CN103556152A - Comprehensive recovery processing method for waste hybrid copper chloride etching liquid - Google Patents
Comprehensive recovery processing method for waste hybrid copper chloride etching liquid Download PDFInfo
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- 238000005530 etching Methods 0.000 title claims abstract description 64
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 title claims abstract description 45
- 239000007788 liquid Substances 0.000 title claims abstract description 39
- 238000011084 recovery Methods 0.000 title claims abstract description 38
- 239000002699 waste material Substances 0.000 title abstract description 17
- 238000003672 processing method Methods 0.000 title abstract 2
- 238000000034 method Methods 0.000 claims abstract description 76
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000000460 chlorine Substances 0.000 claims abstract description 71
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 70
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 69
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000010949 copper Substances 0.000 claims abstract description 42
- 229910052802 copper Inorganic materials 0.000 claims abstract description 41
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 31
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000000843 powder Substances 0.000 claims abstract description 29
- 238000005118 spray pyrolysis Methods 0.000 claims abstract description 28
- 238000004070 electrodeposition Methods 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 13
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 12
- 230000002378 acidificating effect Effects 0.000 claims abstract description 9
- 238000002386 leaching Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 95
- 229960004643 cupric oxide Drugs 0.000 claims description 36
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 32
- 238000001816 cooling Methods 0.000 claims description 32
- 150000001879 copper Chemical class 0.000 claims description 23
- 229910001431 copper ion Inorganic materials 0.000 claims description 23
- 241000370738 Chlorion Species 0.000 claims description 18
- 230000002572 peristaltic effect Effects 0.000 claims description 17
- 229960003280 cupric chloride Drugs 0.000 claims description 16
- 238000005660 chlorination reaction Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- UCNNJGDEJXIUCC-UHFFFAOYSA-L hydroxy(oxo)iron;iron Chemical compound [Fe].O[Fe]=O.O[Fe]=O UCNNJGDEJXIUCC-UHFFFAOYSA-L 0.000 claims description 8
- 239000007921 spray Substances 0.000 claims description 8
- 238000006298 dechlorination reaction Methods 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims description 7
- 230000008020 evaporation Effects 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 7
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
- 238000005137 deposition process Methods 0.000 claims description 3
- 238000007885 magnetic separation Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000000197 pyrolysis Methods 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 239000002184 metal Substances 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 229910000365 copper sulfate Inorganic materials 0.000 abstract description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 abstract description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000005751 Copper oxide Substances 0.000 abstract 2
- 239000002131 composite material Substances 0.000 abstract 2
- 229910000431 copper oxide Inorganic materials 0.000 abstract 2
- -1 chlorine ions Chemical class 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000012159 carrier gas Substances 0.000 description 15
- 238000005516 engineering process Methods 0.000 description 12
- 239000013078 crystal Substances 0.000 description 10
- 239000000377 silicon dioxide Substances 0.000 description 10
- 239000000443 aerosol Substances 0.000 description 5
- 238000000889 atomisation Methods 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 238000002663 nebulization Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 230000026683 transduction Effects 0.000 description 5
- 238000010361 transduction Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 238000013459 approach Methods 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000006246 high-intensity magnetic separator Substances 0.000 description 4
- 238000005373 pervaporation Methods 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000012047 saturated solution Substances 0.000 description 3
- 239000001117 sulphuric acid Substances 0.000 description 3
- 235000011149 sulphuric acid Nutrition 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- ALKZAGKDWUSJED-UHFFFAOYSA-N dinuclear copper ion Chemical class [Cu].[Cu] ALKZAGKDWUSJED-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 208000001491 myopia Diseases 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010187 selection method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- ing And Chemical Polishing (AREA)
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Abstract
The invention discloses a comprehensive recovery processing method for waste hybrid copper chloride etching liquid, which belongs to the field of non-ferrous metal and metallurgical valuable metal recover. The technological process of the method mainly comprises the following steps: (1) concentrating copper chloride etching liquid; (2) carrying out spray pyrolysis on a concentrated copper chloride solution so as to form copper oxide composite powder; (3) recovering chlorine so as to prepare a refined hydrochloric acid; (4) leaching the copper oxide composite powder by using a sulfuric acid; and (5) carrying out selective electrodeposition on copper sulfate leaching liquid by using a rotational flow electrolysis system so as to obtain a cathode copper product which of chemical compositions reach 1# copper product standards. The method disclosed by the invention is simple in process, short in flow, environment-friendly, and simple and feasible in operation, can effectively implement the comprehensive recovery of acidic and alkaline copper chloride etching liquid and the direct production of high-quality copper products, and effectively converts chlorine ions in waste liquid into refined hydrochloric acid products, thereby achieving the efficient and comprehensive utilization of resources.
