CN107419105B - A method of iron, copper, nickel, chromium in classification recycling electroplating sludge - Google Patents
A method of iron, copper, nickel, chromium in classification recycling electroplating sludge Download PDFInfo
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- CN107419105B CN107419105B CN201710612163.9A CN201710612163A CN107419105B CN 107419105 B CN107419105 B CN 107419105B CN 201710612163 A CN201710612163 A CN 201710612163A CN 107419105 B CN107419105 B CN 107419105B
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- chromium
- iron
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- iron aluminium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/008—Wet processes by an alkaline or ammoniacal leaching
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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
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/006—Electrochemical treatment, e.g. electro-oxidation or electro-osmosis
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- 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
Abstract
The applicant provides a kind of method that iron, copper, nickel, chromium in electroplating sludge are recycled in classification, includes the following steps：Electroplating sludge and lysate are sufficiently mixed and carry out ammonia leaching, 1. the solution obtained when being soaked to ammonia uses electrolysis mode to obtain corronil；2. the solution generated in electrolytic process is returned to ammonia leaching link recycled；To obtaining smart iron aluminium mixture except the crude iron aluminium mixture obtained after iron aluminium carries out multi-stage water wash, and heats copolymerization with hydrochloric acid and obtain polymer- cement based composite；5. 4. the solution generated during multi-stage water wash is returned to solution；To 4. carrying out concentrating the obtained chromium sulfate of cooling centrifugation except the solution obtained after iron aluminium.The present invention provides it is a kind of it is easy to operate, feasibility is high, the electroplating sludge treatment process of a variety of valuable metals is recycled in good separating effect, classification.
Description
Technical field
The present invention relates to environmental protection technical field, more particularly, to a kind of classification recycle iron in electroplating sludge, copper, nickel,
(copper content is more than 5wt%, and nickel content is more than 5wt%, and chromium content is more than by the method for chromium, especially high-copper, nickelic, Gao Ge
2wt%) iron, copper, nickel, the separation of chromium and method of resource in electroplating sludge.
Background technology
It is higher and higher to different types of electroplating sludge material requirements, demand is more next with the high speed development of modern industry
Bigger, the high speed development of electroplating industry brings that national economy is increasingly flourishing, and living standards of the people step up, concurrently band
What is come is that the electroplating sludge that electroplating industry generates is increasing, especially chromium-bearing sludge, its toxicity of chromium metal and its valence state direct ratio.
Currently, effectively having burning, landfill etc. to electroplating sludge processing both at home and abroad.Although such method is by electroplating sludge
Leaching, which is reduced to, infinitely tends to nothing, but can not make full use of the value of valuable metal in electroplated mud, especially copper,
The metals such as nickel, chromium.
CN103725886A provides a kind of using the method that cupro-nickel chromium zinc-iron prepares multicomponent alloy in mud, and method is
After sulfuric acid dissolution electroplating sludge, it is directly added under piece alkali precipitates cupro-nickel chromium zinc-iron in the form of its corresponding hydroxide
Come, the method alkali charge and the extraction that cupro-nickel chromium zinc-iron can not be classified, and extracts the solution of cupro-nickel chromium zinc-iron without corresponding disposition
Method.
CN101608336 provides a kind of method for realizing electric plating sludge resource, utilizes ferriammonium sulfate method precipitation chromium, iron
When dosing and its stringent, otherwise can introduce other impurities " NH3" " pollution " follow-up nickel electroplating solution, and chromium in the method
It is only trivalent chromium.
CN106244811A provides that a kind of copper and iron content is low, recoverying and utilizing method of the high electroplating sludge of tin nickel content,
It is only capable of recycling Copper in Electroplating Sludge, nickel, iron, tin, other valuable metal chromium, and the process cannot be recycled from technique
The technique missing handled about Ammonia valatilization in middle electrolysis recycling nickel technique can not judge ammonia during its electrolysis recycling nickel
How gas volatilization is handled.
