JP2013208551A - Method for treating cyanogen-containing waste water - Google Patents
Method for treating cyanogen-containing waste water Download PDFInfo
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- 239000002351 wastewater Substances 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 30
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title abstract 18
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000000460 chlorine Substances 0.000 claims abstract description 59
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 59
- -1 cyanogen compound Chemical class 0.000 claims abstract description 19
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 9
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 39
- 239000003513 alkali Substances 0.000 claims description 22
- 239000002455 scale inhibitor Substances 0.000 claims description 18
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 239000005416 organic matter Substances 0.000 claims description 8
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 claims description 6
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000000126 substance Substances 0.000 abstract description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 230000003449 preventive effect Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 7
- 229910000831 Steel Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000005708 Sodium hypochlorite Substances 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 150000007661 iron cyano complex Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- QPJDMGCKMHUXFD-UHFFFAOYSA-N cyanogen chloride Chemical compound ClC#N QPJDMGCKMHUXFD-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 239000000243 solution Substances 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
- 239000002211 L-ascorbic acid Substances 0.000 description 1
- 235000000069 L-ascorbic acid Nutrition 0.000 description 1
- 229910019093 NaOCl Inorganic materials 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 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
- 239000000843 powder Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- LIXWSNVLHFNXAJ-UHFFFAOYSA-N sodium;oxidoazaniumylidynemethane Chemical compound [Na+].[O-][N+]#[C-] LIXWSNVLHFNXAJ-UHFFFAOYSA-N 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- Chemical & Material Sciences (AREA)
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- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
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Abstract
Description
本発明はシアン含有排水の処理方法に係り、特に、シアン含有排水をアルカリ塩素法により処理する方法に関する。 The present invention relates to a method for treating cyan-containing wastewater, and more particularly, to a method for treating cyan-containing wastewater by an alkali chlorine method.
めっき工場、製鉄所、製錬所、発電所、コークス製造工場などの産業施設から排出されるシアン含有排水の処理方法として、現在最も広く採用されている方法は、アルカリ塩素法である。この方法では、塩素源、例えば次亜塩素酸ナトリウムをアルカリ性下にシアン含有排水に添加して排水中のシアンを酸化処理する（特許文献１，２）。 The most widely used method for treating cyanide-containing wastewater discharged from industrial facilities such as plating factories, ironworks, smelters, power plants, and coke factories is the alkali chlorine method. In this method, a chlorine source, for example, sodium hypochlorite is added to cyanide-containing wastewater under alkalinity to oxidize cyanide in the wastewater (Patent Documents 1 and 2).
特許文献１のアルカリ塩素法では、以下に示すようなｐＨ及びＯＲＰ制御値における２段階の反応でシアン化合物を酸化分解する。 In the alkali chlorine method of Patent Document 1, the cyanide compound is oxidatively decomposed by a two-stage reaction at pH and ORP control values as shown below.
一段反応：ｐＨ１０以上，ＯＲＰ制御値３００〜３５０ｍＶ
ＮａＣＮ＋ＮａＯＣｌ→ＮａＣＮＯ＋ＮａＣｌ …（１）
二段反応：ｐＨ７〜８，ＯＲＰ制御値６００〜６５０ｍＶ
２ＮａＣＮＯ＋３ＮａＣｌＯ＋Ｈ２Ｏ→Ｎ２＋３ＮａＣｌ＋２ＮａＨＣＯ３ …（２）
特許文献２には、アンモニアを含むシアン含有排水をアルカリ塩素法の２段階の反応によって処理する方法が記載されている。
One-step reaction: pH 10 or higher, ORP control value 300 to 350 mV
NaCN + NaOCl → NaCNO + NaCl (1)
Two-stage reaction: pH 7-8, ORP control value 600-650 mV
2NaCNO + 3NaClO + H 2 O → N 2 + 3NaCl + 2NaHCO 3 (2)
Patent Document 2 describes a method of treating cyanide-containing wastewater containing ammonia by a two-stage reaction of the alkali chlorine method.