Description
Technical field
The invention belongs to non-ferrous metal hydrometallurgy valuable metal recovery technical field, be specifically related to the comprehensive recovery and treatment method of a kind of mixed chlorinated copper spent etching solution.
Background technology
In recent years, brass work industry the develop rapidly generation that brought a large amount of contained waste liquids.In this simultaneously, country grows with each passing day to environmental requirement, and therefore, the processing of copper-bearing waste material and discharge have become a great problem of enterprise.Technically, the removal of free state bivalent cupric ion is comparative maturity, and after processing, in solution, the mass concentration of remaining copper ion can drop to below 1mg/L.Yet in the industry copper-containing wastewaters such as dyestuff, plating, circuit card (PCB), cupric ion often exists with complex pattern, wherein the most representative with the spent etching solution in PCB industry.In spent etching solution, contain a large amount of resources, more than spent etching solution cupric 120kg per ton, more than muriate 250kg, more than ammonia 80kg, and contain 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 environmental safety, economy and the social Sustainable development of factory surrounding area.
At present, the treatment process of spent etching solution mainly concentrates on two kinds of technology, processes copper sulfate technology and circulation and regeneration technology, other new technologies all take these two kinds of technology as basis develop.Its know-why of processing copper sulfate technology is: with the cupric ion in precipitation agent precipitation waste liquid, then with the mantoquita precipitating and sulfuric acid reaction, produce copper sulfate, 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 after precipitation is still higher simultaneously, need just to reach discharging standards after further decopper(ing), thus this kind of method be a kind ofly sacrifice future gains to satisfy present needs, shortsighted part resource reclaims, and large to environmental hazard.The spent etching solution of the main ShiPCB of circulation and regeneration technology factory etching work procedure output is raw material, obtain after treatment qualified etching solution and solid metal copper, the etching solution of this regeneration is back to PCB etching work procedure again, thereby forms circulation loop, is a kind of good method.But the method has strong requirement to spent etching solution itself, for a large amount of various channels form spent etching solution, PCB spent etching solution is one of them part.Therefore, circulation and regeneration technology has its significant limitation.
The invention provides the comprehensive recovery and treatment method of a kind of mixed chlorinated copper spent etching solution, mixed chlorinated copper spent etching solution reclaims the technical process such as copper by the choice of technology of evaporation concentration+spray pyrolysis+sulfuric acid dissolution+cyclone electrolytic cell, not only the cupric ion efficient recovery in the cupric chloride spent etching solution of various complexity is become to Chemical Composition and arrive 1# electro deposited copper product, and make the chlorion in solution fully recycle Chemicals such as making chlorine or refining hydrochloric acid.This method technique is simple, flow process is short, environment is good, the rate of recovery is high, has increased the economic benefit of enterprise, has realized the high efficiente callback of resource simultaneously, also meets the principle of recycling economy.
Summary of the invention
The object of the invention is the deficiency existing for prior art, provide that a kind of technique is simple, flow process is short, environment is good, with low cost, can effectively extract selective separation and the efficient recycling method of mixed chlorinated copper copper from waste etching solution and chlorion.
