JP4901315B2 - Method for recycling molten fly ash - Google Patents
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- JP4901315B2 JP4901315B2 JP2006156564A JP2006156564A JP4901315B2 JP 4901315 B2 JP4901315 B2 JP 4901315B2 JP 2006156564 A JP2006156564 A JP 2006156564A JP 2006156564 A JP2006156564 A JP 2006156564A JP 4901315 B2 JP4901315 B2 JP 4901315B2
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- 239000010881 fly ash Substances 0.000 title claims description 57
- 238000000034 method Methods 0.000 title claims description 28
- 238000004064 recycling Methods 0.000 title claims description 20
- 239000010949 copper Substances 0.000 claims description 56
- 229910052802 copper Inorganic materials 0.000 claims description 25
- 238000002844 melting Methods 0.000 claims description 25
- 230000008018 melting Effects 0.000 claims description 25
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- 239000002893 slag Substances 0.000 claims description 14
- 239000002956 ash Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000000571 coke Substances 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 11
- 239000003638 chemical reducing agent Substances 0.000 claims description 10
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 150000002367 halogens Chemical class 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 4
- 230000006698 induction Effects 0.000 claims description 3
- 230000002829 reductive effect Effects 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 description 20
- 239000002184 metal Substances 0.000 description 20
- 238000003723 Smelting Methods 0.000 description 19
- 239000000428 dust Substances 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000460 chlorine Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 229910001385 heavy metal Inorganic materials 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 229910052745 lead Inorganic materials 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- -1 easily soluble NaCl Chemical class 0.000 description 3
- 238000002309 gasification Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000010309 melting process Methods 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910000519 Ferrosilicon Inorganic materials 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 238000005695 dehalogenation reaction Methods 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- 239000010791 domestic waste Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Processing Of Solid Wastes (AREA)
- Manufacture And Refinement Of Metals (AREA)
Description
本発明は溶融飛灰の再資源化処理方法に関し、より詳しくは、溶融飛灰から金属成分のうち特に銅を銅製錬にきわめて有利な原料として回収する溶融飛灰の再資源化処理方法に関する。 The present invention relates to a method for recycling molten fly ash, and more particularly, to a method for recycling molten fly ash, in which copper is recovered from molten fly ash as a particularly advantageous raw material for copper smelting.
近年、埋立処分場の枯渇やダイオキシン低減化対策として、生活ゴミに代表される一般廃棄物や、カーシュレッダーダスト等の廃プラスチックに代表される産業廃棄物の処理設備としてガス化溶融炉や灰溶融炉が多数建設されており、それらの設備から排出される溶融飛灰の量は年間１５万トンを超え、今後更に増加することが予想されている。 In recent years, gasification melting furnaces and ash melting have been used as treatment facilities for general waste represented by household waste and industrial waste represented by waste plastics such as car shredder dust, as measures to deplete landfill sites and reduce dioxins. Many furnaces have been built, and the amount of molten fly ash discharged from these facilities exceeds 150,000 tons per year, and is expected to increase further in the future.
溶融飛灰はその大半がキレート材等により不溶出処理を実施した後、埋立処分場で最終処分されている。しかし、埋立処分場の残余量が問題であるばかりでなく、ガス化溶融炉や灰溶融炉のような高度濃縮型の炉によって処理した結果として一桁台の％に濃縮されたＰｂやＣｄのような有害重金属についてはキレート材等による不溶出処理ではその長期安定性が問題であり、更にそのように高い含有量を有する有害重金属を埋立処分すること自体が問題視されている。又、二桁台の％で含有されることもある易溶性ＮａＣｌ等の塩類の最終処分場での溶出も問題となっている。 Most of the molten fly ash is subjected to non-eluting treatment with a chelating material and the like, and then finally disposed at a landfill site. However, not only is the residual amount of the landfill site a problem, but as a result of processing by a highly concentrated furnace such as a gasification melting furnace or an ash melting furnace, the concentration of Pb and Cd concentrated to single-digit percentages For such toxic heavy metals, long-term stability is a problem in non-eluting treatment with a chelating material or the like, and landfill disposal of toxic heavy metals having such a high content is regarded as a problem. In addition, elution of salts such as easily soluble NaCl, which may be contained in double digit%, at the final disposal site is also a problem.
