CN105399187B - A kind of method of recycling steel wire rope pickle liquor - Google Patents
A kind of method of recycling steel wire rope pickle liquor Download PDFInfo
- Publication number
- CN105399187B CN105399187B CN201510804590.8A CN201510804590A CN105399187B CN 105399187 B CN105399187 B CN 105399187B CN 201510804590 A CN201510804590 A CN 201510804590A CN 105399187 B CN105399187 B CN 105399187B
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- waste liquid
- lead
- liquid
- cathode
- anode
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/18—Electrolytic production, recovery or refining of metals by electrolysis of solutions of lead
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/02—Electrodes; Connections thereof
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/04—Diaphragms; Spacing elements
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
The present invention relates to a kind of methods of recycling steel wire rope pickle liquor.It carries out according to the following steps：1）Waste liquid is sent into cathode electrolytic cell, galvanization is electrolysed, and contains Fe in the waste liquid2+And Pb2+Two metal ion species add in hydrochloric acid in waste liquid, and make pH concentration control electrolysis obtains lead sponge and except lead liquid in 2~4mol/L；2）By 1）What step obtained removes lead liquid feeding anode electrolytic tank, makes under the action of chlorine except the Fe in lead liquid2+Generate Fe3+.After the processing method purified treatment of the present invention, the iron ion in waste liquid can be used for producing FeCl3Or iron powder Restore All is added in into FeCl2Recycling afterwards.Lead in waste liquid can extract lead sponge.The present invention has following characteristics：Solution closed cycle, operational safety, reliable, pollution-free, environmental benefit is notable；In the environment-friendly and energy-saving emission-reduction that country is advocated, Developing Circulation Economy field can fully develop talents.
Description
Technical field
The invention belongs to steel wire rope pickle liquor resource treatment technique field, more particularly to utilization cyclone electrolytic cell technology
The method of leaded waste hydrochloric acid containing iron extraction lead regeneration FeCl3 in place.
Background technology
The technology of processing lead waste water can generally be divided into physical processing techniques, chemical treatment method and life both at home and abroad at present
Object treatment technology three categories.
Physical processing techniques refer to that the lead in waste water does not change chemical form in absorption, extraction and separation process, mainly
Including physisorphtion, membrane separation process and ion liquid abstraction method etc..Biologic treating technique mainly using some organisms and
Its derivative removes toxic Pb to the absorption of lead ion, flocculation and enrichment2+, wad a quilt with cotton including biosorption process, microorganism
Solidifying method etc..These two kinds of methods are easily recycled heavy metal, but technology is more demanding, and the most of difficult recycling of obtained enriched product needs
Want further harmless treatment.
Chemical treatment method refers to make lead by adding in chemical reagent, chemosorbent or logical direct current into lead waste water
Ion occurs chemical reaction and generates new substance such as Pb (OH)2, lead chelate or metal Pb remove the Pb in waste water.Mainly
Chemical treatment method include chemical precipitation method, chemiadsorption etc..This kind of method is applied than wide, but recycles heavy metal
Process it is more complicated, while generate heavy metal sewage sludge can generate secondary pollution.
In addition it is that heavy metal ion obtains electronics in cathode surface and is reduced to metal to also have a kind of principle of electrolysis.
Treatment of Wastewater by Electrolysis need not generally add in many chemicals, and processing is simple, floor space is small, management is convenient, sludge quantity is small,
So it is referred to as cleaning treatment method.But electrolysis processing effluent containing heavy metal ions severe corrosion to equipment, power consumption is big, pushes away
Wide application difficult, thus gradually replaced by other methods.
Invention content
The present invention provides a kind of utilize in order to solve above-mentioned waste liquid technical problem present in existing treatment technology and revolves
The leaded waste hydrochloric acid containing iron extraction lead regeneration FeCl of galvanic electricity solution technical finesse3Method.
The technical solution adopted by the present invention is thus：The present invention carries out according to the following steps：
1）Waste liquid is sent into cathode electrolytic cell, galvanization is electrolysed, and contains Fe in the waste liquid2+And Pb2+Two kinds of metals from
Son adds in hydrochloric acid in waste liquid, and makes pH concentration control electrolysis obtains lead sponge and except lead liquid in 2~4mol/L；
2）By 1）What step obtained removes lead liquid feeding anode electrolytic tank, makes under the action of chlorine except the Fe in lead liquid2+It is raw
Into Fe3+。
It carries out according to the following steps：The waste liquid is with 1~3m3The flow of/h enters cathode electrolytic cell, in 500~900A/m2Electricity
It is electrolysed under the action of current density.