CN104263941B provides a kind of technique of the comprehensively recovering valuable metal from electroplating sludge, can from technique
It realizes copper, nickel, gold, silver recycling, but can not judge whether recycle iron aluminium and its method of resource in electroplating sludge, cupro-nickel recycling
The method for using extraction power-up solution in the process detaches cupro-nickel, and technique is relatively cumbersome, zinc powder has been used in the recycling of gold and silver, and nothing is returned
Knock off skill, is the waste of zinc resource to a certain extent.
Invention content
In view of the above-mentioned problems existing in the prior art, this application provides a kind of classification recycle electroplating sludge in iron, copper,
The method of nickel, chromium.The present invention is easy to operate, feasibility is high, good separating effect, can classify recycling valuable metal containing there are many
Electroplating sludge.
Technical scheme is as follows：
A method of iron, copper, nickel, chromium in classification recycling electroplating sludge include the following steps：
Electroplating sludge and lysate are sufficiently mixed and carry out ammonia leaching, 1. the solution obtained when being soaked to ammonia is obtained using electrolysis mode
Obtain corronil；
2. the solution generated in electrolytic process is returned to ammonia leaching link recycled；
To obtaining smart iron aluminium mixture except the crude iron aluminium mixture obtained after iron aluminium carries out multi-stage water wash, and heated with hydrochloric acid
Copolymerization obtains polymer- cement based composite；
To 4. carrying out concentrating the obtained chromium sulfate of cooling centrifugation except the solution obtained after iron aluminium；
5. 4. the solution generated during multi-stage water wash is returned to solution.
Concrete operation method includes the following steps：
(1) ammonia soaks：Lysate is added into electroplating sludge to carry out being sufficiently stirred dissolving, lysate quality and electroplating sludge matter
Amount is than being 4~6：1；30~40 DEG C, 1~2h of mixing time of solution temperature, obtain after separation of solid and liquid solid 1. with solution 1.；
(2) 1. the solution generated in step (1) is sent to electrowinning process electrolysis, product corronil and solution is made 2.,
2. solution is returned to ammonia leaching link and is recycled；
(3) solid generated into step (1) is 1. middle is added dilute sulfuric acid dissolving, and NaHSO is added4It restores, is filled under room temperature
Stirring, 1~2h of mixing time is divided to obtain solution 3.；
(4) to the solution generated in step (3) 3. in aeration aerating, using chromium carbonate adjust the pH value of solution 3. be 2~
3, it is then separated by solid-liquid separation, obtains crude iron aluminium mixture and solution 4.；
(5) multi-stage water wash is carried out to the crude iron aluminium mixture generated in step (4), added into smart iron aluminium mixture after washing
Enter hydrochloric acid and be heated to 80~100 DEG C, 1~2h of reaction time prepares polymer- cement based composite solution product；The amount of the substance of hydrochloric acid used
It it is 3~5 times of the amount summation of iron, aluminum material in smart polymer- cement based composite, hydrochloric acid mass fraction is 36~38wt%, multi-stage water wash process
The solution of middle generation 5. return to solution 4. in recycle；
(6) 4. the solution generated in step (4) being concentrated, concentration proportion is 1.4~1.6, it is subsequently cooled to 30~
40 DEG C prepare crude product chromium sulfate.
Preferably, lysate ingredient used is ammonium hydroxide and ammonium sulfate in step (1), and total ammonia density is 6mol/L, ammonia and ammonium
Salinity ratio is 2~3：1.
Preferably, the cathode material that electrolysis uses in step (2) is stainless steel, and anode material is to apply ruthenium titanium material；Electrolysis ginseng
Number is that room temperature is electrolysed, and electrolysis time is 24~48h, current density 0.5-1A/cm2。
Preferably, the mass ratio of sulfuric acid and water is 1 in dilute sulfuric acid in step (3)：10.
Preferably, NaHSO in step (3)4I.e. quality needed for sodium hydrogensulfite is 4-6 times of chromium matter amount.
