JP2015066491A - Method for treating cyan-containing soil - Google Patents
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- JP2015066491A JP2015066491A JP2013201927A JP2013201927A JP2015066491A JP 2015066491 A JP2015066491 A JP 2015066491A JP 2013201927 A JP2013201927 A JP 2013201927A JP 2013201927 A JP2013201927 A JP 2013201927A JP 2015066491 A JP2015066491 A JP 2015066491A
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- 239000002689 soil Substances 0.000 title claims abstract description 105
- 238000000034 method Methods 0.000 title claims abstract description 32
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000000460 chlorine Substances 0.000 claims abstract description 52
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 52
- 239000007800 oxidant agent Substances 0.000 claims abstract description 38
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 33
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims description 17
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 15
- 230000001590 oxidative effect Effects 0.000 claims description 14
- 150000007661 iron cyano complex Chemical class 0.000 claims description 9
- -1 cyanide compound Chemical class 0.000 claims description 7
- 238000003672 processing method Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 22
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 239000002893 slag Substances 0.000 description 18
- 239000003814 drug Substances 0.000 description 10
- 239000002002 slurry Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000012545 processing Methods 0.000 description 9
- 230000035699 permeability Effects 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 229940079593 drug Drugs 0.000 description 6
- 238000010828 elution Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000007664 blowing Methods 0.000 description 5
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003673 groundwater Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000002798 spectrophotometry method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- CIWBSHSKHKDKBQ-SZSCBOSDSA-N 2-[(1s)-1,2-dihydroxyethyl]-3,4-dihydroxy-2h-furan-5-one Chemical compound OC[C@H](O)C1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-SZSCBOSDSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Natural products OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 239000004155 Chlorine dioxide Substances 0.000 description 1
- 239000002211 L-ascorbic acid Substances 0.000 description 1
- 235000000069 L-ascorbic acid Nutrition 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 235000019398 chlorine dioxide Nutrition 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- KMZJQQHWMFWLEK-UHFFFAOYSA-N pyrazol-3-one;pyridine Chemical compound C1=CC=NC=C1.O=C1C=CN=N1 KMZJQQHWMFWLEK-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000008215 water for injection Substances 0.000 description 1
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Abstract
Description
本発明は、シアン含有土壌の処理方法に係り、詳しくは、シアン含有土壌にアルカリ剤と塩素系酸化剤を注入すると共に必要に応じて加温することで、土壌中の全シアンを効率的に分解処理する方法に関する。 The present invention relates to a method for treating cyan-containing soil, and more specifically, by injecting an alkali agent and a chlorine-based oxidant into cyan-containing soil and heating as necessary, all cyan in the soil is efficiently removed. The present invention relates to a decomposition method.
従来、シアン化合物で汚染された土壌の処理方法として、シアン汚染土壌のスラリー液をアルカリでｐＨ１０〜１３とし、３０分以上加熱撹拌後、次亜塩素酸塩をスラリー液に分割添加して前記ｐＨ範囲及び８０〜１００℃の温度範囲で、遊離シアン、錯シアン及び難溶性シアン化合物と反応させる方法が提案されている（特許文献１）。 Conventionally, as a method for treating soil contaminated with cyanide, the slurry solution of cyan contaminated soil is adjusted to pH 10 to 13 with alkali, heated and stirred for 30 minutes or more, and hypochlorite is added separately to the slurry solution to obtain the pH. A method of reacting with free cyanide, complex cyanide and a hardly soluble cyanide compound in a temperature range of 80 to 100 ° C. has been proposed (Patent Document 1).
しかしながら、特許文献１に記載の方法は、
・汚染土壌を水に分散させてスラリーとするため、スラリー化のための混練機、スラリー液貯槽、処理液貯槽等、大掛かりな処理装置が必要である。
・スラリーを扱うため、処理装置のメンテナンス費が高くなる。
・上記理由により、大量の汚染土壌を処理することは困難である。
といった問題がある。
However, the method described in
-In order to disperse the contaminated soil in water to form a slurry, a large-scale processing device such as a kneading machine for slurrying, a slurry liquid storage tank, and a processing liquid storage tank is required.
-Since the slurry is handled, the maintenance cost of the processing equipment becomes high.
・ For the above reasons, it is difficult to treat a large amount of contaminated soil.
There is a problem.
本発明は上記従来の問題点を解決し、シアン含有土壌をスラリー化することなく、大掛かりな装置を必要とすることなく、簡易な操作で、シアン含有土壌中の全シアンを効率的に分解処理することができるシアン含有土壌の処理方法を提供することを課題とする。 The present invention solves the above-mentioned conventional problems, and efficiently decomposes all cyan in the cyan-containing soil with a simple operation without slurrying the cyan-containing soil and without requiring a large-scale apparatus. It is an object of the present invention to provide a method for treating cyan-containing soil that can be used.
