CN109930007A - A kind of processing method of Copper making electric dust - Google Patents
A kind of processing method of Copper making electric dust Download PDFInfo
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- CN109930007A CN109930007A CN201910257003.6A CN201910257003A CN109930007A CN 109930007 A CN109930007 A CN 109930007A CN 201910257003 A CN201910257003 A CN 201910257003A CN 109930007 A CN109930007 A CN 109930007A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The present invention provides a kind of processing methods of Copper making electric dust, process object is Copper making electric dust, the arsenic-containing waste residue generated after sulfurization-precipitation method is handled using nonferrous metallurgy waste water simultaneously, by acidleach, heavy copper, vulcanization, except iron, propose zinc process, the multistage synthetical recovery for realizing lead, copper, arsenic, iron, zinc respectively, makes full use of valuable metal.Present invention process is simple and easy to control, and production cost is low, efficiently solves the technical problem of electric dust and arsenic sulfide slag processing and resource utilization difficulty in Copper making industry；Turn waste into wealth, create economic benefit and avoid problem of environmental pollution caused by debris dump is built, economic value is big with environmental value.
Description
Technical field
The present invention relates to the processing of Copper making electric dust and field of environment protection, are concretely a kind of Copper making electric dusts
Processing method.
Background technique
In copper smelting by pyrometallurgy production, smelting furnace, which makes sulfonium and the process of bessemerizing, can generate volume of smoke, pass through electric precipitation skill
Art collects a large amount of electric dusts.If electric dust is stacked for a long time, not only waste of resource, occupancy large area place, also will cause ring
Border problem.Electric dust is complex in composition, is that the oxide of various metals and the mixture of salt have wherein containing a large amount of valuable metals
Higher refinement value；If but electric dust directly returns to pyrometallurgical smelting system, will increase the impurity content into furnace material, reduces smelting
The processing capacity of furnace, while influencing metal production and quality；Therefore need to study a kind of processing method of Copper making electric dust,
The multi-stage separation and synthetical recovery that can be realized a variety of valuable metals, make effective use of resource, create economic value
And problem of environmental pollution caused by the wasting of resources in Copper making industry and debris dump block is solved, is turned waste into wealth, realization economy,
The multiple benefits of environmental protection.
Summary of the invention
The purpose of the present invention is overcoming the processing technique of Copper making electric dust insufficient, provide it is a kind of will be in Copper making electric dust
Lead, copper, arsenic, iron, zinc multi-stage separation and recycling method, while solve nonferrous metallurgy wastewater treatment generation arsenic sulfide slag processing
Difficult problem, realizes Copper making electric dust resource utilization and colored metallurgical industrial Linking Development.
The technical scheme of the present invention is realized as follows: a kind of processing method of Copper making electric dust, comprising the following steps:
(1), acidleach: electric dust adds water slurry, sulfuric acid is added, electric dust and sulfuric acid solid-to-liquid ratio are 1:(3 ~ 4), slurries acidity is 50
SO is added in the g/L of g/L ~ 804 2-/Fe x O y Solid acid catalyst, amount ratio are 1 ‰ ~ the 2 ‰ of electric dust weight, and heating temperature is
60oC~85oC, leaching time are 2 ~ 4 hours, are separated by solid-liquid separation after reaction, and leached mud lead tolerance is 30% ~ 40%, are used for pyrometallurgical smelting of lead
Ore matching, pickle liquor are spare；
(2), heavy copper: pickle liquor is put in proportion into arsenic sulfide slag, and investment ratio is that arsenical copper ratio is 1:(1 ~ 1.3), copper arsenic displacement temperature
Degree is 60oC~85 oC, leaching time are 2 ~ 4 hours, are separated by solid-liquid separation after reaction, and copper ashes copper content of sinking is 40% ~ 60%, heavy copper ashes
