する廃蛍光管が破棄されているが、廃棄された蛍光管
は、そのほとんどが埋立てによって処分されている。2. Description of the Related Art Fluorescent tubes are widely used for household and business purposes because they can obtain brighter light with less electricity than incandescent lamps. The annual number reaches about 450 million. In this case, since more than ten and several milligrams of mercury are used for each fluorescent tube, it means that several tons of mercury are used per year, at least under estimation. Therefore, the problem is the treatment of old fluorescent tubes, and the discarded fluorescent tubes corresponding to the production amount are discarded every year, but most of the discarded fluorescent tubes are disposed of by landfill.
【０００３】[0003]
【発明が解決しようとする課題】ところで、この廃蛍光
管の埋立て処分は二つの問題を抱えており、一つは、埋
立てに適当な土地を確保することの難しさである。これ
は、全国各地に広がる産業廃棄物処理場設置を巡るトラ
ブルの深刻さからもその難しさの程度が推測される。も
う一つの問題は、水銀流出の問題であり、処理場で様々
な対策を取っていても、年月が経つと設備が古くなり、
水銀流出の可能性が出てくる。また、蛍光管のみなら
ず、水銀灯も街灯等に多く使用されており、蛍光管と同
様の問題を抱えている。蛍光管や水銀灯からの水銀の流
出を事前に防ぐことは水俣病の惨事を繰り返さないため
の緊急の課題である。水銀の毒性は非常に高く、また、
ひとたび外部に排出されると回収は非常に難しく、現在
まで回収の有効な手段が見出されていない。The landfill disposal of the waste fluorescent tubes has two problems, one of which is the difficulty of securing a suitable land for landfilling. The degree of difficulty is inferred from the seriousness of the troubles associated with the installation of industrial waste treatment plants spread across the country. Another problem is the outflow of mercury, and even if various measures are taken at the treatment plant, the equipment will become old over the years,
There is a possibility of mercury outflow. Further, not only fluorescent tubes but also mercury lamps are widely used for street lamps and the like, and have the same problems as fluorescent tubes. Preventing the outflow of mercury from fluorescent tubes and mercury lamps in advance is an urgent task in order not to repeat the Minamata disease disaster. Mercury is very toxic, and
Once it is discharged to the outside, it is very difficult to collect it, and no effective means of recovery has been found until now.
【０００４】一方、蛍光管や水銀灯に用いられているガ
ラスは、通常のガラスと異なり特に高品質であり、年間
数万トンに及ぶ高品質ガラスを埋めずにリサイクルする
ことは、省資源や省エネルギーの点からも意義深いと考
えられる。On the other hand, the glass used in fluorescent tubes and mercury lamps is of a particularly high quality, unlike ordinary glass, and it is resource and energy efficient to recycle tens of thousands of tons of high quality glass without filling it. From the point of view, it is considered significant.
【０００５】本発明は、上記従来の廃棄物の水銀回収方
法が有する問題点に鑑み、廃棄物に含まれる水銀を除去
して回収し、かつ水銀を除去した廃棄物を有効に再利用
することができる廃棄物の水銀回収方法を提供すること
を目的とする。In view of the problems of the above-mentioned conventional methods for recovering mercury from wastes, the present invention removes and recovers mercury contained in wastes and effectively reuses the wastes from which mercury has been removed. It is an object of the present invention to provide a method of recovering mercury from waste that can be used.
【０００６】[0006]
【課題を解決するための手段】上記目的を達成するた
め、本発明の廃棄物の水銀回収方法は、廃棄物から取り
出した気体状の水銀を、硫黄架橋三核モリブデン錯体溶
液中に通すことにより錯体と結合させて水銀を捕獲する
ことを特徴とする。In order to achieve the above object, the method for recovering mercury from waste according to the present invention is a method in which gaseous mercury taken out from the waste is passed through a sulfur-bridged trinuclear molybdenum complex solution. It is characterized in that it binds to a complex and captures mercury.