本発明者らは、上記課題を解決すべく鋭意検討を重ねた結果、シアン含有土壌をスラリー化せずにそのままの状態で、アルカリ剤と塩素系酸化剤、或いは場合によっては塩素系酸化剤のみを注入すると共に、必要に応じて加温し、所定時間保持することにより、シアン含有土壌中の全シアンを難分解性の鉄シアノ錯体も含めて効率的に分解処理することができることを見出した。 As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention do not slurry the cyan-containing soil as it is, but only an alkali agent and a chlorine-based oxidizing agent, or in some cases, a chlorine-based oxidizing agent. It was found that all cyan in the cyan-containing soil can be efficiently decomposed including the difficult-to-decompose iron cyano complex by injecting and heating the mixture as needed and holding it for a predetermined time. .
本発明はこのような知見に基いて達成されたものであり、以下を要旨とする。 The present invention has been achieved on the basis of such findings, and the gist thereof is as follows.
［１］ シアン化合物を含有する土壌に、塩素系酸化剤、或いはアルカリ剤及び塩素系酸化剤を添加して所定時間保持することにより、該土壌中のシアン化合物を分解することを特徴とするシアン含有土壌の処理方法。 [1] Cyanide which decomposes cyanide in soil by adding chlorine-based oxidant or alkali agent and chlorine-based oxidant to the soil containing cyanide and holding it for a predetermined time Treatment method of contained soil.
［２］ ［１］において、必要に応じて熱源を用いて加温することで、前記土壌を２０℃以上１００℃以下の温度に前記所定時間保持することを特徴とするシアン含有土壌の処理方法。 [2] A method for treating cyan-containing soil according to [1], wherein the soil is maintained at a temperature of 20 ° C. or higher and 100 ° C. or lower for a predetermined time by heating using a heat source as necessary. .
［３］ ［１］又は［２］において、前記所定時間は、前記土壌温度に応じて、以下の(1)〜(3）のいずれかであることを特徴とするシアン含有土壌の処理方法。
(1) 土壌温度が２０℃以上４０℃未満の場合、２０００時間以上
(2) 土壌温度が４０℃以上６０℃未満の場合、３００時間以上
(3) 土壌温度が６０℃以上１００℃以下の場合、２４時間以上
[3] The method for treating cyan-containing soil according to [1] or [2], wherein the predetermined time is any one of the following (1) to (3) according to the soil temperature.
(1) 2000 hours or more when soil temperature is 20 ℃ or more and less than 40 ℃
(2) 300 hours or more when soil temperature is 40 ℃ or more and less than 60 ℃
(3) 24 hours or more when soil temperature is 60 ℃ or more and 100 ℃ or less
［４］ ［１］ないし［３］のいずれかにおいて、前記土壌から採水した浸出水のｐＨと遊離塩素濃度に基いて該土壌へのアルカリ剤、或いはアルカリ剤及び塩素系酸化剤の添加を制御することを特徴とするシアン含有土壌の処理方法。 [4] In any one of [1] to [3], an alkali agent or an alkali agent and a chlorine-based oxidizing agent are added to the soil based on the pH and free chlorine concentration of leachate collected from the soil. A method for treating cyan-containing soil, comprising controlling the soil.
［５］ ［４］において、前記浸出水のｐＨが１１〜１３、遊離塩素濃度が１０ｍｇ／Ｌ以上となるように、該土壌にアルカリ剤、或いはアルカリ剤及び塩素系酸化剤を添加することを特徴とするシアン含有土壌の処理方法。 [5] In [4], adding an alkaline agent, or an alkaline agent and a chlorine-based oxidizing agent to the soil so that the pH of the leachate is 11 to 13 and the free chlorine concentration is 10 mg / L or more. A method for treating cyan-containing soil, which is characterized.
［６］ ［１］ないし［５］のいずれかにおいて、前記シアン化合物が鉄シアノ錯体を含むことを特徴とするシアン含有土壌の処理方法。 [6] The method for treating cyan-containing soil according to any one of [1] to [5], wherein the cyanide compound contains an iron cyano complex.
