JP2013081882A - Method for treatment of waste liquid discharged in manufacturing tnt - Google Patents
Method for treatment of waste liquid discharged in manufacturing tnt Download PDFInfo
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- JP2013081882A JP2013081882A JP2011222433A JP2011222433A JP2013081882A JP 2013081882 A JP2013081882 A JP 2013081882A JP 2011222433 A JP2011222433 A JP 2011222433A JP 2011222433 A JP2011222433 A JP 2011222433A JP 2013081882 A JP2013081882 A JP 2013081882A
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- tnt
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- 238000011282 treatment Methods 0.000 title claims abstract description 21
- 239000007788 liquid Substances 0.000 title claims abstract description 18
- 239000002699 waste material Substances 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 title claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 10
- 230000003647 oxidation Effects 0.000 claims abstract description 9
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 7
- 238000004065 wastewater treatment Methods 0.000 claims abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 238000003672 processing method Methods 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 15
- 235000011121 sodium hydroxide Nutrition 0.000 abstract description 5
- 239000007787 solid Substances 0.000 abstract description 3
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 abstract description 2
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 125000000962 organic group Chemical group 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- VLZLOWPYUQHHCG-UHFFFAOYSA-N nitromethylbenzene Chemical compound [O-][N+](=O)CC1=CC=CC=C1 VLZLOWPYUQHHCG-UHFFFAOYSA-N 0.000 description 1
- 238000011369 optimal treatment Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
Landscapes
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
Description
本発明は、ＴＮＴ製造工程において廃出され、有機物を含有する廃液を生物処理することができるレベルまで処理する処理方法に関する。 The present invention relates to a treatment method for treating a waste liquid which is discarded in a TNT production process and contains an organic substance to a level at which it can be biologically treated.
砲弾などの火薬類の主成分として幅広く使用されているＴＮＴは、０ニトロトルエン（０ＮＴ）を硝酸と硫酸の混酸を用いて二段階硝化することにより生成され、その際にＴＮＴの異性体（非対象ＴＮＴ）も生成される。ＴＮＴの最も一般的な精製法は、亜硫酸ソーダ水溶液を使用するセライト法で、亜硫酸ソーダ水溶液を加えることにより非対称ＴＮＴの反応活性なニトロ基はスルホン酸ナトリウムに置換され、水溶性のスルホン酸塩となるためセライト法により容易に除去される。 TNT, which is widely used as the main component of explosives such as shells, is produced by two-stage nitrification of 0 nitrotoluene (0NT) using a mixed acid of nitric acid and sulfuric acid. TNT) is also generated. The most common purification method of TNT is a celite method using an aqueous sodium sulfite solution. By adding an aqueous sodium sulfite solution, the reactive nitro group of the asymmetric TNT is replaced with sodium sulfonate. Therefore, it is easily removed by the celite method.
この廃液は特有の赤い色を呈し（以下、この廃液を赤水廃液という）、有機物及び硝酸性窒素等の量が多く、ＣＯＤ（化学的酸素要求量）が極めて高いため、そのまま処理する場合には、１００倍以上の希釈が必要であり、コスト高となり実用的でない。従って従来は重油を燃料として燃焼処理していた。 This waste liquid has a unique red color (hereinafter, this waste liquid is referred to as red water waste liquid), has a large amount of organic matter and nitrate nitrogen, and has a very high COD (chemical oxygen demand). , A dilution of 100 times or more is necessary, which is expensive and impractical. Therefore, conventionally, the combustion process is performed using heavy oil as fuel.
重油による燃焼処理は、温室効果のあるCO２を発生させ最適な処理方法ではない。
本発明は、ＴＮＴ製造工程において排出される廃液を生物処理できるレベルまで処理する赤水廃液の処理方法を提供することを目的とする。
Combustion treatment by heavy oil is not an optimal treatment method to generate CO 2 with a greenhouse effect.
An object of this invention is to provide the processing method of the red water waste liquid which processes the waste liquid discharged | emitted in a TNT manufacturing process to the level which can be biologically processed.
請求項１に係わる発明は、ＴＮＴ製造に伴って排出される赤水廃液に鉄を含む化合物と銅を含む化合物よりなる触媒を添加し、ついで過酸化水素を加えて酸化処理することを特徴とし、
請求項２に係わる発明は、請求項１に係わる発明において、過酸化水素を加える前に消泡剤を添加することを特徴とする。
The invention according to claim 1 is characterized in that a catalyst composed of a compound containing iron and a compound containing copper is added to a red water waste liquid discharged along with the production of TNT, and then an oxidation treatment is performed by adding hydrogen peroxide.
