CN115259208A - Process for producing anhydrous copper sulfate by spray pyrolysis of high-purity leaching solution of waste copper foil - Google Patents
Process for producing anhydrous copper sulfate by spray pyrolysis of high-purity leaching solution of waste copper foil Download PDFInfo
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- CN115259208A CN115259208A CN202210760079.2A CN202210760079A CN115259208A CN 115259208 A CN115259208 A CN 115259208A CN 202210760079 A CN202210760079 A CN 202210760079A CN 115259208 A CN115259208 A CN 115259208A
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- Prior art keywords
- copper sulfate
- purity
- leaching
- anhydrous copper
- spray pyrolysis
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- 229910000365 copper sulfate Inorganic materials 0.000 title claims abstract description 54
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 title claims abstract description 54
- 238000002386 leaching Methods 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 30
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000005118 spray pyrolysis Methods 0.000 title claims abstract description 24
- 239000002699 waste material Substances 0.000 title claims abstract description 21
- 239000011889 copper foil Substances 0.000 title claims abstract description 18
- 238000000197 pyrolysis Methods 0.000 claims abstract description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 13
- 239000010949 copper Substances 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 238000010521 absorption reaction Methods 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 238000004064 recycling Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 239000007921 spray Substances 0.000 claims description 4
- 239000003595 mist Substances 0.000 claims description 2
- 239000003345 natural gas Substances 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000013078 crystal Substances 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 238000005507 spraying Methods 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000005272 metallurgy Methods 0.000 abstract description 2
- 238000004806 packaging method and process Methods 0.000 abstract description 2
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/10—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a process for producing anhydrous copper sulfate by utilizing spray pyrolysis of a high-purity leaching solution of waste copper foil, belonging to the technical field of wet metallurgy. The invention abandons the traditional process for producing anhydrous copper sulfate by directly heating copper sulfate solution, shortens the process flow, improves the stability of the product and reduces the production cost. The process comprises the steps of taking waste copper foil as a raw material, taking a sulfuric acid solution as leaching acid, heating and leaching, spraying liquid drops in a vaporific form by using a spray pyrolysis furnace after leaching, controlling the temperature and flow rate of an inlet and an outlet of the pyrolysis furnace, instantly losing crystal water through high temperature, dehydrating, packaging without drying, producing an anhydrous copper sulfate product, and enabling tail gas to enter an absorption tower through a cyclone separator to form absorption liquid, wherein the absorption liquid is used for returning to a leaching system. The production of the anhydrous copper sulfate realizes the direct spray pyrolysis of the high-purity leaching solution to produce the anhydrous copper sulfate, improves the production efficiency of the anhydrous copper sulfate, and ensures that the obtained anhydrous copper sulfate product has a main grade of more than or equal to 38 percent and acid content of less than or equal to 0.25 percent, calculated by Cu, and the product quality is guaranteed.
Description
Technical Field
The invention belongs to the technical field of wet metallurgy, and particularly relates to a process for producing anhydrous copper sulfate by utilizing spray pyrolysis of a high-purity leaching solution of waste copper foil.
Background
At present, in the traditional process for producing anhydrous copper sulfate by using a copper sulfate solution, a chemical concentrating agent (consisting of calcium and a sulfur compound) is added into the prepared copper sulfate solution for chemical concentration, 70 to 90 percent of water is removed, then the copper sulfate solution is heated and evaporated, and a copper sulfate finished product is prepared by cooling, crystallizing, centrifugal separation and air drying. However, the method has long process flow and high energy consumption, and the produced anhydrous copper sulfate has poor dispersibility, uneven particle size distribution, poor chemical activity and no guarantee on product quality.
The spray pyrolysis method is a production method for spraying the solution into a high-temperature atmosphere for drying, and then performing heat treatment to form powder. However, the conventional spray pyrolysis method is used for treating materials containing free water, and 5 crystal waters contained in copper sulfate crystals are required to be completely removed in the preparation of anhydrous copper sulfate, so that the conventional spray pyrolysis process cannot be simply adopted for preparing the anhydrous copper sulfate by simply adjusting parameters. Therefore, how to use the spray pyrolysis method for the production of anhydrous copper sulfate is a technical problem to be overcome by the invention.