本発明によれば、シアン含有土壌をスラリー化せずにそのままの状態で、アルカリ剤と塩素系酸化剤、或いは場合によっては塩素系酸化剤のみを注入すると共に、必要に応じて熱源を利用して加温することにより、シアン含有土壌中の全シアンを難分解性の鉄シアノ錯体も含めて効率的に分解処理することができる。
本発明では、汚染土壌をスラリー化する必要がないため、スラリー化のための混練機、スラリー液貯槽、処理液貯槽等の大掛かりな処理装置が不要となり、簡易な装置で実施することができると共に、メンテナンス費を低く抑えることができる。
また、土壌処理の場合、長時間反応させることが許容される場合があり、加温せずに薬剤注入だけの処理も可能であり、コストを低くおさえることができる。
このため、大量の汚染土壌の処理にも十分に対応することができる。
According to the present invention, an alkali agent and a chlorine-based oxidizer, or in some cases only a chlorine-based oxidizer, are injected without using a slurry containing cyan as a slurry, and a heat source is used as necessary. By heating in this manner, it is possible to efficiently decompose all cyan in the cyan-containing soil including the hardly decomposable iron cyano complex.
In the present invention, since it is not necessary to slurry contaminated soil, a large-scale processing device such as a kneading machine for slurrying, a slurry liquid storage tank, and a processing liquid storage tank is unnecessary, and can be implemented with a simple apparatus. Maintenance costs can be kept low.
In the case of soil treatment, it may be allowed to react for a long time, and it is possible to perform treatment only by injecting a medicine without heating, and the cost can be reduced.
For this reason, it can fully cope with the treatment of a large amount of contaminated soil.
以下に本発明のシアン含有土壌の処理方法の実施の形態を詳細に説明する。 Hereinafter, embodiments of the method for treating cyan-containing soil of the present invention will be described in detail.
本発明のシアン含有土壌の処理方法は、シアン化合物を含有する土壌に塩素系酸化剤、或いは、アルカリ剤及び塩素系酸化剤を添加すると共に、必要に応じて加温用の蒸気を吹き込むなどして加温することにより、該土壌中のシアン化合物を分解することを特徴とする。 In the method for treating cyan-containing soil according to the present invention, a chlorine-containing oxidizing agent, or an alkali agent and a chlorine-containing oxidizing agent are added to soil containing a cyanide, and a heating steam is blown as necessary. The cyanide compound in the soil is decomposed by heating.
本発明によるシアン含有土壌の処理は、蒸気等の熱源を利用し、土壌を２０℃以上１００℃以下、好ましくは４０℃以上８０℃未満、より好ましくは６０℃以上８０℃未満の温度に維持することが好ましく、また、土壌の浸出水のｐＨが１１〜１３、遊離塩素濃度が１０ｍｇ／Ｌ以上となるように、アルカリ剤、或いはアルカリ剤及び塩素系酸化剤を添加することが、難分解性の鉄シアノ錯体をも効率的に分解処理する上で好ましい。これは、ｐＨ１１以上、遊離塩素濃度１０ｍｇ／Ｌ以上の条件では、シアンの酸化分解反応が活発となり、土壌中の難分解性の鉄シアノ錯体も徐々に分解していくことによるものと推定される。 The treatment of the cyan-containing soil according to the present invention uses a heat source such as steam to maintain the soil at a temperature of 20 ° C. or higher and 100 ° C. or lower, preferably 40 ° C. or higher and lower than 80 ° C., more preferably 60 ° C. or higher and lower than 80 ° C. It is also preferable to add an alkaline agent, or an alkaline agent and a chlorine-based oxidizing agent so that the soil leachate has a pH of 11 to 13 and a free chlorine concentration of 10 mg / L or more. The iron cyano complex is also preferable for efficient decomposition treatment. This is presumably due to the fact that cyan oxidative decomposition reaction becomes active under the conditions of pH 11 or more and free chlorine concentration of 10 mg / L or more, and the hardly decomposable iron cyano complex in the soil is gradually decomposed. .
本発明において、処理対象となる土壌とは、シアン化合物を含む土壌やスラグであって、めっき工場跡地などのフェロシアン錯体、フェリシアン錯体などの鉄シアノ錯体含有土壌や、スラグなどが挙げられる。その溶出液の全シアン濃度としては特に制限はないが、後述の実施例の項に記載される土壌溶出試験による溶出液の全シアン濃度で、通常０．５〜１０ｍｇ／Ｌ程度である。特に、塩基度（ｍａｓｓ％ＣａＯ／ｍａｓｓ％ＳｉＯ２）が１．２以上の塩基性のスラグである場合は、アルカリ剤が不要であるか、アルカリ剤の必要量が少なくて済み、塩素系酸化剤と蒸気、或いは塩素系酸化剤のみで処理することも可能であり、本発明に好適である。
また、処理対象土壌は、注入した薬剤の浸透性に優れる点から、透水性の高い土壌であることが好ましく、例えば自由落下させて山積みした状態での透水係数が１×１０−２〜１×１０ｃｍ／ｓ程度のものが好ましい。この透水係数の点においても、スラグを用いた土木工事用材料である場合は、透水係数が比較的高いため本発明に好適である。
In the present invention, the soil to be treated is soil or slag containing a cyanide compound, and examples include ferrocyan complex such as a site of a plating plant, soil containing iron cyano complex such as ferricyan complex, and slag. Although there is no restriction | limiting in particular as the total cyan density | concentration of the eluate, The total cyan density | concentration of the eluate by the soil elution test described in the term of the below-mentioned Example is about 0.5-10 mg / L normally. In particular, when the basicity (mass% CaO / mass% SiO 2 ) is a basic slag of 1.2 or more, an alkali agent is unnecessary or the amount of the alkali agent required is small, and chlorine-based oxidation It is also possible to treat only with an agent and steam, or a chlorine-based oxidizing agent, which is suitable for the present invention.
