CN115558795A - Treatment method and system for copper smelting complex waste acid - Google Patents
Treatment method and system for copper smelting complex waste acid Download PDFInfo
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- CN115558795A CN115558795A CN202211205907.2A CN202211205907A CN115558795A CN 115558795 A CN115558795 A CN 115558795A CN 202211205907 A CN202211205907 A CN 202211205907A CN 115558795 A CN115558795 A CN 115558795A
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- 229910052802 copper Inorganic materials 0.000 title claims abstract description 175
- 239000010949 copper Substances 0.000 title claims abstract description 175
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 167
- 239000002253 acid Substances 0.000 title claims abstract description 122
- 239000002699 waste material Substances 0.000 title claims abstract description 111
- 238000000034 method Methods 0.000 title claims abstract description 68
- 238000003723 Smelting Methods 0.000 title claims abstract description 58
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 71
- 239000007788 liquid Substances 0.000 claims abstract description 49
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000002893 slag Substances 0.000 claims abstract description 37
- 229910052742 iron Inorganic materials 0.000 claims abstract description 35
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 33
- 230000008569 process Effects 0.000 claims abstract description 28
- 238000004073 vulcanization Methods 0.000 claims abstract description 25
- 239000002351 wastewater Substances 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- CUGMJFZCCDSABL-UHFFFAOYSA-N arsenic(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[As+3].[As+3] CUGMJFZCCDSABL-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000003825 pressing Methods 0.000 claims abstract description 17
- 238000001556 precipitation Methods 0.000 claims abstract description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006073 displacement reaction Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000002244 precipitate Substances 0.000 claims abstract description 9
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 7
- 239000011707 mineral Substances 0.000 claims abstract description 7
- 229910052785 arsenic Inorganic materials 0.000 claims description 16
- 238000003860 storage Methods 0.000 claims description 13
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 11
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 11
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 10
- 229910001431 copper ion Inorganic materials 0.000 claims description 10
- 230000001698 pyrogenic effect Effects 0.000 claims description 7
- 229910052797 bismuth Inorganic materials 0.000 claims description 6
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 6
- 229910052714 tellurium Inorganic materials 0.000 claims description 6
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 6
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 3
- -1 arsenic ions Chemical class 0.000 claims description 3
- HAYXDMNJJFVXCI-UHFFFAOYSA-N arsenic(5+) Chemical compound [As+5] HAYXDMNJJFVXCI-UHFFFAOYSA-N 0.000 claims description 3
- CJDPJFRMHVXWPT-UHFFFAOYSA-N barium sulfide Chemical compound [S-2].[Ba+2] CJDPJFRMHVXWPT-UHFFFAOYSA-N 0.000 claims description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 3
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 claims description 3
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 18
- 230000008021 deposition Effects 0.000 abstract description 8
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 13
- 238000000151 deposition Methods 0.000 description 9
- 239000012295 chemical reaction liquid Substances 0.000 description 7
- 229910052711 selenium Inorganic materials 0.000 description 7
- 239000011669 selenium Substances 0.000 description 7
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000010970 precious metal Substances 0.000 description 6
- 238000010306 acid treatment Methods 0.000 description 5
- 238000005987 sulfurization reaction Methods 0.000 description 5
- 230000008719 thickening Effects 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000010812 mixed waste Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- 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
- C22B15/0084—Treating solutions
- C22B15/0089—Treating solutions by chemical methods
- C22B15/0091—Treating solutions by chemical methods by cementation
-
- 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
- C22B15/0084—Treating solutions
- C22B15/0089—Treating solutions by chemical methods
-
- 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
-
- 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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- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Removal Of Specific Substances (AREA)
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Abstract
The invention discloses a method and a system for treating complex waste acid in copper smelting, wherein the method comprises the following steps: the method comprises the following steps: adding scrap iron into the selenium-removed solution to perform a displacement reaction to obtain copper precipitate and a first reaction solution; carrying out filter pressing treatment on the first reaction solution to obtain sponge copper and copper precipitation solution; mixing the copper-precipitated solution with the beneficiation wastewater to obtain low-copper-content waste acid; adding a vulcanizing agent into the low-copper-content waste acid, and then performing filter pressing treatment to obtain copper sulfide slag and a liquid after copper sulfide removal; and adding sulfuric acid and a vulcanizing agent into the liquid after copper sulfide removal to obtain arsenic sulfide slag. According to the invention, the selenium-removed liquid is used as the high-copper-content waste acid, so that a process of replacing copper deposition with scrap iron is added, the recovery rate of copper in the complex waste acid in copper smelting can be greatly improved, and the usage amount of a vulcanizing agent can be reduced; and then, the solution after copper precipitation and the mineral processing wastewater are used as low-copper-containing waste acid, and two-stage vulcanization treatment is carried out on the low-copper-containing waste acid, so that the recovery rate of copper can be effectively improved, and the copper content of arsenic sulfide slag can be reduced.