本発明者らの研究の結果、シアン含有排水がアンモニウムイオン及び有機物を含んでいる場合、アルカリ塩素法を適用すると、第一段目の反応でシアン化合物が十分には酸化されないことが見出された。 As a result of our research, it was found that when cyanide-containing wastewater contains ammonium ions and organic substances, the cyanide compound is not sufficiently oxidized in the first-stage reaction when the alkali chlorine method is applied. It was.
即ち、アンモニウムイオン及び有機物を含有するシアンを従来のアルカリ塩素法の第１段目反応における一般的なｐＨ範囲のｐＨ１０〜１０．５、ＯＲＰ３００〜３５０ｍＶで処理した場合、シアン化合物の分解は不十分である。また、ＮａＣｌＯを追加しＯＲＰを４００ｍＶ以上に上げても全シアン濃度は下がらない。ｐＨ１１以上でＯＲＰ３００〜３５０ｍＶとなるように制御するには、さらに過剰の塩素源が必要となり、コスト高になると共に、鋼材が腐食するおそれがある。 That is, when cyanide containing ammonium ions and organic substances is treated at pH 10 to 10.5 in the general pH range in the first step reaction of the conventional alkali chlorine method and ORP 300 to 350 mV, decomposition of cyanide is insufficient. It is. Further, even if NaClO is added and ORP is raised to 400 mV or higher, the total cyan density does not decrease. In order to control the ORP to be 300 to 350 mV at a pH of 11 or more, an excessive chlorine source is required, which increases the cost and corrodes the steel material.
このようにアルカリ塩素法の第１段目反応においてシアン化合物が十分に酸化されないと、第２段目の反応が進行しないだけでなく、第２段目反応においてシアン化合物が次亜塩素酸ナトリウムと反応して塩化シアン（ＣＮＣｌ）が発生するおそれがある。 As described above, if the cyanide compound is not sufficiently oxidized in the first stage reaction of the alkali chlorine method, not only the second stage reaction does not proceed, but also the cyanide compound and sodium hypochlorite in the second stage reaction. There is a risk that cyanogen chloride (CNCl) may be generated upon reaction.
また、アンモニウムイオン及び有機物を含有するシアン含有排水に塩素源を添加した場合、ｐＨが１１未満であると、アンモニウムイオンと塩素源とが反応して結合塩素が生じる。この結合塩素は有機物と反応してシアンを生成させるので、シアン含有排水のシアン濃度が低下しなかったり、逆に上昇することもある。 In addition, when a chlorine source is added to cyanide-containing wastewater containing ammonium ions and organic substances, if the pH is less than 11, the ammonium ions and the chlorine source react to produce combined chlorine. Since this bonded chlorine reacts with organic matter to produce cyan, the cyan concentration of the cyanate-containing wastewater does not decrease or may increase.
本発明は、上記従来の問題点を解決し、シアン含有排水がアンモニウムイオン及び有機物を含有する場合でもシアン化合物を十分に酸化分解することができ、またスケール生成が防止されるシアン含有排水の処理方法を提供することを目的とする。 The present invention solves the above-described conventional problems, and even when cyanide-containing wastewater contains ammonium ions and organic matter, the cyanide compound can be sufficiently oxidatively decomposed, and the treatment of cyanide-containing wastewater can be prevented from generating scale. It aims to provide a method.
本発明のシアン含有排水の処理方法は、シアン化合物を含有するシアン含有排水に塩素源を添加してシアン化合物を分解するシアン含有排水の処理方法において、該シアン含有排水がアンモニウムイオン及び有機物を含有しており、該シアン含有排水のｐＨを１１以上とし、シアン化合物分解反応後においても遊離残留塩素濃度が０．１ｍｇ／Ｌ以上となるように前記塩素源を添加すると共に、ホスホン酸系スケール防止剤を添加することを特徴とするものである。 The method for treating cyan-containing wastewater of the present invention is a method for treating cyanide-containing wastewater in which a cyanide is decomposed by adding a chlorine source to cyanide-containing wastewater containing cyanide, wherein the cyanate-containing wastewater contains ammonium ions and organic matter. The pH of the waste water containing cyan is 11 or more, and the chlorine source is added so that the free residual chlorine concentration is 0.1 mg / L or more even after the cyanide decomposition reaction, and the phosphonic acid scale is prevented. It is characterized by adding an agent.