The described comprehensive recovery and treatment method of a kind of mixed chlorinated copper spent etching solution, is characterized in that comprising the following steps:
Acid copper chloride etching liquid, alkaline copper chloride etching solution or both mixed solutions are carried out to evaporation concentration and obtain high density chlorination copper solutions, wherein copper ion concentration is 250-350g/L, and chlorion is 800-950g/L;
2) to the high density chlorination copper solutions obtaining in step 1), by peristaltic pump, add spray pyrolysis unit to carry out spray pyrolysis, by this solution spray to the high-temperature atmosphere of 700-900 ℃ of tubular oven, solution evaporation, Cupric Chloride Solution generation pyrolysis simultaneously, obtains rough cupric oxide powder and chlorine; When this method requires spray pyrolysis, droplet can not complete drying process before reaching tubular oven wall, so product is generally trickle particle;
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, adopt two sections of process for cooling to carry out cooling, cooled chlorine obtains high-purity hydrochloric acid and clorox with delivering to He Cina unit, high purity hydrochloric acid unit after Nash pump pressurization, thereby realizes the efficient recovery of original solution chlorion;
4) by step 2) in the cupric oxide powder that obtains remove magnetic oxide impurity after by simple magnetic separation, then dissolve with sulfuric acid the copper-bath that obtains copper ions concentration 40-60 g/L;
5) copper-bath obtaining in step 4) is directly entered to 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) step 5) is obtained to eddy flow electrodeposition that copper ions is low after liquid turn back to step poly-4) in, serve as sulfuric acid and obtain copper-bath for leaching rough cupric oxide powder, thereby realize the acidic high efficiente callback utilization of electrolytic deposition process.
The described comprehensive recovery and treatment method of a kind of mixed chlorinated copper spent etching solution, is characterized in that in the high density chlorination copper solutions described in step 1), content of copper ion is 300-350g/L, and chloride ion content is 900-950g/L.
The described comprehensive recovery and treatment method of a kind of mixed chlorinated copper spent etching solution, it is characterized in that step poly-2) in Cupric Chloride Solution after concentrated carry out spray pyrolysis condition and be: hot blast temperature 180-220 ℃, hot blast flow velocity 180-220L/min, compressed air pressure 50-70MPa, compressed air require is 65-75L/min, tubular oven front end temperature 700-900 ℃, tubular oven rear end temperature 700-900 ℃, peristaltic pump pusher intensity 1.5-2.5MPa.
The described comprehensive recovery and treatment method of a kind of mixed chlorinated copper spent etching solution, it is characterized in that step poly-2) in Cupric Chloride Solution after concentrated carry out spray pyrolysis condition and be: 200 ℃ of hot blast temperatures, hot blast flow velocity 200L/min, compressed air pressure 60MPa, compressed air require: 65-75L/min, 800 ℃ of tubular oven front end temperature, 800 ℃ of tubular oven rear end temperature, peristaltic pump pusher intensity 2MPa.
The described comprehensive recovery and treatment method of a kind of mixed chlorinated copper spent etching solution, is characterized in that step poly-3) described dechlorinator's vacuum tightness is-0.090～-0.095MPa, and Chlorine Cooler temperature out is 38-42 ℃, and Nash pump top hole pressure is 0.13-0.16MPa.
The described comprehensive recovery and treatment method of a kind of mixed chlorinated copper spent etching solution, is characterized in that step poly-3) described dechlorinator's vacuum tightness :-0.093MPa, Chlorine Cooler temperature out is 40 ℃, Nash pump top hole pressure is 0.15MPa.
The described comprehensive recovery and treatment method of a kind of mixed chlorinated copper spent etching solution, is characterized in that step poly-3) two sections of process for cooling comprise directly cooling and indirect process for cooling, direct cooling with the direct spraying cooling of chlorine water, chlorine water is closed cycle; Indirectly be cooled to recirculated water indirectly cooling.