一般廃棄物処理の溶融炉から排出される溶融飛灰中のＣｕ分は１％程度であるが、自動車のリサイクル法制定の結果、カーシュレッダーダスト処理の溶融炉から排出される溶融飛灰中のＣｕ分は１０％を超える高濃度となっており、そのような溶融飛灰の発生量及びＣｕ含有率を考慮するとそのような溶融飛灰は有効な資源として考えることができる。 The Cu content in the molten fly ash discharged from the general waste treatment melting furnace is about 1%, but as a result of the establishment of the automobile recycling law, the molten fly ash discharged from the car shredder dust treatment melting furnace The Cu content has a high concentration exceeding 10%, and such molten fly ash can be considered as an effective resource in consideration of the amount of molten fly ash generated and the Cu content.
溶融飛灰中の銅の再資源化処理方法としては、溶融飛灰中に大量に含まれている塩素を利用して溶融飛灰中の重金属成分を塩化物として揮発させ、ダストとして回収する塩化揮発法（乾式法）が提案されている（例えば、特許文献１及び２参照。）が、Ｃｕ、Ｚｎ、Ｐｂ等の重金属を、製錬に利用可能な品位となるように揮発させるための塩素濃度の制御が難しいこと、回収したダストは吸湿性であるため取り扱いが煩雑であること、更には、製錬原料化のためにはＣｕとＺｎ、Ｐｂ等の重金属との複雑な湿式分離操作を必要とし、過大なコストを必要とすること等の問題を有している。 As a method for recycling copper in the molten fly ash, the heavy metal components in the molten fly ash are volatilized as chloride using chlorine contained in large quantities in the molten fly ash and recovered as dust. Volatilization methods (dry methods) have been proposed (see, for example, Patent Documents 1 and 2), but chlorine for volatilizing heavy metals such as Cu, Zn, and Pb so that they can be used for smelting Concentration is difficult to control, the collected dust is hygroscopic and handling is complicated, and moreover, complicated wet separation operation of heavy metals such as Cu and Zn and Pb is required for smelting raw materials. It has problems such as need and excessive cost.
溶融飛灰中のＣｕを回収する方法として湿式処理方法も提案されている（例えば、特許文献３及び４参照。）が、処理操作が多段となり複雑であること、又、処理の過程で二次的に発生する廃液の処理も複雑であり、最終的に発生する残渣の処理も必要であること等により処理コストが高いこと、更に湿式処理自体が大規模処理に不向きであること等の問題がある。 A wet processing method has also been proposed as a method for recovering Cu in molten fly ash (see, for example, Patent Documents 3 and 4). However, the processing operation is multi-stage and complicated, and a secondary process is performed during the processing. The treatment of the waste liquid that is generated is complicated, the processing cost is high due to the necessity of processing the residue that finally occurs, and the wet processing itself is not suitable for large-scale processing. is there.
本発明は、上記のような諸問題を根本的に解決すると共に、溶融飛灰中のＣｕや貴金属をそれらの金属の製錬に利用可能な濃度で含有する製錬原料として回収する溶融飛灰の再資源化処理方法を提供することを目的としている。 The present invention fundamentally solves the various problems as described above, and recovers molten fly ash as a smelting raw material containing Cu and precious metals in molten fly ash at a concentration that can be used for smelting those metals. The purpose of this is to provide a recycling method.
本発明の溶融飛灰の再資源化処理方法は、銅を含有する溶融飛灰と水とアルカリとを含むスラリーを形成し、該スラリーの固液分離操作、洗浄によってハロゲン濃度が１質量％以下である残渣を回収し、回収した残渣を還元剤、スラグ調整剤及びマット形成剤と混合して混合物とすること、この際に、マット形成剤中のＳと溶融飛灰中のＳとの合計量と溶融飛灰中のＣｕとの原子比が（Ｓ／Ｃｕ）≧０.２となる量でマット形成剤を配合すること、該混合物を還元型灰溶融炉中で１４５０℃以上で熱処理することによって銅をマットの形態として回収することを特徴とする。 The method for recycling molten fly ash according to the present invention forms a slurry containing molten fly ash containing copper, water and alkali, and the halogen concentration is 1% by mass or less by solid-liquid separation operation and washing of the slurry. The residue is recovered, and the recovered residue is mixed with a reducing agent, a slag adjusting agent and a mat forming agent to form a mixture. At this time, the sum of S in the mat forming agent and S in the molten fly ash The mat forming agent is blended in such an amount that the atomic ratio of the amount and Cu in the molten fly ash is (S / Cu) ≧ 0.2, and the mixture is heat-treated at 1450 ° C. or higher in a reduction ash melting furnace. Thus, copper is recovered in the form of a mat.
