CN104086030A - Method for treating pickling wastewater in iron and steel industry - Google Patents

Method for treating pickling wastewater in iron and steel industry Download PDF

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Publication number
CN104086030A
CN104086030A CN201410354864.3A CN201410354864A CN104086030A CN 104086030 A CN104086030 A CN 104086030A CN 201410354864 A CN201410354864 A CN 201410354864A CN 104086030 A CN104086030 A CN 104086030A
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heavy metal
separating
tank
metal chelating
water
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CN104086030B (en
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黄祁
杨明富
张鸣球
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JIANGSU BESITE WATER SCIENCE AND TECHNOLOGY Co Ltd
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JIANGSU BESITE WATER SCIENCE AND TECHNOLOGY Co Ltd
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Abstract

The invention discloses a method for treating pickling wastewater in iron and steel industry. The method comprises the following steps: a) introducing pickling wastewater into a regulating tank, a chromium reduction tank and a heavy metal catcher; b) separating heavy metal precipitate produced in reaction from clear liquor through an ultramicro separating machine, carrying out primary fluoride removal on the clear liquor in a fluoride removal filter; c) feeding the mixed solution subjected to primary fluoride removal into a primary precipitating tank for separating non-ferrous precipitate from water, then carrying out secondary fluoride removal on the clear liquor in a fluoride reaction tank; and d) feeding the mixed solution subjected to secondary fluoride removal into a secondary precipitating tank for separating non-ferrous precipitate from water, and emitting the separated clear liquor into a clear water tank for storage. The method has high metal particle separation efficiency, the ultramicro separation machine has concentration effect, so no concentration tank is required for separating the precipitate from the clear liquor to save space and the labor force, the indexes of iron, chromium, nickel, fluoride and the like in the clear liquor emitted from the secondary precipitating tank can all meet the national-level standard requirement.