ホスホン酸系スケール防止剤としては、１−ヒドロキシエチリデン−１，１−ジホスホン酸、２−ホスホノブタン−１，２，４−トリカルボン酸、及びそれらの塩から選ばれる少なくとも１種が好適である The phosphonic acid scale inhibitor is preferably at least one selected from 1-hydroxyethylidene-1,1-diphosphonic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, and salts thereof.
本発明では、前記遊離残留塩素濃度が０．１〜１ｍｇ／Ｌとなるように前記塩素源を添加することが好ましい。 In this invention, it is preferable to add the said chlorine source so that the said free residual chlorine concentration may be 0.1-1 mg / L.
また、前記シアン含有排水にアルカリ源を添加してｐＨを１１〜１２．５とすることが好ましい。この場合、アルカリ源とスケール防止剤とを混合して一液化して添加することが好ましい。 Moreover, it is preferable to add an alkali source to the cyanate-containing wastewater to adjust the pH to 11 to 12.5. In this case, it is preferable to add the alkali source and the scale inhibitor after mixing them into one liquid.
前記シアン含有排水の溶解性鉄の濃度が０．４ｍｇ／Ｌ以下であることが好ましい。 It is preferable that the concentration of soluble iron in the cyanide-containing wastewater is 0.4 mg / L or less.
シアン含有排水の水温を４０℃以上例えば４０〜８０℃特に５０〜７０℃とすることが好ましい。 The water temperature of the cyanate-containing wastewater is preferably 40 ° C. or higher, for example, 40 to 80 ° C., particularly 50 to 70 ° C.
本発明のシアン含有排水の処理方法では、アンモニウムイオン及び有機物を含むシアン含有排水に対しｐＨ１１以上にて塩素源を添加する。ｐＨ１１以上であると、塩素源とアンモニウムイオンとの反応が抑制され、これにより結合塩素の生成が抑制し、その結果、結合塩素と有機物との反応によるシアン生成も抑制される。本発明では、ホスホン酸系スケール防止剤を添加するので、スケールの発生が防止（抑制を包含する。）される。 In the method for treating cyanide-containing wastewater of the present invention, a chlorine source is added at a pH of 11 or more to cyanide-containing wastewater containing ammonium ions and organic matter. When the pH is 11 or more, the reaction between the chlorine source and ammonium ions is suppressed, whereby the generation of bonded chlorine is suppressed, and as a result, the generation of cyan due to the reaction between the combined chlorine and organic matter is also suppressed. In the present invention, since a phosphonic acid scale inhibitor is added, generation of scale is prevented (including suppression).
ｐＨを１１以上とするにはアルカリ源を添加するのが好ましい。このアルカリ源とスケール防止剤とを混合して一液化して添加すると、薬注（薬剤注入）ポンプや薬注配管でのスケールトラブルが防止される。 In order to adjust the pH to 11 or more, it is preferable to add an alkali source. When this alkali source and the scale inhibitor are mixed and added as a single solution, scale troubles in the chemical injection (chemical injection) pump and chemical injection piping are prevented.
なお、本発明では、反応終了後においてもｐＨ１１以上であることが好ましい。 In the present invention, the pH is preferably 11 or more even after completion of the reaction.
また、アンモニウムイオン及び有機物含有排水に対しｐＨ１１以上で塩素源を添加し、且つ反応後においても遊離残留塩素濃度を０．１ｍｇ／Ｌとすることによりシアンが十分に酸化され、被処理排水中のシアン濃度が十分に低下する。 Moreover, by adding a chlorine source at a pH of 11 or more to ammonium ion and organic matter-containing wastewater and setting the residual residual chlorine concentration to 0.1 mg / L even after the reaction, cyan is sufficiently oxidized, The cyan density is sufficiently reduced.
反応後の遊離残留塩素濃度を１ｍｇ／Ｌ以下とすることにより、鋼材等よりなる接液部材の腐食が抑制される。 By setting the free residual chlorine concentration after the reaction to 1 mg / L or less, corrosion of the wetted member made of steel or the like is suppressed.
