JP4258315B2 - Processing method of collected ash of two-stage series dust collector - Google Patents
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- 239000000428 dust Substances 0.000 title claims description 122
- 238000003672 processing method Methods 0.000 title description 3
- 239000002956 ash Substances 0.000 claims description 182
- 229910001385 heavy metal Inorganic materials 0.000 claims description 111
- 239000003795 chemical substances by application Substances 0.000 claims description 87
- 239000010881 fly ash Substances 0.000 claims description 62
- 239000002253 acid Substances 0.000 claims description 56
- 238000000034 method Methods 0.000 claims description 43
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 34
- 229910019142 PO4 Inorganic materials 0.000 claims description 26
- 239000013522 chelant Substances 0.000 claims description 24
- 239000010452 phosphate Substances 0.000 claims description 23
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 19
- 239000003513 alkali Substances 0.000 claims description 15
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 15
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 13
- 239000000920 calcium hydroxide Substances 0.000 claims description 13
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 13
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 13
- 238000012545 processing Methods 0.000 claims description 11
- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- 239000000834 fixative Substances 0.000 claims description 4
- 239000012716 precipitator Substances 0.000 claims 1
- 239000007789 gas Substances 0.000 description 31
- 235000021317 phosphate Nutrition 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 235000011007 phosphoric acid Nutrition 0.000 description 16
- 238000010828 elution Methods 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 11
- 238000011282 treatment Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 229910052793 cadmium Inorganic materials 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052745 lead Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000007922 dissolution test Methods 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- -1 alkali metal salts Chemical class 0.000 description 2
- 239000010791 domestic waste Substances 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- 150000002505 iron Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000010309 melting process Methods 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000004071 soot Substances 0.000 description 2
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- FAZZEPKGCXXHHD-UHFFFAOYSA-M [K+].C(N)([S-])=S.N1CCNCC1 Chemical compound [K+].C(N)([S-])=S.N1CCNCC1 FAZZEPKGCXXHHD-UHFFFAOYSA-M 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 150000007513 acids Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- AGKZZTAKVYWQLA-UHFFFAOYSA-N carbamodithioic acid;piperazine Chemical compound NC(S)=S.C1CNCCN1 AGKZZTAKVYWQLA-UHFFFAOYSA-N 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
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- 238000007796 conventional method Methods 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
- LMBWSYZSUOEYSN-UHFFFAOYSA-N diethyldithiocarbamic acid Chemical compound CCN(CC)C(S)=S LMBWSYZSUOEYSN-UHFFFAOYSA-N 0.000 description 1
- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- TVZISJTYELEYPI-UHFFFAOYSA-N hypodiphosphoric acid Chemical compound OP(O)(=O)P(O)(O)=O TVZISJTYELEYPI-UHFFFAOYSA-N 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- 238000006386 neutralization reaction Methods 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
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- 239000011734 sodium Substances 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
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- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- 229940048102 triphosphoric acid Drugs 0.000 description 1
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Description
本発明は焼却炉又は溶融炉から発生する排ガスを２段直列に設置した集塵機で処理する際に、集塵機で捕集される捕集灰を効果的に処理して、捕集灰からの重金属の溶出を確実に防止する２段直列集塵機の捕集灰の処理方法に関する。 The present invention effectively treats the collected ash collected by the dust collector when the exhaust gas generated from the incinerator or melting furnace is processed in two stages in series, and the heavy metal from the collected ash is treated. The present invention relates to a method for treating collected ash of a two-stage series dust collector that reliably prevents elution.
一般家庭ごみや産業廃棄物の焼却炉又は溶融炉から発生する排ガス中には、焼却過程又は溶融過程で揮散された鉛等の重金属を含むダストや塩化水素（ＨＣｌ）などの強酸性のガスが含まれていることから、これらの処理を施してから大気中に放散する必要がある。 In the exhaust gas generated from incinerators or melting furnaces for general household waste or industrial waste, dust containing heavy metals such as lead, volatilized in the incineration or melting process, and strongly acidic gases such as hydrogen chloride (HCl) Because it is contained, it is necessary to dissipate into the atmosphere after applying these treatments.
この排ガスの効果的な処理方法として、集塵機を２段直列に設置し、排ガスを２段集塵処理する方法が提案されている（特公平７−１０３９８０号公報）。この方法は、焼却炉から排出された排ガスを冷却する工程、冷却された排ガスから第１バグフィルタで煤塵を除去する工程、煤塵除去後の排ガスに消石灰を粉体又はスラリー状で噴霧して中和する工程、次いで中和された排ガスを第２バグフィルタで浄化する工程とからなっている。 As an effective method for treating the exhaust gas, a method in which dust collectors are installed in two stages in series and the exhaust gas is subjected to a two-stage dust collection process has been proposed (Japanese Patent Publication No. 7-103980). This method includes a step of cooling exhaust gas discharged from an incinerator, a step of removing soot dust from the cooled exhaust gas with a first bag filter, and spraying slaked lime in the form of powder or slurry on the exhaust gas after soot removal. And a step of purifying the neutralized exhaust gas with a second bag filter.
第１バグフィルタの主機能は、焼却過程又は溶融過程で発生する低沸点重金属類を含んだ飛灰の捕集であり、第２バグフィルタの主機能は塩化水素等の酸性ガスの除去である。即ち、第２バグフィルタでは、第１バグフィルタと第２バグフィルタとの間の中和工程で噴霧された消石灰が飛灰と共に濾布表面に堆積し、この消石灰を含む堆積層で、排ガス中の塩化水素等の酸性ガスを効果的に吸収除去することができる。このため、第１バグフィルタで捕集された灰は重金属類を多く含有するが、消石灰成分はなく、第２バグフィルタで捕集された灰は、重金属類の含有量は少なく、未反応の消石灰を多く含むものとなる。 The main function of the first bag filter is to collect fly ash containing low boiling point heavy metals generated in the incineration process or melting process, and the main function of the second bag filter is to remove acidic gases such as hydrogen chloride. . That is, in the second bag filter, the slaked lime sprayed in the neutralization step between the first bag filter and the second bag filter is deposited on the filter cloth surface together with the fly ash. It is possible to effectively absorb and remove acidic gases such as hydrogen chloride. For this reason, the ash collected by the first bag filter contains a lot of heavy metals, but there is no slaked lime component, and the ash collected by the second bag filter has a low content of heavy metals and has not been reacted. It will contain a lot of slaked lime.
なお、消石灰を第１バグフィルタの入口側で噴霧し、塩化水素などの酸性ガスの一部を第１バグフィルタで除去する場合もあり、この場合には、第１バグフィルタの捕集灰は重金属類を多く含有すると共に未反応の消石灰も含むものとなる。 In some cases, slaked lime is sprayed on the inlet side of the first bag filter, and a part of acidic gas such as hydrogen chloride is removed by the first bag filter. In this case, the collected ash of the first bag filter is It contains a lot of heavy metals and also contains unreacted slaked lime.