Moreover, from the point which is excellent in the permeability | transmittance of the inject | poured chemical | medical agent, it is preferable that a process target soil is soil with high water permeability, for example, the water permeability coefficient in the state piled up freely and piled up is 1 * 10 <-2 > -1 *. The thing of about 10 cm / s is preferable. Also in terms of the water permeability coefficient, the civil engineering material using slag is suitable for the present invention because the water permeability coefficient is relatively high.
本発明において、土壌に注入するアルカリ剤としては、通常の水処理等で使用される水酸化ナトリウム（ＮａＯＨ）、水酸化カリウム（ＫＯＨ）等を用いることができ、アルカリ剤は通常１０〜４８重量％の水溶液として用いられる。
アルカリ剤は、土壌浸出水のｐＨが、好ましくは１１〜１３、より好ましくは１１〜１２．５、特に好ましくは１１〜１２となるように添加される。浸出水のｐＨが１１未満では、鉄シアノ錯体等のシアン化合物を十分に分解除去し得ない場合があり、ｐＨ１３を超えても、それに見合う分解効果の向上効果は得られず、アルカリ剤の使用量の増加、使用設備の耐アルカリ性、高ｐＨ土壌の取り扱い性といった問題が生じ、経済性、安全性の点において実用上不利である。
In the present invention, as the alkaline agent to be injected into the soil, sodium hydroxide (NaOH), potassium hydroxide (KOH) and the like used in usual water treatment can be used, and the alkaline agent is usually 10 to 48 weights. % Aqueous solution.
The alkaline agent is added so that the pH of the soil leachate is preferably 11 to 13, more preferably 11 to 12.5, and particularly preferably 11 to 12. If the pH of the leachate is less than 11, cyan compounds such as iron cyano complexes may not be sufficiently decomposed and removed, and if the pH exceeds 13, the effect of improving the decomposition effect corresponding to that cannot be obtained. Problems such as an increase in the amount, alkali resistance of the equipment used, and handleability of high pH soil arise, which is practically disadvantageous in terms of economy and safety.
また、土壌に添加する塩素系酸化剤としては、次亜塩素酸ナトリウム（ＮａＣｌＯ）、さらし粉、塩素ガス、二酸化塩素などを用いることができ、塩素系酸化剤は通常１０〜２０重量％の水溶液として用いられる。これらの塩素系酸化剤のうち、ＮａＣｌＯは安価であり好ましい。これらの塩素系酸化剤は１種のみを用いてもよく、ＮａＣｌＯと他の塩素系酸化剤とを用いるなど２種以上を併用してもよい。
塩素系酸化剤は、土壌浸出水の遊離塩素濃度が１０ｍｇ／Ｌ以上、好ましくは１０〜１０００ｍｇ／Ｌとなるように添加される。浸出水の遊離塩素濃度が１０ｍｇ／Ｌ未満では鉄シアノ錯体等のシアン化合物を十分に分解除去し得ない場合がある。ただし、遊離塩素濃度が過度に高くても、それに見合う分解効果の向上効果は得られず、塩素系酸化剤の使用量の増加、使用設備の耐酸化剤性といった問題が生じ、経済性、安全性の点において実用上不利である。
Moreover, sodium hypochlorite (NaClO), bleaching powder, chlorine gas, chlorine dioxide, etc. can be used as the chlorine-based oxidant added to the soil, and the chlorine-based oxidant is usually in an aqueous solution of 10 to 20% by weight. Used. Of these chlorinated oxidants, NaClO is preferred because it is inexpensive. These chlorine-based oxidants may be used alone or in combination of two or more, such as using NaClO and other chlorine-based oxidants.