The described comprehensive recovery and treatment method of a kind of mixed chlorinated copper spent etching solution, 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 comprehensive recovery and treatment method of mixed chlorinated copper spent etching solution providing of the present invention, reasonable in design, compared with prior art, there is following beneficial effect:
(1) technological operation of the present invention is simple, flow process is short, cost is low, environmental friendliness;
(2) the present invention is thoroughly separated with chlorion moment realization under hot conditions by cupric ion in solution by the method for spray pyrolysis, copper with the isolated in form of cupric oxide out, chlorion is combined into chlorine and enters comprehensive recovery system, the rate of recovery is high, and directly enters next unit utilization;
(3) the present invention carries out separation by the magnetic oxide in spray pyrolysis cupric oxide powder out as Z 250, nickel oxide etc. by magnetic selection method, realized the selective separation of copper and iron, nickel etc., separation efficiency more than 95%, is conducive to the extraction to copper below, 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 reach more than 99%, and purity is high, reach the requirement that Chemical Composition reaches 1# copper, remarkable in economical benefits;
(5) mode of the present invention by spray pyrolysis realized effective separation of chlorion etc. in mixed chlorinated copper spent etching solution and made chlorine or the Chemicals such as refining hydrochloric acid, produced 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:
The comprehensive recovery and treatment method of copper spent etching solution, concrete grammar is as follows:
1) get a certain amount of acid copper chloride etching liquid/alkaline copper chloride etching solution or both mixed solutions carry out evaporation concentration, after concentrated, copper ion concentration reaches 250-350g/L, chloride ion content reaches the saturated Cupric Chloride Solution of approaching of 900-950g/L, preferably copper ion content is 300-350g/L, and chloride ion content is 900-950g/L;
2) to the high density chlorination copper solutions obtaining in step 1), by peristaltic pump, add spray pyrolysis unit to carry out spray pyrolysis, by this solution spray to the high-temperature atmosphere of 600-800 ℃ of tubular oven, solution evaporation, Cupric Chloride Solution generation pyrolysis simultaneously, obtains cupric oxide powder and chlorine; When this method requires spray pyrolysis, droplet can not complete drying process before reaching tubular oven wall, so product is generally trickle particle powder; Wherein spray pyrolysis condition is: hot blast temperature 180-220 ℃, hot blast flow velocity 180-220L/min, compressed air pressure 50-70MPa, compressed air require is 65-75L/min, tubular oven front end temperature 700-900 ℃, tubular oven rear end temperature 700-900 ℃, peristaltic pump pusher intensity 1.5-2.5MPa; 200 ℃ of preferred hot blast temperatures, hot blast flow velocity 200L/min, compressed air pressure 60MPa, compressed air require: 65-75L/min, 800 ℃ of tubular oven front end temperature, 800 ℃ of tubular oven rear end temperature, peristaltic pump pusher intensity 2MPa;
Spray pyrolysis unit in this step, comprises carrier gas device, ultrasonic atomizing device, tubular oven and four parts of collection device, adopts pressurized air as carrier gas, and 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 ℃; Spray droplet is approximately 0.6 s left and right by the time of whole silica tube;
Specific operation process is as follows: the above-mentioned high density chlorination copper solutions preparing is added in ultrasonic atomizing device, and keep its liquid level at certain position, to guarantee best nebulization efficiency, open air and keep certain flow rate, start ultrasonic atomizing device, solution forms through atomization the aerosol that a large amount of fine droplets form, and by air, is fed through in crystal reaction tube, evaporates, is dried, obtains cupric oxide powder after the process such as decomposition, 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, adopt directly cooling and indirect cooling two sections of process for cooling to carry out cooling, directly cooling with the direct spraying cooling of chlorine water, chlorine water is closed cycle; Indirectly be cooled to recirculated water indirectly cooling; Cooled chlorine obtains high-purity hydrochloric acid and clorox with delivering to He Cina unit, high purity hydrochloric acid unit after Nash pump pressurization, thereby realizes the efficient recovery of original solution chlorion; Dechlorinator's vacuum tightness is-0.090～-0.095MPa, Chlorine Cooler temperature out is 38-42 ℃, and Nash pump top hole pressure is 0.13-0.16MPa, preferred dechlorinator's vacuum tightness :-0.093MPa, Chlorine Cooler temperature out is 40 ℃, 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 remove magnetic oxide impurity after by simple magnetic separation, then dissolve with sulfuric acid the copper-bath that obtains copper ions concentration 40-60 g/L;