【０００７】この廃棄物の水銀回収方法は、廃棄物から
取り出した気体状の水銀を、硫黄架橋三核モリブデン錯
体溶液中に通すことから、水銀を、強い親和性を示す硫
黄架橋三核モリブデン錯体と結合させて捕獲することが
でき、水銀を容易に回収するとともに、水銀を除去した
廃棄物をリサイクルにより有効に再利用することができ
る。In this method of recovering mercury from waste, since the gaseous mercury taken out from the waste is passed through the sulfur-bridged trinuclear molybdenum complex solution, the mercury has a strong affinity with the sulfur-bridged trinuclear molybdenum complex. The mercury can be easily recovered and the waste from which the mercury has been removed can be effectively reused by recycling.
【０００８】この場合において、水銀を捕獲した錯体溶
液の溶媒を蒸発させることにより減容化することができ
る。In this case, it is possible to reduce the volume by evaporating the solvent of the complex solution in which mercury is captured.
【０００９】これにより、廃棄物の量を低減して、廃棄
物の処理コストを低減することができる。As a result, the amount of waste can be reduced, and the processing cost of waste can be reduced.
【００１０】また、廃棄物に付着した水銀を還元剤を含
む水溶液中で溶出させ、気体状にして取り出すようにす
ることができる。Further, mercury adhering to the waste can be eluted in an aqueous solution containing a reducing agent and turned into a gas to be taken out.
【００１１】これにより、廃棄物に付着した水銀を、廃
棄物から確実に分離することができ、水銀の回収率を高
めるとともに、水銀を除去した後の廃棄物の再利用を促
進することができる。Thus, the mercury adhering to the waste can be reliably separated from the waste, the recovery rate of mercury can be increased, and the reuse of the waste after removing the mercury can be promoted. .
【００１２】そして、本発明の廃棄物の水銀回収方法
は、特に、蛍光管や水銀灯の廃棄物処理に好適に利用す
ることができ、この場合、水銀を除去した後のガラス及
び金属を再利用に供することができる。The method for recovering mercury from waste according to the present invention can be suitably used particularly for waste treatment of fluorescent tubes and mercury lamps. In this case, the glass and metal after removing mercury are reused. Can be used for
【００１３】[0013]
【発明の実施の形態】以下、本発明の廃棄物の水銀回収
方法の実施の形態を図面に基づいて説明する。BEST MODE FOR CARRYING OUT THE INVENTION An embodiment of a method for recovering mercury from waste according to the present invention will be described below with reference to the drawings.
【００１４】図１〜図２に、本発明の廃棄物の水銀回収
方法の一実施例を示す。この廃棄物の水銀回収方法は、
廃棄物から取り出した気体状の水銀を、硫黄架橋三核モ
リブデン錯体溶液中に通すことにより錯体と結合させて
水銀を捕獲することにより水銀を回収するものである。1 and 2 show an embodiment of a method for recovering mercury from waste according to the present invention. The mercury recovery method for this waste is
Gaseous mercury taken out from the waste is passed through a sulfur-bridged trinuclear molybdenum complex solution to combine with the complex and capture the mercury to recover the mercury.
【００１５】そして、水銀を捕獲した錯体溶液の溶媒を
蒸発させるほか、水銀を捕獲した錯体溶液に適宜の薬品
を加えることにより水銀成分を沈殿させて濾過すること
により、廃棄物の減容化を行うことができる。The volume of the waste is reduced by evaporating the solvent of the mercury-captured complex solution and precipitating and filtering the mercury component by adding an appropriate chemical to the mercury-captured complex solution. It can be carried out.
【００１６】この場合において、廃棄物に封入されてい
た気体状の水銀は、そのまま取り出すことができるが、
例えば、長期間使用した蛍光管や水銀灯中では、水銀
は、Ｈｇ0、ＨｇI又はＨｇIIを含む複雑な組成をもつ化
合物になっていると推定され、蛍光管や水銀灯のガラス
管に強く付着し、簡単には除去することができない。In this case, the gaseous mercury enclosed in the waste can be taken out as it is.