反応時の水温を４０℃以上とすると、シアン分解反応効率が向上し、シアン濃度が短時間で低下する。また、反応時間が短くなると、遊離残留塩素を含有する被処理水と接液部材との接触時間が短くなり、鋼材等よりなる接液部材の腐食が抑制される。 When the water temperature during the reaction is 40 ° C. or higher, the cyanide decomposition reaction efficiency is improved, and the cyan density is lowered in a short time. Moreover, when reaction time becomes short, the contact time of the to-be-processed water containing free residual chlorine and a liquid-contacting member will become short, and corrosion of the liquid-contacting member which consists of steel materials etc. will be suppressed.
以下、本発明についてさらに詳細に説明する。 Hereinafter, the present invention will be described in more detail.
本発明において、処理対象となるシアン含有排水は、めっき工場、発電所、製鉄所、製錬所、コークス製造工場などの産業施設から排出される、シアンを金属のシアン錯体例えば、Ｎｉ，Ａｇ，Ｃｕ，Ｚｎ，Ｃｄ等の金属のシアン錯体として含有するシアン含有排水が例示されるが、これに限定されない。 In the present invention, cyanide-containing wastewater to be treated is discharged from industrial facilities such as a plating plant, a power plant, a steel mill, a smelter, a coke production plant, and cyan is a metal cyan complex such as Ni, Ag, Although the cyan containing waste water contained as a cyan complex of metals, such as Cu, Zn, Cd, is illustrated, it is not limited to this.
通常の場合、このようなシアン含有排水のシアン濃度は０．１〜１００ｍｇ／Ｌ程度であり、またｐＨは６〜１０程度である。 Normally, the cyan concentration of such cyan-containing wastewater is about 0.1 to 100 mg / L, and the pH is about 6 to 10.
本発明では、アンモニウムイオン及び有機物を含有するシアン含有排水を処理対象とする。このアンモニウムイオンの濃度は５ｍｇ／Ｌ以上例えば５〜２５０ｍｇ／Ｌ程度であることが好ましい。また、有機物としては石炭やコークス由来のものなどが例示され、その濃度は１ｍｇ／Ｌ以上例えば１〜３０ｍｇ／Ｌ程度であることが好ましい。 In the present invention, cyanide-containing wastewater containing ammonium ions and organic substances is treated. The concentration of this ammonium ion is preferably 5 mg / L or more, for example, about 5 to 250 mg / L. Moreover, as an organic substance, the thing derived from coal, coke, etc. are illustrated, It is preferable that the density | concentration is 1 mg / L or more, for example, about 1-30 mg / L.
シアン化合物が含まれるｐＨ中性以上の工場廃水中に含まれる溶解性鉄は、大部分が鉄シアノ錯体で存在している。本発明方法のアルカリ塩素法によるシアン化合物酸化分解反応では鉄シアノ錯体は分解されにくい。そのため、本発明方法が処理対象とするシアン含有排水は、鉄シアノ錯体の全シアン濃度が１．０ｍｇ／Ｌ以下であり、溶解性鉄の濃度としては０．４ｍｇ／Ｌ未満であることが好ましい。 Most of the soluble iron contained in industrial wastewater containing a cyanide and having a pH neutrality or higher exists as an iron cyano complex. In the cyanide oxidative decomposition reaction by the alkali chlorine method of the present invention, the iron cyano complex is hardly decomposed. Therefore, the cyan-containing wastewater to be treated by the method of the present invention preferably has a total cyan concentration of iron cyano complex of 1.0 mg / L or less and a concentration of soluble iron of less than 0.4 mg / L. .
シアン含有排水に添加する塩素源としては、塩素、さらし粉、次亜塩素酸ナトリウムなどが例示される。また、シアン含有排水に添加するホスホン酸系スケール防止剤としては、１−ヒドロキシエチリデン−１，１−ジホスホン酸（ＨＥＤＰ）、２−ホスホノブタン−１，２，４−トリカルボン酸（ＰＢＴＣ）、及びそれらの塩から選ばれる少なくとも１種が例示され、塩としてはナトリウム塩、カリウム塩などが例示されるが、中でも１−ヒドロキシエチリデン−１，１−ジホスホン酸が好ましい。 Examples of the chlorine source added to the cyanate-containing wastewater include chlorine, bleached powder, and sodium hypochlorite. Examples of phosphonic acid scale inhibitors to be added to cyanate-containing wastewater include 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC), and those At least one selected from these salts is exemplified, and examples of the salt include sodium salt and potassium salt, among which 1-hydroxyethylidene-1,1-diphosphonic acid is preferable.