5) copper-bath obtaining in step 4) is directly entered to 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 that copper ion concentration is 8-12g/L; Preferred current density 640-660A/m
2, electrolysis cycle amount is 550-580L/h;
6) step 5) is obtained to eddy flow electrodeposition that copper ions is low after liquid turn back to step poly-4) in, serve as sulfuric acid and obtain copper-bath for leaching cupric oxide powder, thereby 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 and mix (this ratio and two kinds of etching waste liquors are suitable on the market at present) with alkaline etching waste liquid for producing 1L, being uniformly mixed rear pH value is probably 1.2;
2) mixing etching solution is concentrated into and approaches saturated Cupric Chloride Solution, and its content is cupric ion 336g/L, chlorion 875g/L;
3) Cupric Chloride Solution after concentrated enters spray pyrolysis unit by peristaltic pump, and this device comprises carrier gas device, ultrasonic atomizing device, tubular oven and four parts of collection device, 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 ℃; Spray droplet is approximately 0.6s left and right, peristaltic pump pusher intensity 2MPa by the time of whole silica tube;
The detailed process of spray pyrolysis: the above-mentioned high density chlorination copper solutions having concentrated is added in ultrasonic atomizing device, and keep its liquid level at 50% of device height, to guarantee best nebulization efficiency, 180 ℃ of hot blast temperatures, hot blast flow velocity 220L/min, start ultrasonic atomizing device, solution forms through atomization the aerosol that a large amount of fine droplets form, in the crystal reaction tube that is fed through tubular oven by air, 800 ℃ of tubular oven front end temperature, 800 ℃ of tubular oven rear end temperature, compressed air pressure 70MPa, compressed air require is that 65/min is through pervaporation, dry, decompose, after the processes such as crystallization reaction, obtain rough cupric oxide powder and chlorine, the chlorine producing is delivered in dechlorinator and is adopted vacuum dechlorination method to obtain chlorine product, chlorine product introduction chlorine house steward delivers to Chlorine Cooler, adopt two sections of process for cooling to carry out cooling, cooled chlorine obtains high-purity hydrochloric acid and clorox with delivering to He Cina unit, high purity hydrochloric acid unit after Nash pump pressurization, thereby realize the efficient recovery of original solution chlorion, rough cupric oxide powder is collected by collection device, described dechlorinator's vacuum tightness is-0.090MPa, Chlorine Cooler temperature out is 42 ℃, Nash pump top hole pressure is 0.13MPa,
4) rough cupric oxide powder, by high-intensity magnetic separator to the wherein classification of magnetic and nonmagnetic oxide, is removed magnetic oxide, as impurity such as Z 250s, obtains cupric oxide;
5) cupric oxide obtaining dissolves and obtains the copper-bath that content of copper ion is 50g/L left and right through sulfuric acid;
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) getting above-mentioned acidic etching waste liquid 4L mixes with alkaline etching waste liquid for producing 2L;
2) mix etching solution and concentrate, be concentrated into the saturated solution that approaches cupric chloride, its content is cupric ion 328g/L, chlorion 869g/L;
3) Cupric Chloride Solution after concentrated enters spray pyrolysis unit by peristaltic pump, and this device comprises carrier gas device, ultrasonic atomizing device, tubular oven and four parts of collection device, 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 ℃; Spray droplet is approximately 0.6s left and right, peristaltic pump pusher intensity 1.5MPa by the time of whole silica tube;