いずれの場合も、第２バグフィルタの捕集灰は重金属類含有量が低いため、少量の重金属固定剤の添加で重金属の溶出を防止することが可能であるが、第１バグフィルタの捕集灰は重金属類の含有量が高いため、重金属の溶出防止処理が難しいという問題があった。また、第１バグフィルタの捕集灰と第２バグフィルタの捕集灰とを混合して処理する場合は、混合灰は重金属類と未反応の消石灰とを多く含むものとなるため、重金属固定剤を多量に添加する必要があるという問題があった。 In any case, since the collection ash of the second bag filter has a low heavy metal content, it is possible to prevent elution of heavy metals by adding a small amount of heavy metal fixing agent. Since ash has a high content of heavy metals, there has been a problem that it is difficult to prevent elution of heavy metals. In addition, when the collected ash from the first bag filter and the collected ash from the second bag filter are mixed and processed, the mixed ash contains a large amount of heavy metals and unreacted slaked lime. There was a problem that a large amount of the agent had to be added.
従来、このような２段直列集塵機から発生する飛灰の処理方法として、第１バグフィルタから発生する飛灰に、鉄塩と第２バグフィルタから発生する飛灰を添加し、水を加えて湿潤状態で混練して処理する方法が提案されている（特開２０００−２０２３９５号公報）。 Conventionally, as a method for treating fly ash generated from such a two-stage series dust collector, iron salt and fly ash generated from the second bag filter are added to the fly ash generated from the first bag filter, and water is added. A method of kneading and processing in a wet state has been proposed (Japanese Patent Laid-Open No. 2000-202395).
また、本出願人は先に、このような２段直列集塵機から発生する飛灰の処理方法として、第１集塵機の捕集灰と第２集塵機の捕集灰との混合灰を水と重金属固定剤と炭酸ガスを組み合わせて処理する方法を提案した（特開２００３−１４５０９１号公報）。 In addition, as a method for treating fly ash generated from such a two-stage series dust collector, the present applicant previously fixed mixed ash of collected ash of the first dust collector and collected ash of the second dust collector with water and heavy metal. Proposed a method of treating with a combination of an agent and carbon dioxide (Japanese Patent Application Laid-Open No. 2003-145091).
この方法は、焼却排ガスなどの炭酸ガスを用いて飛灰中のアルカリ成分を低減することによって、
(i) 重金属固定剤の必要添加量を低減して飛灰処理コストの低減を図り、更に酸性雨に曝された際等においても重金属の溶出を確実に抑制する。
(ii) スケール生成成分の溶出を抑制する。
という効果を奏するものである。この方法によって混合灰を処理するためには、混合灰と水と炭酸ガスと重金属固定剤とを混合して反応させる必要があり、そのような処理装置として、特開２００１−６２４２６号公報のようなアルカリ飛灰処理装置が提案されている。
This method reduces the alkaline components in fly ash using carbon dioxide such as incineration exhaust gas,
(i) Reduce the amount of heavy metal fixing agent required to reduce fly ash treatment costs, and also reliably suppress elution of heavy metals even when exposed to acid rain.
(ii) Suppress the elution of scale-generating components.
This is an effect. In order to treat the mixed ash by this method, it is necessary to mix and react the mixed ash, water, carbon dioxide gas, and heavy metal fixing agent. As such a processing apparatus, as disclosed in JP-A-2001-62426. An alkaline fly ash treatment apparatus has been proposed.
なお、本出願人は先に、飛灰の酸消費量を測定し、測定した酸消費量に基いて重金属固定剤の必要添加率を把握する方法を提案している（特開平８−１０１１８６号公報）。
２段直列集塵機から発生する飛灰の処理方法として提案されている上記の特開２０００−２０２３９５号公報記載の方法は、第１バグフィルタの捕集灰のｐＨ調整剤として第２バグフィルタの捕集灰を用いる方法であり、新たなｐＨ調整剤としてのアルカリ剤を添加する必要はないという利点があるが、酸性化合物である鉄塩とアルカリ性である第２バグフィルタの捕集灰の添加量を調整して最適なｐＨ域に設定する必要があるため、ｐＨ制御が難しく実用的ではないという問題があった。 The method described in Japanese Patent Application Laid-Open No. 2000-202395, which has been proposed as a method for treating fly ash generated from a two-stage series dust collector, uses a second bag filter as a pH adjuster for collected ash of the first bag filter. This method uses ash collection, and has the advantage that it is not necessary to add an alkaline agent as a new pH adjuster, but the added amount of ash collected from an iron salt that is an acidic compound and an alkaline second bag filter Therefore, there is a problem that pH control is difficult and impractical.
また、上記特開２００１−６２４２６号公報に記載の方法は、炭酸ガスと混合灰を反応させるための処理装置を新たに設置する必要があり、既存の焼却場には適用しにくいという問題があった。 In addition, the method described in the above-mentioned Japanese Patent Application Laid-Open No. 2001-62426 requires a new processing device for reacting carbon dioxide gas and mixed ash, which is difficult to apply to existing incinerators. It was.
なお、上記特開平８−１０１１８６号公報の方法は、飛灰の酸消費量の測定値から重金属固定剤の必要添加量を計算するものであるが、酸消費量が少なすぎる場合は重金属固定剤の添加量が少なすぎて重金属の溶出を十分防止できない場合があり、酸消費量が大きすぎる場合には重金属固定剤の添加量が多くなりすぎるという問題があった。 The method disclosed in JP-A-8-101186 calculates the necessary amount of heavy metal fixing agent from the measurement value of the acid consumption of fly ash. If the acid consumption is too small, the heavy metal fixing agent is calculated. In some cases, the amount of the metal added is too small to prevent the elution of heavy metals, and when the acid consumption is too large, the amount of the heavy metal fixing agent added is too large.
本発明は、上記従来の問題点を解決し、２段直列集塵機から発生する飛灰を適切に処理する方法を提供することを目的とする。 An object of the present invention is to solve the above-mentioned conventional problems and to provide a method for appropriately treating fly ash generated from a two-stage series dust collector.
即ち、本発明は２段直列集塵機から発生する飛灰を特別な装置を必要とすることなく、また、煩雑な制御を必要とすることなく、少ない重金属固定剤添加量で容易かつ効率的に処理して処理物からの重金属の溶出を確実に防止する２段直列集塵機の捕集灰の処理方法を提供することを目的とする。 That is, the present invention treats fly ash generated from a two-stage series dust collector easily and efficiently with a small amount of heavy metal fixing agent without requiring a special device or requiring complicated control. Then, it aims at providing the processing method of the collection ash of the two-stage serial dust collector which prevents reliably the elution of the heavy metal from a processed material.