The invention according to claim 2 is characterized in that, in the invention according to claim 1, an antifoaming agent is added before hydrogen peroxide is added.
請求項３に係わる発明は、請求項１又は２に係わる発明において、酸化処理後、触媒を除去し、ついで排水処理場で処理した原水又は水で希釈することを特徴とする。 The invention according to claim 3 is characterized in that, in the invention according to claim 1 or 2, after the oxidation treatment, the catalyst is removed and then diluted with raw water or water treated in a wastewater treatment plant.
請求項１に係わる発明によると、ＴＮＴ製造に伴って排出される廃液に触媒と過酸化水素を加えて酸化処理することにより溶液のＣＯＤ（化学的酸素要求量）等が低下し、生物処理が可能となる。 According to the first aspect of the invention, by adding a catalyst and hydrogen peroxide to the waste liquid discharged during the production of TNT and oxidizing the solution, the COD (chemical oxygen demand) of the solution is reduced, and biological treatment is reduced. It becomes possible.
過酸化水素を加えると、発泡が激しくなるために赤水処理に大きな処理槽が必要となる。この点、請求項２に係わる発明のように、消泡剤を加えれば、発泡が抑えられ、より小さな処理槽でも赤水処理が可能となる。 When hydrogen peroxide is added, foaming becomes intense, so a large treatment tank is required for red water treatment. In this regard, as in the invention according to claim 2, if an antifoaming agent is added, foaming can be suppressed and red water treatment can be performed even in a smaller treatment tank.
請求項３に係わる発明のように、酸化処理後に触媒を除去し、希釈することで生物処理がより確実に行えるようになる。 As in the invention according to claim 3, biological treatment can be performed more reliably by removing and diluting the catalyst after the oxidation treatment.
以下、本発明の実施形態について図１に基づいて説明する。
ＴＮＴ製造に伴って排出される赤水廃液は酸化処理槽においてＰＨ調整したのち、触媒の鉄を含む化合物である硫酸第一鉄七水和物FeSO4・7H2Oと助触媒の銅を含む化合物である硫酸銅五水和物CuSO4・5H2Oを加え、更に過酸化水素H2O2と消泡剤を加えて酸化処理する。ここで触媒と助触媒は、どちらが前後して加えられてもよいが、過酸化水素は触媒と助触媒の添加と同時に又は添加後に加えられ、消泡剤は過酸化水素に先立って添加される。消泡剤としては例えばオルガノ株式会社製のオルデフォームＦＣ−１３１、１２０、１００（商品名）、栗田工業株式会社製のクリデスＳ−１１５（商品名）等を用いることができる。
Hereinafter, an embodiment of the present invention will be described with reference to FIG.
Red water waste discharged with TNT production is adjusted to pH in the oxidation treatment tank, and then the compound containing ferrous sulfate heptahydrate FeSO 4 · 7H 2 O, which is a compound containing iron as catalyst, and copper as the promoter Then, copper sulfate pentahydrate CuSO 4 · 5H 2 O is added, and hydrogen peroxide H 2 O 2 and an antifoaming agent are further added for oxidation treatment. Here, either the catalyst or the cocatalyst may be added before or after, but hydrogen peroxide is added simultaneously with or after the addition of the catalyst and the cocatalyst, and the antifoaming agent is added prior to the hydrogen peroxide. . As an antifoaming agent, for example, Ordeform FC-131, 120, 100 (trade name) manufactured by Organo Corporation, Cleides S-115 (trade name) manufactured by Kurita Kogyo Co., Ltd., or the like can be used.
その後、ろ過機を備えた触媒除去設備に移され、苛性ソーダNaOHが加えられる。これにより触媒が水酸化物として析出し、ろ過機で分離除去される。触媒を除去した酸化処理水は中和後、下水処理場等の排水処理場において使用される原水又は山水で希釈される。 Then, it moves to the catalyst removal equipment provided with the filter, and caustic soda NaOH is added. Thereby, a catalyst precipitates as a hydroxide and is separated and removed by a filter. The oxidized water from which the catalyst has been removed is neutralized and then diluted with raw water or mountain water used in a wastewater treatment plant such as a sewage treatment plant.
