CN104445720A - Pickling waste liquid treatment process of steel industry - Google Patents
Pickling waste liquid treatment process of steel industry Download PDFInfo
- Publication number
- CN104445720A CN104445720A CN201410644701.9A CN201410644701A CN104445720A CN 104445720 A CN104445720 A CN 104445720A CN 201410644701 A CN201410644701 A CN 201410644701A CN 104445720 A CN104445720 A CN 104445720A
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- China
- Prior art keywords
- heavy metal
- treatment process
- waste liquid
- water
- steel industry
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Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a pickling waste liquid treatment process of the steel industry. The pickling waste liquid treatment process comprises the following technical steps: a, primarily filtering a pickling waste liquid so as to filter off solid impurities and grease; b, adding alkali into the filtrate to adjust the pH value; c, feeding the solution obtained in the step b into a heavy metal capturer, and performing reaction on various metal ions in the solution and a heavy metal capturing agent, thereby forming a heavy metal precipitate; d, feeding the reactant obtained in the step c into a filter, filtering and recycling the heavy metal precipitate, and collecting the filtrate for later use; and e, feeding the filtrate obtained in the step d into a reverse osmosis device, and deeply treating, thereby obtaining water which almost meets the standard of pure water and can be recycled for production of washing water, wherein the thick water can be recycled to be used as primary pickling water used in a pickling process. The pickling waste liquid treatment process is simple and convenient to operate, low in cost, and applicable to industrialization popularization and application; the pickling waste liquid can be thoroughly treated, the recycling rate of heavy metal ions is high, and no secondary pollution is caused as the waste liquid is circulated and reused in a completely sealed manner after being treated.
Description
Technical field
The present invention relates to a kind of iron and steel industry spent pickle liquor treatment process, belong to environment protection field of waste water treatment.
Background technology
Steel members blank electroplating surface, spray last as all will through overpickling, to remove the oxide compound on surface, thus produce spent pickle liquor and pickling waste waters.Wherein spent pickle liquor is higher containing acid concentration, recyclable regenerating acid.And a large amount of wash-down waters, namely pickling waste waters acid content is lower, be used for reclaim then very uneconomical, so arrange outward as waste water.Wherein, in pickling waste waters, main component is Fe
2+, Fe
3+, Na
+, Cr
6+, Mn
2+, Ni
+, SO4
2-, F
-, H
+deng.At present, the common method of high density steel pickling waste liquor process utilizes lime supernatant liquid neutralizing treatment pickling waste waters, and this method process is not thorough, causes secondary pollution.Remove metal ion by evaporation and crystallization mode, investment goods, energy expenditure are high, and process is not thorough, and produce a large amount of acid mist, to equipment, environmental influence is severe.
Chinese patent CN201410354864 discloses a kind for the treatment of process of steel industry pickling waste waters, comprises the following steps: a) pickling waste waters introduce in equalizing tank, chromium reduction pond, in heavy metal chelating device; B) utilize ultra micro separating machine to be separated with clear liquid by the heavy metal precipitation that reaction produces, clear liquid is imported in fluorine removing filter, carry out one-level except fluorine; C) by through one-level except the mixing solutions after fluorine is introduced after first stage precipitation tank carries out being separated of nonmetal throw out and water, then clear liquid is flowed into fluorine reaction tank, carries out secondary except fluorine; D) carry out being separated of nonmetal throw out and water by introducing second-level settling pond through secondary except the mixing solutions after fluorine, the clear liquid discharging after separation stores to clean water basin; The present invention has higher metallic particles separation efficiency, ultra micro separating machine has concentrated effect simultaneously, do not need to establish concentration basin to be separated with clear liquid by throw out again, save space with artificial, in the clear liquid of being discharged by second-level settling pond, the index such as iron, chromium, nickel, fluorine all meets the requirement of national standard one-level; It can thus be appreciated that: complex process in this method, facility place demand is large; Secondly, additionally add the medicaments such as calcium chloride, not only cost increases, and introduces added ingredient, increases separating difficulty; 3rd, resource fails to fully utilize, and waste is large.