本発明（請求項１）の２段直列集塵機の捕集灰の処理方法は、焼却炉又は溶融炉から発生する排ガスを、２段直列に配置した集塵機の第１集塵機に通して飛灰を捕集し、次いで第１集塵機から排出される排ガスに消石灰を噴霧した後第２集塵機に通して飛灰を捕集することにより該排ガスを処理するに当たり、該集塵機で捕集された灰を処理する方法において、該第１集塵機の捕集灰と該第２集塵機の捕集灰とを混合し、該混合灰にリン酸系重金属固定剤とキレート系重金属固定剤を添加する方法であって、該第１集塵機の捕集灰の酸消費量又はアルカリ消費量と該第２集塵機の捕集灰の酸消費量とを測定し、該第１集塵機の捕集灰の酸消費量又はアルカリ消費量の測定値と該第２集塵機の捕集灰の酸消費量の測定値とに基いて、該混合灰の酸消費量が３０〜２００ｍｇ−ＣａＣＯ ３ ／ｇ−灰となるように、該第１集塵機の捕集灰と該第２集塵機の捕集灰との混合比率を決定することを特徴とする。
本発明（請求項４）の２段直列集塵機の捕集灰の処理方法は、焼却炉又は溶融炉から発生する排ガスを、２段直列に配置した集塵機の第１集塵機に通して飛灰を捕集し、次いで第１集塵機から排出される排ガスに消石灰を噴霧した後第２集塵機に通して飛灰を捕集することにより該排ガスを処理するに当たり、該集塵機で捕集された灰を処理する方法において、該第１集塵機の捕集灰と該第２集塵機の捕集灰とを混合し、該混合灰にリン酸系重金属固定剤とキレート系重金属固定剤を添加する方法であって、該第１集塵機の捕集灰と該第２集塵機の捕集灰の混合灰の酸消費量を測定し、該混合灰の酸消費量の測定値に基いて、該混合灰へのリン酸系重金属固定剤の添加率を決定することを特徴とする。
According to the present invention (Claim 1), the method for treating collected ash of a two-stage serial dust collector passes exhaust gas generated from an incinerator or melting furnace through a first dust collector of a dust collector arranged in two stages in series to collect fly ash. After collecting slaked lime on the exhaust gas discharged from the first dust collector and then passing through the second dust collector to collect the fly ash, the ash collected by the dust collector is treated. in the method, mixing the collected ash collecting ashes and the second dust collector of the first dust collector, a method of adding a phosphate heavy metal fixatives and chelate heavy metal fixative mixture ashes, the The acid consumption or alkali consumption of the collected dust of the first dust collector and the acid consumption of the collected ash of the second dust collector are measured, and the acid consumption or alkali consumption of the collected ash of the first dust collector Based on the measured value and the measured value of the acid consumption of the collected ash of the second dust collector, As the consumption is 30~200mg-CaCO 3 / g- ash, and determines the mixing ratio of the collecting ash collecting ashes and the second dust collector of the first dust collector.
According to the present invention (Claim 4), the method for treating collected ash of a two-stage serial dust collector passes exhaust gas generated from an incinerator or melting furnace through a first dust collector of a dust collector arranged in two stages in series to collect fly ash. After collecting slaked lime on the exhaust gas discharged from the first dust collector and then passing through the second dust collector to collect the fly ash, the ash collected by the dust collector is treated. In the method, the collection ash of the first dust collector and the collection ash of the second dust collector are mixed, and a phosphate heavy metal fixing agent and a chelate heavy metal fixing agent are added to the mixed ash, Measure the acid consumption of the mixed ash of the collected ash of the first dust collector and the collected ash of the second dust collector, and based on the measured value of the acid consumption of the mixed ash, phosphate heavy metal to the mixed ash It is characterized by determining the addition rate of the fixative.
本発明においては、第１集塵機の捕集灰と第２集塵機の捕集灰とを混合して、リン酸系重金属固定剤とキレート系重金属固定剤とで処理することにより、処理物からの重金属の溶出を確実に防止することができる。即ち、本発明においては、第１集塵機の捕集灰と第２集塵機の混合灰に対してリン酸系重金属固定剤とキレート系重金属固定剤とを併用することにより、リン酸系重金属固定剤は特にＰｂとＣｄに対して効果的で、キレート系重金属固定剤はＨｇの固定に対して効果的であるという相乗効果で、少ない重金属固定剤添加量で著しく優れた重金属固定化効果を得ることができる。 In the present invention, the collected ash of the first dust collector and the collected ash of the second dust collector are mixed and treated with a phosphoric acid heavy metal fixing agent and a chelate heavy metal fixing agent. Can be surely prevented. That is, in the present invention, by using a phosphate heavy metal fixing agent and a chelate heavy metal fixing agent in combination with the collected ash of the first dust collector and the mixed ash of the second dust collector, the phosphate heavy metal fixing agent is Particularly effective for Pb and Cd, and the synergistic effect that the chelate heavy metal fixing agent is effective for fixing Hg, it is possible to obtain a remarkably excellent heavy metal fixing effect with a small amount of heavy metal fixing agent. it can.
本発明においては、第１集塵機の捕集灰の酸消費量又はアルカリ消費量と該第２集塵機の捕集灰の酸消費量を測定し、これらの測定値に基いて、混合灰の酸消費量が３０〜２００ｍｇ−ＣａＣＯ３／ｇ−灰となるように、第１集塵機の捕集灰と第２集塵機の捕集灰との混合比率を決定することが好ましく、また、第１集塵機の捕集灰の酸消費量又はアルカリ消費量の測定値と第２集塵機の捕集灰の酸消費量の測定値と、第１集塵機の捕集灰と第２集塵機の捕集灰との混合比率に基いて、混合灰の酸消費量Ａ（ｍｇ−ＣａＣＯ３／ｇ−灰）を求め、この酸消費量Ａから下記（１）式により混合灰へのリン酸系重金属固定剤の添加率Ｔ（重量％／灰）を決定することが好ましい。
Ｔ＝（０．０８〜０．２５）×Ａ ‥（１）
In the present invention, the acid consumption or alkali consumption of the collected ash of the first dust collector and the acid consumption of the collected ash of the second dust collector are measured, and based on these measured values, the acid consumption of the mixed ash It is preferable to determine the mixing ratio of the collected ash of the first dust collector and the collected ash of the second dust collector so that the amount is 30 to 200 mg-CaCO 3 / g-ash. The measured value of acid consumption or alkali consumption of ash, the measured value of acid consumption of collected ash of the second dust collector, and the mixing ratio of the collected ash of the first dust collector and the collected ash of the second dust collector Based on this, the acid consumption A (mg-CaCO 3 / g-ash) of the mixed ash is obtained, and the addition rate T of the phosphate heavy metal fixing agent to the mixed ash from the acid consumption A according to the following equation (1) T ( It is preferred to determine weight% / ash).