Preferably, aeration time is 2~4h, aeration quantity 2m in step (4)3/ h, oxygen concentration 21%.
NaHSO is added in step (3)4Without Cr in being meant to ensure that solution 3.6+。
The present invention is beneficial to be had technical effect that：
The present invention overcomes the recycling and valueization of cannot classifying to wherein valuable metal in traditional electroplating sludge processing procedure
The drawbacks of；Corronil, polymer- cement based composite and chromium sulfate work have been directly obtained by techniques such as dissolving, separation of solid and liquid, electrolysis, concentrations
Industry grade product.
Without being arranged outside waste water in implementation process of the present invention, electroplating sludge is reduced to the pollution of water body and the wind of health
Danger.The present invention is easy to operate, feasibility is high, good separating effect, to realize safe and environment-friendly, efficient purpose.
Description of the drawings
Fig. 1 is present invention classification recycling iron, copper, nickel, chromium process flow diagram from electroplating sludge.
Specific implementation mode
Below in conjunction with the accompanying drawings 1, the present invention is specifically described.
Embodiment 1
Take certain factory generate electroplating sludge (hereinafter referred to as solid waste, main component Cu, Ni, Cr, Fe, copper content are more than
5wt%, nickel content are more than 5wt%, and chromium content is more than 2wt%) 600kg, electroplating sludge is fitted into 1# reaction kettles, is added 4 times
The lysate of electroplating sludge quality, is sufficiently stirred 1h at 30 DEG C, filter press press filtration obtain solution 1. with solid 1., lysate ingredient
For ammonium hydroxide and ammonium sulfate, total ammonia density is 6mol/L, and ammonia is 2 with ammonium salt concentration ratio：1；
Solution will be obtained and be 1. sent to electrowinning process electrolysis, room temperature is electrolysed 48h, current density 0.5A/cm2, obtain cupro-nickel conjunction
2., 2. solution is returned to ammonia leaching link and is recycled for gold and solution；1. solid is packed into 2# reaction kettles 10wt% sulphur is added
Acid, and the NaHSO of 4 times of chromium matter amounts is added4It restores, is sufficiently stirred under room temperature, mixing time 1h, obtain solution 3.；
3. oxygenic aeration 2h is carried out to solution, and 3. using steam heated solution, is allowed to temperature and is warming up to 80 DEG C, then lead to
It crosses addition chromium carbonate to be allowed to solution 3. pH reaches 2, insulated and stirred 1h squeezes into press filtration in filter press, obtains thick crude iron aluminium mixing
Object and solution are 4.；
Tap water, multi-stage water wash is used to obtain smart crude iron aluminium mixture, washing iron aluminium mixing thick crude iron aluminium mixture
After object water be solution 5., return to solution and 4. recycle, smart iron aluminium mixture is transferred in 3# reaction kettles, be added 3 times
The hydrochloric acid of the amount of smart iron aluminium mixture substance, hydrochloric acid mass concentration are 36wt%, and polymer- cement based composite is obtained after heating 80 DEG C of reaction 1h
Product；4. solution is pumped into concentration tank, gravity 1.4 is concentrated into, blowing is cooled to 30 DEG C, into centrifuge 1h,
Obtain chromium sulfate product.