Description
Technical Field
The invention relates to the field of copper smelting waste acid treatment, in particular to a method and a system for treating copper smelting complex waste acid.
Background
At present, in the waste acid treatment process of copper smelting enterprises, a mature and common waste acid treatment process is a vulcanization method treatment process. The vulcanizing process mainly comprises the steps of adding a vulcanizing agent, removing copper and arsenic in contaminated acid under an acidic condition, generating copper sulfide and arsenic sulfide precipitates, and achieving the purpose of efficiently removing heavy metals under the acidic condition.
The sulfuration process for treating the waste acid is generally divided into two stages of sulfuration processes if the copper content of the waste acid is slightly high, wherein one stage is sulfuration for copper removal, and the second stage is sulfuration for arsenic removal, so that the copper and the arsenic in the waste acid are effectively removed. When the copper content of the waste acid is low and the arsenic content is high, the waste acid can be directly used for removing arsenic by using a sulfuration reaction.
However, with the increasing complexity of copper concentrate in the copper smelting industry and the diversity of the precious metal dressing and smelting combined process, the content of other valuable metals except copper in the waste acid generated in the precious metal production process is increased, the effective treatment of high-copper waste acid cannot be well met by using the existing vulcanization process, firstly, the copper removal rate is insufficient, the arsenic sulfide residue contains high copper, the copper recovery rate is low, and secondly, the treatment cost of the waste acid is high due to the large amount of vulcanizing agents.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a method and a system for treating complex waste acid in copper smelting, and aims to solve the problems of low copper recovery rate and high treatment cost of the conventional method for treating complex waste acid in copper smelting.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a treatment method of copper smelting complex waste acid comprises selenium-removed liquid and mineral processing wastewater, and comprises the following steps:
adding scrap iron into the selenium-removed liquid to perform a displacement reaction to obtain copper precipitate and a first reaction liquid;
carrying out filter pressing treatment on the first reaction solution to obtain sponge copper and copper precipitation solution;
mixing the copper-precipitated liquid with the beneficiation wastewater to obtain low-copper-content waste acid;
adding a vulcanizing agent into the low-copper-content waste acid, and then performing filter pressing treatment to obtain copper sulfide slag and a liquid after copper removal by vulcanization;
and adding sulfuric acid and a vulcanizing agent into the liquid after copper sulfide and decoppering to obtain arsenic sulfide slag.
The treatment method of the complex waste acid from copper smelting comprises the following steps of removing selenium, wherein the concentration of copper ions in the solution is 8-15 g/L, and the concentration of arsenic ions in the solution is 2-5 g/L.
The treatment method of the complex contaminated acid from copper smelting comprises the following steps of enabling the concentration of copper ions in the mineral processing wastewater to be 2-4 g/L and enabling the concentration of arsenic ions to be 2-4 g/L.
The treatment method of the copper smelting complex contaminated acid is characterized in that the addition amount of the scrap iron is every m 3 11-15 kg of scrap iron is added into the selenium-removed liquid, and the mass percentage of iron in the scrap iron is not lower than 80%.
The treatment method of the complex waste acid in copper smelting is characterized in that the concentration of copper ions in the solution after copper deposition is 2-4 g/L.
The treatment method of the copper smelting complex waste acid comprises the step of adding a vulcanizing agent into a copper smelting complex waste acid, wherein the vulcanizing agent is one or more of sodium sulfide, sodium hydrosulfide, potassium sulfide, barium sulfide and hydrogen sulfide.
The method for treating the copper smelting complex waste acid is characterized in that in the step of adding the vulcanizing agent into the low-copper-content waste acid, the addition amount of the vulcanizing agent is every m 3 7-9 kg of vulcanizing agent is added into the low-copper-content waste acid.
The treatment method for the copper smelting complex waste acid comprises the following steps of:
and (3) treating the sponge copper in a pyrogenic process system, and respectively recovering copper, tellurium and bismuth.
The treatment method of the complex waste acid from copper smelting comprises the following steps after the step of obtaining copper sulfide slag and liquid after copper sulfide removal:
and (3) placing the copper sulfide slag in a pyrogenic process system for treatment, and recovering copper.