Description

A kind for the treatment of process of steel industry pickling waste waters
Technical field
The invention belongs to environment protection field of waste water treatment, particularly a kind for the treatment of process of steel industry pickling waste waters.
Background technology
Along with the fast development of China's industrial economy, drive the fast development of steel industry, iron and steel original paper all will, through overpickling, to remove surperficial oxide compound, produce pickling waste waters before cold rolling, plating, spraying, and the main main component of pickling waste waters is SO 4 2-, H +, Fe 2+, Na +, Cr 6+, F -, Me n+, Ni etc., wherein Cr 6+, F -, Fe 2+, Me n+for principal pollutant.
The method of existing processing pickling waste waters adopts " neutralization+precipitation+sand filtration of chromium reduction+lime ", its key step is that waste water enters after equalizing tank, with pump be promoted to reduction pond, by pH regulator to 2-3, then add the abundant hybrid reaction of reductive agent and waste water, make hexavalent chrome reduction become trivalent chromium, pH regulator pond is delivered in water outlet, then drop into NaOH/ lime, by pH regulator to 8-9, iron, chromium, the metal ion reactions such as nickel generate precipitation of hydroxide, fluorion forms Calcium Fluoride (Fluorspan) precipitation, then enter reaction settling pond and carry out mud-water separation, the mud producing is disposed as dangerous solid waste outward transport after water extracter mummification, supernatant liquor enters sand-bed filter and removes residual suspended substance after pH regulator, final outflow water qualified discharge.
Facts have proved, there is following shortcoming in " neutralization+precipitation+sand filtration of chromium reduction+lime " of the prior art combined treatment process:
(1) sludge creation amount is large, mud composition is complicated, reclaim difficulty, not recycling, hazardness is large, its mud is mainly made up of precipitation of hydroxide, superfluous lime, Calcium Fluoride (Fluorspan), lime powder impurity, PAC/PAM medicament, water (accounting for 50% ∽ 65%) etc., the content of precious metals salt is very low, substantially there is no freshening, recovery value, more impurity and moisture content make sludge creation amount very huge, and due to exist (as the chromium cpd) of heavy metal, this type of mud has been put into hazardous solid waste list;
(2) landfill of mud is disposed, cause the waste of metals resources and the destruction of environment, the mud producing containing acid, chrome waste water, contain the metal values materials such as a large amount of iron, chromium, nickel, carry out landfill disposal, not only need to spend the dangerous solidification disposal of waste expense of great number, carry out landfill but also need to occupy a large amount of land resources, can affect periphery resident's life and the water quality of underground water.
Summary of the invention
For the problems referred to above that exist in current pickling waste waters treatment technology, a kind for the treatment of process of steel industry pickling waste waters is provided, can reclaim metal values ion in cold rolling wastewater, do not produce harmful dangerous solid waste, turn waste into wealth, improve stability and the efficiency of sewage disposal simultaneously, reduce cost of disposal, the present invention is achieved in that
A treatment process for steel industry pickling waste waters, is characterized in that, comprises the following steps:
A) pickling waste waters is introduced in equalizing tank, then flowed in chromium reduction pond, chromium reduction pond is divided into one-level chromium reduction pond and secondary chromium reduction pond, and every grade of chromium reduction pond all adds enough reductive agent reaction 30min;
B) waste water after chromium reduction is introduced to heavy metal chelating device, heavy metal chelating device is divided into one-level heavy metal chelating device and secondary heavy metal chelating device, all adds heavy metal chelating agent and sodium hydroxide reaction 45min in every grade of heavy metal chelating device, controls pH value 8-9;
The heavy metal precipitation that utilizes ultra micro separating machine that the reaction of heavy metal chelating device is produced separates with clear liquid, and the clear liquid after separating is imported in fluorine removing filter, adds calcium chloride reaction 45min, carries out one-level defluorination;
C) mixing solutions after step b one-level defluorination is introduced to one-level settling tank and carried out separating of nonmetal throw out and water, the clear liquid after separating is flowed into fluorine reaction tank, add calcium chloride reaction 45min and carry out secondary defluorination;
D) mixing solutions after step c secondary defluorination is introduced to second-level settling pond and carried out separating of nonmetal throw out and water, the clear liquid discharging after separation to clean water basin store, and determine reuse amount and quantity discharged according to practical situation.
Preferably, in the present invention, reductive agent is the one in Sodium Pyrosulfite, sodium bisulfite, S-WAT, V-Brite B, Sulfothiorine described in step a.
Preferably, in the present invention, the amount that adds heavy metal chelating agent in step b is 1 mg/L.
Preferably, in the present invention, chromium reduction pond internal control oxygenerating reduction potential ORP value is in 200mV described in step a.
Preferably, in the present invention, the separating machine of ultra micro described in step b uses PVDF/PTFE organic membrane, membrane pore size 10 ∽ 200nm, operating pressure 3-5bar, vibrational frequency 40-50Hz, Oscillation Amplitude 10-20mm.
The present invention compared with prior art, has following beneficial effect:
(1) heavy metal chelating device can be transformed into throw out by whole metal pollutants, again by ultra micro separating machine equipment, it has higher metallic particles separation efficiency, ultra micro separating machine has concentrated effect simultaneously, do not need to establish concentration basin again throw out is separated with clear liquid, throw out is concentrated in separating machine, after dehydration and drying, solid content reaches more than 90%, can enter blast furnace freshening or recycle by additive method;