The chlorinated oxidant is added so that the free chlorine concentration of the soil leachate is 10 mg / L or more, preferably 10 to 1000 mg / L. If the free chlorine concentration of the leachate is less than 10 mg / L, cyan compounds such as iron cyano complexes may not be sufficiently decomposed and removed. However, even if the concentration of free chlorine is excessively high, the effect of improving the decomposition effect can not be obtained, resulting in problems such as an increase in the amount of chlorinated oxidant used and the oxidant resistance of the equipment used. It is disadvantageous in terms of sex.
また、本発明では、必要に応じて、蒸気等の熱源を利用して加温することで、土壌の温度を２０℃以上１００℃以下、好ましくは４０℃以上８０℃未満、より好ましくは６０℃以上８０℃未満に加温する。土壌温度が２０℃未満では、鉄シアノ錯体等のシアン化合物を十分に分解除去し得ない場合がある。土壌温度は８０℃以上であってもよいが、経済性、安全性等の観点から土壌温度は８０℃未満とすることが好ましい。なお、処理開始から所定時間経過して浸出水の水温が安定した後は、浸出水の水温は土壌温度とほぼ等しいとみなすことができ、従って土壌温度は浸出水の水温で確認することもできる。 In the present invention, the temperature of the soil is 20 ° C. or higher and 100 ° C. or lower, preferably 40 ° C. or higher and lower than 80 ° C., more preferably 60 ° C., by heating using a heat source such as steam as necessary. Heat to above 80 ° C. If the soil temperature is less than 20 ° C., cyan compounds such as iron cyano complexes may not be sufficiently decomposed and removed. Although the soil temperature may be 80 ° C. or higher, the soil temperature is preferably less than 80 ° C. from the viewpoint of economy, safety, and the like. In addition, after the predetermined time has elapsed from the start of the treatment, after the temperature of the leachate has stabilized, the temperature of the leachate can be regarded as almost equal to the soil temperature, and therefore the soil temperature can be confirmed by the temperature of the leachate. .
本発明の具体的な処理方法として、塩素系酸化剤、或いはアルカリ剤及び塩素系酸化剤（以下、これらを「薬剤」と言う場合がある。）は、土壌中に薬剤が全体に行き渡るように添加されればよく、例えば土壌の複数箇所にホースを差し込んで薬剤の水溶液を注入する方法や、シャワーのように土壌上に薬剤の水溶液を散布する方法などが挙げられる。この際、土壌の間隙に占める水の量が少ない場合には、予め土壌に水を注入して水の飽和度（含水量）を高めることが、薬剤とシアン化合物との反応性、薬剤の浸透性を高める点において好ましい。 As a specific treatment method of the present invention, a chlorinated oxidant, or an alkaline agent and a chlorinated oxidant (hereinafter sometimes referred to as “medicine”) are used so that the drug is distributed throughout the soil. What is necessary is just to add, For example, the method of inserting the hose in the several places of soil and injecting the aqueous solution of a chemical | medical agent, the method of spraying the aqueous solution of a chemical | medical agent on soil like a shower, etc. are mentioned. At this time, when the amount of water in the soil gap is small, it is possible to increase the saturation (water content) of the water in advance by adding water to the soil. It is preferable in terms of enhancing the properties.
加温方法の一つである蒸気の吹き込み方法としては、土壌全体が加温されるような方法であればよく、特に制限はない。例えば、土壌の複数箇所に蒸気吹き込みノズルを挿入して蒸気を吹き込む方法などが挙げられる。
なお、この際、処理対象土壌の表面をビニールシートで覆うなどして、土壌表面からの放熱による温度低下を防止する保温対策を講じることも好ましい。
The steam blowing method, which is one of the heating methods, may be any method that warms the entire soil, and is not particularly limited. For example, a method of blowing steam by inserting steam blowing nozzles at a plurality of locations in the soil can be mentioned.
At this time, it is also preferable to take a heat retaining measure to prevent a temperature drop due to heat radiation from the soil surface by covering the surface of the soil to be treated with a vinyl sheet.
本発明による処理の開始に当っては、必要に応じてまず熱源により処理対象土壌を前述の所定の温度に加温し、その後薬剤の添加を開始し、浸出水のｐＨ及び遊離塩素濃度が前述の範囲となるように薬剤を添加し、浸出水のｐＨ及び遊離塩素濃度がこの範囲で安定した後に薬剤の添加を停止し、この状態で保持する。 At the start of the treatment according to the present invention, if necessary, the soil to be treated is first heated to the above-mentioned predetermined temperature by a heat source, and then the addition of the chemical is started. The drug is added so that the pH of the leachate and the free chlorine concentration are stabilized in this range, and the addition of the drug is stopped and maintained in this state.
