CN109534476A - A kind of method that copper ashes handles arsenic in nonferrous smelting waste acid - Google Patents
A kind of method that copper ashes handles arsenic in nonferrous smelting waste acid Download PDFInfo
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- CN109534476A CN109534476A CN201811294621.XA CN201811294621A CN109534476A CN 109534476 A CN109534476 A CN 109534476A CN 201811294621 A CN201811294621 A CN 201811294621A CN 109534476 A CN109534476 A CN 109534476A
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- copper ashes
- waste acid
- arsenic
- nonferrous smelting
- processing
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- 235000002918 Fraxinus excelsior Nutrition 0.000 title claims abstract description 76
- 239000002956 ash Substances 0.000 title claims abstract description 76
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 73
- 239000010949 copper Substances 0.000 title claims abstract description 73
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000002699 waste material Substances 0.000 title claims abstract description 54
- 239000002253 acid Substances 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 35
- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 33
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000003723 Smelting Methods 0.000 title claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 230000003647 oxidation Effects 0.000 claims abstract description 20
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 20
- 238000002203 pretreatment Methods 0.000 claims abstract description 17
- 239000012535 impurity Substances 0.000 claims abstract description 14
- 238000007885 magnetic separation Methods 0.000 claims abstract description 14
- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000010791 quenching Methods 0.000 claims abstract description 12
- 230000000171 quenching effect Effects 0.000 claims abstract description 12
- 239000002910 solid waste Substances 0.000 claims abstract description 12
- 238000000498 ball milling Methods 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000000227 grinding Methods 0.000 claims abstract description 3
- 239000000706 filtrate Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 6
- 238000001514 detection method Methods 0.000 claims description 5
- 238000003801 milling Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000003860 storage Methods 0.000 abstract description 3
- 238000010306 acid treatment Methods 0.000 abstract description 2
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 2
- 239000010802 sludge Substances 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 239000002893 slag Substances 0.000 description 7
- 239000004615 ingredient Substances 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 150000001879 copper Chemical class 0.000 description 3
- 238000009837 dry grinding Methods 0.000 description 3
- 239000003546 flue gas Substances 0.000 description 3
- 239000006148 magnetic separator Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 238000005272 metallurgy Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 235000021321 essential mineral Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
Classifications
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- 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
-
- 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
- C02F2101/103—Arsenic compounds
-
- 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
Abstract
The invention discloses the methods of arsenic in a kind of copper ashes processing nonferrous smelting waste acid, belong to Heavy Metal Pollution Control and metallurgical solid waste and utilize field；Ball milling magnetic separation is dried in copper ashes first, obtains rich iron copper ashes and other impurities；High temperature pre-processes at rich iron copper ashes is 500 ~ 800 DEG C in temperature；Rich, high temperature iron copper ashes is blown by high speed water and carries out water quenching, the copper ashes drying and grinding after water quenching；By H2O2It is added in waste acid and is mixed, oxidation pre-treatment at being 60 ~ 80 DEG C in temperature；Then copper ashes is added in oxidation pre-treatment waste acid, dearsenification reaction is stirred under normal pressure；Finally it is separated by solid-liquid separation；This method utilizes cheap copper ashes arsenic removal, and the volume of cargo in storage of sludge in waste acid treatment process is not only reduced compared with traditional arsenic removal process, has also achieved to have given up and controls useless effect, and technological operation is simple, production cost is low has broader market prospects.
Description
Technical field
The present invention relates to the methods of arsenic in a kind of copper ashes processing nonferrous smelting waste acid, belong to Heavy Metal Pollution Control and metallurgy
Solid waste utilizes field.
Background technique
China is copper big producer, the world, and annual copper ashes discharge amount is more than 10,000,000 tons, and current whole nation copper ashes pushes away storage
It has been more than 1.2 hundred million t, copper ashes has become a fairly large number of industrial solid castoff generated in metallurgy industry.There are Fe, Cu in copper ashes
With a small amount of noble metal such as a variety of valuable metals such as Ni and Au, Ag, wherein essential mineral is ferrosilicate and magnetic iron oxide,
The grade of middle iron is more than 40%, and the iron ore much higher than 29. 1% is averaged production-grade, however the iron utilization rate in copper ashes is but
Less than 1%.Therefore, the comprehensive utilization for effectively realizing copper ashes is the important channel of current Copper making industry value chain.
For the processing method of waste acid, widely used at present is sulfide precipitation-neutralization precipitation technique, which deposits
Many insufficient；The water treatment residues of a large amount of difficult and difficult stockpilings are generated in practical applications；Water treatment residues are stacked in the environment,
It is not only easy release poisonous element pollution environment, also processing cost is expensive；Treated, and the water hardness is higher, it is difficult to recycle；
The policy for meeting national waste recycling with copper ashes processing waste acid, has very big development prospect.