(2) use first ultra micro separating machine (also claiming vibration-type membrane separating machine) to carry out feed separation work by organic membrane film, metal sludge is separated and concentrated with water, diaphragm is by back and forth high-frequency vibration of special machine device simultaneously, vibrational frequency is between 40-50Hz, Oscillation Amplitude is between 10-20mm, there is the precision of removal high, processing power is large, automatically clean, the advantage of Automatic Control, the present invention adopts ultra micro separating machine to omit traditional settling tank and concentration basin, can make system simplification, save space and operation, reduce investment and working cost;
(3) parting liquid of ultra micro separating machine enters fluorine remover, and fluorine remover automatically regulates and adds calcium chloride according to fluorinion concentration, forms Calcium Fluoride (Fluorspan) precipitation, and then through one-level settling tank by precipitate and separate;
(4) fluorine reactor can automatically regulate and add calcium chloride according to fluorinion concentration, residual fluorine ion is further reacted and forms Calcium Fluoride (Fluorspan) precipitation, and then through second-level settling pond precipitate and separate, after twice solid-liquid separation, in the clear liquid of being discharged by second-level settling pond, the pollutent such as iron, chromium, nickel, fluorine all meets " Iron And Steel Industry water emission standard " (GB13456-2012) primary standard of defined;
(5) heavy metal in waste water of the present invention and other pollutents are that substep is removed, and heavy metal precipitation thing individual curing and collection, can improve the purity of heavy metal precipitation thing.
Brief description of the drawings
Fig. 1 is embodiment of the present invention schematic flow sheet.
Embodiment
Below by specific embodiment, technical scheme of the present invention is described further, following instance does not form limitation of the invention.
embodiment 1adopt method of the present invention to process the pickling waste waters that cold rolling workshop section of certain steel mill discharges
The pickling waste waters of 1, cold rolling certain steel mill workshop section being discharged is introduced equalizing tank, measures total iron 3000mg/L in waste water, chromium ion concentration 800mg/L, and nickel ion concentration 200mg/L, fluorinion concentration 2000mg/L, pH is between 1-2;
2, waste water is introduced in chromium reduction pond by equalizing tank, chromium reduction pond is divided into one-level chromium reduction pond and secondary chromium reduction pond, waste water flow through successively one-level chromium reduction pond and secondary chromium reduction pond, every grade of chromium reduction pond all adds enough reductive agent Sodium Pyrosulfite reaction 30min, all sexavalent chromes are transformed into trivalent chromium, control redox potential ORP value in 200mV;
Waste water after chromium reduction is introduced to heavy metal chelating device, heavy metal chelating device is divided into one-level heavy metal chelating device and secondary heavy metal chelating device, waste water flow through successively one-level heavy metal chelating device and secondary heavy metal chelating device, in every grade of heavy metal chelating device, all add heavy metal chelating agent and sodium hydroxide reaction 45min, control pH value 8-9, heavy metal chelating agent 1 mg/L, heavy metal chelating agent is in order to the auxiliary seizure effect that improves heavy metal ion;
The heavy metal precipitation that utilizes ultra micro separating machine that the reaction of heavy metal chelating device is produced separates with clear liquid, and ultra micro separating machine uses PVDF/PTFE organic membrane, membrane pore size 200nm, membrane flux 200L/ (m 2h), operating pressure 3-5bar, vibrational frequency 50HZ, Oscillation Amplitude 13mm; Measuring total iron mean concns in the rear clear liquid of ultramicro separator separation is 1.2mg/L, and total chromium mean concns is 0.01mg/L, and total nickel mean concns is 0.06mg/L, and turbidity mean concns is 0.001NUT, discharges precipitated metal thing solid content approximately 10%;
Clear liquid after ultra micro separating machine separates is imported in fluorine removing filter, add calcium chloride reaction 45min, fluorion reacts with calcium chloride and generates Calcium Fluoride (Fluorspan) precipitation, carries out one-level defluorination; Fluorine remover can automatically regulate and drop into calcium chloride amount according to fluorinion concentration, in the present embodiment, adds calcium chloride 1529mg/L;
3, mixing solutions after one-level defluorination is introduced to one-level settling tank and carried out separating of nonmetal throw out and water, measuring fluorion mean concns in the clear liquid that one-level settling tank flows out is 18mg/L;
Clear liquid after one-level settling tank separates is introduced to fluorine reaction tank, add calcium chloride reaction 45min and carry out secondary defluorination, fluorine reaction tank can automatically regulate and drop into calcium chloride amount according to fluorinion concentration, in the present embodiment, adds calcium chloride 385 mg/L;
4, mixing solutions after secondary defluorination is introduced to second-level settling pond and carried out separating of nonmetal throw out and water, measuring second-level settling pond water outlet fluorion mean concns is 2mg/L, and the pollutent indexs such as its final outflow water iron, chromium, nickel, fluorine all meet " Iron And Steel Industry water emission standard " (GB13456-2012) requirement;
In implementation and operation, step 1 also can be used one in sodium bisulfite, S-WAT, V-Brite B, Sulfothiorine as reductive agent; Ultra micro separating machine PVDF/PTFE organic membrane membrane pore size can be chosen in the scope of 10 ∽ 200nm.
The above embodiment has only expressed embodiments of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that to those skilled in the art, without departing from the inventive concept of the premise, can also make some improvement, these improve and all should belong to protection scope of the present invention.