For example, in a fluorescent tube or mercury lamp that has been used for a long period of time, it is presumed that mercury is a compound with a complex composition containing Hg 0 , Hg I or Hg II , and it strongly adheres to the fluorescent tube or the glass tube of the mercury lamp. However, it cannot be easily removed.
【００１７】そこで、この点を解決するために、先ず、
還元剤を含む水溶液１中に破砕した蛍光管や水銀灯２を
浸漬し、単体の水銀（Ｈｇ0）として溶かし出すように
する。In order to solve this point, first of all,
A crushed fluorescent tube or a mercury lamp 2 is immersed in an aqueous solution 1 containing a reducing agent so that the mercury (Hg 0 ) as a simple substance is dissolved.
【００１８】この場合、還元剤としては、低級酸素酸塩
（例えば、ＮａＨ2ＰＯ2、Ｎａ2Ｓ2Ｏ3等）、還元性を
有する金属イオン（例えば、Ｆｅ2+、Ｓｎ2+、Ｃｒ
2+等）、及びヒドラジン、ギ酸、アルデヒド、アスコル
ビン酸等がある。In this case, as the reducing agent, a lower oxygen acid salt (eg, NaH 2 PO 2 , Na 2 S 2 O 3, etc.), a reducing metal ion (eg, Fe 2+ , Sn 2+ , Cr) is used.
2+ etc.), and hydrazine, formic acid, aldehydes, ascorbic acid, etc.
【００１９】次いで、還元剤と水銀（Ｈｇ0）を含む水
溶液に不活性ガスとして窒素（又は空気）を吹き込むこ
とにより、溶け出た水銀を気体状にして取り出すように
する。Next, by blowing nitrogen (or air) as an inert gas into an aqueous solution containing a reducing agent and mercury (Hg 0 ), the dissolved mercury is taken out in a gaseous state.
【００２０】このようにして、気体状にして取り出した
水銀（廃棄物に封入され、廃棄物を破砕した際に放出さ
れる気体状の水銀を含む。）を、硫黄架橋三核モリブデ
ン錯体溶液３を入れた別の容器に追い出し、「Ｍｏ3Ｓ4
からなる基本骨格を有する硫黄架橋三核モリブデン錯
体」、例えば、代表的には、図３に示すような[Ｍｏ3Ｓ
4（Ｈｎｔａ）3］2-と結合させて捕獲する。なお、「Ｈ
3ｎｔａ」は、ニトリロ三酢酸である。In this way, it was taken out in a gaseous state.
Mercury (Enclosed in waste and released when the waste is crushed
It contains gaseous mercury. ) Is a sulfur-bridged trinuclear molybde
Eject it into another container containing the complex solution 3,3SFour
Bridged trinuclear molybdenum complex with basic skeleton
Body ”, for example, [Mo3S
Four(Hnta)3]2-Combine with and capture. In addition, "H
3"nta" is nitrilotriacetic acid.
【００２１】水銀を捕獲した錯体溶液は、溶媒を蒸発さ
せることにより、水銀をごく少量の体積の固体として回
収し保管する。The complex solution in which mercury has been captured recovers and stores mercury as a solid having a very small volume by evaporating the solvent.
【００２２】この場合、水銀の気化や結合には、気化装
置や反応装置等を組み合わせたシステムで操作するが、
少スケールでは、図２に示すような装置を用いることが
できる。なお、システムの構成は、図２に示す装置に限
定されるものでない。In this case, a system in which a vaporizer, a reaction device and the like are combined is used for vaporizing and binding mercury.
On a small scale, a device as shown in Figure 2 can be used. The system configuration is not limited to the device shown in FIG.