In addition, Chinese patent 201210311772.8 (CN102828192A) discloses a kind of recycling processing method of steel industry spent pickle liquor, it is characterized in that comprising following consecutive steps: a) spent pickle liquor is introduced that freezing and crystallizing tank carries out cooling, crystallization; B) salt, acid separation is carried out with whizzer; C) strongly basic anion exchange resin is passed through in the acid after above-mentioned desalination, then use distilled water wash-out, the sulfuric acid of recovery returns pickle house complex acid and uses; D) being dissolved in above-mentioned resin flow fluid by being separated the ferrous sulfate obtained, under the condition stirred, adding catalyzer and the vitriol oil, until obtain reddish-brown transparent liquid, being bodied ferric sulfate PFS; It can thus be appreciated that, although the method exists its distinctive feature, for the steel industry spent pickle liquor that component is comparatively complicated, except ferrous ion obtains efficient recovery, other ion is still present in waste liquid, needs further purifying treatment, can reach discharging of waste liquid standard.
Summary of the invention
Goal of the invention: the defect existed for prior art, the invention provides a kind of iron and steel industry spent pickle liquor treatment process, by the recovery to metal values ion in waste liquid, the concentrated acid after process turns back to pickling process and reaches recycle, this technological process is simple to operate, and cost is low.
For achieving the above object, a kind of iron and steel industry spent pickle liquor treatment process, comprises following technological step: a, tentatively filtered by spent pickle liquor, filtering solid impurity and grease; B, add alkali and carry out pH regulator in the filtrate after filtering; C, step b gained solution is sent into heavy metal chelating device, in solution, each metal ion species and heavy metal chelating agent react, formation heavy metal precipitation thing; D, by the reactant of step c send into strainer, filtered and recycled heavy metal precipitation thing, filtrate is stand-by; E, steps d gained filtrate is sent into reverse osmosis unit, produces water after advanced treatment close to pure water standard, production wash water can be back to, dense water can reuse to the elementary acid washing water of acid cleaning process.
In described step b, pH value is 3 ~ 5;
In described step c, heavy metal chelating agent is xanthate;
In described step c, heavy metal chelating agent consumption is 1mg/l;
Described strainer has folded membrane filter core, and the precision of described folded membrane filter core is 10 ~ 20 μm;
A kind of iron and steel industry spent pickle liquor treatment process provided by the invention, compared to existing technology, has following beneficial effect:
1, method of the present invention is easy and simple to handle, and cost is low, is suitable for industrial application;
2, thorough to spent pickle liquor process, heavy metal removal rate is high, and waste liquid is closed cycle use completely after treatment, non-secondary pollution.
Specific embodiment
By the following examples the present invention is further explained:
Embodiment 1
The spent pickle liquor Main Components that cold rolling workshop section of certain steel mill discharges: Fe
2+1680mg/L, Fe
3+1850mg/L, Cr
6+1000mg/L, Ni
+180mg/L, F
-2200mg/L, hydrochloric acid 2500mg/L, insolubles 180mg/L.
A, by 1000kg spent pickle liquor introduce pressure filter tentatively filter, filtering solid impurity and grease;
B, to filter after filtrate in add sodium hydroxide adjust ph 3;
C, above-mentioned steps gained solution is sent into heavy metal chelating device, in heavy metal chelating device, add xanthate class heavy metal chelating agent, stirring reaction 50 minutes, metal ion in solution and heavy metal chelating agent are fully reacted, formation heavy metal precipitation thing;
D, reactant is sent into strainer, wherein strainer has folded membrane filter core, and the precision of folded membrane filter core is 10 μm, filtered and recycled heavy metal precipitation thing;
E, filtrate send into reverse osmosis unit, produce water close to pure water standard, can be back to production wash water after advanced treatment, dense water can reuse to the elementary acid washing water of acid cleaning process.
Embodiment 2
The spent pickle liquor Main Components that cold rolling workshop section of certain steel mill discharges: Fe
2+1420mg/L, Fe
3+2150mg/L, Cr
6+800mg/L, Ni
+250mg/L, F
-1800mg/L, hydrochloric acid 2200mg/L, insolubles 150mg/L.