Claims (5)

1. a treatment process for steel industry pickling waste waters, is characterized in that, comprises the following steps:
A) pickling waste waters is introduced in equalizing tank, then flowed in chromium reduction pond, chromium reduction pond is divided into one-level chromium reduction pond and secondary chromium reduction pond, and every grade of chromium reduction pond all adds enough reductive agent reaction 30min;
B) waste water after chromium reduction is introduced to heavy metal chelating device, heavy metal chelating device is divided into one-level heavy metal chelating device and secondary heavy metal chelating device, all adds heavy metal chelating agent and sodium hydroxide reaction 45min in every grade of heavy metal chelating device, controls pH value 8-9;
The heavy metal precipitation that utilizes ultra micro separating machine that the reaction of heavy metal chelating device is produced separates with clear liquid, and the clear liquid after separating is imported in fluorine removing filter, adds calcium chloride reaction 45min, carries out one-level defluorination;
C) mixing solutions after step b one-level defluorination is introduced to one-level settling tank and carried out separating of nonmetal throw out and water, the clear liquid after separating is flowed into fluorine reaction tank, add calcium chloride reaction 45min and carry out secondary defluorination;
D) mixing solutions after step c secondary defluorination is introduced to second-level settling pond and carried out separating of nonmetal throw out and water, the clear liquid discharging after separation to clean water basin store, and determine reuse amount and quantity discharged according to practical situation.
2. a kind for the treatment of process of steel industry pickling waste waters according to claim 1, is characterized in that, reductive agent is the one in Sodium Pyrosulfite, sodium bisulfite, S-WAT, V-Brite B, Sulfothiorine described in step a.
3. a kind for the treatment of process of steel industry pickling waste waters according to claim 2, is characterized in that, the amount that adds heavy metal chelating agent in step b is 1 mg/L.
4. a kind for the treatment of process of steel industry pickling waste waters according to claim 3, is characterized in that, chromium reduction pond internal control oxygenerating reduction potential ORP value is in 200mV described in step a.
5. a kind for the treatment of process of steel industry pickling waste waters according to claim 4, is characterized in that, the separating machine of ultra micro described in step b uses PVDF/PTFE organic membrane, membrane pore size 10 ∽ 200nm, operating pressure 3-5bar, vibrational frequency 40-50Hz, Oscillation Amplitude 10-20mm.
CN201410354864.3A 2014-07-24 2014-07-24 A kind for the treatment of process of steel industry pickling waste waters Active CN104086030B (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104370389A (en) * 2014-11-14 2015-02-25 无锡伊佩克科技有限公司 Process for removing fluorine in pickling waste liquid in steel and iron industry
CN105540792A (en) * 2016-01-07 2016-05-04 苏州法斯特信息科技有限公司 Heavy metal wastewater treating agent and preparation method thereof
CN105923840A (en) * 2016-06-20 2016-09-07 宁波宝新不锈钢有限公司 Technology for treating stainless steel nitrate-free pickling waste water
CN106830441A (en) * 2017-03-27 2017-06-13 福建欣宇卫浴科技股份有限公司 Solid-liquid separation system
CN107089763A (en) * 2017-04-21 2017-08-25 合肥市瀚坤机械有限公司 A kind of Treatment of Metal Surface method of wastewater treatment
CN108218025A (en) * 2017-12-06 2018-06-29 宜兴市馨德环保科技有限公司 The method that the nitration mixture Sewage treatment that a kind of pickling of metal generates utilizes
CN110182991A (en) * 2019-05-24 2019-08-30 江苏甬金金属科技有限公司 A kind of method that the neutral salt Sewage treatment that pickling of metal generates utilizes

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CN102107963A (en) * 2010-12-30 2011-06-29 天津市环境保护科学研究院 Method for treating acid-washing wastewater and metallic ions in iron and steel industry
CN202465416U (en) * 2011-12-27 2012-10-03 广东爱康太阳能科技有限公司 Fluoride wastewater treatment system
CN203284233U (en) * 2013-05-19 2013-11-13 苏州众禹环境科技有限公司 High-frequency dual-power film separation system
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CN101269889A (en) * 2007-03-23 2008-09-24 宁波宝新不锈钢有限公司 Processing method for stainless steel acid cleaning waste water and liquid
KR20100060260A (en) * 2008-11-27 2010-06-07 현대제철 주식회사 Method for treating waste water contained heavy metal
CN102107963A (en) * 2010-12-30 2011-06-29 天津市环境保护科学研究院 Method for treating acid-washing wastewater and metallic ions in iron and steel industry
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104370389A (en) * 2014-11-14 2015-02-25 无锡伊佩克科技有限公司 Process for removing fluorine in pickling waste liquid in steel and iron industry
CN105540792A (en) * 2016-01-07 2016-05-04 苏州法斯特信息科技有限公司 Heavy metal wastewater treating agent and preparation method thereof
CN105923840A (en) * 2016-06-20 2016-09-07 宁波宝新不锈钢有限公司 Technology for treating stainless steel nitrate-free pickling waste water
CN106830441A (en) * 2017-03-27 2017-06-13 福建欣宇卫浴科技股份有限公司 Solid-liquid separation system
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CN107089763A (en) * 2017-04-21 2017-08-25 合肥市瀚坤机械有限公司 A kind of Treatment of Metal Surface method of wastewater treatment
CN108218025A (en) * 2017-12-06 2018-06-29 宜兴市馨德环保科技有限公司 The method that the nitration mixture Sewage treatment that a kind of pickling of metal generates utilizes
CN110182991A (en) * 2019-05-24 2019-08-30 江苏甬金金属科技有限公司 A kind of method that the neutral salt Sewage treatment that pickling of metal generates utilizes

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