CN103556152B - A kind of mixed chlorinated copper spent etching solution synthetical recovery treatment process - Google Patents
A kind of mixed chlorinated copper spent etching solution synthetical recovery treatment process Download PDFInfo
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Abstract
A kind of mixed chlorinated copper spent etching solution synthetical recovery treatment process, belongs to Non-ferrous Metallurgy valuable metal recovery field.Mainly comprising the following steps of its technological process: (1) concentrates cupric chloride etching solution; (2) Cupric Chloride Solution after concentrating carries out spray pyrolysis and forms cupric oxide composite powder; (3) chlorine carries out the refining hydrochloric acid of recovery preparation; (4) cupric oxide composite powder is through sulfuric acid leaching; (5) copper sulfate leaching liquid carries out selectivity electrodeposition through cyclone electrolytic cell system, obtains the cathode copper product that Chemical Composition reaches 1# copper products standard.Method technique of the present invention is simple, flow process is short, environmental friendliness, operation is simple and feasible, can effectively realize acid with alkaline copper chloride etching solution synthetical recovery and direct production high-quality copper products, and effectively the chlorion in waste liquid is converted into purified salt acid product, reach the high-efficiency comprehensive utilization of resource.
Description
Technical field
The invention belongs to non-ferrous metal hydrometallurgy valuable metal recovery technical field, be specifically related to a kind of mixed chlorinated copper spent etching solution synthetical recovery treatment process.
Background technology
In recent years, brass work industry develop rapidly bring the generation of a large amount of contained waste liquids.Simultaneously, country grows with each passing day to environmental requirement, and therefore, the process of copper-bearing waste material and discharge have become a great problem of enterprise.Technically, the removal comparative maturity of free state bivalent cupric ion, after process, in solution, the mass concentration of remaining copper ion can drop to below 1mg/L.But in the industry copper-containing wastewaters such as dyestuff, plating, circuit card (PCB), cupric ion often exists with complex pattern, wherein representative with the spent etching solution most in PCB industry.Containing a large amount of resources in spent etching solution, spent etching solution more than cupric 120kg per ton, muriate more than 250kg, more than ammonia 80kg, and containing other each metal ion species.Therefore, the selection of spent etching solution treatment technology and the quality for the treatment of effect are not only related to the recycling of resource, are also related to the environmental safety of factory surrounding area, economy and social Sustainable development.
At present, the treatment process of spent etching solution mainly concentrates on two kinds of technology, i.e. producing copper sulfate technology and circulation and regeneration technology, and other new technologies all develop based on these two kinds of technology.Its know-why of producing copper sulfate technology is: with the cupric ion in precipitation agent precipitation waste liquid, then copper sulfate is produced with the mantoquita precipitated and sulfuric acid reaction, but due to general very high containing acid in the middle of acidic etching liquid, need to consume a large amount of alkaline precipitating agents, waste liquid copper content simultaneously after precipitation is still higher, just can reach discharging standards after needing further decopper(ing), therefore this kind of method is that one is sacrificed future gains to satisfy present needs, shortsighted part resource reclaims, and large to environmental hazard.The spent etching solution of circulation and regeneration technology mainly PCB factory etching work procedure output is raw material, obtain qualified etching solution and solid metal copper after treatment, the etching solution of this regeneration is back to PCB etching work procedure again, thus forms circulation loop, is a kind of method preferably.But the method has strong requirement to spent etching solution itself, formed for spent etching solution relative to a large amount of various channel, PCB spent etching solution is one of them part.Therefore, circulation and regeneration technology has its significant limitation.
The invention provides a kind of mixed chlorinated copper spent etching solution synthetical recovery treatment process, mixed chlorinated copper spent etching solution reclaims the technical process such as copper by evaporation concentration+spray pyrolysis+sulfuric acid dissolution+cyclone electrolytic cell choice of technology, not only the cupric ion efficient recovery in the cupric chloride spent etching solution of various complexity is become Chemical Composition and arrive 1# electro deposited copper product, and the chlorion in solution is fully recycled make the Chemicals such as chlorine or refining hydrochloric acid.This method technique is simple, flow process is short, environment is good, the rate of recovery is high, adds the economic benefit of enterprise, achieves the high efficiente callback of resource simultaneously, also meet the principle of recycling economy.