The detailed process of spray pyrolysis: the above-mentioned high density chlorination copper solutions having concentrated is added in ultrasonic atomizing device, and keep its liquid level at 2/3rds of device height, to guarantee best nebulization efficiency, 220 ℃ of hot blast temperatures, hot blast flow velocity 180L/min, start ultrasonic atomizing device, solution forms through atomization the aerosol that a large amount of fine droplets form, in the crystal reaction tube that is fed through tubular oven by air, 700 ℃ of tubular oven front end temperature, 700 ℃ of tubular oven rear end temperature, compressed air pressure 50MPa, compressed air require is that 75/min is through pervaporation, dry, decompose, after the processes such as crystallization reaction, obtain rough cupric oxide powder and chlorine, the chlorine producing is delivered in dechlorinator and is adopted vacuum dechlorination method to obtain chlorine product, chlorine product introduction chlorine house steward delivers to Chlorine Cooler, adopt two sections of process for cooling to carry out cooling, cooled chlorine obtains high-purity hydrochloric acid and clorox with delivering to He Cina unit, high purity hydrochloric acid unit after Nash pump pressurization, thereby realize the efficient recovery of original solution chlorion, rough cupric oxide powder is collected by collection device, described dechlorinator's vacuum tightness is-0.095MPa, Chlorine Cooler temperature out is 38 ℃, Nash pump top hole pressure is 0.16MPa,
4) rough cupric oxide powder classification to magnetic in metal oxide and nonmagnetic oxide by high-intensity magnetic separator, removes magnetic oxide impurity, obtains cupric oxide;
5) cupric oxide obtaining dissolves and obtains the copper-bath that content of copper ion is 40g/L through sulfuric acid;
6) copper-bath enters swirl electrolysis device and carries out electrodeposition, controls current density 600A/m
2, solution circulated amount 600L/h, after continuous electrodeposition, obtain cathode copper product and electrodeposition after liquid, after cathode copper product analysis, reach the requirement of 1# copper Chemical Composition, after electrodeposition, liquid continues to dissolve rough cupric oxide powder as sulphuric acid soln.
Embodiment 3
1) getting above-mentioned acidic etching waste liquid 6L mixes;
2) mix etching solution and concentrate, be concentrated into the saturated solution that approaches cupric chloride, its content is cupric ion 350g/L, chlorion 950g/L;
3) Cupric Chloride Solution after concentrated enters spray pyrolysis unit by peristaltic pump, and this device comprises carrier gas device, ultrasonic atomizing device, tubular oven and four parts of collection device, 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 ℃; Spray droplet is approximately 0.6s left and right, peristaltic pump pusher intensity 2.5MPa by the time of whole silica tube;
The detailed process of spray pyrolysis: the above-mentioned high density chlorination copper solutions having concentrated is added in ultrasonic atomizing device, and keep its liquid level device height 3/4ths, to guarantee best nebulization efficiency, 200 ℃ of hot blast temperatures, hot blast flow velocity 200L/min, start ultrasonic atomizing device, solution forms through atomization the aerosol that a large amount of fine droplets form, in the crystal reaction tube that is fed through tubular oven by air, 785 ℃ of tubular oven front end temperature, 785 ℃ of tubular oven rear end temperature, compressed air pressure 62MPa, compressed air require is that 68/min is through pervaporation, dry, decompose, after the processes such as crystallization reaction, obtain rough cupric oxide powder and chlorine, the chlorine producing is delivered in dechlorinator and is adopted vacuum dechlorination method to obtain chlorine product, chlorine product introduction chlorine house steward delivers to Chlorine Cooler, adopt two sections of process for cooling to carry out cooling, cooled chlorine obtains high-purity hydrochloric acid and clorox with delivering to He Cina unit, high purity hydrochloric acid unit after Nash pump pressurization, thereby realize the efficient recovery of original solution chlorion, rough cupric oxide powder is collected by collection device, described dechlorinator's vacuum tightness is-0.094MPa, Chlorine Cooler temperature out is 40 ℃, Nash pump top hole pressure is 0.12MPa,
4) rough cupric oxide powder classification to magnetic in metal oxide and nonmagnetic oxide by high-intensity magnetic separator, removes magnetic oxide impurity, obtains cupric oxide;
5) cupric oxide obtaining dissolves and obtains the copper-bath that content of copper ion is 40g/L through sulfuric acid;
6) copper-bath enters swirl electrolysis device and carries out electrodeposition, controls current density 650A/m
2, solution circulated amount 550L/h, after continuous electrodeposition, obtain cathode copper product and electrodeposition after liquid, after cathode copper product analysis, reach the requirement of 1# copper Chemical Composition, after electrodeposition, liquid continues to dissolve rough cupric oxide powder as sulphuric acid soln.