シアン含有排水に塩素源を添加する場合、必要に応じアルカリ例えばＮａＯＨ及び／又はＫＯＨを添加することによりシアン含有排水のｐＨを１１以上、好ましくは１１〜１２．５特に１１〜１２とする。アルカリ添加は塩素源の添加の前又は後に行われてもよく、同時に行われてもよい。シアン含有排水のｐＨが１１以上であれば、アルカリは添加しなくてもよい。なお、処理反応後の水のｐＨが１１以上であることが好ましい。 When the chlorine source is added to the cyanide-containing wastewater, the pH of the cyanate-containing wastewater is adjusted to 11 or more, preferably 11 to 12.5, particularly 11 to 12 by adding an alkali such as NaOH and / or KOH as necessary. The alkali addition may be performed before or after the addition of the chlorine source, or may be performed simultaneously. If the pH of the cyanate-containing wastewater is 11 or more, the alkali may not be added. In addition, it is preferable that pH of the water after process reaction is 11 or more.
アルカリ源を添加する場合、アルカリ源とスケール防止剤とを混合して一液化しておいてもよい。このようにすれば、薬注ポンプや薬注配管でのスケール発生が防止される。スケール防止剤の添加量は、シアン含有排水の水質に応じて実験的に定めるのが好ましいが、通常の場合１〜１００ｍｇ／Ｌ特に５〜３０ｍｇ／Ｌ程度が好ましい。 When an alkali source is added, the alkali source and the scale inhibitor may be mixed to form a single solution. In this way, scale generation in the chemical injection pump and chemical injection piping is prevented. The amount of the scale inhibitor added is preferably determined experimentally according to the water quality of the cyanide-containing wastewater, but in the usual case, it is preferably about 1 to 100 mg / L, particularly about 5 to 30 mg / L.
塩素源の添加量は、反応後の遊離残留塩素濃度が０．１ｍｇ／Ｌ以上、好ましくは０．１〜１ｍｇ／Ｌ特に０．１〜０．５ｍｇ／Ｌとなるように制御される。 The addition amount of the chlorine source is controlled so that the concentration of free residual chlorine after the reaction is 0.1 mg / L or more, preferably 0.1 to 1 mg / L, particularly 0.1 to 0.5 mg / L.
シアン含有排水の処理を槽内でバッチ式に行う場合には、槽内の液の遊離残留塩素濃度を経時後に測定し、遊離残留塩素濃度の低下速度がゼロ又は所定値以下となった時点を反応終了時とすればよい。この所定値としては０〜０．１ｍｇ／Ｌ／ｍｉｎの間から選択された値とするのが好ましい。 When processing cyanide-containing wastewater batchwise in the tank, measure the free residual chlorine concentration of the liquid in the tank after time, and determine when the rate of decrease in free residual chlorine concentration is zero or below the specified value. It may be at the end of the reaction. The predetermined value is preferably a value selected from 0 to 0.1 mg / L / min.
シアン含有排水を反応槽に連続的に流入させ、かつ該反応槽から連続的に流出させ、該反応槽にてシアン分解反応を行う場合には、槽内滞留時間を反応終了時間よりも長くし、反応槽出口にて測定される遊離残留塩素濃度を反応後の遊離残留塩素濃度として扱うのが好ましい。 When cyanide-containing wastewater is continuously flowed into and out of the reaction tank and the cyanide decomposition reaction is performed in the reaction tank, the residence time in the tank is made longer than the reaction end time. The free residual chlorine concentration measured at the reaction vessel outlet is preferably treated as the free residual chlorine concentration after the reaction.