本発明の溶融飛灰の再資源化処理方法により、溶融飛灰からＣｕをＣｕの製錬に利用可能な高濃度で含有するマット形態の製錬原料として回収することができ、銀や金等の貴金属もマット中に効率的に濃縮、回収することができる。 By the molten fly ash recycling method of the present invention, Cu can be recovered from molten fly ash as a smelting raw material in a mat form containing Cu at a high concentration that can be used for smelting of Cu, such as silver and gold Can be efficiently concentrated and recovered in the mat.
本発明の溶融飛灰の再資源化処理方法においては、例えば産業廃棄物をガス化溶融炉や灰溶融炉で処理した場合に排出される溶融飛灰を用い、また脱ハロゲン処理、具体的には脱塩素処理のためにＮａＯＨ、ＫＯＨ、Ｎａ2ＣＯ3等のアルカリを添加する。 In the method for recycling molten fly ash according to the present invention, for example, molten fly ash discharged when industrial waste is processed in a gasification melting furnace or an ash melting furnace is used, and dehalogenation treatment, specifically, Add an alkali such as NaOH, KOH, Na 2 CO 3 for the dechlorination treatment.
本発明の溶融飛灰の再資源化処理方法においては、先ず最初に溶融飛灰と水とアルカリとを含むスラリーを形成する必要がある。このスラリーの形成方法としては、溶融飛灰と水とアルカリ又はアルカリ水溶液とを混合装置中にそれぞれ別個に同時に又は順次装入するか、溶融飛灰とアルカリ水溶液とを混合装置中にそれぞれ別個に同時に又は順次装入するか、或いは溶融飛灰を含有する水性スラリーとアルカリ又はアルカリ水溶液とを混合装置中にそれぞれ別個に同時に又は順次装入するかした後、所定の時間、攪拌混合を実施する。この攪拌混合により、溶融飛灰中に存在していた塩素を中心とするハロゲンは液中に移行する。 In the method for recycling molten fly ash according to the present invention, it is necessary to first form a slurry containing molten fly ash, water, and alkali. As a method for forming this slurry, molten fly ash, water, and alkali or alkaline aqueous solution are separately or simultaneously charged in a mixing device, or molten fly ash and alkaline aqueous solution are separately charged in a mixing device. The mixture is charged simultaneously or sequentially, or the aqueous slurry containing molten fly ash and the alkali or alkaline aqueous solution are separately charged simultaneously or sequentially into the mixing device, and then stirred and mixed for a predetermined time. . By this stirring and mixing, the halogen, mainly chlorine, present in the molten fly ash is transferred into the liquid.
次いで、上記のスラリーを濾過設備を用いて固液分離する。大部分のハロゲンが濾液中に存在しているが、濾過された残渣の付着水中にもハロゲンが存在するので回収した残渣中にハロゲンが残存する。この残渣中のハロゲン濃度が１質量％以下であることが好ましく、０.５質量％以下であることがより好ましい。このハロゲン濃度の調整は残渣を水洗すること、その洗浄水の量、洗浄時間を調整すること等により可能であり、また、スラリー中の水の量を調整することによっても可能である。このように残渣中のハロゲン濃度を低く抑える理由は、残渣（脱ハロゲン溶融飛灰）を還元型灰溶融炉中で熱処理する際に、残渣中の高価なＣｕが塩素により塩化揮発することがないようにしてＣｕの最大限の回収を可能とするためである。 Next, the slurry is subjected to solid-liquid separation using a filtration facility. Most of the halogen is present in the filtrate. However, since halogen is also present in the adhering water of the filtered residue, the halogen remains in the collected residue. The halogen concentration in the residue is preferably 1% by mass or less, and more preferably 0.5% by mass or less. The adjustment of the halogen concentration can be performed by washing the residue with water, adjusting the amount of washing water, washing time, and the like, and can also be performed by adjusting the amount of water in the slurry. Thus, the reason for keeping the halogen concentration in the residue low is that when the residue (dehalogenated molten fly ash) is heat-treated in a reduction ash melting furnace, the expensive Cu in the residue is not chlorinated and volatilized by chlorine. In this way, the maximum recovery of Cu is possible.