【００２３】そして、蛍光管や水銀灯２の廃棄物から水
銀を除去した後のガラス及び金属は、レンガはもちろん
のこと、多くの分野で再利用が可能であり、用途に応
じ、選別、粉砕サイズの調整を行うようにする。The glass and metal after removing mercury from the waste of the fluorescent tube and the mercury lamp 2 can be reused not only in bricks but also in many fields. Make adjustments.
【００２４】次に、本発明で使用する硫黄架橋三核モリ
ブデン錯体について説明する。硫化物イオン（Ｓ2-）や
多硫化物イオン（Ｓn 2-；ｎ≧２）は、同種又は異種の
金属を強く結び付けて、多核金属錯体を形成する能力が
ある。Next, the sulfur-bridged trinuclear molybdenum complex used in the present invention will be described. Sulfide ions (S 2− ) and polysulfide ions (S n 2− ; n ≧ 2) have the ability to strongly bind the same or different metals to form a polynuclear metal complex.
【００２５】ちなみに、本件発明者は、多くの硫黄架橋
多核金属錯体の合成に成功し、一例として、硫黄架橋三
核モリブデンアクア錯体［Ｍｏ3Ｓ4（Ｈ2Ｏ）9］4+（図
４中符号４）が鉄を取り込み、混合金属アクア錯体［Ｍ
ｏ3ＦｅＳ4（Ｈ2Ｏ）10］4+を生成することを見出して
いる。硫化水銀ＨｇＳの水に対する溶解度が非常に小さ
いことからもわかるように、水銀は、硫黄と非常に大き
な親和性を示す。水銀は、硫黄架橋三核モリブデンアク
ア錯体［Ｍｏ3Ｓ4（Ｈ2Ｏ）9］4+（緑色）と反応する
と、紫色に強く発色する。水銀の量が多い場合は、目視
でも色の変化から水銀の存在を確認できる。また、分光
光度計を用いることにより、微量の水銀も定量できる。
また、硫黄架橋三核モリブデンアクア錯体［Ｍｏ3Ｓ
4（Ｈ2Ｏ）9］4+は、酸性水溶液中でのみ安定である
が、中性水溶液中でも安定なニトリロ三酢酸（Ｈ3ｎｔ
ａ）を配位子とする硫黄架橋三核モリブデン錯体[Ｍｏ3
Ｓ4（Ｈｎｔａ）3］2-となり、この錯体[Ｍｏ3Ｓ4（Ｈ
ｎｔａ）3］2-も、前記硫黄架橋三核モリブデンアクア
錯体［Ｍｏ3Ｓ4（Ｈ2Ｏ）9］4+と同様に水銀との親和性
が非常に強い特性を備えている。Incidentally, the present inventors have succeeded in synthesizing many sulfur-bridged polynuclear metal complexes, and as an example, the sulfur-bridged trinuclear molybdenum aqua complex [Mo 3 S 4 (H 2 O) 9 ] 4+ (see FIG. 4). Medium code 4) incorporates iron, mixed metal aqua complex [M
It has been found to produce o 3 FeS 4 (H 2 O) 10 ] 4+ . As can be seen from the extremely low solubility of mercury sulfide HgS in water, mercury has a very high affinity with sulfur. When mercury reacts with a sulfur-bridged trinuclear molybdenum aqua complex [Mo 3 S 4 (H 2 O) 9 ] 4+ (green), it strongly develops a purple color. When the amount of mercury is large, the presence of mercury can be visually confirmed by the color change. Further, a trace amount of mercury can be quantified by using a spectrophotometer.
In addition, sulfur-bridged trinuclear molybdenum aqua complex [Mo 3 S
4 (H 2 O) 9] 4+ is the only stable in an acidic aqueous solution, even in neutral aqueous solution stable nitrilotriacetic acid (H 3 nt
Sulfur-bridged trinuclear molybdenum complex having a) as a ligand [Mo 3
S 4 (Hnta) 3 ] 2- becomes the complex [Mo 3 S 4 (H
nta) 3 ] 2− also has a very strong affinity with mercury, like the sulfur-bridged trinuclear molybdenum aqua complex [Mo 3 S 4 (H 2 O) 9 ] 4+ .