Embodiment 2
Take certain factory generate electroplating sludge (hereinafter referred to as solid waste, main component Cu, Ni, Cr, Fe, copper content are more than
5wt%, nickel content are more than 5wt%, and chromium content is more than 2wt%) 800kg, electroplating sludge is fitted into 1# reaction kettles, is added 5 times
The lysate of electroplating sludge quality, is sufficiently stirred 1.5h at 35 DEG C, filter press press filtration obtain solution 1. with solid 1., lysate at
It is divided into ammonium hydroxide and ammonium sulfate, total ammonia density is 6mol/L, and ammonia is 2.5 with ammonium salt concentration ratio：1；
Solution will be obtained and be 1. sent to electrowinning process electrolysis, room temperature is electrolysed 36h, current density 0.75A/cm2, obtain cupro-nickel conjunction
2., 2. solution is returned to ammonia leaching link and is recycled for gold and solution；1. solid is packed into 2# reaction kettles 10wt% sulphur is added
Acid, and the NaHSO of 5 times of chromium matter amounts is added4It restores, is sufficiently stirred under room temperature, mixing time 1.5h, obtain solution 3.；
3. oxygenic aeration 3h is carried out to solution, and 3. using steam heated solution, is allowed to temperature and is warming up to 80 DEG C, then lead to
It crosses addition chromium carbonate to be allowed to solution 3. pH reaches 2.5, insulated and stirred 1h squeezes into press filtration in filter press, and it is mixed to obtain thick crude iron aluminium
Close object and solution 4.；
Tap water, multi-stage water wash is used to obtain smart crude iron aluminium mixture, washing iron aluminium mixing thick crude iron aluminium mixture
After object water be solution 5., return to solution and 4. recycle, smart iron aluminium mixture is transferred in 3# reaction kettles, be added 4 times
The hydrochloric acid of the amount of smart iron aluminium mixture substance, hydrochloric acid mass concentration are 37wt%, and polymeric iron is obtained after heating 80 DEG C of reaction 1.5h
Aluminium product；4. solution is pumped into concentration tank, gravity 1.5 is concentrated into, blowing is cooled to 35 DEG C, into centrifuge
1h obtains chromium sulfate product.
Embodiment 3
Take certain factory generate electroplating sludge (hereinafter referred to as solid waste, main component Cu, Ni, Cr, Fe, copper content are more than
5wt%, nickel content are more than 5wt%, and chromium content is more than 2wt%) 1000kg, electroplating sludge is fitted into 1# reaction kettles, is added 6 times
The lysate of electroplating sludge quality, is sufficiently stirred 1h at 40 DEG C, filter press press filtration obtain solution 1. with solid 1., lysate ingredient
For ammonium hydroxide and ammonium sulfate, total ammonia density is 6mol/L, and ammonia is 3 with ammonium salt concentration ratio：1；
Solution will be obtained and be 1. sent to electrowinning process electrolysis, room temperature is electrolysed for 24 hours, current density 1A/cm2, obtain corronil
2. with solution, 2. solution is returned to ammonia leaching link and is recycled；1. solid is packed into 2# reaction kettles 10wt% sulfuric acid is added,
And the NaHSO of 6 times of chromium matter amounts is added4It restores, is sufficiently stirred under room temperature, mixing time 2h, obtain solution 3.；
3. oxygenic aeration 4h is carried out to solution, and 3. using steam heated solution, is allowed to temperature and is warming up to 80 DEG C, then lead to
It crosses addition chromium carbonate to be allowed to solution 3. pH reaches 3, insulated and stirred 1h squeezes into press filtration in filter press, obtains thick crude iron aluminium mixing
Object and solution are 4.；
Tap water, multi-stage water wash is used to obtain smart crude iron aluminium mixture, washing iron aluminium mixing thick crude iron aluminium mixture
After object water be solution 5., return to solution and 4. recycle, smart iron aluminium mixture is transferred in 3# reaction kettles, be added 5 times
The hydrochloric acid of the amount of smart iron aluminium mixture substance, hydrochloric acid mass concentration are 38wt%, and polymeric iron is obtained after heating 80 DEG C of reaction 1.5h
Aluminium product；4. solution is pumped into concentration tank, gravity 1.6 is concentrated into, blowing is cooled to 40 DEG C, into centrifuge
1h obtains chromium sulfate product.
Detect example：
The concentration or purity and the rate of recovery for the product that Examples 1 to 3 recycles are as shown in table 1.
Table 1
The above is illustrative without being restrictive, therefore scope of protection of the present invention is not limited thereto,
Any one skilled in the art is in the technical scope that the present invention discloses, the variation that can be readily occurred in or replacement,
It should be covered by the protection scope of the present invention.