Summary of the invention
The object of the invention is the deficiency existed for prior art, provide that a kind of technique is simple, flow process is short, environment is good, with low cost, effectively can extract selective separation and the efficient recycling method of mixed chlorinated copper copper from waste etching solution and chlorion.
Described one mixed chlorinated copper spent etching solution synthetical recovery treatment process, is characterized in that comprising the following steps:
Carry out evaporation concentration to acid copper chloride etching liquid, alkaline copper chloride etching solution or both mixed solutions and obtain high density Cupric Chloride Solution, wherein copper ion concentration is 250-350g/L, and chlorion is 800-950g/L;
2) by peristaltic pump, spray pyrolysis unit is added to the high density Cupric Chloride Solution obtained in step 1) and carry out spray pyrolysis, by this solution spray in the high-temperature atmosphere of 700-900 DEG C of tubular oven, solution evaporation, Cupric Chloride Solution generation pyrolysis simultaneously, obtains crude oxidation copper powder and chlorine; During this method requirement spray pyrolysis, droplet can complete drying process, so product is generally trickle particle before not reaching tubular oven wall;
3) by step 2) chlorine that produces of pyrolytic process delivers in dechlorinator and adopts vacuum dechlorination method to obtain chlorine product, chlorine product introduction chlorine house steward delivers to Chlorine Cooler, two sections of process for cooling are adopted to cool, deliver to high purity hydrochloric acid unit after cooled chlorine Nash pump pressurization and obtain high-purity hydrochloric acid and clorox with time sodium unit, thus realize the efficient recovery of original solution chlorion;
4) by step 2) in the cupric oxide powder that obtains by removing magnetic oxide impurity after simple magnetic separation, then carry out with sulfuric acid dissolving the copper-bath obtaining copper ions concentration 40-60 g/L;
5) copper-bath obtained in step 4) is directly entered cyclone electrolytic cell system and produce electro deposited copper product, at current density 600-700A/m
2, electrolysis cycle amount is selective extraction under 500 ~ 600L/h condition, obtain Chemical Composition and reach liquid after the high-quality copper products of 1# copper and the low eddy flow electrodeposition of copper ions;
6) after step 5) being obtained the low eddy flow electrodeposition of copper ions, liquid turns back to step poly-4) in, serve as sulfuric acid and obtain copper-bath for leaching crude oxidation copper powder, thus realize the acidic high efficiente callback utilization of electrolytic deposition process.
Described one mixed chlorinated copper spent etching solution synthetical recovery treatment process, it is characterized in that in the high density Cupric Chloride Solution described in step 1), content of copper ion is 300-350g/L, chloride ion content is 900-950g/L.
Described one mixed chlorinated copper spent etching solution synthetical recovery treatment process, it is characterized in that walking poly-2) in concentrated after Cupric Chloride Solution carry out spray pyrolysis condition and be: hot blast temperature 180-220 DEG C, hot blast flow velocity 180-220L/min, compressed air pressure 50-70MPa, compressed air require is 65-75L/min, tubular oven head temperature 700-900 DEG C, tubular oven rear end temperature 700-900 DEG C, peristaltic pump pusher intensity 1.5-2.5MPa.
Described one mixed chlorinated copper spent etching solution synthetical recovery treatment process, it is characterized in that walking poly-2) in concentrated after Cupric Chloride Solution carry out spray pyrolysis condition and be: hot blast temperature 200 DEG C, hot blast flow velocity 200L/min, compressed air pressure 60MPa, compressed air require: 65-75L/min, tubular oven head temperature 800 DEG C, tubular oven rear end temperature 800 DEG C, peristaltic pump pusher intensity 2MPa.
Described one mixed chlorinated copper spent etching solution synthetical recovery treatment process, is characterized in that walking poly-3) described in dechlorinator's vacuum tightness be-0.090 ~-0.095MPa, Chlorine Cooler temperature out is 38-42 DEG C, and Nash pump top hole pressure is 0.13-0.16MPa.