【００２６】かくして、本実施例の廃棄物の水銀回収方
法は、取り出した気体状の水銀を、硫黄架橋三核モリブ
デン錯体溶液中に通すことから、水銀を、強い親和性を
示す硫黄架橋三核モリブデン錯体と結合させて捕獲する
ことができ、これにより、水銀を容易に回収することが
できるとともに、水銀を除去した廃棄物をリサイクルに
より有効に再利用することができる。硫黄架橋三核モリ
ブデン錯体と水銀との反応は非常に速く、かつ鋭敏であ
るため、水銀を確実に結合させて捕獲することができ
る。ちなみに、上記の硫黄架橋三核モリブデンアクア錯
体［Ｍｏ3Ｓ4（Ｈ2Ｏ）9］ 4+やニトリロ三酢酸（Ｈ3ｎ
ｔａ）を配位子とする硫黄架橋三核モリブデン錯体[Ｍ
ｏ3Ｓ4（Ｈｎｔａ）3］2-等は、水に溶け易いため、一
般的には、溶媒として水を使用し、水溶液として用いる
ようにするが、水以外の溶媒（非水溶媒）に溶け易い硫
黄架橋三核モリブデン錯体も存在するので、水より気化
し易い非水溶媒を用いれば、溶媒として使用する水と比
較して、原料コストは上昇するものの、気化し易いた
め、速やかに水銀を固体として回収することができ、処
理効率を向上することができる利点がある。このため、
使用する硫黄架橋三核モリブデン錯体及び溶媒の種類
は、廃棄物の処理形態等に応じて、コストや処理効率等
を勘案して、適宜選定するようにする。Thus, the method of recovering mercury from the waste of this embodiment
The method is to remove the gaseous mercury from the sulfur-bridged trinuclear molybdenum.
Since it is passed through the den complex solution, it has a strong affinity for mercury.
Capture by binding with the sulfur-bridged trinuclear molybdenum complex shown
This allows mercury to be easily recovered.
We can do it, and also recycle the waste from which mercury has been removed.
It can be reused more effectively. Sulfur bridged trinuclear molybdenum
The reaction between the butene complex and mercury is very fast and sensitive.
As a result, mercury can be reliably bound and captured.
It By the way, the above sulfur-bridged trinuclear molybdenum aqua complex is used.
Body [Mo3SFour(H2O)9] 4+And nitrilotriacetic acid (H3n
sulfur-bridged trinuclear molybdenum complex [ta] as a ligand [M
o3SFour(Hnta)3]2-Are easily dissolved in water,
Generally, water is used as a solvent and used as an aqueous solution.
However, sulfur that is easily dissolved in a solvent other than water (non-aqueous solvent)
There is also a yellow-bridged trinuclear molybdenum complex, so it vaporizes from water.
If you use a non-aqueous solvent that is easy to
In comparison, the raw material cost rises, but it is easy to vaporize.
Therefore, it is possible to quickly recover mercury as a solid.
There is an advantage that the efficiency can be improved. For this reason,
Type of sulfur-bridged trinuclear molybdenum complex and solvent used
Depending on the type of waste disposal
In consideration of the above, make an appropriate selection.
【００２７】そして、水銀を捕獲した錯体溶液の溶媒を
蒸発等させることによって、廃棄物の減容化を行うこと
ができる。The volume of the waste can be reduced by evaporating the solvent of the complex solution that has captured the mercury.
【００２８】また、廃棄物に付着した水銀は、還元剤を
含む水溶液中で溶出させ、気体状にして取り出すように
することにより、廃棄物に付着した水銀を、廃棄物から
確実に分離することができ、水銀の回収率を高めるとと
もに、水銀を除去した後の廃棄物の再利用を促進するこ
とができる。Further, mercury adhering to the waste is eluted in an aqueous solution containing a reducing agent and is taken out in a gas state so that the mercury adhering to the waste can be reliably separated from the waste. As a result, the recovery rate of mercury can be increased and the reuse of waste after removing mercury can be promoted.