Summary of the invention
For the above-mentioned problems of the prior art and deficiency, the present invention is provided in a kind of copper ashes processing nonferrous smelting waste acid
The method of arsenic；This method utilizes cheap copper ashes arsenic removal, not only reduces the volume of cargo in storage of sludge in waste acid treatment process, has also achieved
The effect of the treatment of wastes with processes of wastes against one another, technological operation is simple, production cost is low has broader market prospects.
The method of arsenic in copper ashes processing nonferrous smelting waste acid of the present invention, the specific steps are as follows:
(1) dry copper ashes is subjected to ball milling magnetic separation, obtains rich iron copper ashes and other impurities；Other impurities stockpiling processing, Fu Tie
High temperature pre-processes 6 ~ 8h at copper ashes is 500 ~ 800 DEG C in temperature；
(2) rich, high temperature iron copper ashes is blown by high speed water and carries out water quenching, the copper ashes drying and grinding after water quenching, copper ashes granularity control exists
Below 200 mesh；
(3) H is pressed2O2The ratio that molar ratio with arsenic is 1 ~ 1.2:1, by H2O2It is mixed with nonferrous smelting waste acid, is in temperature
2 ~ 3h of oxidation pre-treatment at 60 ~ 80 DEG C；
(4) step (2) copper ashes is added in step (3) oxidation pre-treatment waste acid, is stirred to react under normal pressure, reaction product solid-liquid
Separation obtains rich arsenic solid waste and filtrate, carries out subsequent processing processing after detection filtrate is up to standard, rich arsenic solid waste send safe disposal.
Nonferrous smelting waste acid is the spent acid generated in copper blast furnace off-gas washing process in the present invention.
Rotational speed of ball-mill is 760 ~ 910r/min in the step (1), and milling time is 8 ~ 11min.
The magnetic separation strength of magnetic separation is 800 ~ 1100mT in the step (1).
The flow velocity of step (2) the high speed water is 11 ~ 14m/s.
The liquid-solid ratio mL:g of oxidation pre-treatment waste acid and copper ashes is 20 ~ 25:1 in the step (4).
Mixing speed is 180 ~ 200r/min in the step (4), and the reaction time is 24 ~ 36h.
The beneficial effects of the present invention are:
(1) waste recycling, economic and environment-friendly, copper ashes belongs to solid waste, and the main method of the copper ashes of China's processing at present is stockpiling pipe
Reason, this method is not only taken up an area, but also administration fee is also very high；The waste residue amount generated with iron salt method processing waste acid is larger, stablizes
Property it is poor, be easy toxicity leach；The present invention handles waste acid using high-speed rail copper ashes, and the production quantity of slag is smaller, and cost is relatively low；
(2) this method handles waste acid, comprehensively utilizes copper ashes, and economic cost is low, and copper ashes toxicity that treated is leached lower than country's mark
Standard, the copper ashes after ball milling magnetic separation can recycle；
(3) this method operating process is simple, and effect of removing arsenic is good.
Specific implementation method
Below by embodiment, invention is further described in detail, but the scope of the present invention is not limited to the content.