この処理時間は、処理対象土壌の透水性によっても異なるが、比較的透水性の高い土壌であれば、土壌温度が２０℃以上４０℃未満の場合は２０００時間以上、好ましくは２０００〜４０００時間、４０℃以上６０℃未満の場合は３００時間以上、好ましくは３００〜２０００時間、６０℃以上１００℃以下の場合は２４時間以上、好ましくは２４〜１４４０時間の間で設定すればよい。 This treatment time varies depending on the permeability of the soil to be treated, but if the soil is relatively highly permeable, if the soil temperature is 20 ° C. or more and less than 40 ° C., 2000 hours or more, preferably 2000 to 4000 hours, When it is 40 ° C. or more and less than 60 ° C., it may be set for 300 hours or more, preferably 300 to 2000 hours, and when it is 60 ° C. or more and 100 ° C. or less, it may be set for 24 hours or more, preferably 24 to 1440 hours.
本発明による処理は、埋り出した土壌を別の場所へ移送して処理する場合に限らず、現位置での処理も可能である。現位置で処理する場合には、地下水の採水井戸を設け、浸出水として地下水を採水してｐＨ及び遊離塩素濃度の測定を行えばよい。
井戸を設けた場合、地下水の流れが速くなるため、井戸を中心に地下水の処理をすることが、より好ましい。
The processing according to the present invention is not limited to the case where the buried soil is transferred to another place for processing, and processing at the current position is also possible. In the case of processing at the current position, a groundwater sampling well is provided, and groundwater is sampled as leachate, and the pH and free chlorine concentration are measured.
When a well is provided, since the flow of groundwater becomes faster, it is more preferable to treat the groundwater around the well.
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、以下の実施例に何ら制限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 as long as the gist thereof is not exceeded.
なお、以下の実施例及び比較例では、処理対象土壌としてはシアン化合物（遊離シアン、鉄シアノ錯体）を含むスラグ（透水係数１０ｃｍ／ｓ）を用い、また、アルカリ剤としては４８重量％ＮａＯＨ水溶液を、塩素系酸化剤としては１２重量％ＮａＣｌＯ水溶液を、注入用の水としては工業用水を用いて処理を行った。 In the following Examples and Comparative Examples, slag (water permeability 10 cm / s) containing a cyanide compound (free cyan, iron cyano complex) is used as the soil to be treated, and a 48 wt% NaOH aqueous solution is used as the alkali agent. Was treated using a 12 wt% NaClO aqueous solution as the chlorine-based oxidant and industrial water as the water for injection.
また、全シアン及び遊離塩素濃度の分析方法は以下の通りである。 The analysis method of total cyanide and free chlorine concentration is as follows.
スラグ溶出水中の全シアン：処理後のスラグを用いて、環境庁告示４６号（平成３年８月２３日）で定められた土壌溶出試験により得られた溶出液を、ＪＩＳ Ｋ０１０２に準拠した４−ピリジン−ピラゾロン吸光光度法により測定した。
浸出水中の全シアン：浸出水を濾過せずに、ＪＩＳ Ｋ０１０２に準拠した４−ピリジン−ピラゾロン吸光光度法により測定した。
なお、上記全シアンの測定は、Ｌ（＋）−アスコルビン酸を添加して水中の残留塩素を還元した後、行った。
浸出水中の遊離塩素：浸出水をガラスフィルター製濾紙で濾過後、純水で所定濃度に希釈し、ＪＩＳ Ｋ０１０２に準拠したＤＰＤ法にて測定した。
All cyanides in slag elution water: Using the treated slag, the eluate obtained by the soil elution test specified in the Environmental Agency Notification No. 46 (August 23, 1991) was compliant with JIS K0102. -Measured by pyridine-pyrazolone spectrophotometry.
Total cyanide in leachate: Measured by a 4-pyridine-pyrazolone spectrophotometric method according to JIS K0102, without filtering leachate.
The measurement of all cyan was performed after adding L (+)-ascorbic acid to reduce residual chlorine in water.
Free chlorine in leachate: The leachate was filtered through filter paper made of glass filter, diluted with pure water to a predetermined concentration, and measured by the DPD method according to JIS K0102.