Claims (2)
1. a kind of method of iron, copper, nickel, chromium in classification recycling electroplating sludge, it is characterised in that include the following steps：
(1) ammonia soaks：Lysate is added into electroplating sludge to carry out being sufficiently stirred dissolving, lysate quality and electroplating sludge mass ratio
It is 4~6：1；30~40 DEG C, 1~2h of mixing time of solution temperature, obtain after separation of solid and liquid solid 1. with solution 1.；Step (1)
In lysate ingredient used be ammonium hydroxide and ammonium sulfate, total ammonia density is 6mol/L, and ammonia and ammonium salt concentration ratio are 2~3：1；
(2) 1. the solution generated in step (1) is sent to electrowinning process electrolysis, product corronil and solution is made 2., solution
It is recycled 2. returning to ammonia leaching link；The cathode material that electrolysis uses in step (2) is stainless steel, and anode material is to apply
Ruthenium titanium material；Electrolytic parameter is electrolysed for room temperature, and electrolysis time is 24~48h, current density 0.5-1A/cm2；
(3) solid generated into step (1) is 1. middle is added dilute sulfuric acid dissolving, and NaHSO is added3 It restores, is fully stirred under room temperature
It mixes, 1~2h of mixing time, obtains solution 3.；NaHSO in step (3)3 I.e. quality needed for sodium hydrogensulfite is the 4-6 of chromium matter amount
Times；
(4) to the solution generated in step (3) 3. in aeration aerating, it is 2~3 to adjust the pH value of solution 3. using chromium carbonate, so
After be separated by solid-liquid separation, obtain crude iron aluminium mixture and solution 4.；Aeration time is 2~4h, aeration quantity 2m in step (4)3/
H, oxygen concentration 21%；
(5) multi-stage water wash is carried out to the crude iron aluminium mixture generated in step (4), salt is added into smart iron aluminium mixture after washing
Acid is simultaneously heated to 80~100 DEG C, and 1~2h of reaction time prepares polymer- cement based composite solution product；The amount of the substance of hydrochloric acid used is essence
3~5 times of the amount summation of iron, aluminum material in polymer- cement based composite, hydrochloric acid mass fraction are 36~38wt%, are produced during multi-stage water wash
Raw solution 5. return to solution 4. in recycle；
(6) 4. the solution generated in step (4) is concentrated, concentration proportion is 1.4~1.6, is subsequently cooled to 30~40 DEG C
Prepare crude product chromium sulfate.
2. according to the method described in claim 1, it is characterized in that：The mass ratio of sulfuric acid and water is in dilute sulfuric acid in step (3)
1：10.
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| CN102910716A (en) * | 2012-08-27 | 2013-02-06 | 浙江大学 | Method for preparing polymeric ferric aluminum by utilizing metal chlorohydric acid pickling waste liquor |
| CN103214067B (en) * | 2013-05-10 | 2014-03-19 | 中国水电顾问集团中南勘测设计研究院 | Electrolytic reaction tank and integrated preparing and casting device for iron and aluminum compound flocculant |
| CN104263943B (en) * | 2014-09-25 | 2017-02-15 | 池州西恩新材料科技有限公司 | Method for simultaneously separating chromium, iron and aluminum from acidic metal solution containing chromium, iron and aluminum |
| CN104928478B (en) * | 2015-06-09 | 2018-04-27 | 衡阳师范学院 | A kind of method of electroplating sludge comprehensively recovering valuable metal |
| CN105648224B (en) * | 2016-03-25 | 2017-08-01 | 大连理工大学 | A kind of chromium is extracted and harmful waste administers the method for reclaiming and preparing chromium compound |
| CN105886779B (en) * | 2016-06-08 | 2018-01-02 | 浙江奇彩环境科技股份有限公司 | A kind of recycling processing method of chromium-contained aluminum mud |
| CN106636651B (en) * | 2016-12-16 | 2018-05-08 | 江苏理工学院 | The separation method of chromium and iron aluminium in a kind of sulfuric acid system solution of aluminium containing ferrochrome |
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