Described one mixed chlorinated copper spent etching solution synthetical recovery treatment process, is characterized in that walking poly-3) described in dechlorinator's vacuum tightness :-0.093MPa, Chlorine Cooler temperature out is 40 DEG C, and Nash pump top hole pressure is 0.15MPa.
Described one mixed chlorinated copper spent etching solution synthetical recovery treatment process, is characterized in that walking poly-3) two sections of process for cooling comprise directly cooling and indirect process for cooling, the direct spraying cooling of direct cooling chlorine water, chlorine water is closed cycle; Indirectly be cooled to and indirectly cool with recirculated water.
Described one mixed chlorinated copper spent etching solution synthetical recovery treatment process, is characterized in that the electrolytic condition described in step 5) is: current density 640-660A/m
2, electrolysis cycle amount is 550-580L/h.
By adopting above-mentioned technology, the mixed chlorinated copper spent etching solution synthetical recovery treatment process provided of the present invention, reasonable in design, compared with prior art, there is following beneficial effect:
(1) present invention process is simple to operate, flow process is short, cost is low, environmental friendliness;
(2) cupric ion in solution and chlorion realize thoroughly being separated by the method for spray pyrolysis by the present invention under the high temperature conditions instantaneously, copper with the isolated in form of cupric oxide out, chloride binding becomes chlorine and enters comprehensive recovery system, the rate of recovery is high, and directly enters next unit and utilize;
(3) magnetic oxide such as Z 250, the nickel oxide etc. in spray pyrolysis cupric oxide powder is out separated by magnetic selection method by the present invention, achieve the selective separation of copper and iron, nickel etc., separation efficiency more than 95%, to the extraction of copper after being conducive to, improves purity;
(4) the present invention utilizes the rough copper-bath of cyclone electrolytic cell technical finesse spray pyrolysis cupric oxide out after sulfuric acid dissolution simultaneously, efficient selective electrolysis production high-purity copper product, copper recovery is high, can more than 99% be reached, and purity is high, reach the requirement that Chemical Composition reaches 1# copper, remarkable in economical benefits;
(5) the present invention achieves effective separation of chlorion etc. in mixed chlorinated copper spent etching solution by the mode of spray pyrolysis and makes the Chemicals such as chlorine or refining hydrochloric acid, creates economic worth.
Embodiment
Below in conjunction with embodiment, the invention will be further described, but protection scope of the present invention is not limited in this:
A kind of mixed chlorinated copper spent etching solution synthetical recovery treatment process, concrete grammar is as follows:
1) a certain amount of acid copper chloride etching liquid/alkaline copper chloride etching solution is got or both mixed solutions carry out evaporation concentration, after concentrated, copper ion concentration reaches 250-350g/L, chloride ion content reach 900-950g/L close to saturated Cupric Chloride Solution, preferably copper ion content is 300-350g/L, and chloride ion content is 900-950g/L;
