CN110316858A - A method of smelting waste acid separation and Extraction copper bismuth heavy metal - Google Patents
A method of smelting waste acid separation and Extraction copper bismuth heavy metal Download PDFInfo
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- CN110316858A CN110316858A CN201910470068.9A CN201910470068A CN110316858A CN 110316858 A CN110316858 A CN 110316858A CN 201910470068 A CN201910470068 A CN 201910470068A CN 110316858 A CN110316858 A CN 110316858A
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- heavy metal
- waste acid
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B30/00—Obtaining antimony, arsenic or bismuth
- C22B30/06—Obtaining bismuth
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/62—Heavy metal compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F2001/007—Processes including a sedimentation step
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Water Supply & Treatment (AREA)
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- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The present invention provides a kind of method for smelting waste acid separation and Extraction copper bismuth heavy metal, flue gas during smelting is washed into acid water preliminary sedimentation first, then by the supernatant waste acid of settlement treatment after filter press filters for the first time, heavy metal precipitation slag is recycled for copper bismuth by the filter residue that secondary filter obtains after heavy metal precipitator calcium polysulfide is added in reactor tank, is stirred to react by a certain percentage for obtained first time filtrate；The method that the present invention separates and recovers heavy metal ion in waste acid using chemical precipitation, its principle is that polysulfide couples vulcanization and flocculation sedimentation with the heavy metal ion in waste acid in calcium polysulfide, make heavy metal ion enrichment recycling in slag, to effectively solve Heavy metals in waste acid, the comprehensive utilization of resource is realized；The present invention have the characteristics that simple process, it is at low cost, be easily industrialized, can valuable metal effectively in synthetical recovery waste acid, there is applications well prospect.
Description
Technical field
The invention belongs to smelt waste acid processing technology field, and in particular to a kind of smelting waste acid separation and Extraction copper bismuth heavy metal
Method.
Background technique
Non-ferrous metal metallurgy waste acid is the spent acid for washing flue gas in flue gas during smelting process of preparing sulfuric acid and generating, in the process cigarette
The heavy metals such as copper, lead, bismuth, mercury also enter waste acid in gas, and waste acid acidity is high, and the high simultaneously complicated component of heavy metal ion content, is weight
One of the major pollutants of non-ferrous metal metallurgy production.Traditional waste acid processing uses the processing method of the waste acid directly neutralized, no
Only valuable metal ions cannot recycle in waste acid, and can generate the largely neutralization calcium slag containing heavy metal, cause tight
The environmental pollution of weight.Therefore the processing of waste acid is one of problem of metallurgy industry.Lime stone-gypsum method, chemistry are mainly used at this stage
The various methods such as the precipitation method, lime iron salt method, vulcanization, embrane method are combined processing, and there are valuable metals to obtain not for treatment process
There is the problems such as pollution environment hidden danger to recycling, neutralizing heavy metal ion height stockpiling in slag, it is difficult to it is new to meet national environmental protection
The requirement of policy.How valuable metal becomes a difficult problem urgently to be resolved at present in high efficiente callback acid heavy metal waste acid.
Summary of the invention
The object of the present invention is to provide a kind of methods for smelting waste acid separation and Extraction copper bismuth heavy metal, to solve the prior art
In how in high efficiente callback acid heavy metal waste acid the problem of valuable metal.
