JPH01254214A - Production of flocculating agent having deodorization function - Google Patents
Production of flocculating agent having deodorization functionInfo
- Publication number
- JPH01254214A JPH01254214A JP8222488A JP8222488A JPH01254214A JP H01254214 A JPH01254214 A JP H01254214A JP 8222488 A JP8222488 A JP 8222488A JP 8222488 A JP8222488 A JP 8222488A JP H01254214 A JPH01254214 A JP H01254214A
- Authority
- JP
- Japan
- Prior art keywords
- iron
- sulfuric acid
- zinc
- waste sulfuric
- flocculating agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 238000004332 deodorization Methods 0.000 title abstract description 6
- 239000008394 flocculating agent Substances 0.000 title abstract 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 56
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000011701 zinc Substances 0.000 claims abstract description 32
- 229910052742 iron Inorganic materials 0.000 claims abstract description 22
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 21
- 239000002699 waste material Substances 0.000 claims abstract description 15
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 8
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 8
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 8
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 8
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims abstract description 5
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims abstract description 5
- 230000001590 oxidative effect Effects 0.000 claims abstract description 4
- 230000001877 deodorizing effect Effects 0.000 claims description 3
- 238000005189 flocculation Methods 0.000 abstract description 3
- 230000016615 flocculation Effects 0.000 abstract description 3
- 238000005246 galvanizing Methods 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract 4
- 238000000034 method Methods 0.000 description 11
- 238000006386 neutralization reaction Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000010802 sludge Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- -1 iron ions Chemical class 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003311 flocculating effect Effects 0.000 description 1
- 239000010800 human waste Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、鉄鋼関係の亜鉛表面処理工場、亜鉛メツキ工
場などより排出される含亜鉛廃硫酸の有効利用方法に関
するものである。詳しくは含亜鉛廃硫酸中の鉄濃度等を
調整し、２価の鉄を酸化することにより、し尿処理場、
下水処理場、製紙工場、製鉄所等の排水の脱臭、凝集処
理をすることができる凝集剤の製造法に関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for effectively utilizing zinc-containing waste sulfuric acid discharged from iron and steel-related zinc surface treatment factories, galvanizing factories, and the like. In detail, by adjusting the iron concentration etc. in zinc-containing waste sulfuric acid and oxidizing divalent iron, human waste treatment plants,
This invention relates to a method for producing a flocculant that can deodorize and coagulate wastewater from sewage treatment plants, paper mills, steel mills, etc.
（従来の技術）
従来、鉄鋼関係の酸洗工程より排出される廃硫酸は１種
々の有効利用方法が検討されたが、実用化されているも
のは、（１）アルカリ排水の中和用の酸としての利用法
、（２）廃硫酸を濃縮して硫酸第１鉄結晶と回収硫酸に
分離し、これらを再利用する方法、（３）廃硫酸を冷却
して硫酸第１鉄結晶と硫酸に分離し、これらを再利用す
る方法などであった。しかしながら含亜鉛廃硫酸は、亜
鉛成分の有効利用方法がないため、上記方法が不可とな
り、ただ中和処理方法のみが行なわれている。(Prior technology) In the past, various effective ways to use waste sulfuric acid discharged from the pickling process of steel-related processes have been considered, but the ones that have been put into practical use are: (1) for neutralizing alkaline wastewater; (2) Method of concentrating waste sulfuric acid and separating it into ferrous sulfate crystals and recovered sulfuric acid, and reusing these; (3) Cooling waste sulfuric acid to form ferrous sulfate crystals and sulfuric acid. The method was to separate them into different parts and reuse them. However, since there is no method for effectively utilizing the zinc component of zinc-containing waste sulfuric acid, the above method is not possible, and only a neutralization treatment method is used.
（発明が解決しようとする問題点）
そして上記の中和処理方法は、（１）中和用のアルカリ
使用量が多く必要で処理コストが高くなること、（２）
中和処理のＰＨが適正でないと亜鉛が処理水へ流出して
問題となること（ＺｎはＳｐｐｍ以下）、（３）中和ス
ラッジの処分が問題となることなどの欠点があるため適
切な有効利用方法の開発が望まれている。(Problems to be Solved by the Invention) The above neutralization treatment method requires (1) a large amount of alkali to be used for neutralization, which increases the treatment cost; (2)
If the pH of neutralization treatment is not appropriate, zinc will flow into the treated water, causing problems (Zn is less than Sppm), and (3) disposing of neutralized sludge will be a problem. Development of usage methods is desired.
（問題点を解決するための手段およびその作用）本発明
者らは、亜鉛を含む廃硫酸を有効に利用する方法につい
て研究を行なった結果、（１）亜鉛が硫化水素、メチー
ルメル力ブタン等の硫化物と反応すること、（２）硫化
物との反応は亜鉛の方が鉄より速いこと、（３）硫酸根
とアンモニアは反応するのでアンモニアを吸収すること
ができること、（４）鉄イオンと硫酸根とアンモニウム
イオンとで錯体を作り易いこと、（５）鉄と亜鉛は水酸
化物を作るときに共沈し易いこと、（６）亜鉛が多すぎ
ると処理水中に亜鉛が残留することなどを知見した。(Means for Solving the Problems and Their Effects) As a result of research into a method for effectively utilizing waste sulfuric acid containing zinc, the present inventors found that (1) zinc can be (2) Zinc reacts faster with sulfide than iron; (3) sulfate groups and ammonia react, so ammonia can be absorbed; (4) iron ions and Complexes are easily formed between sulfate radicals and ammonium ions, (5) iron and zinc tend to co-precipitate when forming hydroxides, and (6) too much zinc may remain in the treated water. I found out.