シアン含有排水を配管に流し、この配管に塩素源、スケール防止剤及び必要に応じアルカリを添加してライン処理する場合には、ライン下流側の複数箇所で遊離残留塩素濃度を測定し、２以上の箇所での遊離残留塩素濃度測定値が実質的に同一となった場合、当該測定箇所又はそれよりも上流域において反応が終了したものと扱うことができる。この測定箇所は５ｍ以上特に１０〜３０ｍ程度離隔していることが好ましい。 When draining cyan-containing wastewater into a pipe and adding a chlorine source, scale inhibitor, and alkali as needed to the pipe, measure the free residual chlorine concentration at multiple locations downstream of the line. When the measured values of the free residual chlorine concentration at the point are substantially the same, it can be treated that the reaction has been completed at the measurement point or in the upstream region. It is preferable that this measurement location is 5 m or more, especially 10-30 m apart.
このような条件でシアン含有排水を処理した場合、ｐＨ１１以上としたことにより、結合塩素の生成が抑制され、結合塩素と有機物との反応によるシアン生成も抑制される。また、スケール防止剤を添加したことによりスケール付着が防止され、シアン含有排水の処理を安定して行うことができる。反応終了後の遊離残留塩素濃度が０．１ｍｇ／Ｌ以上となるように塩素源を添加することにより、シアンが十分に分解される。遊離残留塩素濃度を１ｍｇ／Ｌ以下とすることにより、塩素源の過剰添加が防止され、塩素源コストが抑制される。また、接液部材を構成する鋼材等の金属材の腐食も抑制される。 When cyanide-containing wastewater is treated under such conditions, by setting the pH to 11 or more, generation of bonded chlorine is suppressed, and generation of cyan due to reaction between bonded chlorine and organic matter is also suppressed. Moreover, scale adhesion is prevented by adding a scale inhibitor, and cyanide-containing wastewater can be treated stably. By adding a chlorine source such that the concentration of free residual chlorine after the reaction is 0.1 mg / L or more, cyan is sufficiently decomposed. By setting the free residual chlorine concentration to 1 mg / L or less, excessive addition of the chlorine source is prevented, and the chlorine source cost is suppressed. Moreover, corrosion of metal materials, such as steel materials which comprise a liquid-contact member, is also suppressed.
本発明では、シアン含有排水の水温を４０℃以上例えば４０〜８０℃特に５０〜７０℃程度とし、これによりシアン分解反応速度を大きくすることが好ましい。シアン分解速度を大きくすると、遊離残留塩素を含んだ被処理水と鋼材等よりなる接液部材との接触時間が短くて済み、該接液部材の腐食が抑制される。加熱コストを抑制するために、水温は８０℃以下、特に７０℃以下とすることが好ましい。 In the present invention, the water temperature of the cyanide-containing wastewater is preferably 40 ° C. or higher, for example, 40 to 80 ° C., particularly about 50 to 70 ° C., thereby increasing the cyan decomposition reaction rate. When the cyan decomposition rate is increased, the contact time between the water to be treated containing free residual chlorine and the liquid contact member made of steel or the like is short, and corrosion of the liquid contact member is suppressed. In order to suppress the heating cost, the water temperature is preferably 80 ° C. or lower, particularly 70 ° C. or lower.
以下実施例及び比較例について説明する。なお、以下の実施例及び比較例ではアルカリ剤としてＮａＯＨ（４８％）を用い、塩素源としてＮａＣｌＯ（１２％）を用い、スケール防止剤としてＨＥＤＰ、ＰＢＴＣ、アクリル酸系ポリマー、又はマレイン酸系ポリマーを用いた。また、全ＣＮ分析は、Ｌ（＋）−アスコルビン酸を添加し残留塩素を還元し、ＮａＯＨでｐＨ１２に調整し、濾過せずＪＩＳ Ｋ ０１０２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。スケール防止効果については、カルシウムイオン濃度と、反応容器内のＳＵＳ製のテストピースへのスケール付着の有無に基づいて判断した。 Examples and comparative examples will be described below. In the following examples and comparative examples, NaOH (48%) is used as an alkali agent, NaClO (12%) is used as a chlorine source, and HEDP, PBTC, acrylic acid polymer, or maleic acid polymer is used as a scale inhibitor. Was used. Further, the total CN analysis was performed by adding L (+)-ascorbic acid to reduce residual chlorine, adjusting the pH to 12 with NaOH, and measuring by a 4-pyridine-pyrazolone spectrophotometry method according to JIS K 0102 without filtration. . About the scale prevention effect, it judged based on the calcium ion concentration and the presence or absence of the scale adherence to the SUS test piece in the reaction vessel.