2) by peristaltic pump, spray pyrolysis unit is added to the high density Cupric Chloride Solution obtained in step 1) and carry out spray pyrolysis, by this solution spray in the high-temperature atmosphere of 600-800 DEG C of tubular oven, solution evaporation, Cupric Chloride Solution generation pyrolysis simultaneously, obtains cupric oxide powder and chlorine; During this method requirement spray pyrolysis, droplet can complete drying process, so product is generally trickle particle powder before not reaching tubular oven wall; Wherein spray pyrolysis condition is: hot blast temperature 180-220 DEG C, hot blast flow velocity 180-220L/min, compressed air pressure 50-70MPa, compressed air require is 65-75L/min, tubular oven head temperature 700-900 DEG C, tubular oven rear end temperature 700-900 DEG C, peristaltic pump pusher intensity 1.5-2.5MPa; Preferred hot blast temperature 200 DEG C, hot blast flow velocity 200L/min, compressed air pressure 60MPa, compressed air require: 65-75L/min, tubular oven head temperature 800 DEG C, tubular oven rear end temperature 800 DEG C, peristaltic pump pusher intensity 2MPa;
Spray pyrolysis unit in this step, comprises carrier gas device, ultrasonic atomizing device, tubular oven and collection device four parts, and adopt pressurized air as carrier gas, flow rate of carrier gas is 70 L/min; Ultrasonic atomizing device is equipped with the ultrasonic transduction sheet that 6 frequencies are 1.75MHz; Crystal reaction tube (caliber 55 mm, long 1000 mm), controlling temperature in silica tube is 800 DEG C; Spray droplet is approximately about 0.6 s by the time of whole silica tube;
Specific operation process is as follows: add in ultrasonic atomizing device by the above-mentioned high density Cupric Chloride Solution prepared, and keep its liquid level at certain position, to ensure best nebulization efficiency, open air and keep certain flow rate, start ultrasonic atomizing device, solution forms the aerosol of a large amount of fine droplet composition through atomization, is fed through in crystal reaction tube by air, carries out evaporating, drying, decomposition, obtains cupric oxide powder after the process such as crystallization reaction;
3) by step 2) chlorine that produces of pyrolytic process delivers in dechlorinator and adopts vacuum dechlorination method to obtain chlorine product, chlorine product introduction chlorine house steward delivers to Chlorine Cooler, directly cooling and indirect cooling two sections of process for cooling are adopted to cool, the direct spraying cooling of direct cooling chlorine water, chlorine water is closed cycle; Indirectly be cooled to and indirectly cool with recirculated water; Deliver to high purity hydrochloric acid unit after cooled chlorine Nash pump pressurization and obtain high-purity hydrochloric acid and clorox with time sodium unit, thus realize the efficient recovery of original solution chlorion; Dechlorinator's vacuum tightness is-0.090 ~-0.095MPa, Chlorine Cooler temperature out is 38-42 DEG C, and Nash pump top hole pressure is 0.13-0.16MPa, preferred dechlorinator's vacuum tightness :-0.093MPa, Chlorine Cooler temperature out is 40 DEG C, and Nash pump top hole pressure is 0.15MPa; Two sections of process for cooling comprise 4) by step 2) in the cupric oxide powder that obtains by removing magnetic oxide impurity after simple magnetic separation, then carry out with sulfuric acid dissolving the copper-bath obtaining copper ions concentration 40-60 g/L;
5) copper-bath obtained in step 4) is directly entered cyclone electrolytic cell system and produce electro deposited copper product, at current density 600-700A/m
2, electrolysis cycle amount is selective extraction under 500 ~ 600L/h condition, obtaining Chemical Composition, to reach the high-quality copper products of 1# copper and copper ion concentration be liquid after the eddy flow electrodeposition that the copper ions of 8-12g/L is low; Preferred current density 640-660A/m
2, electrolysis cycle amount is 550-580L/h;
6) after step 5) being obtained the low eddy flow electrodeposition of copper ions, liquid turns back to step poly-4) in, serve as sulfuric acid and obtain copper-bath for leaching cupric oxide powder, thus realize the acidic high efficiente callback utilization of electrolytic deposition process.