T = (0.08-0.25) × A (1)
或いは、第１集塵機の捕集灰と第２集塵機の捕集灰の混合灰の酸消費量を測定し、この混合灰の酸消費量の測定値Ａ（ｍｇ−ＣａＣＯ３／ｇ−灰）から、下記（１）式により混合灰へのリン酸系重金属固定剤の添加率Ｔ（重量％／灰）を決定することが好ましい。
Ｔ＝（０．０８〜０．２５）×Ａ ‥（１）
Alternatively, the acid consumption of the mixed ash of the collected ash of the first dust collector and the collected ash of the second dust collector is measured, and from the measured value A (mg-CaCO 3 / g-ash) of the acid consumption of the mixed ash It is preferable to determine the addition rate T (wt% / ash) of the phosphate heavy metal fixing agent to the mixed ash according to the following formula (1).
T = (0.08-0.25) × A (1)
このようにすることで、第１集塵機の捕集灰と第２集塵機の捕集灰との混合比の制御を容易に行うことができる。また、混合灰の酸消費量は、一般的にはリン酸系重金属固定剤の添加量の算出に適当な値であるため、リン酸系重金属固定剤の過不足を防止して、適切なリン酸系重金属固定剤の添加制御を行うことができる。 By doing in this way, control of the mixing ratio of the collection ash of a 1st dust collector and the collection ash of a 2nd dust collector can be performed easily. In addition, the acid consumption of the mixed ash is generally an appropriate value for calculating the addition amount of the phosphate heavy metal fixing agent. Addition control of an acid type heavy metal fixing agent can be performed.
本発明において、キレート系重金属固定剤の添加量は、混合灰に対して１０重量％以下、特に０．２〜３．０重量％とすることが好ましい。 In the present invention, the addition amount of the chelate heavy metal fixing agent is preferably 10% by weight or less, particularly preferably 0.2 to 3.0% by weight with respect to the mixed ash.
以上詳述した通り、本発明の２段直列集塵機の捕集灰の処理方法によれば、２段直列集塵機から発生する飛灰を特別な装置を必要とすることなく、また、煩雑な制御を必要とすることなく、少ない重金属固定剤添加量で容易かつ効率的に処理して処理物からの重金属の溶出を確実に防止することができる。 As described above in detail, according to the method for treating collected ash of the two-stage series dust collector of the present invention, the fly ash generated from the two-stage series dust collector can be controlled without requiring a special device. Without being necessary, it is possible to easily and efficiently treat with a small amount of the heavy metal fixing agent to prevent the elution of heavy metal from the treated product.
以下に図面を参照して本発明の２段直列集塵機の捕集灰の処理方法の実施の形態を詳細に説明する。 Embodiments of a method for treating collected ash of a two-stage series dust collector of the present invention will be described in detail below with reference to the drawings.
図１は、本発明の２段直列集塵機の捕集灰の処理方法の実施の形態を示す排ガス処理工程図である。 FIG. 1 is an exhaust gas treatment process diagram showing an embodiment of a method for treating collected ash of a two-stage series dust collector of the present invention.
図１において、焼却炉や溶融炉からの排ガスは、排ガス流路１を通って第１集塵機（第１の排ガス処理手段又は第１のバグフィルタ）２で飛灰（ダスト）が捕集され、更に排ガス流路３を通って第２集塵機（ガス浄化装置。第２の排ガス処理手段または第２のバグフィルタ）４で脱塩・脱硫されると共に飛灰が捕集され、浄化された排ガスは誘引送風機６により誘引され、クリーンな煙道ガスとなって煙突７から排出される。このとき、第２集塵機４で脱塩・脱硫するための消石灰粉５が排ガス流路３に供給される。 In FIG. 1, the exhaust gas from the incinerator or melting furnace passes through the exhaust gas passage 1 and fly ash (dust) is collected by the first dust collector (first exhaust gas processing means or first bag filter) 2. Further, the exhaust gas flowed through the exhaust gas flow path 3 is demineralized and desulfurized by a second dust collector (gas purification device, second exhaust gas treatment means or second bag filter) 4 and fly ash is collected. It is attracted by the induction blower 6 and is discharged from the chimney 7 as clean flue gas. At this time, slaked lime powder 5 for desalting and desulfurization by the second dust collector 4 is supplied to the exhaust gas flow path 3.
第１集塵機２で捕集された飛灰は、貯留槽８に貯留され、第２集塵機４で捕集された飛灰は、貯留槽９に貯留される。貯留された捕集灰は、所定の比率で混合され、この混合灰に処理槽１０において、水１２とリン酸系重金属固定剤１３とキレート系重金属固定剤１４を添加して混練処理し、処理灰１１を得る。
Fly ash collected by the first dust collector 2 is stored in the storage tank 8, and fly ash collected by the second dust collector 4 is stored in the
本発明においては、第１集塵機の捕集灰の酸消費量又はアルカリ消費量と該第２集塵機の捕集灰の酸消費量を測定し、これらの測定値に基いて、混合灰の酸消費量が３０〜２００ｍｇ−ＣａＣＯ３／ｇ−灰となるように、第１集塵機の捕集灰と第２集塵機の捕集灰との混合比率を決定することが好ましい。この混合灰の酸消費量が３０ｍｇ−ＣａＣＯ３／ｇ−灰未満であるとリン酸系重金属固定剤を添加したときにｐＨが低下しすぎて、重金属固定が充分でない場合があり、２００ｍｇ−ＣａＣＯ３／ｇ−灰を超えるとリン酸系重金属固定剤の必要添加量が多くなってしまうからである。 In the present invention, the acid consumption or alkali consumption of the collected ash of the first dust collector and the acid consumption of the collected ash of the second dust collector are measured, and based on these measured values, the acid consumption of the mixed ash It is preferable to determine the mixing ratio of the collected ash of the first dust collector and the collected ash of the second dust collector so that the amount is 30 to 200 mg-CaCO 3 / g-ash. If the acid consumption of the mixed ash is less than 30 mg-CaCO 3 / g-ash, the pH may be lowered too much when the phosphate heavy metal fixing agent is added, and heavy metal fixation may not be sufficient. It is because the required addition amount of a phosphoric acid type heavy metal fixing agent will increase when it exceeds 3 / g-ash.