For this purpose, the technical solution adopted by the present invention are as follows: a method of waste acid separation and Extraction copper bismuth heavy metal is smelted, first
Flue gas during smelting is washed into acid water preliminary sedimentation, then by the supernatant waste acid of settlement treatment after filter press filters for the first time,
By obtained first time filtrate by a certain percentage in reactor tank be added heavy metal precipitator calcium polysulfide, be stirred to react after by
The filter residue that secondary filter obtains is that copper bismuth recycles heavy metal precipitation slag, specific steps are as follows:
Step A, flue gas during smelting washing acid water waste acid sedimentation filtration: is squeezed into settling tank settlement treatment, preliminary sedimentation flue gas
The lead sulfate flocculate formed in waste acid after middle lead volatility, supernatant waste acid is filtered through filter press after sedimentation, and is obtained after filtering
First-time filtrate and filter residue, filter residue are lead mud；
Step B, heavy metal ion precipitating enrichment: squeezing into reactor tank for first time filtrate filtered in step A, leads to steam heating
Calcium polysulfide solution is added to 50-60 DEG C, then with 80-150L/min speed, utilizes polysulfide in calcium polysulfide and first
Heavy metal ion coupling vulcanization and flocculation sedimentation in secondary filtrate, make that copper, to obtain copper bismuth compound for the enrichment of bismuth heavy metal ion precipitating
Aggregate, and it is stirred to react 0.5-2h；
Step C, filter: the compound aggregate of copper bismuth that step B is reacted through the secondary filters pressing of filter press, pressing by heavy metal accumulation
Copper bismuth slag is obtained in filter residue, is sold as copper ashes, and filtrate is adjusting pH by environment friendly system and further precipitating a huge sum of money therein
Qualified discharge after category.
Further, first time filtrate controlling pH is 50-200g/L after filtering in the step A.
Further, calcium polysulfide additional amount is 2.0-3.0 times of heavy metal copper element molar content in the step B.
The beneficial effects of the present invention are: using the method for heavy metal ion in chemical precipitation separation and recovery waste acid, principle
Vulcanization and flocculation sedimentation are coupled with the heavy metal ion in waste acid for polysulfide in calcium polysulfide, makes heavy metal ion enrichment
The recycling in slag realizes the comprehensive utilization of resource to effectively solve Heavy metals in waste acid；The present invention has technique letter
Single, at low cost, the characteristics of being easily industrialized, can valuable metal effectively in synthetical recovery waste acid, there is applications well
Prospect.
Specific embodiment
Below with reference to specific embodiment, the present invention will be further described.
Embodiment 1
Waste acid used in the present embodiment comes from a kind of copper metallurgy industry waste acid, and waste acid Contents of Main Components is as follows: acidity of sulfuric acid 180g/
L,Cu1540mg/L,Bi200mg/L.Using technology recycling copper therein, bismuth valuable metal.
A method of waste acid separation and Extraction copper bismuth heavy metal is smelted, it is first that flue gas during smelting washing acid water is tentatively heavy
Drop, then by the supernatant waste acid of settlement treatment after filter press filters for the first time, by a certain percentage by obtained first time filtrate
It by filter residue that secondary filter obtains is that copper bismuth recycles after heavy metal precipitator calcium polysulfide is added in reactor tank, is stirred to react
Heavy metal precipitation slag, specific steps are as follows:
Step A, flue gas during smelting washing acid water waste acid sedimentation filtration: is squeezed into settling tank settlement treatment, preliminary sedimentation flue gas
The lead sulfate flocculate formed in waste acid after middle lead vaporization at high temperature, supernatant waste acid is filtered through filter press after sedimentation, after filtering
To first time filtrate and filter residue, filter residue is lead mud, and first time filtrate controlling pH is 180g/L after filtering；
Step B, heavy metal ion precipitating enrichment: squeezing into reactor tank for first time filtrate filtered in step A, leads to steam heating
To 50 DEG C, then 80L/min is slowly added to calcium polysulfide solution, calcium polysulfide additional amount 3kg/m3, utilize sulphur more in calcium polysulfide
Compound couples vulcanization and flocculation sedimentation with the heavy metal ion in first time filtrate, makes copper, the precipitating enrichment of bismuth heavy metal ion
The compound aggregate of copper bismuth is obtained, and is stirred to react 1h；
Step C, filter: the compound aggregate of copper bismuth that step B is reacted through the secondary filters pressing of filter press, pressing by heavy metal accumulation
Copper bismuth slag, copper content>25% are obtained in filter residue, bi content < 5% is sold as copper ashes, Cu ion concentration<1mg/L, Bi in filtrate
< 10mg/L, filtrate qualified discharge after adjusting PH by environment friendly system and further precipitating heavy metal therein.