A, by 1000kg spent pickle liquor introduce pressure filter tentatively filter, filtering solid impurity and grease;
B, to filter after filtrate in add sodium hydroxide adjust ph 4;
C, above-mentioned steps gained solution is sent into heavy metal chelating device, dithiocarbamate salt heavy metal chelating agent is added in heavy metal chelating device, stirring reaction 45 minutes, makes metal ion in solution and heavy metal chelating agent fully react, and forms heavy metal precipitation thing;
D, reactant is sent into strainer, wherein strainer has folded membrane filter core, and the precision of folded membrane filter core is 20 μm, filtered and recycled heavy metal precipitation thing;
E, filtrate send into reverse osmosis unit, produce water close to pure water standard, can be back to production wash water after advanced treatment, dense water can reuse to the elementary acid washing water of acid cleaning process.
Embodiment 3
The spent pickle liquor Main Components that cold rolling workshop section of certain steel mill discharges: Fe
2+1500mg/L, Fe
3+2320mg/L, Cr
6+1200mg/L, Ni
+150mg/L, F
-1500mg/L, hydrochloric acid 1800mg/L, insolubles 200mg/L.
A, by 1000kg spent pickle liquor introduce pressure filter tentatively filter, filtering solid impurity and grease;
B, to filter after filtrate in add sodium hydroxide adjust ph 5;
C, above-mentioned steps gained solution is sent into heavy metal chelating device, dithiocarbamate salt heavy metal chelating agent is added in heavy metal chelating device, stirring reaction 40 minutes, makes metal ion in solution and heavy metal chelating agent fully react, and forms heavy metal precipitation thing;
D, reactant is sent into strainer, wherein strainer has folded membrane filter core, and the precision of folded membrane filter core is 15 μm, filtered and recycled heavy metal precipitation thing;
E, filtrate send into reverse osmosis unit, produce water close to pure water standard, can be back to production wash water after advanced treatment, dense water can reuse to the elementary acid washing water of acid cleaning process.
Embodiment 4
The spent pickle liquor Main Components that cold rolling workshop section of certain steel mill discharges: Fe
2+1520mg/L, Fe
3+1680mg/L, Cr
6+1000mg/L, Ni
+200mg/L, F
-1950mg/L, hydrochloric acid 1860mg/L, insolubles 180mg/L.
A, by 1000kg spent pickle liquor introduce pressure filter tentatively filter, filtering solid impurity and grease;
F, to filter after filtrate in add sodium hydroxide adjust ph 4.5;
G, above-mentioned steps gained solution is sent into heavy metal chelating device, dithiocarbamate salt heavy metal chelating agent is added in heavy metal chelating device, stirring reaction 50 minutes, makes metal ion in solution and heavy metal chelating agent fully react, and forms heavy metal precipitation thing;
H, reactant is sent into strainer, wherein strainer has folded membrane filter core, and the precision of folded membrane filter core is 25 μm, filtered and recycled heavy metal precipitation thing;
I, filtrate send into reverse osmosis unit, produce water close to pure water standard, can be back to production wash water after advanced treatment, dense water can reuse to the elementary acid washing water of acid cleaning process.
The above is only the preferred embodiment of the present invention; be noted that for those skilled in the art; under the premise without departing from the principles of the invention, can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (5)
1. an iron and steel industry spent pickle liquor treatment process, is characterized in that, comprises following technological step: a, tentatively filtered by spent pickle liquor, filtering solid impurity and grease; B, add alkali and carry out pH regulator in the filtrate after filtering; C, step b gained solution is sent into heavy metal chelating device, in solution, each metal ion species and heavy metal chelating agent react, formation heavy metal precipitation thing; D, by the reactant of step c send into strainer, filtered and recycled heavy metal precipitation thing, filtrate is stand-by; E, steps d gained filtrate is sent into reverse osmosis unit, produces water after advanced treatment close to pure water standard, production wash water can be back to, dense water can reuse to the elementary acid washing water of acid cleaning process.
2. a kind of iron and steel industry spent pickle liquor treatment process as claimed in claim 1, it is characterized in that, in step b, pH value is 3 ~ 5.