For copper smelting by pyrometallurgy ore matching, liquid is that heavy copper liquid is spare；
(3), vulcanizing: being slowly introducing hydrogen sulfide gas in heavy copper liquid, stirring precipitates arsenic in liquid, is separated by solid-liquid separation after reaction, Gu
Body is arsenones, and Solid Arsenic amount is 50% ~ 60%, prepares high-purity arsenic trioxide through two-stage roasting system, liquid is heavy arsenic
Liquid is spare；
(4), remove iron: heavy arsenic liquid is passed through oxygen, and lime under agitation is added and adjusts pH value to 3.0 ~ 4.0, precipitates iron in liquid, instead
Should after be separated by solid-liquid separation, sink scum iron-content be 40% ~ 50%, heavy scum can be used as smelting iron and steel raw material or construction material, and liquid is
Heavy iron liquid is spare；
(5), mention zinc: sodium carbonate stirring and adjusting pH value is added to 5.5 ~ 8.0 in heavy iron liquid, makes the raw precipitating of zinc in liquid, after reaction admittedly
Liquid separation, solid are high-purity zinc carbonate, zinc carbonate purity >=99.9%, mention liquid after zinc and can return to acidleach and recycle；
Preferably, the solid acid catalyst is prepared using multiple maceration, Hammett function H0< -11.93, it is specific to make
Preparation Method: the molar ratio that ferrous nitrate and ferric nitrate press 1:1 with water distinguishes wiring solution-forming, and ferrous nitrate solution and ferric nitrate is molten
Liquid mixing, then 30% ammonia spirit is added dropwise to pH=10；It is sufficiently stirred at room temperature 4 hours, Guo Lv ﹑ washing is repeatedly to neutral, baking
Dry, 400 DEG C roast 4 hours, grind, granularity < -200 mesh；30% sulfuric acid solution is added and did not had grinding powder, it is clear to be put into ultrasonic wave
It is impregnated 6 hours in washing machine, filtering, drying, 400 DEG C roast 4 hours, grind, granularity < -200 mesh；60% sulfuric acid solution is added not have
Grinding powder is crossed, is impregnated 6 hours, filtering, drying, 400 DEG C roast 4 hours, grind, granularity < -200 mesh；It is molten that 90% sulfuric acid is added
Liquid did not had grinding powder, impregnated 6 hours, and filtering, drying, 400 DEG C roast 4 hours, ground, granularity < -200 mesh；Catalysis is made
Agent is labeled as SO4 2-/Fe x O y Solid acid catalyst.
Key reaction mechanism according to the present invention:
PbO+H2SO4 = PbSO4+H2O
CuO+H2SO4 = CuSO4+H2O
As2O3+3H2O = 2H3AsO3
FeO+H2SO4 = FeSO4+H2O
ZnO+H2SO4 = ZnSO4+H2O
3CuSO4+As2S3+6H2O = 3CuS+3H2SO4+2H3AsO3
2H3AsO3+3H2S = As2S3+6H2O
4FeSO4+4CaO+O2+6H2O = 4Fe(OH)3+4CaSO4
ZnSO4+Na2CO3 = ZnCO3+Na2SO4
The beneficial effects of the present invention are:
1. simple process, production cost is low；
2. each valuable metal comprehensive utilization ratio is high, acid pickle can be recycled；
3. solving arsenic sulfide slag processing and valuable metal recovery simultaneously, Copper making electric dust resource utilization and nonferrous metallurgy are realized
Industrial Linking Development.
Detailed description of the invention
Fig. 1 is process flow chart of the invention.
Specific implementation method
Embodiment 1:
Electric dust (one) main constituents are as shown in table 1:
The main component of 1. electric dust of table (one)
Example 1: SO is first prepared4 2-/Fe x O y Solid acid catalyst, specific preparation method: ferrous nitrate and ferric nitrate and water press 1:1
Molar ratio distinguish wiring solution-forming, ferrous nitrate solution and iron nitrate solution are mixed, then 30% ammonia spirit is added dropwise to pH=10；
It is sufficiently stirred at room temperature 4 hours, repeatedly to neutral, drying, 400 DEG C are roasted 4 hours for Guo Lv ﹑ washing, are ground, granularity < -200
Mesh；30% sulfuric acid solution is added and did not had grinding powder, is put into supersonic wave cleaning machine and impregnates 6 hours, filtering, drying, 400 DEG C of roastings
It burns 4 hours, grinds, granularity < -200 mesh；60% sulfuric acid solution is added and did not had grinding powder, impregnates 6 hours, filtering, drying, 400
DEG C roasting 4 hours, grind, granularity < -200 mesh；90% sulfuric acid solution is added and did not had grinding powder, impregnates 6 hours, filtering, drying,
400 DEG C roast 4 hours, grind, granularity < -200 mesh；Catalyst is made and is labeled as SO4 2-/Fe x O y Solid acid catalyst.