本発明の溶融飛灰の再資源化処理方法においては、上記のようにして回収した残渣を還元剤、スラグ調整剤及びマット形成剤と混合して混合物とする。還元剤としてコークスを用いることが好ましいが、その他の種々の還元剤、例えばフェロシリコン等を用いることもできる。スラグ調整剤として珪石、石灰石、螢石等を用いることができる。また、マット形成剤としては、還元溶融処理時に化合物のＳ分のみが利用され、他の成分はスラグ化され、かつそのスラグがリサイクル材として利用する上で問題を生じない化合物を用いることが重要である。このような観点で、マット形成剤がＮａ2Ｓ、Ｎａ2ＳＯ3、Ｎａ2ＳＯ4、Ｎａ2Ｓ2Ｏ3、Ｋ2Ｓ、Ｋ2ＳＯ3、Ｋ2ＳＯ4、Ｋ2Ｓ2Ｏ3、ＣａＳ、ＣａＳＯ3、ＣａＳＯ4、ＢａＳ、ＢａＳＯ3及びＢａＳＯ4からなる群より選ばれた少なくとも１種であることが好ましい。 In the method for recycling molten fly ash according to the present invention, the residue collected as described above is mixed with a reducing agent, a slag adjusting agent, and a mat forming agent to obtain a mixture. Coke is preferably used as the reducing agent, but various other reducing agents such as ferrosilicon can also be used. Silica stone, limestone, meteorite and the like can be used as the slag adjusting agent. In addition, it is important to use a compound that does not cause a problem when the slag is used as a recycled material, as the mat forming agent, in which only the S component of the compound is used during the reductive melting treatment, the other components are slag. It is. From this point of view, the mat forming agent is Na 2 S, Na 2 SO 3 , Na 2 SO 4 , Na 2 S 2 O 3 , K 2 S, K 2 SO 3 , K 2 SO 4 , K 2 S 2 O. 3 , preferably at least one selected from the group consisting of CaS, CaSO 3 , CaSO 4 , BaS, BaSO 3 and BaSO 4 .
本発明の溶融飛灰の再資源化処理方法においては、回収した残渣を還元剤、スラグ調整剤及びマット形成剤と混合する際に、マット形成剤中のＳと溶融飛灰中のＳとの合計量と溶融飛灰中のＣｕとの原子比が（Ｓ／Ｃｕ）≧０.２となる量、好ましくは（Ｓ／Ｃｕ）≧０.２５となる量でマット形成剤を配合する。（Ｓ／Ｃｕ）＜０.２である場合にはマットの生成が不十分であったり、生成しなかったりする。 In the method for recycling molten fly ash according to the present invention, when the collected residue is mixed with a reducing agent, a slag adjusting agent, and a mat forming agent, S in the mat forming agent and S in the molten fly ash are mixed. The mat forming agent is blended in such an amount that the atomic ratio of the total amount to Cu in the molten fly ash is (S / Cu) ≧ 0.2, preferably (S / Cu) ≧ 0.25. When (S / Cu) <0.2, the generation of the mat may be insufficient or may not be generated.