Embodiment 2
Waste acid used in the present embodiment comes from a kind of zinc abstraction system waste acid, and waste acid Contents of Main Components is as follows: acidity of sulfuric acid 150g/
L、Cu1870mg/L、Bi300mg/L。
A method of waste acid separation and Extraction copper bismuth heavy metal is smelted, it is first that flue gas during smelting washing acid water is tentatively heavy
Drop, then by the supernatant waste acid of settlement treatment after filter press filters for the first time, by a certain percentage by obtained first time filtrate
It by filter residue that secondary filter obtains is that copper bismuth recycles after heavy metal precipitator calcium polysulfide is added in reactor tank, is stirred to react
Heavy metal precipitation slag, specific steps are as follows:
Step A, flue gas during smelting washing acid water waste acid sedimentation filtration: is squeezed into settling tank settlement treatment, preliminary sedimentation flue gas
The lead sulfate flocculate formed in waste acid after middle lead vaporization at high temperature, supernatant waste acid is filtered through filter press after sedimentation, after filtering
To first time filtrate and filter residue, filter residue is lead mud, and first time filtrate controlling pH is 150g/L after filtering；
Step B, heavy metal ion precipitating enrichment: squeezing into reactor tank for first time filtrate filtered in step A, leads to steam heating
Calcium polysulfide solution, calcium polysulfide additional amount 1kg/m are slowly added to 55 DEG C, then with 120L/min3, using more in calcium polysulfide
Sulphur compound couples vulcanization and flocculation sedimentation with the heavy metal ion in first time filtrate, keeps copper, bismuth heavy metal ion precipitating rich
Collection obtains the compound aggregate of copper bismuth, and is stirred to react 0.5h；
Step C, filter: the compound aggregate of copper bismuth that step B is reacted through the secondary filters pressing of filter press, pressing by heavy metal accumulation
Obtaining copper bismuth slag in filter residue, copper content>21%, bi content < 4% is sold as copper ashes, Cu ion concentration<0.8mg/L in filtrate,
Bi < 10mg/L, filtrate qualified discharge after adjusting PH by environment friendly system and further precipitating heavy metal therein.
Embodiment 3
Waste acid used in the present embodiment comes from a kind of zinc abstraction system waste acid, and waste acid Contents of Main Components is as follows: acidity of sulfuric acid 200g/
L、Cu2570mg/L、Bi100mg/L。
A method of waste acid separation and Extraction copper bismuth heavy metal is smelted, it is first that flue gas during smelting washing acid water is tentatively heavy
Drop, then by the supernatant waste acid of settlement treatment after filter press filters for the first time, by a certain percentage by obtained first time filtrate
It by filter residue that secondary filter obtains is that copper bismuth recycles after heavy metal precipitator calcium polysulfide is added in reactor tank, is stirred to react
Heavy metal precipitation slag, specific steps are as follows:
Step A, flue gas during smelting washing acid water waste acid sedimentation filtration: is squeezed into settling tank settlement treatment, preliminary sedimentation flue gas
The lead sulfate flocculate formed in waste acid after middle lead vaporization at high temperature, supernatant waste acid is filtered through filter press after sedimentation, after filtering
To first time filtrate and filter residue, filter residue is lead mud, and first time filtrate controlling pH is 200g/L after filtering；
Step B, heavy metal ion precipitating enrichment: squeezing into reactor tank for first time filtrate filtered in step A, leads to steam heating
Calcium polysulfide solution, calcium polysulfide additional amount 4kg/m are slowly added to 60 DEG C, then with 150L/min3, using more in calcium polysulfide
Sulphur compound couples vulcanization and flocculation sedimentation with the heavy metal ion in first time filtrate, keeps copper, bismuth heavy metal ion precipitating rich
Collection obtains the compound aggregate of copper bismuth, and is stirred to react 2h；
Step C, filter: the compound aggregate of copper bismuth that step B is reacted through the secondary filters pressing of filter press, pressing by heavy metal accumulation
Obtaining copper bismuth slag in filter residue, copper content>23%, bi content < 3% is sold as copper ashes, Cu ion concentration<1.5mg/L in filtrate,