［実施例１〜３、比較例１〜４］
試験水として次の水質の発電設備の集塵水を用いた。
ｐＨ：８．７、
全シアン：３ｍｇ／Ｌ、
アンモニウムイオン：１２０ｍｇ／Ｌ、
ＴＯＣ：１０ｍｇ／Ｌ、
溶解性鉄：０．１ｍｇ／Ｌ未満
[Examples 1 to 3, Comparative Examples 1 to 4]
As test water, the collected water from the following power generation facilities was used.
pH: 8.7
Total cyan: 3 mg / L,
Ammonium ion: 120 mg / L,
TOC: 10 mg / L,
Soluble iron: less than 0.1 mg / L
試験水５００ｍＬを蓋付きのガラス製容器に収容し、水温を６０℃に保ち、スケール防止剤、アルカリ剤及び塩素源を表１の条件となるように添加した。なお、容器内にＳＵＳ製テストピースを入れた。反応時間は６０分とした。 500 mL of test water was placed in a glass container with a lid, the water temperature was kept at 60 ° C., and a scale inhibitor, an alkali agent and a chlorine source were added so as to satisfy the conditions shown in Table 1. In addition, the test piece made from SUS was put in the container. The reaction time was 60 minutes.
薬剤添加から５分経過後及び上記６０分経過後のｐＨ、ＮａＣｌＯ添加量、上記反応時間経過後のカルシウムイオン濃度、テストピースへのスケール付着の有無及び全シアン濃度を表１に示す。 Table 1 shows the pH after the lapse of 5 minutes and 60 minutes after the addition of the chemical, the added amount of NaClO, the calcium ion concentration after the lapse of the reaction time, the presence or absence of scale adhesion to the test piece, and the total cyan concentration.
表１の通り、本発明によるとシアンを十分に分解することができると共に、スケールも防止される。比較例１ではｐＨを１１未満としているため、残留シアン濃度が高い。比較例２ではスケール防止剤を添加しておらず、スケールが発生した。比較例３，４では、スケール防止剤を添加したが、ホスホン酸系スケール防止剤ではないため、スケールが付着した。 As shown in Table 1, according to the present invention, cyan can be sufficiently decomposed and scale is also prevented. In Comparative Example 1, since the pH is less than 11, the residual cyan density is high. In Comparative Example 2, no scale inhibitor was added, and scale was generated. In Comparative Examples 3 and 4, the scale inhibitor was added, but the scale adhered because it was not a phosphonic acid scale inhibitor.
Claims (6)
該シアン含有排水がアンモニウムイオン及び有機物を含有しており、
該シアン含有排水のｐＨを１１以上とし、シアン化合物分解反応後においても遊離残留塩素濃度が０．１ｍｇ／Ｌ以上となるように前記塩素源を添加すると共に、ホスホン酸系スケール防止剤を添加することを特徴とするシアン含有排水の処理方法。 In a method for treating cyanide-containing wastewater, which adds a chlorine source to cyanide-containing wastewater containing cyanide to decompose cyanide,
The cyanate-containing wastewater contains ammonium ions and organic matter;
The pH of the cyanate-containing wastewater is adjusted to 11 or more, and the chlorine source is added so that the free residual chlorine concentration is 0.1 mg / L or more after the cyanide decomposition reaction, and a phosphonic acid scale inhibitor is added. A method for treating cyanate-containing wastewater.
該アルカリ源と前記スケール防止剤とを混合して一液化して添加することを特徴とするシアン含有排水の処理方法。 The method according to any one of claims 1 to 3, wherein an alkali source is added to the cyanate-containing wastewater to adjust the pH to 11 to 12.5.
A method for treating cyanide-containing wastewater, wherein the alkali source and the scale inhibitor are mixed and added as one solution.
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