通常の焼却炉又は溶融炉における２段直列集塵機において、混合灰の酸消費量が上記範囲となるように混合するための第１集塵機の捕集灰と第２集塵機の捕集灰の混合比率は、第１集塵機の捕集灰：第２集塵機の捕集灰＝１０：９０〜９０：１０、好ましくは２５：７５〜７５：２５（いずれも重量比）程度である。 In a two-stage series dust collector in a normal incinerator or melting furnace, the mixing ratio of the collected ash of the first dust collector and the collected ash of the second dust collector for mixing so that the acid consumption of the mixed ash is in the above range is The collected ash of the first dust collector: The collected ash of the second dust collector = 10: 90 to 90:10, preferably about 25:75 to 75:25 (both weight ratios).
また、本発明においては、第１集塵機の捕集灰の酸消費量又はアルカリ消費量の測定値と第２集塵機の捕集灰の酸消費量の測定値と、第１集塵機の捕集灰と第２集塵機の捕集灰との混合比率に基いて、混合灰の酸消費量Ａ（ｍｇ−ＣａＣＯ３／ｇ−灰）を求め、この酸消費量Ａから下記（１）式により混合灰へのリン酸系重金属固定剤の添加率Ｔ（重量％／灰）を決定することが好ましい。
Ｔ＝（０．０８〜０．２５）×Ａ ‥（１）
Moreover, in this invention, the measured value of the acid consumption or alkali consumption of the collection ash of a 1st dust collector, the measured value of the acid consumption of the collection ash of a 2nd dust collector, the collection ash of a 1st dust collector, Based on the mixing ratio with the collected ash of the second dust collector, the acid consumption A (mg-CaCO 3 / g-ash) of the mixed ash is obtained, and the acid consumption A is converted into the mixed ash by the following formula (1). It is preferable to determine the addition rate T (wt% / ash) of the phosphoric acid heavy metal fixing agent.
T = (0.08-0.25) × A (1)
リン酸系重金属固定剤の添加率Ｔが上記範囲よりも少ないとリン酸系重金属固定剤による十分な重金属の固定化効果を得ることができず、多いとｐＨが低下しすぎて重金属の溶出防止が充分でない場合がある。 If the addition rate T of the phosphoric acid heavy metal fixing agent is less than the above range, a sufficient heavy metal immobilization effect by the phosphoric acid heavy metal fixing agent cannot be obtained. May not be sufficient.
より好ましいリン酸系重金属固定剤の添加率Ｔは、下記（２）式の範囲である。
Ｔ＝（０．０８〜０．１５）×Ａ ‥（２）
The addition rate T of the phosphoric acid heavy metal fixing agent is more preferably in the range of the following formula (2).
T = (0.08-0.15) × A (2)
なお、混合灰の酸消費量Ａは、第１集塵機の捕集灰の酸消費量又はアルカリ消費量の測定値と第２集塵機の捕集灰の酸消費量の測定値と、第１集塵機の捕集灰と第２集塵機の捕集灰との混合比率とから計算により求めることができるが、混合灰の酸消費量を測定し、この測定値をリン酸系重金属固定剤添加量の算出に用いても良い。 The acid consumption A of the mixed ash includes the measured value of the acid consumption or alkali consumption of the collected ash of the first dust collector, the measured value of the acid consumption of the collected ash of the second dust collector, and the measured value of the first dust collector. It can be obtained by calculation from the mixing ratio of the collected ash and the collected ash of the second dust collector, but the acid consumption of the mixed ash is measured and this measured value is used to calculate the phosphate heavy metal fixing agent addition amount. It may be used.
一方、キレート系重金属固定剤の添加量は、混合灰に対して１０重量％以下、特に０．２〜３．０重量％とすることが好ましい。キレート系重金属固定剤の添加量が１０重量％を超えても重金属固定効果に影響はないが、過剰添加となり経済的でない。キレート系重金属固定剤の添加量は０．２重量％未満ではリン酸系重金属固定剤とキレート系重金属固定剤との併用による十分な相乗効果を得ることができない。 On the other hand, the addition amount of the chelate heavy metal fixing agent is preferably 10% by weight or less, particularly preferably 0.2 to 3.0% by weight with respect to the mixed ash. Even if the addition amount of the chelating heavy metal fixing agent exceeds 10% by weight, the effect of fixing the heavy metal is not affected, but excessive addition is not economical. When the addition amount of the chelate heavy metal fixing agent is less than 0.2% by weight, a sufficient synergistic effect cannot be obtained by the combined use of the phosphate heavy metal fixing agent and the chelate heavy metal fixing agent.
水の添加量は、重金属固定剤の混練効率の面から混合灰に対して５〜５０重量％、特に１０〜３０重量％とするのが好ましい。なお、この添加量は、混合灰に対する合計の水の好適添加量であり、重金属固定剤を後述の如く水溶液として添加する場合には、この水溶液として添加される水量も含めることが好ましい。 The amount of water added is preferably 5 to 50% by weight, particularly 10 to 30% by weight, based on the mixed ash, from the viewpoint of the kneading efficiency of the heavy metal fixing agent. This addition amount is a preferable addition amount of water to the mixed ash, and when the heavy metal fixing agent is added as an aqueous solution as described later, it is preferable to include the amount of water added as this aqueous solution.
なお、本発明において、酸消費量及びアルカリ消費量の測定は、灰に水を混合して得られた溶液に対して常法に従って行うことができ、このとき水と飛灰との混合比は、固液比、即ち飛灰に対する水の重量比で１０〜１０００、特に１００〜１０００、とりわけ５００〜１０００程度とすることが好ましい。 In the present invention, acid consumption and alkali consumption can be measured according to a conventional method for a solution obtained by mixing water with ash. At this time, the mixing ratio of water and fly ash is The solid-liquid ratio, that is, the weight ratio of water to fly ash is preferably about 10 to 1000, particularly about 100 to 1000, especially about 500 to 1000.