Bi < 20mg/L, filtrate qualified discharge after adjusting PH by environment friendly system and further precipitating heavy metal therein.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (3)
1. a kind of method for smelting waste acid separation and Extraction copper bismuth heavy metal, it is characterised in that: flue gas during smelting is washed waste acid first
Waste water preliminary sedimentation, then by the supernatant waste acid of settlement treatment after filter press filters for the first time, the first time filtrate that will obtain
The filter residue that is obtained by secondary filter after heavy metal precipitator calcium polysulfide is added in reactor tank by a certain percentage, is stirred to react
Heavy metal precipitation slag, specific steps are recycled for copper bismuth are as follows:
Step A, flue gas during smelting washing acid water waste acid sedimentation filtration: is squeezed into settling tank settlement treatment, preliminary sedimentation flue gas
The lead sulfate flocculate formed in waste acid after middle lead volatility, supernatant waste acid is filtered through filter press after sedimentation, and is obtained after filtering
First-time filtrate and filter residue, filter residue are lead mud；
Step B, heavy metal ion precipitating enrichment: squeezing into reactor tank for first time filtrate filtered in step A, leads to steam heating
Calcium polysulfide solution is added to 50-60 DEG C, then with 80-150L/min speed, utilizes polysulfide in calcium polysulfide and first
Heavy metal ion coupling vulcanization and flocculation sedimentation in secondary filtrate, make that copper, to obtain copper bismuth compound for the enrichment of bismuth heavy metal ion precipitating
Aggregate, and it is stirred to react 0.5-2h；
Step C, filter: the compound aggregate of copper bismuth that step B is reacted through the secondary filters pressing of filter press, pressing by heavy metal accumulation
Copper bismuth slag is obtained in filter residue, is sold as copper ashes, and filtrate is adjusting pH by environment friendly system and further precipitating a huge sum of money therein
Qualified discharge after category.
2. a kind of method for smelting waste acid separation and Extraction copper bismuth heavy metal according to claim 1, it is characterised in that: described
First time filtrate controlling pH is 50-200g/L after filtering in step A.
3. a kind of method for smelting waste acid separation and Extraction copper bismuth heavy metal according to claim 1, it is characterised in that: described
Calcium polysulfide additional amount is 2.0-3.0 times of heavy metal copper element molar content in step B.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910470068.9A CN110316858A (en) | 2019-05-28 | 2019-05-28 | A method of smelting waste acid separation and Extraction copper bismuth heavy metal |
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| CN201910470068.9A CN110316858A (en) | 2019-05-28 | 2019-05-28 | A method of smelting waste acid separation and Extraction copper bismuth heavy metal |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112458292A (en) * | 2020-11-17 | 2021-03-09 | 湖南仁发材料科技有限公司 | Classification and recovery process for valuable metals in waste acid |
| CN116282118A (en) * | 2022-12-28 | 2023-06-23 | 广西国盛稀土新材料有限公司 | Method for producing industrial calcium chloride by utilizing rare earth smelting high-salt wastewater |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104017996A (en) * | 2014-06-06 | 2014-09-03 | 白银有色集团股份有限公司 | Comprehensive recovery device and method for valuable metal in copper smelting acidic wastewater |
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2019
- 2019-05-28 CN CN201910470068.9A patent/CN110316858A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104017996A (en) * | 2014-06-06 | 2014-09-03 | 白银有色集团股份有限公司 | Comprehensive recovery device and method for valuable metal in copper smelting acidic wastewater |
Non-Patent Citations (2)
| Title |
|---|
| 罗琳等: "《环境工程学》", 30 April 2014 * |
| 衷水平等: "《有色金属冶金800问》", 31 March 2019 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112458292A (en) * | 2020-11-17 | 2021-03-09 | 湖南仁发材料科技有限公司 | Classification and recovery process for valuable metals in waste acid |
| CN116282118A (en) * | 2022-12-28 | 2023-06-23 | 广西国盛稀土新材料有限公司 | Method for producing industrial calcium chloride by utilizing rare earth smelting high-salt wastewater |
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Application publication date: 20191011 |