【００２９】以上、本発明の実施例を蛍光管や水銀灯を
例にして説明したが、本発明は、この実施例の記載に限
定されるものではなく、その趣旨を逸脱しない範囲にお
いて適宜に変更することが可能である。例えば、水銀は
唯一の液状金属であるとともに、熱や電気の良導体であ
り、多くの計量器や電気機器等に用いられている。そし
て、これらの機器が古くなったとき、付着した水銀のた
め簡単に廃棄できなくなり、産業廃棄物として埋立て処
理されることになるが、本発明の廃棄物の水銀回収方法
は、このような器機に対しても有効であり、付着した水
銀を回収するとともに、これらの機器のリサイクルを可
能とすることができる。Although the embodiment of the present invention has been described above by taking the fluorescent tube and the mercury lamp as an example, the present invention is not limited to the description of this embodiment, and is appropriately modified within a range not departing from the gist thereof. It is possible to For example, mercury is the only liquid metal, and is also a good conductor of heat and electricity, and is used in many measuring instruments and electric devices. Then, when these devices become old, they cannot be easily discarded due to the attached mercury, and they are landfilled as industrial waste. It is also effective for equipment, and it is possible to collect the attached mercury and to recycle these equipments.
【００３０】[0030]
【発明の効果】本発明の廃棄物の水銀回収方法によれ
ば、廃棄物から取り出した気体状の水銀を、硫黄架橋三
核モリブデン錯体溶液中に通すことから、水銀を、強い
親和性を示す硫黄架橋三核モリブデン錯体と結合させて
捕獲することができ、これにより、水銀を容易に回収す
ることができるとともに、水銀を除去した廃棄物、特
に、蛍光管や水銀灯の廃棄物から水銀を除去した後のガ
ラス及び金属を再利用に供することができる。EFFECTS OF THE INVENTION According to the method for recovering mercury from waste of the present invention, since the gaseous mercury taken out from the waste is passed through the sulfur-bridged trinuclear molybdenum complex solution, mercury has a strong affinity. It can be combined with a sulfur-bridged trinuclear molybdenum complex to be captured, which makes it possible to easily recover mercury, and also to remove mercury from waste from which mercury has been removed, especially from fluorescent tube and mercury lamp waste. The glass and metal after being processed can be reused.
【００３１】また、水銀を捕獲した錯体溶液の溶媒を蒸
発させて減容化することにより、廃棄物の量を低減し
て、廃棄物の処理コストを低減することができる。Further, by evaporating the solvent of the complex solution that has captured the mercury to reduce the volume, the amount of waste can be reduced and the processing cost of waste can be reduced.
【００３２】また、廃棄物に付着した水銀を還元剤を含
む水溶液中で溶出させ、気体状にして取り出すようにす
ることにより、廃棄物に付着した水銀を、廃棄物から確
実に分離することができ、水銀の回収率を高めるととも
に、水銀を除去した後の廃棄物の再利用を促進すること
ができる。Further, the mercury adhering to the waste can be reliably separated from the waste by eluting the mercury adhering to the waste in an aqueous solution containing a reducing agent and taking it out in a gaseous state. Therefore, the recovery rate of mercury can be increased, and the reuse of waste after removing mercury can be promoted.
【図１】本発明の廃棄物の水銀回収方法の一実施例を示
すチャート図である。FIG. 1 is a chart showing an embodiment of a method for recovering mercury from waste according to the present invention.
【図２】同実施例の廃棄物の水銀回収方法の反応装置を
示す図である。FIG. 2 is a diagram showing a reactor of a method for recovering waste mercury according to the same example.
【図３】硫黄架橋三核モリブデン錯体の一例を示す化学
構造式である。FIG. 3 is a chemical structural formula showing an example of a sulfur-bridged trinuclear molybdenum complex.