Disclosure of Invention
The invention aims to provide a process for producing anhydrous copper sulfate by utilizing waste copper foil high-purity leaching solution through spray pyrolysis, aiming at the problems that the existing process for producing the anhydrous copper sulfate by utilizing a copper sulfate solution is long in process flow and product quality cannot be guaranteed.
In order to realize the purpose, the invention adopts the following technical scheme:
a process for producing anhydrous copper sulfate by utilizing spray pyrolysis of high-purity leaching solution of waste copper foil comprises the following steps:
step one, leaching the waste copper foil in a leaching tank by using a sulfuric acid solution to control the liquid-solid ratio to be 5:1 at 80-85 ℃ to obtain high-purity leaching liquid;
pumping the high-purity leachate into a spray pyrolysis tower, controlling the spray amount of an atomizing nozzle to be 160-180L/h, introducing hot air into a pyrolysis furnace of the pyrolysis tower, and carrying out high-temperature pyrolysis on the vaporous high-purity leachate, wherein the hot air is obtained by heating air with natural gas; controlling the air inlet temperature at 580-600 ℃ and the air outlet temperature at 135-140 ℃ to obtain an anhydrous copper sulfate product;
and step three, the tail gas discharged by the pyrolysis furnace is subjected to acid mist absorption through an absorption tower and then returns to the leaching system for recycling, and the rest heat is used for heating the high-purity leaching solution after being subjected to heat exchange with air.
As the technical scheme of the invention is preferable, in the first step, the concentration of the sulfuric acid solution is 120-150g/L.
Further, in the first step, the leaching time is 5 hours.
Further, in the second step, the main grade of the anhydrous copper sulfate product is more than or equal to 38 percent calculated by Cu;
further, in the second step, the acid content of the anhydrous copper sulfate product is less than or equal to 0.25%.
Compared with the prior art for producing anhydrous copper sulfate by using a copper sulfate solution, the invention has the beneficial effects that:
1. the process takes the waste copper foil as a raw material, the sulfuric acid solution as leaching acid for heating and leaching, the leached liquid is sprayed out in a fog form by using a spray pyrolysis furnace, the temperature and the flow at the inlet and the outlet of the pyrolysis furnace are controlled, and the crystal water is instantly lost through high temperature, so that the technical problem that all 5 crystal water contained in copper sulfate crystals is removed is solved, the anhydrous copper sulfate product is produced without drying and packaging after dehydration, the process flow is short, and the production efficiency is high; the anhydrous copper sulfate product obtained by the method has the main grade more than or equal to 38 percent calculated by Cu, the acid content less than or equal to 0.25 percent, good dispersity, uniform particle size distribution, good chemical activity and guaranteed product quality.
2. The main raw material of the invention is waste copper foil, the source is wide, the cost is low, the production cost of anhydrous copper sulfate is greatly reduced, the effect of recycling waste is achieved, and the invention is environment-friendly.
3. The tail gas discharged by the pyrolysis furnace is absorbed by the absorption tower and then returns to the leaching system for recycling, and the rest heat is used for heating the high-purity leaching solution after exchanging heat with air, so that the pyrolysis energy consumption can be reduced, and the production cost of anhydrous copper sulfate is further reduced.
Detailed Description
The process for producing anhydrous copper sulfate by direct spray pyrolysis of high-purity leachate and the technical effects thereof according to the present invention will be further described by the following specific examples.
The spray pyrolysis tower used in the invention is purchased from Youbo Dry engineering, inc., changzhou, and has the product types: QPG-10.
Example 1
The process for producing anhydrous copper sulfate by directly spraying and pyrolyzing high-purity leachate provided by the embodiment specifically comprises the following operations:
2050kg of waste copper foil containing 99.9% of copper was taken and placed in a 316L leaching tank heated with steam at a rate of 10m3And leaching the mixture for 5 hours at the temperature of between 80 and 85 ℃ by using a sulfuric acid solution with the concentration of 120g/L to obtain high-purity leachate. The copper content in the high-purity leachate was measured to be 90g/L and the acid content was measured to be 13g/L.
And (3) feeding the high-purity leachate into a spray pyrolysis tower at a spray amount of 160L/h, and pyrolyzing the atomized high-purity leachate in a pyrolysis furnace through hot air. The inlet air temperature of the pyrolysis furnace is controlled at 580 ℃, the outlet air temperature is controlled at 135 ℃, and an anhydrous copper sulfate product is obtained.