Embodiment 4
1) getting above-mentioned alkaline etching waste liquid for producing 6L mixes;
2) mix etching solution and concentrate, be concentrated into the saturated solution that approaches cupric chloride, its content is cupric ion 300g/L, chlorion 800g/L;
3) Cupric Chloride Solution after concentrated enters spray pyrolysis unit by peristaltic pump, and this device comprises carrier gas device, ultrasonic atomizing device, tubular oven and four parts of collection device, 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 ℃; Spray droplet is approximately 0.6s left and right, peristaltic pump pusher intensity 2.5MPa by the time of whole silica tube;
The detailed process of spray pyrolysis: the above-mentioned high density chlorination copper solutions having concentrated is added in ultrasonic atomizing device, and keep its liquid level at 50% of device height, to guarantee best nebulization efficiency, 200 ℃ of hot blast temperatures, hot blast flow velocity 200L/min, start ultrasonic atomizing device, solution forms through atomization the aerosol that a large amount of fine droplets form, in the crystal reaction tube that is fed through tubular oven by air, 900 ℃ of tubular oven front end temperature, 900 ℃ of tubular oven rear end temperature, compressed air pressure 60MPa, compressed air require is that 70/min is through pervaporation, dry, decompose, after the processes such as crystallization reaction, obtain rough cupric oxide powder and chlorine, the chlorine producing is delivered in dechlorinator and is adopted vacuum dechlorination method to obtain chlorine product, chlorine product introduction chlorine house steward delivers to Chlorine Cooler, adopt two sections of process for cooling to carry out cooling, cooled chlorine obtains high-purity hydrochloric acid and clorox with delivering to He Cina unit, high purity hydrochloric acid unit after Nash pump pressurization, thereby realize the efficient recovery of original solution chlorion, rough cupric oxide powder is collected by collection device, described dechlorinator's vacuum tightness is-0.092MPa, Chlorine Cooler temperature out is 39 ℃, Nash pump top hole pressure is 0.14MPa,
4) rough cupric oxide powder classification to magnetic in metal oxide and nonmagnetic oxide by high-intensity magnetic separator, removes magnetic oxide impurity, obtains cupric oxide;
5) cupric oxide obtaining dissolves and obtains the copper-bath that content of copper ion is 50g/L through sulfuric acid;
6) copper-bath enters swirl electrolysis device and carries out electrodeposition, controls current density 660A/m
2, solution circulated amount 580L/h, after continuous electrodeposition, obtain cathode copper product and electrodeposition after liquid, after cathode copper product analysis, reach the requirement of 1# copper Chemical Composition, after electrodeposition, liquid continues to dissolve rough cupric oxide powder as sulphuric acid soln.