Embodiment 1: the method that this copper ashes handles nonferrous smelting waste acid is as follows:
1, by dry copper ashes (copper ashes ingredient is shown in Table 1) progress ball milling magnetic separation, (revolving speed of ball mill is 760r/min, and milling time is
11min, the magnetic separation strength of magnetic separator are 800mT), obtain rich iron copper ashes and other impurities；Other impurities stockpiling processing, Fu Tietong
Slag high temperature at 800 DEG C pre-processes 6h；
Table 1
；
2, rich, high temperature iron copper ashes is blown with high speed water and carries out water quenching, the flow velocity of high speed water is 14m/s, and the copper ashes after water quenching is dry
Grinding, copper ashes granularity control below 200 mesh；
3, H is pressed2O2The ratio that molar ratio with arsenic is 1.2:1, by H2O2With waste acid (waste acid certain regional copper smelting plant southwest
The waste acid containing impurity such as a large amount of arsenic that sulfuric acid plant generates after washing to flue gas during smelting, main component are as shown in table 2) into
Row mixing, oxidation pre-treatment 2h at being 80 DEG C in temperature；
Table 2
；
4, step (2) copper ashes is added in step (3) oxidation pre-treatment waste acid, the liquid-solid ratio of oxidation pre-treatment waste acid and copper ashes
ML:g is 20:1, under normal pressure stirring and air oxidation, and mixing speed 180r/min, reaction time 36h make waste acid and copper
Slag carries out dearsenification reaction；Reactant is separated by solid-liquid separation, and obtains rich arsenic solid waste and filtrate, and detection filtrate (ingredient is as shown in table 3) is up to standard
Subsequent processing processing is carried out afterwards, and rich arsenic solid waste send safe disposal；
Table 3
。
Embodiment 2: the method that this copper ashes handles nonferrous smelting waste acid is as follows:
1, by dry copper ashes (copper ashes ingredient such as table 1) ball milling magnetic separation, (revolving speed of ball mill is 910r/min, and milling time is
8min, the magnetic separation strength of magnetic separator are 1000mT), obtain rich iron copper ashes and other impurities；Other impurities stockpiling processing, Fu Tietong
The pre- place of high temperature is 8h at slag is 500 DEG C in temperature；
Table 1
2, rich, high temperature iron copper ashes is blown with high speed water and carries out water quenching, the flow velocity of high speed water is 12m/s, and the copper ashes after water quenching is dry
Grinding, copper ashes granularity control below 200 mesh；
3, H is pressed2O2The ratio that molar ratio with arsenic is 1:1, by H2O2With waste acid (waste acid certain regional copper smelting plant sulphur southwest
The waste acid containing impurity such as a large amount of arsenic that sour workshop generates after washing to flue gas during smelting, main component are as shown in table 2) it carries out
Mixing, oxidation pre-treatment 2.5h at being 70 DEG C in temperature；
Table 2
4, step (2) copper ashes is added in step (3) oxidation pre-treatment waste acid, the liquid-solid ratio of oxidation pre-treatment waste acid and copper ashes
ML:g is 25:1, under normal pressure stirring and air oxidation, mixing speed 200r/min, and the reaction time is for 24 hours, to make waste acid and copper
Slag carries out dearsenification reaction；Reactant is separated by solid-liquid separation, and obtains rich arsenic solid waste and filtrate, and detection filtrate (ingredient is as shown in table 3) is up to standard
Subsequent processing processing is carried out afterwards, and rich arsenic solid waste send safe disposal.
Table 3
。
Embodiment 3: the method that this copper ashes handles nonferrous smelting waste acid is as follows:
1, by dry copper ashes (copper ashes ingredient is shown in Table 1) progress ball milling magnetic separation, (revolving speed of ball mill is 800r/min, and milling time is
9min, the magnetic separation strength of magnetic separator are 900mT), obtain rich iron copper ashes and other impurities；Other impurities stockpiling processing, Fu Tietong
Slag high temperature at 650 DEG C pre-processes 7h；
Table 1
2, rich, high temperature iron copper ashes is blown with high speed water and carries out water quenching, the flow velocity of high speed water is 11m/s, and the copper ashes after water quenching is dry
Grinding, copper ashes granularity control below 200 mesh；
3, H is pressed2O2The ratio that molar ratio with arsenic is 1.1:1, by H2O2With waste acid (waste acid certain regional copper smelting plant southwest
The waste acid containing impurity such as a large amount of arsenic that sulfuric acid plant generates after washing to flue gas during smelting, main component are as shown in table 2) into
Row mixing, oxidation pre-treatment 3h at being 60 DEG C in temperature；
Table 2
4, step (2) copper ashes is added in step (3) oxidation pre-treatment waste acid, the liquid-solid ratio of oxidation pre-treatment waste acid and copper ashes
ML:g is 23:1, under normal pressure stirring and air oxidation, and mixing speed 190r/min, reaction time 30h make waste acid and copper
Slag carries out dearsenification reaction；Reactant is separated by solid-liquid separation, and obtains rich arsenic solid waste and filtrate, and detection filtrate (ingredient is as shown in table 3) is up to standard
Subsequent processing processing is carried out afterwards, and rich arsenic solid waste send safe disposal；
Table 3
。
Claims (6)
1. a kind of method of arsenic in copper ashes processing nonferrous smelting waste acid, which is characterized in that specifically includes the following steps:
(1) dry copper ashes is subjected to ball milling magnetic separation, obtains rich iron copper ashes and other impurities；Other impurities stockpiling processing, Fu Tie
High temperature pre-processes 6 ~ 8h at copper ashes is 500 ~ 800 DEG C in temperature；
(2) rich, high temperature iron copper ashes is blown with high speed water and carries out water quenching, the copper ashes drying and grinding after water quenching, copper ashes granularity control exists
Below 200 mesh；
(3) H is pressed2O2The ratio that molar ratio with arsenic is 1 ~ 1.2:1, by H2O2It is mixed with nonferrous smelting waste acid, is in temperature
2 ~ 3h of oxidation pre-treatment at 60 ~ 80 DEG C；
(4) step (2) copper ashes is added in step (3) oxidation pre-treatment waste acid, is stirred to react under normal pressure, reaction product solid-liquid
Separation obtains rich arsenic solid waste and filtrate, carries out subsequent processing processing after detection filtrate is up to standard.