Absorbing the tail gas discharged by the pyrolysis furnace by an absorption tower to obtain 2.5m3The waste acid containing 0.8g/l of copper is returned to the leaching system for recycling, and the rest heat is used for heating the high-purity leaching solution after heat exchange with air.
The composition of the anhydrous copper sulfate product obtained is shown in table 1 below.
TABLE 1 composition Table of anhydrous copper sulfate obtained by the method in example 1
Example 2
The process for producing anhydrous copper sulfate by directly spraying and pyrolyzing high-purity leachate provided by the embodiment specifically comprises the following operations:
2410kg of waste copper foil containing 99.9% copper was taken and extracted at a rate of 12m in a leaching tank heated with steam to 316L3And leaching the mixture for 5 hours at the temperature of between 80 and 85 ℃ by using a sulfuric acid solution with the concentration of 150g/L to obtain a high-purity leaching solution. The copper content in the high-purity leachate was found to be 95g/L and the acid content was found to be 17g/L.
And (3) feeding the high-purity leachate into a spray pyrolysis tower at a spray amount of 180L/h, and pyrolyzing the atomized high-purity leachate in a pyrolysis furnace through hot air. The inlet air temperature of the pyrolysis furnace is controlled at 600 ℃, the outlet air temperature is controlled at 140 ℃, and an anhydrous copper sulfate product is obtained.
Absorbing the tail gas by an absorption tower to obtain 2.7m3The waste acid containing 1.2g/l of copper is returned to the leaching system for recycling, and the rest heat is used for heating the high-purity leaching solution after being subjected to heat exchange with air.
The composition of the anhydrous copper sulfate product obtained is shown in table 2 below.
TABLE 2 composition Table of anhydrous copper sulfate obtained by the method in example 2
As can be seen from the results in tables 1 and 2, the main grade of the anhydrous copper sulfate product obtained by the method is more than or equal to 38 percent in terms of Cu, the acid content is less than or equal to 0.25 percent, the product quality is guaranteed, and the method completely meets the existing anhydrous copper sulfate use standard.
While the preferred embodiments of the present invention have been illustrated and described, it will be appreciated that various modifications, equivalent changes and variations may be made therein without departing from the spirit and scope of the invention.
Claims (5)
1. A process for producing anhydrous copper sulfate by utilizing spray pyrolysis of high-purity leaching solution of waste copper foil is characterized by comprising the following steps of:
step one, leaching the waste copper foil in a leaching tank by using a sulfuric acid solution to control the liquid-solid ratio to be 5:1 at 80-85 ℃ to obtain high-purity leaching liquid;
pumping the high-purity leachate into a spray pyrolysis tower, controlling the spray amount of an atomizing nozzle to be 160-180L/h, introducing hot air into a pyrolysis furnace of the pyrolysis tower, and carrying out high-temperature pyrolysis on the vaporous high-purity leachate, wherein the hot air is obtained by heating air with natural gas; controlling the air inlet temperature at 580-600 ℃ and the air outlet temperature at 135-140 ℃ to obtain an anhydrous copper sulfate product;
and step three, the tail gas discharged by the pyrolysis furnace is absorbed by acid mist through an absorption tower and then returns to the leaching system for recycling, and the rest heat is used for heating the high-purity leaching solution after being subjected to heat exchange with air.
2. The process for producing anhydrous copper sulfate by utilizing spray pyrolysis of high-purity leachate of waste copper foil according to claim 1, wherein in the first step, the concentration of the sulfuric acid solution is 120-150g/L.
3. The process for producing anhydrous copper sulfate by utilizing spray pyrolysis of high-purity leachate of waste copper foil according to claim 1, wherein in the first step, the leaching time is 5 hours.
4. The process for producing anhydrous copper sulfate by spray pyrolysis of high-purity leachate of waste copper foil according to any one of claims 1 to 3, wherein in the second step, the primary grade of the anhydrous copper sulfate product is not less than 38% calculated as Cu.