Get certain cupric chloride spent etching solution, measure its concrete chemical composition as follows:
| Composition | Cu 2+(g.L -1) | Cl +(g.L -1) | PH value |
| Acidic etching waste liquid | 63.40 | 70.80 | 0.82 |
| Alkaline etching waste liquid for producing | 52.12 | 52.12 | 9.10 |
Embodiment 1
1) get above-mentioned acidic etching waste liquid 5L to carry out with alkaline etching waste liquid for producing 1L mixing (this ratio and two kinds of etching waste liquors are suitable on the market at present), being uniformly mixed rear pH value is probably 1.2;
2) mix etching solution to carry out being concentrated into the Cupric Chloride Solution close to saturated, its content is cupric ion 336g/L, chlorion 875g/L;
3) Cupric Chloride Solution after concentrating enters spray pyrolysis unit by peristaltic pump, and this device comprises carrier gas device, ultrasonic atomizing device, tubular oven and collection device four parts, and carrier gas device adopts pressurized air as carrier gas; Ultrasonic atomizing device is equipped with the ultrasonic transduction sheet that 6 frequencies are 1. 75MHz; Crystal reaction tube (caliber 55 mm, long 1000 mm), controlling temperature in silica tube is 800 DEG C; Spray droplet is approximately about 0.6s by the time of whole silica tube, peristaltic pump pusher intensity 2MPa;
The detailed process of spray pyrolysis: the above-mentioned high density Cupric Chloride Solution concentrated is added in ultrasonic atomizing device, and keep its liquid level at 50% of device height, to ensure best nebulization efficiency, hot blast temperature 180 DEG C, hot blast flow velocity 220L/min, start ultrasonic atomizing device, solution forms the aerosol of a large amount of fine droplet composition through atomization, be fed through in the crystal reaction tube of tubular oven by air, tubular oven head temperature 800 DEG C, tubular oven rear end temperature 800 DEG C, compressed air pressure 70MPa, compressed air require is that 65/min is through pervaporation, dry, decompose, crude oxidation copper powder and chlorine is obtained after the processes such as crystallization reaction, the chlorine produced is delivered in dechlorinator and is adopted vacuum dechlorination method to obtain chlorine product, chlorine product introduction chlorine house steward delivers to Chlorine Cooler, two sections of process for cooling are adopted to cool, deliver to high purity hydrochloric acid unit after cooled chlorine Nash pump pressurization and obtain high-purity hydrochloric acid and clorox with time sodium unit, thus realize the efficient recovery of original solution chlorion, crude oxidation copper powder is collected by collection device, described dechlorinator's vacuum tightness is-0.090MPa, Chlorine Cooler temperature out is 42 DEG C, Nash pump top hole pressure is 0.13MPa,
4) crude oxidation copper powder is by the classification of high-intensity magnetic separator to wherein magnetic and nonmagnetic oxide, and removing magnetic oxide, as impurity such as Z 250s, obtains cupric oxide;
5) cupric oxide obtained carries out dissolving through sulfuric acid and obtains the copper-bath that content of copper ion is about 50g/L;
6) copper-bath enters swirl electrolysis device and carries out electrodeposition, current density 650A/m
2, solution circulated amount 500L/h carries out selectivity electrodeposition and obtains electro deposited copper product, reaches the requirement of 1# copper Chemical Composition after product analysis.
Embodiment 2
1) get above-mentioned acidic etching waste liquid 4L to mix with alkaline etching waste liquid for producing 2L;
2) mix etching solution to concentrate, be concentrated into the saturated solution close to cupric chloride, its content is cupric ion 328g/L, chlorion 869g/L;
3) Cupric Chloride Solution after concentrating enters spray pyrolysis unit by peristaltic pump, and this device comprises carrier gas device, ultrasonic atomizing device, tubular oven and collection device four parts, and carrier gas device adopts pressurized air as carrier gas; Ultrasonic atomizing device is equipped with the ultrasonic transduction sheet that 6 frequencies are 1. 75MHz; Crystal reaction tube (caliber 55 mm, long 1000 mm), controlling temperature in silica tube is 800 DEG C; Spray droplet is approximately about 0.6s by the time of whole silica tube, peristaltic pump pusher intensity 1.5MPa;