By electric dust, dilute sulfuric acid and SO4 2-/Fe x O y Solid acid catalyst is added surge tank and the mine that solid-to-liquid ratio is 1:3 is made
Slurry, acidity be 50 g/L, 80oC constant temperature is stirred to react 2 hours, has been leached and has been squeezed into filter press separation of solid and liquid, leached mud lead tolerance
40%, melt down refining lead；Filtrate is stirred to react 2 hours by arsenical copper ratio 1:1 investment arsenic sulfide slag, filters pressing, and heavy copper ashes copper content 60% is returned
Furnace copper metallurgy；Heavy copper liquid is passed through hydrogen sulfide gas under stirring at normal temperature and sufficiently reacts, filters pressing, Solid Arsenic amount 60%, through two-stage roasting
High-purity arsenic trioxide；Dioxygen oxidation Fe is passed through under heavy arsenic liquid stirring2+, and lime is added and adjusts pH value 3.0~4.0
Between precipitate Fe3+, filters pressing, heavy scum iron-content 50%, for making smelting steel raw material or construction material etc.；Sodium carbonate is added in heavy iron liquid
PH is adjusted between 5.5~8.0, sufficiently filters pressing after reaction, solid is washed, drying obtain high-purity zinc carbonate (purity >=
99.9%) it, is recycled in liquid return surge tank after heavy zinc.
Metal recovery rate in 1 Copper making electric dust of example: lead > 95%, copper > 95%, arsenic > 95%, zinc > 90%.
The arsenic sulfide slag being added in sulfidation of the present invention is what nonferrous metallurgy waste water generated after sulfurization-precipitation method is handled
Lead, copper, arsenic, iron, zinc in Copper making electric dust is being realized the same of multi-stage separation and recycling by arsenic-containing waste residue, method of the invention
When, the difficult problem of the arsenic sulfide slag processing of nonferrous metallurgy wastewater treatment generation is also solved, Copper making electric dust resource is realized
Change and utilizes and colored metallurgical industrial Linking Development.
Claims (2)
1. a kind of processing method of Copper making electric dust, it is characterised in that the following steps are included:
(1), acidleach: electric dust adds water slurry, sulfuric acid is added, electric dust and sulfuric acid solid-to-liquid ratio are 1:(3 ~ 4), slurries acidity is 50
SO is added in the g/L of g/L ~ 804 2-/Fe x O y Solid acid catalyst, amount ratio are 1 ‰ ~ the 2 ‰ of electric dust weight, and heating temperature is
60oC~85oC, leaching time are 2 ~ 4 hours, are separated by solid-liquid separation after reaction, and leached mud lead tolerance is 30% ~ 40%, are used for pyrometallurgical smelting of lead
Ore matching, pickle liquor are spare；
(2), heavy copper: pickle liquor is put in proportion into arsenic sulfide slag, and investment ratio is that arsenical copper ratio is 1:(1 ~ 1.3), copper arsenic displacement temperature
Degree is 60oC~85 oC, leaching time are 2 ~ 4 hours, are separated by solid-liquid separation after reaction, and copper ashes copper content of sinking is 40% ~ 60%, heavy copper ashes
For copper smelting by pyrometallurgy ore matching, liquid is that heavy copper liquid is spare；
(3), vulcanizing: being slowly introducing hydrogen sulfide gas in heavy copper liquid, stirring precipitates arsenic in liquid, is separated by solid-liquid separation after reaction, Gu
Body is arsenones, and Solid Arsenic amount is 50% ~ 60%, prepares high-purity arsenic trioxide through two-stage roasting system, liquid is heavy arsenic
Liquid is spare；
(4), remove iron: heavy arsenic liquid is passed through oxygen, and lime under agitation is added and adjusts pH value to 3.0 ~ 4.0, precipitates iron in liquid, reaction
After be separated by solid-liquid separation, sink scum iron-content be 40% ~ 50%, heavy scum can be used as smelting iron and steel raw material or construction material, and liquid is heavy
Iron liquid is spare；
(5), mention zinc: sodium carbonate stirring and adjusting pH value is added to 5.5 ~ 8.0 in heavy iron liquid, precipitates zinc in liquid, after reaction
It is separated by solid-liquid separation, solid is high-purity zinc carbonate, zinc carbonate purity >=99.9%, mentions liquid after zinc and can return to acidleach and recycles.