本発明の溶融飛灰の再資源化処理方法においては、上記の混合物を還元型灰溶融炉中で１４５０℃以上で熱処理し、揮発したＺｎ、Ｐｂ、Ｃｄ等の金属成分をダスト中に濃縮させてそれらの金属の製錬に利用可能な濃度で含有する製錬原料として回収し、銅及び貴金属をマット中及び溶融金属中に濃縮させてそれらの金属の製錬に利用可能な濃度で含有する製錬原料として回収し、溶融しなかった残りのＳｉＯ2、ＣａＯ、Ａｌ2Ｏ3、ＭｇＯ等の成分を細骨材や粗骨材として利用可能な清浄なスラグとして回収することができる。なお、生成するスラグをより清浄なスラグとして回収するために炉内に１５００℃以上で１.５時間以上を滞留させることが好ましい。 In the method for recycling molten fly ash according to the present invention, the above mixture is heat-treated at 1450 ° C. or higher in a reduced ash melting furnace to concentrate volatilized metal components such as Zn, Pb, and Cd into dust. Recovered as a smelting raw material containing a concentration that can be used for smelting those metals, and concentrating copper and precious metals in mats and molten metals to contain them in a concentration that can be used for smelting those metals The remaining components such as SiO 2 , CaO, Al 2 O 3 , and MgO that are recovered as a smelting raw material and have not been melted can be recovered as clean slag that can be used as fine aggregate or coarse aggregate. In addition, in order to collect | recover produced | generated slag as cleaner slag, it is preferable to make 1.5 hours or more stay in a furnace at 1500 degreeC or more.
還元型灰溶融炉中での熱処理温度が１４５０℃未満である場合には、該混合物中の銅及び貴金属以外の金属成分の揮発又は溶融が不十分となる傾向がある。還元型灰溶融炉中での熱処理温度が１３５０℃程度である場合にはＣｕ2Ｓのマットが安定であるが、１４５０℃を超える場合にはＣｕＳが安定となり生成する。 When the heat treatment temperature in the reduction ash melting furnace is less than 1450 ° C., volatilization or melting of metal components other than copper and noble metals in the mixture tends to be insufficient. When the heat treatment temperature in the reduction ash melting furnace is about 1350 ° C., the Cu 2 S mat is stable, but when it exceeds 1450 ° C., CuS is stabilized and formed.
本発明の溶融飛灰の再資源化処理方法においては還元型灰溶融炉として大容量処理に適している高周波誘導炉又は直流型又は交流型の抵抗加熱電気炉を用いることが好ましい。高周波誘導炉を用いる場合には、還元剤、例えばコークスを、残渣中の金属酸化物を還元するのに必要な還元化学当量の１.１〜１.３倍となる量で用いることが好ましい。コークスの量が還元化学当量の１.１倍未満である場合には、金属酸化物の還元が不十分となるか又は長時間の還元処理が必要になる傾向があり、逆に１.３倍を超えてもそれに見合った効果は得られない。また、抵抗加熱電気炉を用いる場合には、還元剤、例えばコークスを、残渣中の金属酸化物を還元するのに必要な還元化学当量の１.１〜１.２倍となる量で用いることが好ましい。コークスの量が還元化学当量の１.１倍未満である場合には、金属酸化物の還元が不十分となるか又は長時間の還元処理が必要になる傾向があり、逆に１.２倍を超える場合には、コークスが導電体として機能し、電熱効率を阻害する。 In the method for recycling molten fly ash according to the present invention, it is preferable to use a high-frequency induction furnace or a direct current or alternating current type resistance heating electric furnace suitable for large-capacity treatment as a reduction ash melting furnace. When using a high frequency induction furnace, it is preferable to use a reducing agent, for example, coke, in an amount that is 1.1 to 1.3 times the reducing chemical equivalent required to reduce the metal oxide in the residue. When the amount of coke is less than 1.1 times the reduction chemical equivalent, there is a tendency that the reduction of the metal oxide is insufficient or a reduction treatment for a long time is required, and conversely 1.3 times. Even if it exceeds, an effect commensurate with it cannot be obtained. When a resistance heating electric furnace is used, a reducing agent such as coke is used in an amount that is 1.1 to 1.2 times the reducing chemical equivalent required to reduce the metal oxide in the residue. Is preferred. When the amount of coke is less than 1.1 times the reducing chemical equivalent, there is a tendency that the reduction of the metal oxide is insufficient or a reduction treatment for a long time is required, and conversely 1.2 times. In the case of exceeding the coke, the coke functions as a conductor and hinders electrothermal efficiency.