The detailed process of spray pyrolysis: the above-mentioned high density Cupric Chloride Solution concentrated is added in ultrasonic atomizing device, and keep its liquid level at 2/3rds of device height, to ensure best nebulization efficiency, hot blast temperature 220 DEG C, hot blast flow velocity 180L/min, start ultrasonic atomizing device, solution forms the aerosol of a large amount of fine droplet composition through atomization, be fed through in the crystal reaction tube of tubular oven by air, tubular oven head temperature 700 DEG C, tubular oven rear end temperature 700 DEG C, compressed air pressure 50MPa, compressed air require is that 75/min is through pervaporation, dry, decompose, crude oxidation copper powder and chlorine is obtained after the processes such as crystallization reaction, the chlorine produced is delivered in dechlorinator and is adopted vacuum dechlorination method to obtain chlorine product, chlorine product introduction chlorine house steward delivers to Chlorine Cooler, two sections of process for cooling are adopted to cool, deliver to high purity hydrochloric acid unit after cooled chlorine Nash pump pressurization and obtain high-purity hydrochloric acid and clorox with time sodium unit, thus realize the efficient recovery of original solution chlorion, crude oxidation copper powder is collected by collection device, described dechlorinator's vacuum tightness is-0.095MPa, Chlorine Cooler temperature out is 38 DEG C, Nash pump top hole pressure is 0.16MPa,
4) crude oxidation copper powder is by the classification of high-intensity magnetic separator to magnetic in metal oxide and nonmagnetic oxide, and removing magnetic oxide impurity, obtains cupric oxide;
5) cupric oxide obtained carries out dissolving through sulfuric acid and obtains the copper-bath that content of copper ion is 40g/L;
6) copper-bath enters swirl electrolysis device and carries out electrodeposition, controls current density 600A/m
2, solution circulated amount 600L/h, obtains liquid after cathode copper product and electrodeposition, reaches the requirement of 1# copper Chemical Composition after cathode copper product analysis after continuous electrodeposition, and after electrodeposition, liquid continues to dissolve rough cupric oxide powder as sulphuric acid soln.
Embodiment 3
1) get above-mentioned acidic etching waste liquid 6L to mix;
2) mix etching solution to concentrate, be concentrated into the saturated solution close to cupric chloride, its content is cupric ion 350g/L, chlorion 950g/L;
3) Cupric Chloride Solution after concentrating enters spray pyrolysis unit by peristaltic pump, and this device comprises carrier gas device, ultrasonic atomizing device, tubular oven and collection device four parts, and carrier gas device adopts pressurized air as carrier gas; Ultrasonic atomizing device is equipped with the ultrasonic transduction sheet that 6 frequencies are 1. 75MHz; Crystal reaction tube (caliber 55 mm, long 1000 mm), controlling temperature in silica tube is 785 DEG C; Spray droplet is approximately about 0.6s by the time of whole silica tube, peristaltic pump pusher intensity 2.5MPa;
The detailed process of spray pyrolysis: the above-mentioned high density Cupric Chloride Solution concentrated is added in ultrasonic atomizing device, and keep its liquid level device height 3/4ths, to ensure best nebulization efficiency, hot blast temperature 200 DEG C, hot blast flow velocity 200L/min, start ultrasonic atomizing device, solution forms the aerosol of a large amount of fine droplet composition through atomization, be fed through in the crystal reaction tube of tubular oven by air, tubular oven head temperature 785 DEG C, tubular oven rear end temperature 785 DEG C, compressed air pressure 62MPa, compressed air require is that 68/min is through pervaporation, dry, decompose, crude oxidation copper powder and chlorine is obtained after the processes such as crystallization reaction, the chlorine produced is delivered in dechlorinator and is adopted vacuum dechlorination method to obtain chlorine product, chlorine product introduction chlorine house steward delivers to Chlorine Cooler, two sections of process for cooling are adopted to cool, deliver to high purity hydrochloric acid unit after cooled chlorine Nash pump pressurization and obtain high-purity hydrochloric acid and clorox with time sodium unit, thus realize the efficient recovery of original solution chlorion, crude oxidation copper powder is collected by collection device, described dechlorinator's vacuum tightness is-0.094MPa, Chlorine Cooler temperature out is 40 DEG C, Nash pump top hole pressure is 0.12MPa,
4) crude oxidation copper powder is by the classification of high-intensity magnetic separator to magnetic in metal oxide and nonmagnetic oxide, and removing magnetic oxide impurity, obtains cupric oxide;
5) cupric oxide obtained carries out dissolving through sulfuric acid and obtains the copper-bath that content of copper ion is 40g/L;
6) copper-bath enters swirl electrolysis device and carries out electrodeposition, controls current density 650A/m
2, solution circulated amount 550L/h, obtains liquid after cathode copper product and electrodeposition, reaches the requirement of 1# copper Chemical Composition after cathode copper product analysis after continuous electrodeposition, and after electrodeposition, liquid continues to dissolve rough cupric oxide powder as sulphuric acid soln.