Claims (9)
1. the comprehensive recovery and treatment method of mixed chlorinated copper spent etching solution, is characterized in that comprising the following steps:
1) acid copper chloride etching liquid, alkaline copper chloride etching solution or both mixed solutions are carried out to evaporation concentration and obtain high density chlorination copper solutions, wherein copper ion concentration is 250-350 g/L, and chlorion is 800-950 g/L;
2) to the high density chlorination copper solutions obtaining in step 1), by peristaltic pump, add spray pyrolysis unit to carry out spray pyrolysis, by this solution spray to the high-temperature atmosphere of 700-900 ℃ of tubular oven, solution evaporation, Cupric Chloride Solution generation pyrolysis simultaneously, obtains rough cupric oxide powder and chlorine;
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, adopt two sections of process for cooling to carry out cooling, cooled chlorine obtains high-purity hydrochloric acid and clorox with delivering to He Cina unit, high purity hydrochloric acid unit after Nash pump pressurization, thereby realizes the efficient recovery of original solution chlorion;
4) by step 2) in the rough cupric oxide powder that obtains remove magnetic oxide impurity after by simple magnetic separation, then dissolve with sulfuric acid the copper-bath that obtains copper ions concentration 40-60g/L;
5) copper-bath obtaining in step 4) is directly entered to 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) step 5) is obtained to eddy flow electrodeposition that copper ions is low after liquid turn back to step poly-4) in, serve as sulfuric acid and obtain copper-bath for leaching rough cupric oxide powder, thereby realize the acidic high efficiente callback utilization of electrolytic deposition process.
2. the comprehensive recovery and treatment method of a kind of mixed chlorinated copper spent etching solution according to claim 1, is characterized in that in the high density chlorination copper solutions described in step 1), content of copper ion is 300-350g/L, and chloride ion content is 900-950g/L.
3. the comprehensive recovery and treatment method of a kind of mixed chlorinated copper spent etching solution according to claim 1, it is characterized in that step poly-2) in Cupric Chloride Solution after concentrated carry out spray pyrolysis condition and be: hot blast temperature 180-220 ℃, hot blast flow velocity 180-220L/min, compressed air pressure 50-70MPa, compressed air require is 65-75L/min, tubular oven front end temperature 700-900 ℃, tubular oven rear end temperature 700-900 ℃, peristaltic pump pusher intensity 1.5-2.5MPa.
4. the comprehensive recovery and treatment method of a kind of mixed chlorinated copper spent etching solution according to claim 3, it is characterized in that step poly-2) in Cupric Chloride Solution after concentrated carry out spray pyrolysis condition and be: 200 ℃ of hot blast temperatures, hot blast flow velocity 200L/min, compressed air pressure 60MPa, compressed air require: 65-75L/min, 800 ℃ of tubular oven front end temperature, 800 ℃ of tubular oven rear end temperature, peristaltic pump pusher intensity 2MPa.
5. the comprehensive recovery and treatment method of a kind of mixed chlorinated copper spent etching solution according to claim 1, it is characterized in that step poly-3) described dechlorinator's vacuum tightness is-0.090～-0.095MPa, Chlorine Cooler temperature out is 38-42 ℃, and Nash pump top hole pressure is 0.13-0.16MPa.
6. the comprehensive recovery and treatment method of a kind of mixed chlorinated copper spent etching solution according to claim 5, is characterized in that step poly-3) described dechlorinator's vacuum tightness :-0.093MPa, Chlorine Cooler temperature out is 40 ℃, Nash pump top hole pressure is 0.15MPa.
7. the comprehensive recovery and treatment method of a kind of mixed chlorinated copper spent etching solution according to claim 1, it is characterized in that step poly-3) two sections of process for cooling comprise directly cooling and indirect process for cooling, directly cooling with the direct spraying cooling of chlorine water, chlorine water is closed cycle; Indirectly be cooled to recirculated water indirectly cooling.
8. the comprehensive recovery and treatment method of a kind of mixed chlorinated copper spent etching solution according to claim 1, 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.
9. the comprehensive recovery and treatment method of a kind of mixed chlorinated copper spent etching solution according to claim 1, is characterized in that after eddy flow electrodeposition that the copper ions described in step 5) is low in liquid that copper ion concentration is 8-12g/L.
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| CN112151387A (en) * | 2019-06-28 | 2020-12-29 | 株式会社Flosfia | Etching method, semiconductor device manufacturing method, product manufacturing method, and etching apparatus |
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