It is an advantage of the invention that：After the processing method purified treatment of the present invention, the iron ion in waste liquid can be used for producing
FeCl3Or iron powder Restore All is added in into FeCl2Recycling afterwards.Lead in waste liquid can extract lead sponge.In waste liquid
Various compositions be obtained for and recycle again, not only pollute environment without any emission, thoroughly solve environmental issue,
And reusing for various composition also increases benefit for enterprise.The present invention has following characteristics：Solution closed cycle,
Operational safety, reliable, pollution-free, environmental benefit is notable；In the environment-friendly and energy-saving emission-reduction that country is advocated, Developing Circulation Economy
Field can fully develop talents.
Description of the drawings
Fig. 1 is the structure diagram of electrolysis unit of the present invention.
Specific embodiment
The present invention first pre-processes solution, and pretreated waste liquid is inputted in holding vessel, will be useless in holding vessel
Liquid is sent into cathode circulation slot, and solution is with 1~3m3The flow of/h enters cathode electrolytic cell and carries out forced circulation, in 500~900A/m2
It being electrolysed under the action of current density, the liquid in cathode electrolytic cell recycling lead sponge, cathode circulation slot achievees the purpose that except lead,
Lead content is less than 5mg/L.
Cathode reaction：
Metal ion obtains electronically forming metal in cathode：
Me+(aq)+e- →Me(S)
Contain Fe in solution2+And Pb2+Two metal ion species can be seen that iron prior to lead elder generation according to the electrode potential of metal
It is come out by electrolysis, so the present invention needs to adjust the pH concentration control of solution in pretreatment in 2~4mol/L so that electricity
The iron of solution out is reacted with the acid in solution, and reduces the content of iron in the lead that catholyte comes out.
The cathode reaction is set to be：Pb2+(aq)+e- →Pb(S)
Lead liquid will be removed simultaneously with 4~5m3/ h flow velocitys enter anode electrolytic tank and carry out forced circulation, anode reaction：
2Cl-（aq） - 2e- → Cl2（g）↑
Cl2 (g)+2 Fe2+（aq）→ 2Fe3+ （aq）+2 Cl-（aq）
Fe in the chlorine and solution that are generated in closed environment Anodic2+Reaction generates Fe3+.It is molten in cathode circulation slot
Liquid can be subsequently as production FeCl3Raw material or add in iron powder Restore All into FeCl2Recycling afterwards.
Case study on implementation one：Electrolysis time 2.5 hours, current density 600A/ ㎡, catholyte circular flow 1000L/H, anode
After the completion of 3000 L/H of internal circulating load electrolysis, cathode sheets, a small amount of metallics of output are taken out.It cleans to dry and weigh, be 2.2g.It calculates
Electrolytic efficiency is less than 5%.
Compare the variation of Pb concentration before and after being electrolysed, Pb contents are measured before electrolysis as 0.282g/L, after the completion of electrolysis, anolyte
Pb contents are 0.00438g/L, and the removal efficiency for calculating lead is 98.5%.
Using the diaphragm cyclone electrolytic cell technical finesse feed liquid, can effectively remove lead content in feed liquid, removal efficiency up to 98.5%,
And energy consumption is relatively low.
Electrolysis unit of the present invention is a kind of eddy flow diaphragm electrolysis apparatus, and electrolysis region is separated into cathodic region and anode region,
The feed liquid independent loops of cathodic region and anode region use, and for the present apparatus by the use of titanium as cathode cylinder, anode is Ti-Ru anode stick.Rotation
The core for flowing electrolysis unit is electrolytic cell, and electrolytic solution is tangentially flowed into from bottom of electrolytic tank, and forms spiral in slot inner wall
Upper up-flow.For electrolytic solution during spiral, metal cation obtains electronic deposition analysis to cathode motion at cathode
Go out；Spiral flow can weaken the negative effect of concentration polarization
The present invention can adjust the pressure differential of cathodic region and anode region compared with traditional diaphragm electrolysis apparatus, can prevent to contain
The anolyte of ferric ion enters cathode chamber, and then ferric ion is prevented to discharge on cathode, improves lead and is precipitated in cathode
Efficiency.
The pressure differential of cathodic region and anode region is adjusted, Fe can be prevented3+Ion is entered by the mass transfer mode spread with convection current
Cathode electrolytic cell, but cannot prevent to enter cathode chamber by electromigration mode.Therefore, it is necessary to control the flow velocity of anolyte 4~
5m3/ h, to reduce the current density of anolyte, current density is excessively high to lead to more Fe3+Into cathode electrolytic cell.