【図４】Ｈ2Ｏを省略した硫黄架橋三核モリブデン錯体
と金属との反応を示す図である。FIG. 4 is a diagram showing a reaction between a sulfur-bridged trinuclear molybdenum complex without H 2 O and a metal.
１ 還元剤を含む水溶液 ２ 蛍光管 ３ 硫黄架橋三核モリブデン錯体溶液 1 Aqueous solution containing reducing agent 2 fluorescent tube 3 Sulfur-bridged trinuclear molybdenum complex solution
フロントページの続き (72)発明者 柴原 隆志 岡山県岡山市津島南２丁目６−30−６ (72)発明者 愛甲 博美 岡山県赤磐郡山陽町桜が丘西８−10−８ (72)発明者 田中 康宏 兵庫県姫路市飾磨区中島1094−３ Ｆターム(参考） 4D002 AA29 AC10 BA02 CA06 DA61 EA07 4D004 AA50 AB03 BA05 BA06 CA34 CA37 CA40 CC06 CC11 CC15Continued front page (72) Inventor Takashi Shibahara 2-6-30-6 Tsushima Minami, Okayama City, Okayama Prefecture (72) Inventor Hiromi Aiko 8-10-8 Sakuragaoka West, Sanyo-cho, Akaban-gun, Okayama Prefecture (72) Inventor Yasuhiro Tanaka 1094-3 Nakajima, Shikama-ku, Himeji City, Hyogo Prefecture F-term (reference) 4D002 AA29 AC10 BA02 CA06 DA61 EA07 4D004 AA50 AB03 BA05 BA06 CA34 CA37 CA40 CC06 CC11 CC15
Claims (4)
硫黄架橋三核モリブデン錯体溶液中に通すことにより錯
体と結合させて水銀を捕獲することを特徴とする廃棄物
の水銀回収方法。1. Gaseous mercury extracted from waste is
A method for recovering mercury from wastes, which comprises passing through a sulfur-bridged trinuclear molybdenum complex solution to bind with the complex and capture mercury.
せることにより減容化することを特徴とする請求項１記
載の廃棄物の水銀回収方法。2. The method for recovering mercury from waste according to claim 1, wherein the volume of the complex solution containing mercury is reduced by evaporating the solvent of the complex solution.
溶液中で溶出させ、気体状にして取り出すことを特徴と
する請求項２記載の廃棄物の水銀回収方法。3. The method for recovering mercury from waste according to claim 2, wherein the mercury adhering to the waste is eluted in an aqueous solution containing a reducing agent and is taken out in a gaseous state.
除去した後のガラス及び金属を再利用することを特徴と
する請求項１、２又は３記載の廃棄物の水銀回収方法。4. The method for recovering mercury in waste according to claim 1, 2 or 3, wherein the waste is a fluorescent tube or a mercury lamp, and the glass and the metal after removing the mercury are reused.
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| JP2002111763A JP3429753B1 (en) | 2002-04-15 | 2002-04-15 | Mercury recovery method for waste |
| KR1020020064191A KR100373106B1 (en) | 2002-04-15 | 2002-10-21 | Method for recovering mercury from waste |
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| JP2002111763A JP3429753B1 (en) | 2002-04-15 | 2002-04-15 | Mercury recovery method for waste |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010042346A (en) * | 2008-08-12 | 2010-02-25 | Jfe Mineral Co Ltd | Pretreatment method for recovering rare earth element from disposed fluorescent lamp and method of recovering rare earth element using solid matter obtained by the pretreatment method |
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2002
- 2002-04-15 JP JP2002111763A patent/JP3429753B1/en not_active Expired - Lifetime
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010042346A (en) * | 2008-08-12 | 2010-02-25 | Jfe Mineral Co Ltd | Pretreatment method for recovering rare earth element from disposed fluorescent lamp and method of recovering rare earth element using solid matter obtained by the pretreatment method |
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