［実施例１〜５］
図１に示すように、プラスチック製（耐熱性）の貯槽（内寸：１ｍ×１ｍ×０．３ｍ）１に、シアン化合物を有するスラグ２の山を形成して、スラグの山の上部を平らにならして略角錐台形とし、蒸気と薬剤の注入個所を設けた。図１（ａ）において、Ａは薬剤（アルカリ剤及び塩素系酸化剤）の注入点を示し、Ｂは蒸気の注入点を示す。また、図１（ｂ）において、ＣはこれらＡ，Ｂの位置をまとめて示すものである。
また、スラグ山の上面から３ｃｍの深さの位置において、蒸気が直接当たらない箇所に温度計（図示せず）を設けた。
まず、蒸気の吹き込みによりスラグの山を加温し、温度計の測定温度が設定温度以上になっていることを確認した後、薬剤を注入した。また、貯槽下部のバルブから浸出水が採取できない場合には、分析に必要な量の浸出水を採取出来るまでスラグ山の上部中央から所定濃度の薬剤を混合した水を注入した。
浸出水のｐＨ、水温、遊離塩素濃度を調べ、ｐＨ１１〜１２、遊離塩素濃度１０ｍｇ／Ｌ以上、水温が所定温度となるように薬剤および蒸気の注入量を調節して反応時間の間維持した。
スラグの平均温度、浸出水の平均ｐＨ及び遊離塩素濃度、処理時間と、処理後の浸出水及びスラグ溶出水の全シアン濃度は表１に示す通りであった。
[Examples 1 to 5]
As shown in FIG. 1, in a plastic (heat-resistant) storage tank (inner dimensions: 1 m × 1 m × 0.3 m) 1, a slag 2 peak containing cyanide is formed, and the upper part of the slag ridge is flattened. It was made into a substantially pyramidal trapezoidal shape, and a place for injecting steam and medicine was provided. In FIG. 1 (a), A indicates the injection point of chemicals (alkali agent and chlorine-based oxidant), and B indicates the injection point of steam. In FIG. 1B, C indicates the positions of A and B together.
In addition, a thermometer (not shown) was provided at a position where the steam did not directly hit at a position 3 cm deep from the upper surface of the slag mountain.
First, the slag pile was heated by blowing in steam, and after confirming that the temperature measured by the thermometer was equal to or higher than the set temperature, the drug was injected. When leachate could not be collected from the valve at the bottom of the storage tank, water mixed with a predetermined concentration of drug was injected from the upper center of the slag mountain until the amount of leachate required for analysis could be collected.
The pH of the leachate, the water temperature, and the free chlorine concentration were examined, and the amounts of drug and vapor injected were adjusted so that the water temperature would be a predetermined temperature at pH 11-12, free chlorine concentration of 10 mg / L or more, and maintained for the reaction time.
Table 1 shows the average temperature of the slag, the average pH and the free chlorine concentration of the leachate, the treatment time, and the total cyan concentration of the leachate and slag elution water after the treatment.
［実施例６〜１２］
実施例１において、蒸気の吹き込み量、薬剤の注入量を変え、表１に示す処理条件としたこと以外は同様にして処理を行った。処理後の浸出水及びスラグ溶出水の全シアン濃度は表１に示す通りであった。
[Examples 6 to 12]
In Example 1, the treatment was carried out in the same manner except that the treatment conditions shown in Table 1 were changed by changing the amount of steam blown and the amount of medicine injected. The total cyan concentration of the leachate and slag elution water after the treatment was as shown in Table 1.
［比較例１］
シアン化合物含有スラグについて、何ら処理することなく、そのまま前述の方法で全シアン濃度の測定を行い、結果を表１に示した。
[Comparative Example 1]
With respect to the cyanide-containing slag, the total cyan density was measured by the above method without any treatment, and the results are shown in Table 1.
表１より、本発明によれば、土壌にアルカリ剤と塩素系酸化剤を注入すると共に必要に応じて加温用の蒸気を吹き込むなどして加温することにより、土壌中の全シアンを難分解性の鉄シアノ錯体も含めて効率的に分解処理することができ、特に温度６０℃以上、浸出水のｐＨ１１以上で遊離塩素濃度１０ｍｇ／Ｌ以上となるように、薬剤の注入と蒸気の吹き込みを行うことが好ましいことが分かる。また、本条件範囲において、土壌温度が２０℃の場合には処理時間２１６０時間に、４０℃の場合には処理時間を３６０時間にまで保持時間を延ばすことにより、浸出水あるいは溶出水の全シアンを環境基準である検出限界値未満に分解できることが分かる。 From Table 1, according to the present invention, it is difficult to prevent all cyanides in the soil by injecting an alkali agent and a chlorine-based oxidizing agent into the soil and blowing it with steam for heating as necessary. Decomposable iron cyano complex can be efficiently decomposed, and injecting chemicals and injecting steam so that the free chlorine concentration is 10 mg / L or more when the temperature is 60 ° C. or higher and the pH of leachate is 11 or higher. It can be seen that it is preferable to perform. In this range of conditions, when the soil temperature is 20 ° C., the treatment time is 2160 hours, and when the soil temperature is 40 ° C., the treatment time is extended to 360 hours, thereby increasing the total cyanide content of the leachate or elution water. It can be seen that can be decomposed below the detection limit value, which is the environmental standard.