2. electric dust processing method according to claim 1, it is characterised in that the solid acid catalyst is using multiple
Infusion process preparation, Hammett function H0< -11.93, specific preparation method: ferrous nitrate and ferric nitrate and water rubbing by 1:1
You mix ferrous nitrate solution and iron nitrate solution, then 30% ammonia spirit is added dropwise to pH=10 than wiring solution-forming respectively；In room
It is sufficiently stirred under temperature 4 hours, repeatedly to neutral, drying, 400 DEG C are roasted 4 hours for Guo Lv ﹑ washing, are ground, granularity < -200 mesh；
30% sulfuric acid solution is added and did not had grinding powder, is put into supersonic wave cleaning machine and impregnates 6 hours, filtering, drying, 400 DEG C of roastings 4
Hour, it grinds, granularity < -200 mesh；60% sulfuric acid solution is added and did not had grinding powder, impregnates 6 hours, filtering, drying, 400 DEG C
Roasting 4 hours is ground, granularity < -200 mesh；90% sulfuric acid solution is added and did not had grinding powder, impregnates 6 hours, filtering, drying,
400 DEG C roast 4 hours, grind, granularity < -200 mesh；Catalyst is made and is labeled as SO4 2-/Fe x O y Solid acid catalyst.
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| CN201910257003.6A CN109930007A (en) | 2019-04-01 | 2019-04-01 | A kind of processing method of Copper making electric dust |
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| CN201910257003.6A CN109930007A (en) | 2019-04-01 | 2019-04-01 | A kind of processing method of Copper making electric dust |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110923462A (en) * | 2019-12-20 | 2020-03-27 | 长沙华时捷环保科技发展股份有限公司 | Resourceful treatment method for white smoke |
| CN112458293A (en) * | 2020-11-17 | 2021-03-09 | 湖南仁发材料科技有限公司 | Method for recovering valuable metals in chlorine leaching displacement tail liquid |
| CN113913624A (en) * | 2020-07-10 | 2022-01-11 | 西南科技大学 | Method for resource recovery of copper in reclaimed copper smelting dust |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103014355A (en) * | 2012-12-13 | 2013-04-03 | 马永涛 | Multi-metal comprehensive recycling process for copper smelting ash |
| CN107858519A (en) * | 2017-10-30 | 2018-03-30 | 河南中原黄金冶炼厂有限责任公司 | A kind of comprehensive processing technique of Copper making flue dust and arsenic sulfide slag |
| CN109055759A (en) * | 2018-09-11 | 2018-12-21 | 山东恒邦冶炼股份有限公司 | A kind of combined treatment process of the pickle liquor of Copper making electric dust and arsenic sulfide slag |
-
2019
- 2019-04-01 CN CN201910257003.6A patent/CN109930007A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103014355A (en) * | 2012-12-13 | 2013-04-03 | 马永涛 | Multi-metal comprehensive recycling process for copper smelting ash |
| CN107858519A (en) * | 2017-10-30 | 2018-03-30 | 河南中原黄金冶炼厂有限责任公司 | A kind of comprehensive processing technique of Copper making flue dust and arsenic sulfide slag |
| CN109055759A (en) * | 2018-09-11 | 2018-12-21 | 山东恒邦冶炼股份有限公司 | A kind of combined treatment process of the pickle liquor of Copper making electric dust and arsenic sulfide slag |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110923462A (en) * | 2019-12-20 | 2020-03-27 | 长沙华时捷环保科技发展股份有限公司 | Resourceful treatment method for white smoke |
| CN113913624A (en) * | 2020-07-10 | 2022-01-11 | 西南科技大学 | Method for resource recovery of copper in reclaimed copper smelting dust |
| CN112458293A (en) * | 2020-11-17 | 2021-03-09 | 湖南仁发材料科技有限公司 | Method for recovering valuable metals in chlorine leaching displacement tail liquid |
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Application publication date: 20190625 |
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