本発明において用いるリン酸系重金属固定剤としては特に制限はなく、リン酸又はその塩が用いられ、このうち、リン酸としては正リン酸や次亜リン酸、メタ亜リン酸、ピロ亜リン酸、正亜リン酸、次リン酸、メタリン酸、ピロリン酸、三リン酸、縮合リン酸が挙げられ、リン酸塩としては、これらのリン酸のナトリウム塩、カリウム塩等のアルカリ金属塩、第１リン酸塩、第２リン酸塩が挙げられる。特に好適なものは、正リン酸（Ｈ３ＰＯ４）、リン酸二水素−ナトリウム（ＮａＨ２ＰＯ４）、リン酸−水素二ナトリウム（Ｎａ２ＨＰＯ４）である。これらのリン酸系重金属固定剤は１種を単独で用いても、２種以上を併用しても良い。 There is no restriction | limiting in particular as a phosphoric acid heavy metal fixing agent used in this invention, Phosphoric acid or its salt is used, Among these, as orthophosphoric acid, hypophosphorous acid, metaphosphorous acid, pyrophosphorous Acid, orthophosphorous acid, hypophosphoric acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, condensed phosphoric acid, and phosphates include alkali metal salts such as sodium salt and potassium salt of these phosphoric acids, Examples include primary phosphates and secondary phosphates. Particularly preferred are orthophosphoric acid (H 3 PO 4 ), dihydrogen phosphate-sodium (NaH 2 PO 4 ), and phosphate-disodium hydrogen (Na 2 HPO 4 ). These phosphate heavy metal fixing agents may be used alone or in combination of two or more.
これらのリン酸及び／又はリン酸塩は、好ましくは２０〜８０重量％濃度の水溶液として飛灰に添加して混練される。このような水溶液を用いる場合、前述の如く、水溶液として持ち込まれる水量を、混練水として考慮することが望ましい。 These phosphoric acid and / or phosphate are preferably added to fly ash and kneaded as an aqueous solution having a concentration of 20 to 80% by weight. When such an aqueous solution is used, it is desirable to consider the amount of water brought in as an aqueous solution as kneaded water as described above.
また、キレート系重金属固定剤としては、ジチオカルバミン酸系重金属固定剤が挙げられ、具体的には、ジエチルジチオカルバミン酸及びその塩類（例えばナトリウム塩等）、ピペラジンジチオカルバミン酸及びその塩類、ポリアミンジチオカルバミン酸及びその塩類などがある。これらのキレート系重金属固定剤は１種を単独で用いても、２種以上を併用しても良い。この中でも、取り扱い性の面から、液体としてのジチオカルバミン酸塩水溶液が好適に用いられる。 Examples of the chelate heavy metal fixing agent include dithiocarbamic acid heavy metal fixing agents. Specifically, diethyldithiocarbamic acid and salts thereof (for example, sodium salt), piperazine dithiocarbamic acid and salts thereof, polyamine dithiocarbamic acid and salts thereof. There is salt. These chelate heavy metal fixing agents may be used alone or in combination of two or more. Among these, from the viewpoint of handleability, a dithiocarbamate aqueous solution as a liquid is preferably used.
このようなジチオカルバミン酸系重金属固定剤は、好ましくは２０〜５０重量％濃度の水溶液として添加して混練される。このようなジチオカルバミン酸系重金属固定剤水溶液を用いる場合においても、前述の如く、水溶液として持ち込まれる水量を、混練水として考慮することが望ましい。 Such a dithiocarbamic acid heavy metal fixing agent is preferably added and kneaded as an aqueous solution having a concentration of 20 to 50% by weight. Even when such a dithiocarbamic acid heavy metal fixing agent aqueous solution is used, it is desirable to consider the amount of water brought in as an aqueous solution as kneaded water as described above.
なお、本発明において、混合灰への水、リン酸系重金属固定剤及びキレート系重金属固定剤の添加順序には特に制限はなく、これらを同時に添加しても、順次添加しても良い。混練性、取り扱い性等の面からは、混合灰に水を添加混練した後、リン酸系重金属固定剤及びキレート系重金属固定剤を同時に又は順次に添加するか、或いは、予め水に溶解させたリン酸系重金属固定剤及びキレート系重金属固定剤を混合灰に添加して混練することが好ましい。 In the present invention, the order of adding water, phosphate heavy metal fixing agent and chelate heavy metal fixing agent to the mixed ash is not particularly limited, and these may be added simultaneously or sequentially. From the viewpoint of kneadability, handleability, etc., after adding and kneading water to the mixed ash, the phosphate heavy metal fixing agent and the chelate heavy metal fixing agent are added simultaneously or sequentially, or dissolved in water in advance. It is preferable to add a phosphate heavy metal fixing agent and a chelate heavy metal fixing agent to the mixed ash and knead them.
本発明においては、上記リン酸系重金属固定剤、キレート系重金属固定剤に加えて、更に、活性白土のような粘土鉱物重金属固定剤、澱粉のような高分子系重金属固定剤、セメント系重金属固定剤、硫酸のような酸性溶液系重金属固定剤、アルミニウム化合物系重金属固定剤、鉄化合物系重金属固定剤のような他の重金属固定剤を併用することができる。 In the present invention, in addition to the above-mentioned phosphate heavy metal fixing agent and chelate heavy metal fixing agent, clay mineral heavy metal fixing agent such as activated clay, polymer heavy metal fixing agent such as starch, cement heavy metal fixing Other heavy metal fixing agents such as an acidic solution-based heavy metal fixing agent such as sulfuric acid, an aluminum compound-based heavy metal fixing agent, and an iron compound-based heavy metal fixing agent can be used in combination.
以下に実施例及び比較例を挙げて本発明をより具体的に説明するが、本発明はその要旨を超えない限り、以下の実施例により何ら限定されるものではない。 Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to the following examples unless it exceeds the gist.
なお、以下の実施例では、都市ゴミの溶融炉から発生する排ガスを２段直列集塵機で処理した場合の１段目のバグフィルタから発生するＡ飛灰と２段目のバグフィルタから発生するＢ飛灰の処理を行った。各飛灰の成分は表１に示す通りであり、Ａ飛灰は重金属類の含有量が多く、Ｂ飛灰は重金属類の含有量は少ないが、残存消石灰成分であるＣａの含有量が多い。 In the following examples, A fly ash generated from the first-stage bag filter and B generated from the second-stage bag filter when the exhaust gas generated from the municipal waste melting furnace is processed by a two-stage serial dust collector. The fly ash was processed. The components of each fly ash are as shown in Table 1. A fly ash has a high content of heavy metals, and B fly ash has a low content of heavy metals, but a high content of Ca, which is a residual slaked lime component. .
実施例１
処理手順は次の通りである。
Example 1
The processing procedure is as follows.
(1) Ａ飛灰のアルカリ消費量（Ｐ酸度）を測定した。アルカリ消費量の測定方法は、次の通りに行った。 (1) The alkali consumption (P acidity) of A fly ash was measured. The measuring method of alkali consumption was performed as follows.
まず、Ａ飛灰を１ｇ採取し、それに脱塩水を１０００ｍｌ加え、５分間攪拌した。攪拌後の溶液を５０ｍｌ採取し、フェノールフタレインを指示薬として、０．０２Ｎ−ＮａＯＨ水溶液を用いて滴定した。Ａ飛灰のアルカリ消費量は、６０ｍｇ−ＣａＣＯ３／ｇ−灰であった。 First, 1 g of A fly ash was collected, 1000 ml of demineralized water was added thereto, and the mixture was stirred for 5 minutes. 50 ml of the stirred solution was collected and titrated with 0.02N-NaOH aqueous solution using phenolphthalein as an indicator. The alkali consumption of A fly ash was 60 mg-CaCO 3 / g-ash.