硫化鉱原料を使用する通常の銅製錬は、自溶炉→転炉→精製炉を経て粗銅を製造する熔錬と、粗銅を電気分解して電気銅を製造する電錬とからなり、熔錬部門の最初の工程である鉱石を溶解、濃縮する自溶炉工程は銅製錬の総コストの４０％程度を占めている。メタル状態の銅の場合は自溶炉から投入する必要があるが、本発明の溶融飛灰の再資源化処理方法で得られるマット形態の銅は転炉の工程に直投可能であり、従って、銅の大半をメタル状態ではなくマット形態で回収できることによる製錬コストの低減の意義は大きい。 Ordinary copper smelting using sulfide ore raw materials consists of smelting to produce crude copper via flash smelting furnace → converter → refining furnace, and smelting to produce electrolytic copper by electrolyzing crude copper. The flash smelting furnace process that melts and concentrates the ore, which is the first process in the department, accounts for about 40% of the total cost of copper smelting. In the case of copper in the metal state, it is necessary to input from the flash smelting furnace, but the copper in the mat form obtained by the recycling method of the molten fly ash of the present invention can be directly thrown into the converter process. In addition, the significance of reducing the smelting cost by being able to recover most of the copper in the form of a mat instead of a metal is significant.
参考例１
カーシュレッダーダスト処理の溶融炉から排出される溶融飛灰５ｔ、水２０ｍ3及び工業用カセイソーダ（ＮａＯＨ含有率４８質量％）１０００Ｌを２５ｍ3の槽中で混合してスラリーを形成した。このスラリーを濾過器で濾過し、その残渣を洗浄して、塩素濃度がそれぞれ０.５４％及び１.１％の脱塩溶融飛灰を得た。
Reference example 1
5 t of molten fly ash discharged from the melting furnace for car shredder dust treatment, 20 m 3 of water and 1000 L of industrial caustic soda (NaOH content 48 mass%) were mixed in a 25 m 3 tank to form a slurry. The slurry was filtered with a filter, and the residue was washed to obtain desalted molten fly ash having a chlorine concentration of 0.54% and 1.1%, respectively.
第１表に示すように、上記の各々の脱塩溶融飛灰（第１表中では脱塩飛灰と記載する）１０ｋｇに珪石１０５０ｇ及びコークス８００ｇを混合し、それらの混合物を別々に集塵設備を有する高周波溶融炉中で溶融処理を実施した。脱塩溶融飛灰の溶解は１４００℃過ぎから始まり、１４５０℃でほぼ完全に溶融した。更に１５００℃まで上昇させ、１５０分間保持した。 As shown in Table 1, 1050 g of silica stone and 800 g of coke are mixed with 10 kg of each of the above desalted molten fly ash (described as desalted fly ash in Table 1), and the mixture is separately collected. The melting process was carried out in a high-frequency melting furnace with equipment. Dissolution of the desalted molten fly ash started after 1400 ° C and almost completely melted at 1450 ° C. The temperature was further raised to 1500 ° C. and held for 150 minutes.
上記のように溶融処理することにより、揮発した金属成分をダスト中に濃縮させて回収し、溶融しているが揮発しなかった金属成分を溶融金属中に濃縮させて回収し、残りの成分を清浄なスラグとして回収することができた。回収したスラグ、溶融金属及びダストの各々の量、及びそれら中に含まれる銅の品位（含有率）及び銅の含有量は第１表に示す通りであった。 By performing the melting treatment as described above, the volatilized metal component is concentrated and recovered in the dust, and the molten but not volatilized metal component is concentrated and recovered in the molten metal, and the remaining components are recovered. It was recovered as clean slag. Table 1 shows the amount of each of the recovered slag, molten metal and dust, and the quality (content) of copper contained therein and the content of copper.
第１表に示すデータからも明らかなように、Ｃｌ品位の差異による溶融金属中に回収されたＣｕの回収率の差異は分配率で５％程度であり、その５％はダスト中に回収されている。しかし、ダスト中に回収されたＣｕはその後の精錬過程での回収率が悪いこと、回収過程が複雑であること、及び脱塩操作で容易にＣｌを制御できることを考え合わせれば、Ｃｌを制御し溶融金属側へのＣｕの回収率を上げることは有効である。 As is apparent from the data shown in Table 1, the difference in the recovery rate of Cu recovered in the molten metal due to the difference in Cl quality is about 5% in the distribution rate, and 5% is recovered in the dust. ing. However, considering the fact that Cu recovered in the dust has a poor recovery rate in the subsequent refining process, that the recovery process is complicated, and that Cl can be easily controlled by a desalting operation, the Cl is controlled. Increasing the recovery rate of Cu to the molten metal side is effective.