5. The process for producing anhydrous copper sulfate by utilizing spray pyrolysis of the high-purity leachate of waste copper foil according to any one of claims 1 to 3, wherein in the second step, the anhydrous copper sulfate product contains acid of less than or equal to 0.25%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210760079.2A CN115259208A (en) | 2022-06-30 | 2022-06-30 | Process for producing anhydrous copper sulfate by spray pyrolysis of high-purity leaching solution of waste copper foil |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210760079.2A CN115259208A (en) | 2022-06-30 | 2022-06-30 | Process for producing anhydrous copper sulfate by spray pyrolysis of high-purity leaching solution of waste copper foil |
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| CN115259208A true CN115259208A (en) | 2022-11-01 |
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| CN202210760079.2A Pending CN115259208A (en) | 2022-06-30 | 2022-06-30 | Process for producing anhydrous copper sulfate by spray pyrolysis of high-purity leaching solution of waste copper foil |
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1414123A (en) * | 2001-10-23 | 2003-04-30 | 金居开发铜箔股份有限公司 | Method of recovering waste copper foil |
| CN1840739A (en) * | 2005-03-04 | 2006-10-04 | 法布罗技术有限公司 | Regeneration of cupric etchants and recovery of copper sulfate |
| CN102357308A (en) * | 2011-10-19 | 2012-02-22 | 江西稀有稀土金属钨业集团有限公司 | Method for directly preparing anhydrous cobalt chloride powder from cobalt chloride solution |
| CN105060332A (en) * | 2015-07-23 | 2015-11-18 | 韦海棉 | Iron-removal easy-filtering process for copper sulfate solution |
| CN105399116A (en) * | 2015-11-16 | 2016-03-16 | 中国科学院过程工程研究所 | System for treating waste acid with organic matters and treatment method and application of system |
| CN207738470U (en) * | 2017-12-18 | 2018-08-17 | 广西雅照钛白有限公司 | The equipment of spray drying production anhydrous slufuric acid ferrous iron |
| KR101966065B1 (en) * | 2018-10-31 | 2019-04-05 | 주황윤 | Manufacturing method of multi-mineral from industrial waste |
| CN112357947A (en) * | 2020-12-21 | 2021-02-12 | 泰兴冶炼厂有限公司 | Preparation method for producing high-purity anhydrous copper sulfate by dynamic drying method |
-
2022
- 2022-06-30 CN CN202210760079.2A patent/CN115259208A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1414123A (en) * | 2001-10-23 | 2003-04-30 | 金居开发铜箔股份有限公司 | Method of recovering waste copper foil |
| CN1840739A (en) * | 2005-03-04 | 2006-10-04 | 法布罗技术有限公司 | Regeneration of cupric etchants and recovery of copper sulfate |
| CN102357308A (en) * | 2011-10-19 | 2012-02-22 | 江西稀有稀土金属钨业集团有限公司 | Method for directly preparing anhydrous cobalt chloride powder from cobalt chloride solution |
| CN105060332A (en) * | 2015-07-23 | 2015-11-18 | 韦海棉 | Iron-removal easy-filtering process for copper sulfate solution |
| CN105399116A (en) * | 2015-11-16 | 2016-03-16 | 中国科学院过程工程研究所 | System for treating waste acid with organic matters and treatment method and application of system |
| CN207738470U (en) * | 2017-12-18 | 2018-08-17 | 广西雅照钛白有限公司 | The equipment of spray drying production anhydrous slufuric acid ferrous iron |
| KR101966065B1 (en) * | 2018-10-31 | 2019-04-05 | 주황윤 | Manufacturing method of multi-mineral from industrial waste |
| CN112357947A (en) * | 2020-12-21 | 2021-02-12 | 泰兴冶炼厂有限公司 | Preparation method for producing high-purity anhydrous copper sulfate by dynamic drying method |
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Effective date of registration: 20240416 Address after: 737199 No. 2 Jianshe Road, Jinchuan District, Jinchang City, Gansu Province (east of Beijing Road, west of Heya Road, south of Guiyang Road) Applicant after: Jinchuan Group Copper Gui Co.,Ltd. Country or region after: China Address before: 737103 No. 98, Jinchuan Road, Jinchang, Gansu Applicant before: JINCHUAN GROUP Co.,Ltd. Country or region before: China Applicant before: Jinchuan Group Copper Co.,Ltd. |
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