１ 貯槽
２ スラグ
1 Storage tank 2 Slag
Claims (6)
(1) 土壌温度が２０℃以上４０℃未満の場合、２０００時間以上
(2) 土壌温度が４０℃以上６０℃未満の場合、３００時間以上
(3) 土壌温度が６０℃以上１００℃以下の場合、２４時間以上 The method for treating cyan-containing soil according to claim 1 or 2, wherein the predetermined time is any one of the following (1) to (3) according to the soil temperature.
(1) 2000 hours or more when soil temperature is 20 ℃ or more and less than 40 ℃
(2) 300 hours or more when soil temperature is 40 ℃ or more and less than 60 ℃
(3) 24 hours or more when soil temperature is 60 ℃ or more and 100 ℃ or less
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105080932A (en) * | 2015-07-30 | 2015-11-25 | 长春黄金研究院 | Biological treatment method of cyanogen-contained tailing slag |
| JP2016049510A (en) * | 2014-09-01 | 2016-04-11 | 新日鉄住金エンジニアリング株式会社 | Purification method of contaminated region |
| CN110078337A (en) * | 2019-05-23 | 2019-08-02 | 东北大学 | A kind of method of low temperature thermal decomposition copper cyano complex |
| CN113185265A (en) * | 2021-07-01 | 2021-07-30 | 北京矿冶研究总院 | Cyanide sludge sintering cyanogen removal process, cyanide-free brick, cyanide sludge sintering cyanogen removal system and application |
| WO2024143649A1 (en) * | 2022-12-30 | 2024-07-04 | (주)에스지알테크 | Method for clearing oil pollutants in soil through oxidizer, additive, and thermal activation |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL8202593A (en) * | 1982-06-25 | 1984-01-16 | Volker Stevin Wegen En Asfalt | Purifying soil contaminated with cyanide - using two=piece two=phase process, to break down cyanide into carbonic acid and nitrogen |
| JPH09225447A (en) * | 1996-02-21 | 1997-09-02 | Hazama Gumi Ltd | Treatment of contaminated soil |
| JP2001009060A (en) * | 1999-06-28 | 2001-01-16 | Maezawa Ind Inc | Method for removing hazardous material in soil |
| JP2004058011A (en) * | 2002-07-31 | 2004-02-26 | Nippon Parkerizing Co Ltd | Decontamination treatment method of soil contaminated with cyanide |
-
2013
- 2013-09-27 JP JP2013201927A patent/JP6213105B2/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL8202593A (en) * | 1982-06-25 | 1984-01-16 | Volker Stevin Wegen En Asfalt | Purifying soil contaminated with cyanide - using two=piece two=phase process, to break down cyanide into carbonic acid and nitrogen |
| JPH09225447A (en) * | 1996-02-21 | 1997-09-02 | Hazama Gumi Ltd | Treatment of contaminated soil |
| JP2001009060A (en) * | 1999-06-28 | 2001-01-16 | Maezawa Ind Inc | Method for removing hazardous material in soil |
| JP2004058011A (en) * | 2002-07-31 | 2004-02-26 | Nippon Parkerizing Co Ltd | Decontamination treatment method of soil contaminated with cyanide |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016049510A (en) * | 2014-09-01 | 2016-04-11 | 新日鉄住金エンジニアリング株式会社 | Purification method of contaminated region |
| CN105080932A (en) * | 2015-07-30 | 2015-11-25 | 长春黄金研究院 | Biological treatment method of cyanogen-contained tailing slag |
| CN105080932B (en) * | 2015-07-30 | 2017-03-22 | 长春黄金研究院 | Biological treatment method of cyanogen-contained tailing slag |
| CN110078337A (en) * | 2019-05-23 | 2019-08-02 | 东北大学 | A kind of method of low temperature thermal decomposition copper cyano complex |
| CN110078337B (en) * | 2019-05-23 | 2021-11-30 | 东北大学 | Method for low-temperature thermal decomposition of copper-cyanogen complex |
| CN113185265A (en) * | 2021-07-01 | 2021-07-30 | 北京矿冶研究总院 | Cyanide sludge sintering cyanogen removal process, cyanide-free brick, cyanide sludge sintering cyanogen removal system and application |
| WO2024143649A1 (en) * | 2022-12-30 | 2024-07-04 | (주)에스지알테크 | Method for clearing oil pollutants in soil through oxidizer, additive, and thermal activation |
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