(2) Ｂ飛灰の酸消費量（Ｐアルカリ度）を測定した。酸消費量の測定方法は、次の通りに行った。 (2) The acid consumption (P alkalinity) of B fly ash was measured. The measuring method of acid consumption was performed as follows.
まず、Ｂ飛灰を１ｇ採取し、それに脱塩水を１０００ｍｌ加え、５分間攪拌した。攪拌後の溶液を５０ｍｌ採取し、フェノールフタレインを指示薬として、０．０２Ｎ−Ｈ２ＳＯ４溶液を用いて滴定した。Ｂ飛灰の酸消費量は、４１０ｍｇ−ＣａＣＯ３／ｇ−灰であった。 First, 1 g of B fly ash was collected, 1000 ml of demineralized water was added thereto, and the mixture was stirred for 5 minutes. 50 ml of the stirred solution was collected and titrated with 0.02N—H 2 SO 4 solution using phenolphthalein as an indicator. The acid consumption of B fly ash was 410 mg-CaCO 3 / g-ash.
(3) Ａ飛灰６５ｇとＢ飛灰３５ｇを混合し、酸消費量（Ｐアルカリ度）を測定した。酸消費量は、１０５ｍｇ−ＣａＣＯ３／ｇ−灰であった。従って、前記(1)式で算出されるリン酸系重金属固定剤の適正添加量は８．４〜２６．２５重量％／灰である。 (3) 65 g of A fly ash and 35 g of B fly ash were mixed, and the acid consumption (P alkalinity) was measured. The acid consumption was 105 mg-CaCO 3 / g-ash. Therefore, the appropriate addition amount of the phosphoric acid heavy metal fixing agent calculated by the formula (1) is 8.4 to 26.25% by weight / ash.
(4) 混合灰５０ｇを１０００ｍｌポリビーカーに採取し、脱塩水１２．５ｇ（混合灰に対して２５重量％）とリン酸系重金属固定剤（７５重量％正リン酸水溶液）を表２に示す割合で添加し、スパーテルで約１時間混練した。次いで、キレート系重金属固定剤（３５重量％ピペラジンジチオカルバミン酸カリウム塩溶液）を表２に示す割合で添加し、スパーテルで約３分間混練した。 (4) 50 g of mixed ash was collected in a 1000 ml poly beaker, and 12.5 g of demineralized water (25% by weight with respect to the mixed ash) and phosphate heavy metal fixing agent (75% by weight normal phosphoric acid aqueous solution) are shown in Table 2. They were added in proportions and kneaded with a spatula for about 1 hour. Next, a chelate heavy metal fixing agent (35 wt% piperazine dithiocarbamate potassium salt solution) was added at a ratio shown in Table 2, and kneaded with a spatula for about 3 minutes.
(5) 得られた処理灰について、環境庁告示１３号試験に準じた溶出試験を行って、溶出液中のｐＨとＰｂ，Ｃｄ，Ｈｇ濃度を測定し、試験結果を表２に示した。 (5) The obtained treated ash was subjected to a dissolution test according to the Environmental Agency Notification No. 13 test, and the pH and Pb, Cd, and Hg concentrations in the eluate were measured. The test results are shown in Table 2.
比較例１〜６
Ａ飛灰とＢ飛灰の混合灰に対して、表２に示す重金属固定剤を表２に示す割合で添加したこと以外は実施例１と同様にして混合灰の処理を行い（ただし、比較例２では重金属固定剤添加せず）、同様に処理灰の溶出試験を行って結果を表２に示した。
Comparative Examples 1-6
The mixed ash was treated in the same manner as in Example 1 except that the heavy metal fixing agent shown in Table 2 was added to the mixed ash of A fly ash and B fly ash in the proportion shown in Table 2. In Example 2, the heavy metal fixing agent was not added), and the dissolution test of the treated ash was conducted in the same manner, and the results are shown in Table 2.
比較例７〜１５
Ａ飛灰とＢ飛灰とを混合せず、Ａ飛灰のみ或いはＢ飛灰のみに表２に示す重金属固定剤を表２に示す割合で添加したこと以外は実施例１と同様にして飛灰の処理を行い、同様に処理灰の溶出試験を行って結果を表２に示した。
Comparative Examples 7-15
A mixture of A fly ash and B fly ash was used in the same manner as in Example 1 except that the heavy metal fixing agent shown in Table 2 was added to only A fly ash or only B fly ash in the ratio shown in Table 2. The ash treatment was performed, and the dissolution test of the treated ash was conducted in the same manner, and the results are shown in Table 2.
比較例１６〜２２
Ａ飛灰６０ｇとＢ飛灰４０ｇとの混合灰に、表２に示す重金属固定剤を表２に示す割合で添加したこと以外は実施例１と同様にして飛灰の処理を行い（ただし、比較例１６では重金属固定剤添加せず）、同様に処理灰の溶出試験を行って結果を表２に示した。
Comparative Examples 16-22
The fly ash was treated in the same manner as in Example 1 except that the heavy metal fixing agent shown in Table 2 was added to the mixed ash of 60 g of A fly ash and 40 g of B fly ash in the proportion shown in Table 2. In Comparative Example 16, a heavy metal fixing agent was not added), and a dissolution ash elution test was conducted in the same manner. The results are shown in Table 2.
表２より明らかなように、Ａ飛灰とＢ飛灰を別々にキレート系重金属固定剤で処理した場合（比較例７〜１５）、Ｐｂ，Ｃｄの溶出を埋立基準値（０．３ｍｇ／ｌ）以下まで防止できる添加量は、Ａ飛灰の場合２５重量％／灰、Ｂ飛灰の場合２重量％／灰と大きく異なっており、実際の処理では添加量制御が難しい。また、Ａ飛灰とＢ飛灰を混合した灰に対してもキレート系重金属固定剤は２０重量％／灰必要となっている（比較例２〜６）。また、Ａ飛灰とＢ飛灰の混合灰にポリ硫酸第２鉄を用いた場合（特開２０００−２０２３９５号公報の方法）、ポリ硫酸第２鉄の添加量が多く必要となるため、実用的ではない（比較例１６〜２２）。 As apparent from Table 2, when A fly ash and B fly ash were separately treated with a chelate heavy metal fixing agent (Comparative Examples 7 to 15), the elution of Pb and Cd was the landfill reference value (0.3 mg / l). The addition amount that can be prevented to the following is greatly different from 25 wt% / ash in the case of A fly ash and 2 wt% / ash in the case of B fly ash, and it is difficult to control the addition amount in actual processing. Moreover, 20 weight% / ash of a chelate type heavy metal fixing agent is required for the ash obtained by mixing A fly ash and B fly ash (Comparative Examples 2 to 6). Further, when polyferric sulfate is used in the mixed ash of A fly ash and B fly ash (method of JP 2000-202395 A), a large amount of polyferric sulfate is required, so that it is practical. (Comparative Examples 16 to 22).