3. a kind of iron and steel industry spent pickle liquor treatment process as claimed in claim 1, it is characterized in that, in step c, heavy metal chelating agent is xanthate.
4. a kind of iron and steel industry spent pickle liquor treatment process as claimed in claim 1, it is characterized in that, heavy metal chelating agent consumption is 1mg/l.
5. a kind of iron and steel industry spent pickle liquor treatment process as claimed in claim 1, it is characterized in that, strainer has folded membrane filter core, and the precision of described folded membrane filter core is 10 ~ 20 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410644701.9A CN104445720A (en) | 2014-11-14 | 2014-11-14 | Pickling waste liquid treatment process of steel industry |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410644701.9A CN104445720A (en) | 2014-11-14 | 2014-11-14 | Pickling waste liquid treatment process of steel industry |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104445720A true CN104445720A (en) | 2015-03-25 |
Family
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|---|---|---|---|
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104787928A (en) * | 2015-04-16 | 2015-07-22 | 南阳师范学院 | Recovery processing method of stainless steel acid pickling waste liquid containing iron, chromium and nickel |
| CN104925986A (en) * | 2015-04-21 | 2015-09-23 | 杭州科瑞特环境技术有限公司 | Near-zero discharge treatment system for pickling waste liquid and washing wastewater in steel industry and process thereof |
| CN106495356A (en) * | 2016-10-01 | 2017-03-15 | 辽宁中成永续水工科技有限公司 | The processing method and system of steel industry nitric hydrofluoric acid mixed acid pickle liquor |
| CN106702398A (en) * | 2017-03-17 | 2017-05-24 | 青岛大仓防腐有限公司 | Anti-corrosive acid washing method for steel pipe |
| CN108529782A (en) * | 2017-03-06 | 2018-09-14 | 天津泰班科技发展有限公司 | A kind of industrial wastewater treatment device and treatment process |
| TWI675008B (en) * | 2018-07-04 | 2019-10-21 | 威威科技有限公司 | Waste acid washing solution treatment method |
| CN114180629A (en) * | 2021-12-10 | 2022-03-15 | 深圳市长隆科技有限公司 | Method for separating and recycling chromium and nickel and recycling waste acid in strong acid environment |
-
2014
- 2014-11-14 CN CN201410644701.9A patent/CN104445720A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104787928A (en) * | 2015-04-16 | 2015-07-22 | 南阳师范学院 | Recovery processing method of stainless steel acid pickling waste liquid containing iron, chromium and nickel |
| CN104787928B (en) * | 2015-04-16 | 2016-10-05 | 南阳师范学院 | A kind of iron content, chromium, the recovery and treatment method of nickel and stainless steel pickle liquor |
| CN104925986A (en) * | 2015-04-21 | 2015-09-23 | 杭州科瑞特环境技术有限公司 | Near-zero discharge treatment system for pickling waste liquid and washing wastewater in steel industry and process thereof |
| CN106495356A (en) * | 2016-10-01 | 2017-03-15 | 辽宁中成永续水工科技有限公司 | The processing method and system of steel industry nitric hydrofluoric acid mixed acid pickle liquor |
| CN108529782A (en) * | 2017-03-06 | 2018-09-14 | 天津泰班科技发展有限公司 | A kind of industrial wastewater treatment device and treatment process |
| CN106702398A (en) * | 2017-03-17 | 2017-05-24 | 青岛大仓防腐有限公司 | Anti-corrosive acid washing method for steel pipe |
| TWI675008B (en) * | 2018-07-04 | 2019-10-21 | 威威科技有限公司 | Waste acid washing solution treatment method |
| CN114180629A (en) * | 2021-12-10 | 2022-03-15 | 深圳市长隆科技有限公司 | Method for separating and recycling chromium and nickel and recycling waste acid in strong acid environment |
| CN114180629B (en) * | 2021-12-10 | 2024-04-05 | 深圳市长隆科技有限公司 | Method for separating, recovering chromium and nickel under strong acid environment and recycling waste acid |
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Application publication date: 20150325 |