The utility model provides a processing system of complicated dirty acid of copper smelting, wherein, includes the replacement groove, the intermediate tank, first plate and frame filter press, heavy copper back cistern, first waste acid storage tank, vulcanization reaction tank, dense pond, second waste acid storage tank that connect gradually through the pipeline, still includes second plate and frame filter press, second plate and frame filter press with dense pond passes through the pipe connection.
Has the advantages that: the invention discloses a method and a system for treating copper smelting complex waste acid, which are characterized in that on the basis of the existing process for treating the copper smelting waste acid by primary vulcanization, a selenium-removed liquid in the copper smelting complex waste acid is used as the high-copper-content waste acid, so that a process for replacing and depositing copper by scrap iron is added, the recovery rate of copper in the copper smelting complex waste acid can be greatly improved, and the consumption of a vulcanizing agent in the subsequent vulcanization treatment can be reduced, thereby reducing the cost; and then mixing the copper-precipitated solution with the beneficiation wastewater to obtain low-copper-content waste acid, and performing two-stage vulcanization treatment on the low-copper-content waste acid, so that the recovery rate of copper can be effectively improved, and the copper content of arsenic sulfide slag can be reduced. The invention treats the complex waste acid in copper smelting by adopting the process of scrap iron replacement and two-stage vulcanization treatment, has simple process, higher copper metal recovery rate, low copper content in arsenic sulfide slag and reduced operation cost.
Drawings
FIG. 1 is a flow chart of a preferred embodiment of the treatment method of copper smelting complex waste acid provided by the invention.
FIG. 2 is a schematic structural diagram of a treatment system for copper smelting complex waste acid according to an embodiment of the invention.
Detailed Description
The invention provides a method and a system for treating complex waste acid in copper smelting, and the method and the system are further described in detail below in order to make the purpose, the technical scheme and the effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the description of the present application, it is to be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "upper", "lower", "front", "rear", and the like, indicate orientations or positional relationships based on those shown in the drawings, and are used merely for convenience in describing the present application and for simplicity in description, and do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed in a particular orientation, and be operated, and thus should not be construed as limiting the present application. Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, features defined as "first" and "second" may explicitly or implicitly include one or more of the described features.
It will be understood by those skilled in the art that, unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the prior art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
Along with the increasing complexity of copper concentrate in the copper smelting industry and the diversity of the precious metal dressing and smelting combined process, the content of other valuable metals except copper in waste acid generated in the precious metal production process is increased continuously, the effective treatment of high-copper waste acid cannot be well met by using the existing vulcanization process, firstly, the copper removal rate is insufficient, the copper content of arsenic sulfide slag is high, the copper recovery rate is low, and secondly, the treatment cost of a large amount of vulcanizing agent waste acid is high.
Based on the above, the invention provides a method for treating complex contaminated acid from copper smelting, wherein the complex contaminated acid comprises a selenium-removed solution and mineral processing wastewater, and the method comprises the following steps of:
s10, adding scrap iron into the selenium-removed liquid to perform a displacement reaction to obtain a copper precipitate and a first reaction liquid;
s20, carrying out filter pressing treatment on the first reaction solution to obtain sponge copper and copper precipitation solution;
s30, mixing the copper-precipitated solution with the beneficiation wastewater to obtain low-copper-content waste acid;
s40, adding a vulcanizing agent into the low-copper-content waste acid, and then performing filter pressing treatment to obtain copper sulfide slag and a liquid after copper sulfide removal;
s50, adding sulfuric acid and a vulcanizing agent into the liquid after copper sulfide removal to obtain arsenic sulfide slag.
Specifically, on the basis of the existing process for treating the copper smelting waste acid by primary vulcanization, the selenium-removed liquid in the copper smelting complex waste acid is used as the high-copper-content waste acid, so that the process for replacing copper deposition by scrap iron is added, the recovery rate of copper in the copper smelting complex waste acid can be greatly improved, and meanwhile, the consumption of vulcanizing agents in the subsequent vulcanization treatment can be reduced, so that the cost is reduced; and then mixing the solution after copper precipitation with beneficiation wastewater to obtain low-copper-content waste acid, and performing two-stage vulcanization treatment on the low-copper-content waste acid, so that the recovery rate of copper can be effectively improved, and the copper content of arsenic sulfide slag can be reduced. The invention treats the complex waste acid in copper smelting by adopting the process of scrap iron replacement and two-stage vulcanization treatment, has simple process, higher copper metal recovery rate, low copper content in arsenic sulfide slag and reduced operation cost.
Specifically, the selenium-removed solution is generated in the reduction process of producing selenium from precious metals, and the beneficiation wastewater is the beneficiation waste liquid of copper electrolysis anode mud.