Claims (3)
1. a kind of method of recycling steel wire rope pickle liquor, is handled by electrolysis unit, which is characterized in that by with
Lower step carries out：
1）Waste liquid is sent into cathode electrolytic cell, galvanization is electrolysed, and contains Fe in the waste liquid2+And Pb2+Two metal ion species, waste liquid
Middle addition hydrochloric acid, and make pH concentration control in 2~4mol/L, electrolysis obtains lead sponge and except lead liquid；
2）By 1）What step obtained removes lead liquid feeding anode electrolytic tank, makes under the action of chlorine except the Fe in lead liquid2+Generate Fe3 +；
The electrolysis unit is eddy flow diaphragm electrolysis apparatus, and electrolysis region is separated into cathodic region and anode region, cathodic region and anode
The feed liquid independent loops in area use；
The waste liquid tangentially flows into cathode electrolytic cell, and form spiral stream in slot inner wall from bottom of electrolytic tank, and waste liquid is in spiral shell
It screws on during rising, metal cation obtains electronic deposition precipitation to cathode motion at cathode；
The cathodic region and anode region are adjustable there are pressure differential, 4~5m of flow velocity of the anolyte3/h。
2. the method for a kind of recycling steel wire rope pickle liquor according to claim 1, which is characterized in that by following
Step carries out：The waste liquid is with 1~3m3The flow of/h enters cathode electrolytic cell, in 500~900A/m2Under the action of current density
Electrolysis.
3. the method for a kind of recycling steel wire rope pickle liquor according to claim 1, which is characterized in that using titanium
For material as cathode cylinder, anode is Ti-Ru anode stick.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510804590.8A CN105399187B (en) | 2015-11-20 | 2015-11-20 | A kind of method of recycling steel wire rope pickle liquor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510804590.8A CN105399187B (en) | 2015-11-20 | 2015-11-20 | A kind of method of recycling steel wire rope pickle liquor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105399187A CN105399187A (en) | 2016-03-16 |
| CN105399187B true CN105399187B (en) | 2018-06-15 |
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| CN201510804590.8A Expired - Fee Related CN105399187B (en) | 2015-11-20 | 2015-11-20 | A kind of method of recycling steel wire rope pickle liquor |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106086937B (en) * | 2016-06-22 | 2018-10-12 | 乐山盛和稀土股份有限公司 | A kind of rare earth chloride liquid electrolysis deleading technique |
| CN107098556B (en) * | 2017-06-23 | 2020-04-10 | 江苏荣信环保科技有限公司 | Method for recycling metal from sludge in steel wire rope production |
| CN107381654A (en) * | 2017-09-15 | 2017-11-24 | 天津益佰碧源环保科技股份有限公司 | A kind of method that liquid industrial frerrous chloride is converted into by hydrochloric acid pickling waste liquor |
| CN108083392B (en) * | 2017-12-21 | 2021-04-16 | 大连交通大学 | Device and method for preparing superfine iron oxide and regenerating pickling solution by using pickling waste liquor |
| CN109735870A (en) * | 2018-12-28 | 2019-05-10 | 祥云高鑫循环科技有限责任公司 | The electrolyte electrochemical purification method of waste lead acid battery lead cream Solid phase electrolysis hydrometallurgic recovery lead |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4226685A (en) * | 1978-10-23 | 1980-10-07 | Kennecott Copper Corporation | Electrolytic treatment of plating wastes |
| CN102633326A (en) * | 2012-04-28 | 2012-08-15 | 云南铜业股份有限公司 | Ion exchange membrane electrolysis method for treating acid waste water containing chloride in copper metallurgy process |
| CN103806019A (en) * | 2014-02-08 | 2014-05-21 | 江西远鑫资源循环投资开发有限公司 | Rotational-flow membrane electrolyzer |
-
2015
- 2015-11-20 CN CN201510804590.8A patent/CN105399187B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4226685A (en) * | 1978-10-23 | 1980-10-07 | Kennecott Copper Corporation | Electrolytic treatment of plating wastes |
| CN102633326A (en) * | 2012-04-28 | 2012-08-15 | 云南铜业股份有限公司 | Ion exchange membrane electrolysis method for treating acid waste water containing chloride in copper metallurgy process |
| CN103806019A (en) * | 2014-02-08 | 2014-05-21 | 江西远鑫资源循环投资开发有限公司 | Rotational-flow membrane electrolyzer |
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| CN105399187A (en) | 2016-03-16 |
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Granted publication date: 20180615 Termination date: 20211120 |