本発明はこれらの知見に基づくものであって、含亜鉛廃
硫酸に硫酸第１鉄、硫酸第２鉄、酸化鉄のいずれか１種
以上を添加し、鉄濃度が３０ｇ／ｌ以上、Ｚｎ／Ｆｅの
重量比の値が１７１０〜１／１５０．８０４／ （Ｆｅ
＋Ｚｎ）のモル比の値が１〜２になるように調整し、こ
の調整溶液中の２価の鉄を酸化することを特徴とする脱
臭機能を有する凝集剤の製造法である。The present invention is based on these findings, and includes adding one or more of ferrous sulfate, ferric sulfate, and iron oxide to zinc-containing waste sulfuric acid, so that the iron concentration is 30 g/l or more, and Zn/ The value of the weight ratio of Fe is 1710 to 1/150.804/ (Fe
This is a method for producing a flocculant having a deodorizing function, which is characterized by adjusting the molar ratio of Zn) to 1 to 2 and oxidizing divalent iron in the adjusted solution.
本発明において用いる含亜鉛廃硫酸は、亜鉛以外に鉄を
含んでいるものでＺ ｎ ／ Ｆ ｅの重量比の値が１
／１０以上のものがほとんどである。従ってＺ ｎ ／
Ｆ ｅの重量比の値を１／１０〜１／１５０に調整す
るために硫酸第１鉄、硫酸第２鉄、酸化鉄（水和酸化鉄
でもよい）の１種以上を添加する必要がある０本発明で
鉄濃度を３０ ｇ ／ ０以上としたのは、２価の鉄を
酸化した時に遊離酸が少ないと加水分解して沈でんを生
ずるためである。The zinc-containing waste sulfuric acid used in the present invention contains iron in addition to zinc, and has a Zn/Fe weight ratio of 1.
/10 or more in most cases. Therefore Z n /
In order to adjust the weight ratio of Fe to 1/10 to 1/150, it is necessary to add one or more of ferrous sulfate, ferric sulfate, and iron oxide (hydrated iron oxide may also be used). The reason why the iron concentration is set to 30 g/0 or more in the present invention is that when divalent iron is oxidized, if there is not enough free acid, it will be hydrolyzed and precipitation will occur.
Ｚ ｎ ／ Ｆ ｅの重量比の値を１／１０〜１／１５
０と限定したのは、第１表で明らかなように１／１０以
上では使用後の処理水中のＺｎの濃度が排水の規制値の
５ ｐｐｍを越えることがあるからであり、１／１５０
以下では硫化水素の除去が悪くなるからである。The value of the weight ratio of Z n / Fe is 1/10 to 1/15
The reason why it is limited to 0 is because, as shown in Table 1, if the Zn concentration is 1/10 or more, the Zn concentration in the treated water after use may exceed the wastewater regulation value of 5 ppm;
This is because hydrogen sulfide removal becomes worse if the temperature is lower than that.
第１表 Ｚｎ／Ｆｅの重量比と凝集・脱臭性能性１
）原汚泥 ： Ｈａ Ｓ ５０ ｐｐ■、汚泥濃度２．
５％注２）添加薬品：Ｆｅ”１６０ｇ／４．Ｓｏ、３７
５ｇ／ｌつぎに本発明でＳ Ｏ４／ （Ｆ ｅ ＋ Ｚ
ｎ ）のモル比の値を１〜２としたのは、１以下では
２価の鉄を酸化すると硫酸根（Ｓ Ｏ，）が不足し塩基
性塩を析出するからであり、２以上では酸性が強く使用
時のｐＨが低下し、中和用のアルカリの使用量が増加し
かつ硫化水素の除去率が悪化するからである。Table 1 Zn/Fe weight ratio and agglomeration/deodorization performance 1
) Raw sludge: HaS 50 pp■, sludge concentration 2.
5% Note 2) Additive chemical: Fe”160g/4.So, 37
5g/l Next, in the present invention, S O4/ (F e + Z
The reason why the molar ratio value of n) was set to 1 to 2 is because when divalent iron is oxidized when it is less than 1, there is a shortage of sulfuric acid radicals (SO,) and basic salts are precipitated, whereas when it is more than 2, acidic This is because the pH during use decreases, the amount of alkali used for neutralization increases, and the removal rate of hydrogen sulfide deteriorates.