これに対して実施例１の場合は、リン酸系重金属固定剤１０重量％／灰とキレート系重金属固定剤３重量％／灰を併用することで、飛灰中のＰｂ，Ｃｄ，Ｈｇの溶出を確実に防止することができる。ただし、リン酸系重金属固定剤のみの添加では、Ｈｇの溶出防止が充分でない（比較例１）。 On the other hand, in the case of Example 1, elution of Pb, Cd, Hg in fly ash by using together 10% by weight of phosphoric acid heavy metal fixing agent / ash and 3% by weight of chelate heavy metal fixing agent / ash. Can be reliably prevented. However, the addition of only the phosphate-based heavy metal fixing agent does not sufficiently prevent Hg elution (Comparative Example 1).
このことより、本発明の処理を行うことにより、重金属固定剤の低添加量で、安定的に処理を行うことができることが分かる。 From this, it can be seen that by performing the treatment of the present invention, the treatment can be stably performed with a low addition amount of the heavy metal fixing agent.
本発明によれば、２段直列集塵機を設けた一般家庭ごみや産業廃棄物の焼却設備又は溶融設備における飛灰処理コストを大幅に低減すると共に、処理物を安全に処分することができる。 ADVANTAGE OF THE INVENTION According to this invention, while reducing the fly ash processing cost in the incineration equipment or melting equipment of the general household waste and industrial waste which provided the 2-stage serial dust collector, a processed material can be disposed of safely.
１，３ 排ガス流路
２ 第１集塵機
４ 第２集塵機
６ 誘引送風機
７ 煙突
８，９ 貯留槽
１０ 処理槽
１１ 処理灰
１２ 水
１３ リン酸系重金属固定剤
１４ キレート系重金属固定剤
DESCRIPTION OF SYMBOLS 1,3 Exhaust gas flow path 2 1st dust collector 4 2nd dust collector 6 Attracting fan 7
Claims (6)
該第１集塵機の捕集灰と該第２集塵機の捕集灰とを混合し、該混合灰にリン酸系重金属固定剤とキレート系重金属固定剤を添加する方法であって、
該第１集塵機の捕集灰の酸消費量又はアルカリ消費量と該第２集塵機の捕集灰の酸消費量とを測定し、該第１集塵機の捕集灰の酸消費量又はアルカリ消費量の測定値と該第２集塵機の捕集灰の酸消費量の測定値とに基いて、該混合灰の酸消費量が３０〜２００ｍｇ−ＣａＣＯ ３ ／ｇ−灰となるように、該第１集塵機の捕集灰と該第２集塵機の捕集灰との混合比率を決定することを特徴とする２段直列集塵機の捕集灰の処理方法。 The exhaust gas generated from the incinerator or melting furnace is passed through the first dust collector of the dust collector arranged in two stages in series to collect fly ash, and then the second dust collector is sprayed with slaked lime on the exhaust gas discharged from the first dust collector In processing the exhaust gas by collecting fly ash through, in a method of processing the ash collected by the dust collector,
A method of mixing the collected ash of the first dust collector and the collected ash of the second dust collector, and adding a phosphate heavy metal fixing agent and a chelate heavy metal fixing agent to the mixed ash ,
The acid consumption or alkali consumption of the collected ash of the first dust collector and the acid consumption of the collected ash of the second dust collector are measured, and the acid consumption or alkali consumption of the collected ash of the first dust collector And the first ash so that the acid consumption of the mixed ash is 30 to 200 mg-CaCO 3 / g-ash , based on the measured value of the collected ash and the measured value of the acid consumption of the collected ash of the second dust collector . A method for treating collected ash of a two-stage series dust collector, wherein a mixing ratio between the collected ash of the dust collector and the collected ash of the second dust collector is determined .
Ｔ＝（０．０８〜０．２５）×Ａ ‥（１） In claim 2, the measured value of the first acid consumption or alkali consumption of the collecting ash precipitator, the measured value of the acid consumption of the collecting ash second dust collector, collecting the first dust collector Based on the mixing ratio of the ash and the collected ash of the second dust collector, the acid consumption A (mg-CaCO 3 / g-ash) of the mixed ash is obtained, and from this acid consumption A, the following (1) A method for treating collected ash of a two-stage series dust collector, wherein an addition rate T (wt% / ash) of a phosphate heavy metal fixing agent to the mixed ash is determined by an equation.
T = (0.08-0.25) × A (1)
該第１集塵機の捕集灰と該第２集塵機の捕集灰とを混合し、該混合灰にリン酸系重金属固定剤とキレート系重金属固定剤を添加する方法であって、
該第１集塵機の捕集灰と該第２集塵機の捕集灰の混合灰の酸消費量を測定し、該混合灰の酸消費量の測定値に基いて、該混合灰へのリン酸系重金属固定剤の添加率を決定することを特徴とする２段直列集塵機の捕集灰の処理方法。 The exhaust gas generated from the incinerator or melting furnace is passed through the first dust collector of the dust collector arranged in two stages in series to collect fly ash, and then the second dust collector is sprayed with slaked lime on the exhaust gas discharged from the first dust collector In processing the exhaust gas by collecting fly ash through, in a method of processing the ash collected by the dust collector,
A method of mixing the collected ash of the first dust collector and the collected ash of the second dust collector, and adding a phosphate heavy metal fixing agent and a chelate heavy metal fixing agent to the mixed ash ,
The acid consumption of the mixed ash of the collected ash of the first dust collector and the collected ash of the second dust collector is measured, and based on the measured value of the acid consumption of the mixed ash, the phosphoric acid system to the mixed ash A method for treating collected ash of a two-stage series dust collector, wherein an addition rate of a heavy metal fixing agent is determined .
Ｔ＝（０．０８〜０．２５）×Ａ ‥（１） In claim 4, the addition rate T (weight of phosphoric acid based heavy metal fixatives from the measured value A of the acid consumption of the mixed ash (mg-CaCO 3 / g- ash) to said mixing ash by the following equation (1) % / Ash) is determined. A method for treating collected ash of a two-stage series dust collector.
T = (0.08-0.25) × A (1)
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