Embodiment 4
1) get above-mentioned alkaline etching waste liquid for producing 6L to mix;
2) mix etching solution to concentrate, be concentrated into the saturated solution close to cupric chloride, its content is cupric ion 300g/L, chlorion 800g/L;
3) Cupric Chloride Solution after concentrating enters spray pyrolysis unit by peristaltic pump, and this device comprises carrier gas device, ultrasonic atomizing device, tubular oven and collection device four parts, and carrier gas device adopts pressurized air as carrier gas; Ultrasonic atomizing device is equipped with the ultrasonic transduction sheet that 6 frequencies are 1. 75MHz; Crystal reaction tube (caliber 55 mm, long 1000 mm), controlling temperature in silica tube is 900 DEG C; Spray droplet is approximately about 0.6s by the time of whole silica tube, peristaltic pump pusher intensity 2.5MPa;
The detailed process of spray pyrolysis: the above-mentioned high density Cupric Chloride Solution concentrated is added in ultrasonic atomizing device, and keep its liquid level at 50% of device height, to ensure best nebulization efficiency, hot blast temperature 200 DEG C, hot blast flow velocity 200L/min, start ultrasonic atomizing device, solution forms the aerosol of a large amount of fine droplet composition through atomization, be fed through in the crystal reaction tube of tubular oven by air, tubular oven head temperature 900 DEG C, tubular oven rear end temperature 900 DEG C, compressed air pressure 60MPa, compressed air require is that 70/min is through pervaporation, dry, decompose, crude oxidation copper powder and chlorine is obtained after the processes such as crystallization reaction, the chlorine produced is delivered in dechlorinator and is adopted vacuum dechlorination method to obtain chlorine product, chlorine product introduction chlorine house steward delivers to Chlorine Cooler, two sections of process for cooling are adopted to cool, deliver to high purity hydrochloric acid unit after cooled chlorine Nash pump pressurization and obtain high-purity hydrochloric acid and clorox with time sodium unit, thus realize the efficient recovery of original solution chlorion, crude oxidation copper powder is collected by collection device, described dechlorinator's vacuum tightness is-0.092MPa, Chlorine Cooler temperature out is 39 DEG C, Nash pump top hole pressure is 0.14MPa,
4) crude oxidation copper powder is by the classification of high-intensity magnetic separator to magnetic in metal oxide and nonmagnetic oxide, and removing magnetic oxide impurity, obtains cupric oxide;
5) cupric oxide obtained carries out dissolving through sulfuric acid and obtains the copper-bath that content of copper ion is 50g/L;
6) copper-bath enters swirl electrolysis device and carries out electrodeposition, controls current density 660A/m
2, solution circulated amount 580L/h, obtains liquid after cathode copper product and electrodeposition, reaches the requirement of 1# copper Chemical Composition after cathode copper product analysis after continuous electrodeposition, and after electrodeposition, liquid continues to dissolve rough cupric oxide powder as sulphuric acid soln.