実施例１
第２表に示すように、上記の参考例１で製造した塩素濃度が０.５４％の脱塩溶融飛灰（第２表中では脱塩飛灰と記載する）１０ｋｇに珪石１０５０ｇ及びコークス８００ｇを混合した２組の混合物（Ｓ／Ｃｕ＝０.１５）を用意した。その一方には、マット形成剤としてＣａＳＯ4５６０ｇを添加してＳ／Ｃｕ＝０.２９の混合物とした。それらの混合物を別々に集塵設備を有する高周波溶融炉中で溶融処理を実施した。脱塩溶融飛灰の溶解は１４００℃過ぎから始まり、１４５０℃でほぼ完全に溶融した。更に１５００℃まで上昇させ、１５０分間保持した。
Example 1
As shown in Table 2, 10 kg of desalted molten fly ash produced in the above Reference Example 1 having a chlorine concentration of 0.54% (described as desalted fly ash in Table 2), 1050 g of silica and 800 g of coke. Two sets of mixtures (S / Cu = 0.15) were prepared. On one side, 560 g of CaSO 4 was added as a mat forming agent to obtain a mixture of S / Cu = 0.29. These mixtures were separately melted in a high-frequency melting furnace having a dust collection facility. Dissolution of the desalted molten fly ash started after 1400 ° C and almost completely melted at 1450 ° C. The temperature was further raised to 1500 ° C. and held for 150 minutes.
上記のように溶融処理することにより、揮発した金属成分をダスト中に濃縮させて回収し、溶融しているが揮発しなかった金属成分、特に、銅及び貴金属をマット中及び溶融金属中に濃縮させて回収し、残りの成分を清浄なスラグとして回収することができた。回収したスラグ、溶融金属、マット及びダストの各々の量、及びそれら中に含まれる銅の品位（含有率）及び銅の含有量は第２表に示す通りであった。 By performing the melting treatment as described above, the volatilized metal component is concentrated and recovered in the dust, and the molten but not volatilized metal components, particularly copper and noble metals, are concentrated in the mat and in the molten metal. And the remaining components could be recovered as clean slag. Table 2 shows the amount of each of the recovered slag, molten metal, mat, and dust, and the quality (content) of copper contained therein and the content of copper.
Ｓ／Ｃｕ＝０.１５の場合には、溶融処理でのマットの生成は目視では確認できなかったが、ＣａＳＯ4の添加によってＳ／Ｃｕ＝０.２９とした場合には、溶融処理で溶融金属層の上部にマットの層が生成しており、そのマット中のＣｕの品位も６２．４５％と高かった。 In the case of S / Cu = 0.15, the formation of the mat in the melting process could not be visually confirmed, but in the case where S / Cu = 0.29 by adding CaSO 4 , the melting was performed in the melting process. A mat layer was formed on the metal layer, and the quality of Cu in the mat was as high as 62.45%.
なお、第２表には示していないが、Ｓ／Ｃｕ＝０.１５の場合には溶融金属中のＡｇは５１０ｐｐｍであったが、Ｓ／Ｃｕ＝０.２９とした場合には生成するマット中のＡｇの品位は８５０ｐｐｍと濃縮されていた。このように、マットを積極的に生成させることによって、Ｃｕ及びＡｇ等の貴金属も濃縮させることができる。
Although not shown in Table 2, Ag in the molten metal was 510 ppm when S / Cu = 0.15, but the mat produced when S / Cu = 0.29. The grade of Ag inside was concentrated to 850 ppm. Thus, noble metals, such as Cu and Ag, can also be concentrated by actively generating a mat.
Claims (5)
Using a direct current or alternating current resistance heating electric furnace as the reducing ash melting furnace, coke as the reducing agent is 1.1 to 1.2 times the reducing chemical equivalent required to reduce the metal oxide in the residue. The method for recycling molten fly ash according to claim 1, 2 or 3 used in an amount of
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