本発明において、２価の鉄を酸化して３価の鉄とするの
は、３価の鉄はｐＨ４以上でフロックを形成するが２価
の鉄はＰＨ９以上でフロックを形成するので、排水の放
流基準（ｐＨ５，８〜８．５）より高いｐＨを必要とす
るからである。つまりｐＨ５，８〜８．５では多くの２
価の鉄が排水中に残留し、規制値（１０ｐｐｍ）を越え
てしまうためである。In the present invention, divalent iron is oxidized to trivalent iron because trivalent iron forms flocs at pH 4 or higher, but divalent iron forms flocs at pH 9 or higher. This is because a pH higher than the discharge standard (pH 5.8 to 8.5) is required. In other words, at pH 5.8 to 8.5, there are many 2
This is because the amount of iron remaining in the wastewater exceeds the regulation value (10 ppm).
（実施例）
亜鉛表面処理工場より排出されたＺ、ｎ１５．５ｇ／ｎ
、Ｆｅ４９．Ｏｇ／ｌ、Ｓｏ４１８９ｇ／ｌの廃硫酸１
イに硫酸第１鉄（Ｆｅ１９．２％。(Example) Z, n15.5g/n discharged from a zinc surface treatment factory
, Fe49. Og/l, So4189g/l waste sulfuric acid 1
Ferrous sulfate (Fe19.2%).
５ｏ４３４．５％）９５５ｋｇを添加し、チッソ酸化物
を触媒として酸素で酸化したところ、Ｆｅ（Ｆ ｅ ”
） １６０ ｇ ／ Ｑ −Ｓ Ｏ４３５０ｇ ／ Ｑ
。5o434.5%) was added and oxidized with oxygen using nitrogen oxide as a catalyst.
) 160g/Q -SO4350g/Q
.
Ｚｎ１０．３ｇ／悲の溶液が１．５ボ得られた。A solution containing 10.3 g of Zn/1.5 units was obtained.
この溶液（凝集剤）を用いて凝集・脱臭試験を行ったと
ころ第２表の結果を得た。When a flocculation and deodorization test was conducted using this solution (flocculant), the results shown in Table 2 were obtained.
第２表 凝集・脱臭試験結果性）処理対象
の原産液
ｐＨ６，７，ＣＯＤ ２７０ｐｐｍ、Ｈ，３３０ｐｐｍ
（発明の効果）
本発明によれば、含亜鉛廃硫酸を低コストで処理するこ
とができ、かつ凝集・脱臭性能の優れた凝集剤を製造す
ることができる。また処理水へ亜鉛が流出して問題とな
ることもないので実用上の価値が大である。Table 2 Coagulation/deodorization test results) Original liquid to be treated pH 6,7, COD 270ppm, H, 330ppm
(Effects of the Invention) According to the present invention, zinc-containing waste sulfuric acid can be treated at low cost, and a flocculant with excellent flocculating and deodorizing performance can be produced. Furthermore, since zinc does not leak into the treated water and cause problems, it is of great practical value.
Claims (1)
れか１種以上を添加し、鉄濃度が３０ｇ／ｌ以上、Ｚｎ
／Ｆｅの重量比の値が１／１０〜１／１５０、ＳＯ＿４
／（Ｆｅ＋Ｚｎ）のモル比の値が１〜２になるように調
整し、この調整溶液中の２価の鉄を酸化することを特徴
とする脱臭機能を有する凝集剤の製造法。One or more of ferrous sulfate, ferric sulfate, and iron oxide is added to zinc-containing waste sulfuric acid, and the iron concentration is 30 g/l or more.
/Fe weight ratio value is 1/10 to 1/150, SO_4
A method for producing a flocculant having a deodorizing function, which comprises adjusting the molar ratio of /(Fe+Zn) to 1 to 2 and oxidizing divalent iron in the adjusted solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8222488A JPH01254214A (en) | 1988-04-05 | 1988-04-05 | Production of flocculating agent having deodorization function |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8222488A JPH01254214A (en) | 1988-04-05 | 1988-04-05 | Production of flocculating agent having deodorization function |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01254214A true JPH01254214A (en) | 1989-10-11 |
| JPH0413002B2 JPH0413002B2 (en) | 1992-03-06 |
Family
ID=13768437
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8222488A Granted JPH01254214A (en) | 1988-04-05 | 1988-04-05 | Production of flocculating agent having deodorization function |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01254214A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2950619A1 (en) * | 2009-09-25 | 2011-04-01 | Serge Ferlay | PROCESS FOR DEULFATATION OF ACID RELEASES FROM THE TITANIUM INDUSTRY |
| JP2011212537A (en) * | 2010-03-31 | 2011-10-27 | Nittetsu Mining Co Ltd | Deodorizer produced by using ferric hydroxide-containing wet neutralized sludge as production raw material, and method for producing the same |
-
1988
- 1988-04-05 JP JP8222488A patent/JPH01254214A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2950619A1 (en) * | 2009-09-25 | 2011-04-01 | Serge Ferlay | PROCESS FOR DEULFATATION OF ACID RELEASES FROM THE TITANIUM INDUSTRY |
| JP2011212537A (en) * | 2010-03-31 | 2011-10-27 | Nittetsu Mining Co Ltd | Deodorizer produced by using ferric hydroxide-containing wet neutralized sludge as production raw material, and method for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0413002B2 (en) | 1992-03-06 |
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