Claims (7)
1. a mixed chlorinated copper spent etching solution synthetical recovery treatment process, is characterized in that comprising the following steps:
1) carry out evaporation concentration to acid copper chloride etching liquid, alkaline copper chloride etching solution or both mixed solutions and obtain high density Cupric Chloride Solution, wherein copper ion concentration is 250-350 g/L, and chlorion is 800-950 g/L;
2) by peristaltic pump, spray pyrolysis unit is added to the high density Cupric Chloride Solution obtained in step 1) and carry out spray pyrolysis, by this solution spray in the high-temperature atmosphere of 700-900 DEG C of tubular oven, solution evaporation, Cupric Chloride Solution generation pyrolysis simultaneously, obtain crude oxidation copper powder and chlorine, Cupric Chloride Solution after concentrated carries out spray pyrolysis condition and is: hot blast temperature 180-220 DEG C, hot blast flow velocity 180-220L/min, compressed air pressure 50-70MPa, compressed air require is 65-75L/min, tubular oven head temperature 700-900 DEG C, tubular oven rear end temperature 700-900 DEG C, peristaltic pump pusher intensity 1.5-2.5MPa,
3) by step 2) chlorine that produces of pyrolytic process delivers in dechlorinator and adopts vacuum dechlorination method to obtain chlorine product, chlorine product introduction chlorine house steward delivers to Chlorine Cooler, two sections of process for cooling are adopted to cool, deliver to high purity hydrochloric acid unit after cooled chlorine Nash pump pressurization and obtain high-purity hydrochloric acid and clorox with time sodium unit, thus realize the efficient recovery of original solution chlorion, described dechlorinator's vacuum tightness is-0.090 ~-0.095MPa, Chlorine Cooler temperature out is 38-42 DEG C, and Nash pump top hole pressure is 0.13-0.16MPa;
4) by step 2) in the crude oxidation copper powder that obtains by removing magnetic oxide impurity after simple magnetic separation, then carry out with sulfuric acid dissolving the copper-bath obtaining copper ions concentration 40-60g/L;
5) copper-bath obtained in step 4) is directly entered cyclone electrolytic cell system and produce electro deposited copper product, at current density 600-700A/m
2, electrolysis cycle amount is selective extraction under 500 ~ 600L/h condition, obtain Chemical Composition and reach liquid after the high-quality copper products of 1# copper and the low eddy flow electrodeposition of copper ions;
6) after step 5) being obtained the low eddy flow electrodeposition of copper ions, liquid turns back to step poly-4) in, serve as sulfuric acid and obtain copper-bath for leaching crude oxidation copper powder, thus realize the acidic high efficiente callback utilization of electrolytic deposition process.
2. one according to claim 1 mixed chlorinated copper spent etching solution synthetical recovery treatment process, it is characterized in that in the high density Cupric Chloride Solution described in step 1), content of copper ion is 300-350g/L, chloride ion content is 900-950g/L.
3. one according to claim 1 mixed chlorinated copper spent etching solution synthetical recovery treatment process, it is characterized in that walking poly-2) in concentrated after Cupric Chloride Solution carry out spray pyrolysis condition and be: hot blast temperature 200 DEG C, hot blast flow velocity 200L/min, compressed air pressure 60MPa, compressed air require: 65-75L/min, tubular oven head temperature 800 DEG C, tubular oven rear end temperature 800 DEG C, peristaltic pump pusher intensity 2MPa.
4. one according to claim 1 mixed chlorinated copper spent etching solution synthetical recovery treatment process, is characterized in that walking poly-3) described in dechlorinator's vacuum tightness :-0.093MPa, Chlorine Cooler temperature out is 40 DEG C, and Nash pump top hole pressure is 0.15MPa.
5. one according to claim 1 mixed chlorinated copper spent etching solution synthetical recovery treatment process, it is characterized in that walking poly-3) two sections of process for cooling comprise directly cooling and indirect process for cooling, the direct spraying cooling of direct cooling chlorine water, chlorine water is closed cycle; Indirectly be cooled to and indirectly cool with recirculated water.
6. one according to claim 1 mixed chlorinated copper spent etching solution synthetical recovery treatment process, is characterized in that the electrolytic condition described in step 5) is: current density 640-660A/m
2, electrolysis cycle amount is 550-580L/h.
7. one according to claim 1 mixed chlorinated copper spent etching solution synthetical recovery treatment process, is characterized in that in liquid, copper ion concentration is 8-12g/L after the eddy flow electrodeposition that copper ions described in step 5) is low.
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| CN110042425A (en) * | 2019-04-23 | 2019-07-23 | 博罗县华盈科技有限公司 | A kind of heavy process for copper of alkaline etching waste liquid for producing direct electrowinning |
| CN111635042A (en) * | 2020-06-29 | 2020-09-08 | 江苏净拓环保科技有限公司 | Copper is metal copper recovery unit for waste water purification treatment |
| CN112553626A (en) * | 2020-11-23 | 2021-03-26 | 无锡市双龙电梯配套有限公司 | Preparation process of elevator etching plate |
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