図２において、ＴＮＴ製造に伴って排出される、以下の表１に示す物性の廃液１４０Ｌに硫酸を加え、ＰＨ調整したのち、オルガノ株式会社製のオルデフォームＦＣ−１２０（商品名）２８g、FeSO4・7H2O ５８５g、CuSO4・5H2O １５０gを加え、ついで３５％過酸化水素水H2O2３５．６gを加えて８５±５℃で酸化反応を生じさせた。その後、これをろ過機でろ過し、固液分離を行って固形分は廃棄する一方、ろ液には苛性ソーダNaOHを加えてＰＨ調整し、ついでこれをろ過機によりろ過し固液分離を行った。そして固形分を廃棄する一方、ろ液には硫酸によりＰＨ調整を行って中和させ、中和済みの処理水にオルガノ株式会社製の排水処理場において処理するオルガノ原水１７２２Ｌを加え、１０倍希釈した。処理水の物性の目標値と実測値及び希釈後の処理水の水質と瀬戸法（瀬戸内海環境保全特別措置法）排水基準を以下の表２及び表３に示す。 In Fig. 2, sulfuric acid is added to waste liquid 140L having the physical properties shown in Table 1 below, which is discharged along with the production of TNT, and the pH is adjusted. Then, Ordeform FC-120 (trade name) 28g manufactured by Organo Corporation, FeSO 585 g of 4 · 7H 2 O and 150 g of CuSO 4 · 5H 2 O were added, and then 35.6 g of 35% hydrogen peroxide water H 2 O 2 was added to cause an oxidation reaction at 85 ± 5 ° C. Then, this was filtered with a filter, solid-liquid separation was performed, and the solid content was discarded. On the other hand, pH was adjusted by adding caustic soda NaOH to the filtrate, and then this was filtered with a filter to perform solid-liquid separation. . While discarding the solid content, the filtrate is neutralized by adjusting the pH with sulfuric acid, and 1722 L of raw organo water to be treated in the wastewater treatment plant made by Organo Corporation is added to the neutralized treated water to dilute it 10 times. did. Tables 2 and 3 below show the target values and measured values of treated water, the quality of treated water after dilution, and the Seto Law (Special Measures Law for Seto Inland Sea Environmental Conservation) drainage standards.
表２中、１０倍希釈後の処理水は中和済み処理水を１０倍希釈した処理水を表し、該処理水中の窒素含有量２７０→１４は、１０倍希釈した処理水中の窒素含有量は２７０mg/Ｌであったが、オルガノ関西株式会社による微生物処理の結果、１４mg/Ｌに低下したことを示している。
表２に示されるように、１０倍希釈後の処理水は瀬戸法排水基準の許可値をクリアできている。
In Table 2, treated water after 10-fold dilution represents treated water obtained by diluting neutralized treated water 10-fold, and nitrogen content 270 → 14 in the treated water is 10-fold diluted nitrogen content in treated water Although it was 270 mg / L, it showed that it decreased to 14 mg / L as a result of the microorganism treatment by Organo Kansai Co., Ltd.
As shown in Table 2, the treated water after 10-fold dilution has cleared the permitted value of the Seto Law drainage standard.
Claims (3)
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104843847A (en) * | 2015-03-25 | 2015-08-19 | 同济大学 | Method for improving activity of pyrite-catalysis type Fenton sustained reaction |
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|---|---|---|---|---|
| JPS5535976A (en) * | 1978-09-08 | 1980-03-13 | Dowa Mining Co Ltd | Treatment of waste water containing oxidizable substance |
| JPH0278488A (en) * | 1988-06-03 | 1990-03-19 | Kankyo Eng Kk | Complete treatment of waste water |
| JPH0440291A (en) * | 1990-06-01 | 1992-02-10 | Fuji Photo Film Co Ltd | Treatment of photograph processing waste liquid |
| US20030173306A1 (en) * | 2002-03-14 | 2003-09-18 | Cha Daniel K. | Process and system for treating waste from the production of energetics |
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- 2011-10-07 JP JP2011222433A patent/JP2013081882A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5535976A (en) * | 1978-09-08 | 1980-03-13 | Dowa Mining Co Ltd | Treatment of waste water containing oxidizable substance |
| JPH0278488A (en) * | 1988-06-03 | 1990-03-19 | Kankyo Eng Kk | Complete treatment of waste water |
| JPH0440291A (en) * | 1990-06-01 | 1992-02-10 | Fuji Photo Film Co Ltd | Treatment of photograph processing waste liquid |
| US20030173306A1 (en) * | 2002-03-14 | 2003-09-18 | Cha Daniel K. | Process and system for treating waste from the production of energetics |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104843847A (en) * | 2015-03-25 | 2015-08-19 | 同济大学 | Method for improving activity of pyrite-catalysis type Fenton sustained reaction |
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