2. the method for arsenic in copper ashes processing nonferrous smelting waste acid according to claim 1, it is characterised in that: in step (1)
Rotational speed of ball-mill is 760 ~ 910r/min, and milling time is 8 ~ 11min.
3. the method for arsenic in copper ashes processing nonferrous smelting waste acid according to claim 1, it is characterised in that: in step (1)
The magnetic separation strength of magnetic separation is 800 ~ 1100mT.
4. the method for arsenic in copper ashes processing nonferrous smelting waste acid according to claim 1, it is characterised in that: in step (2)
The flow velocity of high speed water is 11 ~ 14m/s.
5. the method for arsenic in copper ashes processing nonferrous smelting waste acid according to claim 1, it is characterised in that: in step (4)
The liquid-solid ratio mL:g of oxidation pre-treatment waste acid and copper ashes is 20 ~ 25:1.
6. the method for arsenic in copper ashes processing nonferrous smelting waste acid according to claim 1, it is characterised in that: in step (4)
Mixing speed is 180 ~ 200r/min, and the reaction time is 24 ~ 36h.
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Cited By (8)
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| CN110171886A (en) * | 2019-04-22 | 2019-08-27 | 昆明理工大学 | A method of waste acid containing arsenic is disposed using copper ashes step |
| CN110451573A (en) * | 2019-07-25 | 2019-11-15 | 昆明理工大学 | A method of arsenic in nonferrous smelting waste acid is handled by solid-state source of iron of limonite |
| CN110482672A (en) * | 2019-07-25 | 2019-11-22 | 昆明理工大学 | A method of arsenic in waste acid is efficiently removed for source of iron in situ with magnetic iron ore |
| CN110745986A (en) * | 2019-10-15 | 2020-02-04 | 昆明理工大学 | Method for treating arsenic in nonferrous smelting waste acid by using biochar-loaded aluminum oxide |
| CN110745984A (en) * | 2019-10-15 | 2020-02-04 | 昆明理工大学 | Harmless treatment method for arsenic-containing polluted acid in nonferrous smelting |
| CN111069228A (en) * | 2019-11-22 | 2020-04-28 | 昆明理工大学 | Method for wrapping stabilized scorodite by copper slag gel |
| CN112079486A (en) * | 2020-09-16 | 2020-12-15 | 昆明理工大学 | Method for removing arsenic from waste acid by using copper slag tailings |
| CN116143222A (en) * | 2022-12-21 | 2023-05-23 | 昆明理工大学 | Method for removing arsenic in nonferrous metal smelting wastewater through bimetal |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110171886A (en) * | 2019-04-22 | 2019-08-27 | 昆明理工大学 | A method of waste acid containing arsenic is disposed using copper ashes step |
| CN110451573A (en) * | 2019-07-25 | 2019-11-15 | 昆明理工大学 | A method of arsenic in nonferrous smelting waste acid is handled by solid-state source of iron of limonite |
| CN110482672A (en) * | 2019-07-25 | 2019-11-22 | 昆明理工大学 | A method of arsenic in waste acid is efficiently removed for source of iron in situ with magnetic iron ore |
| CN110451573B (en) * | 2019-07-25 | 2021-11-05 | 昆明理工大学 | Method for treating arsenic in nonferrous smelting waste acid by taking limonite as solid iron source |
| CN110745986A (en) * | 2019-10-15 | 2020-02-04 | 昆明理工大学 | Method for treating arsenic in nonferrous smelting waste acid by using biochar-loaded aluminum oxide |
| CN110745984A (en) * | 2019-10-15 | 2020-02-04 | 昆明理工大学 | Harmless treatment method for arsenic-containing polluted acid in nonferrous smelting |
| CN111069228A (en) * | 2019-11-22 | 2020-04-28 | 昆明理工大学 | Method for wrapping stabilized scorodite by copper slag gel |
| CN112079486A (en) * | 2020-09-16 | 2020-12-15 | 昆明理工大学 | Method for removing arsenic from waste acid by using copper slag tailings |
| CN116143222A (en) * | 2022-12-21 | 2023-05-23 | 昆明理工大学 | Method for removing arsenic in nonferrous metal smelting wastewater through bimetal |
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