In some embodiments, the post-selenium removal solution has a copper ion concentration of 8 to 15g/L and an arsenic ion concentration of 2 to 5g/L.
In some embodiments, the beneficiation wastewater has a copper ion concentration of 2 to 4g/L and an arsenic ion concentration of 2 to 4g/L.
In some embodiments, the iron filings are added in an amount of per m 3 Adding 11-15 kg of scrap iron into the selenium-removed liquid, wherein the mass percent of iron in the scrap iron is not less than 80%, the addition of the scrap iron can influence the recovery rate of copper and the copper deposition efficiency, and when the iron is added per m 3 When the amount of the iron filings added into the liquid after the selenium removal exceeds 15kg, the copper deposition efficiency does not rise any more, so the cost and the efficiency are considered, and each m 3 Adding 11-15 kg iron filings into the selenium-removed liquid.
In some embodiments, the concentration of copper ions in the post-copper deposition solution is 2 to 4g/L, and when the concentration of copper ions in the post-copper deposition solution is 2 to 4g/L, the substitution reaction is completed.
In some embodiments, the sulfurizing agent is one or more of sodium sulfide, sodium hydrosulfide, potassium sulfide, barium sulfide, and hydrogen sulfide, preferably sodium sulfide.
In some embodiments, in the step of adding a vulcanizing agent to the low-copper-containing contaminated acid, the vulcanizing agent is added in an amount of each m 3 Adding 7-9 kg of vulcanizing agent into the low-copper-content waste acid.
In some embodiments, after the step of obtaining the copper sponge and the copper precipitation solution, the method further comprises the steps of:
and (3) treating the sponge copper in a pyrogenic process system, and respectively recovering copper, tellurium and bismuth.
Particularly, the sponge copper is treated by a pyrogenic process system, so that the precious metals such as copper, tellurium, bismuth and the like can be respectively recovered.
In some embodiments, after the step of obtaining the copper sulfide slag and the liquid after copper sulfide removal, the method further comprises the steps of:
and (3) placing the copper sulfide slag in a pyrogenic process system for treatment, and recovering copper.
In this embodiment, the filter pressing treatment is performed by a plate and frame filter press.
The invention also provides a treatment system for the complex waste acid in copper smelting, which comprises a displacement tank, an intermediate tank, a first plate-and-frame filter press, a copper precipitation liquid tank, a first waste acid storage tank, a vulcanization reaction tank, a thickening tank, a second waste acid storage tank and a second plate-and-frame filter press, wherein the displacement tank, the intermediate tank, the first plate-and-frame filter press, the copper precipitation liquid tank, the first waste acid storage tank, the vulcanization reaction tank, the thickening tank and the second waste acid storage tank are sequentially connected through pipelines, and the second plate-and-frame filter press is connected with the thickening tank through a pipeline.
Specifically, the displacement reaction tank can be arranged in multiple stages, and can be selected and changed according to the copper content of the waste acid.
Specifically, the replacement tank is a tank for reacting the selenium-removed liquid with iron chips; the intermediate tank is used for placing reaction solution; the liquid tank after copper precipitation is used for placing filtrate of the filter press; the vulcanization reaction tank is a tank for reacting waste acid and a vulcanizing agent; the thickening tank is used for solid-liquid separation; and the second waste acid storage tank is used for discharging the supernatant of the thickening tank.
The whole reaction flow is as follows: the method comprises the steps of enabling a selenium-removed liquid to enter a replacement tank, adding scrap iron into the replacement tank to perform a replacement reaction to obtain a copper precipitate and a first reaction liquid, enabling the first reaction liquid to enter a filter press through an intermediate tank to perform filter pressing treatment to obtain sponge copper and a copper-deposited liquid, enabling the copper-deposited liquid to enter a copper-deposited liquid tank, conveying the copper-deposited liquid to a first waste acid storage tank through a pipeline, adding ore-dressing wastewater into the first waste acid storage tank to obtain low-copper-containing waste acid, conveying the low-copper-containing waste acid to a vulcanization reaction tank through a pipeline, adding a vulcanizing agent into the vulcanization reaction tank, enabling obtained copper sulfide slag and the copper-removed liquid to enter a concentration tank, enabling the copper sulfide slag to enter a second plate-and frame filter press through a underflow pump to perform filter pressing treatment to obtain copper sulfide slag, enabling the copper sulfide-removed liquid to enter a second storage tank, and adding sulfuric acid and a vulcanizing agent into the second storage tank to obtain arsenic sulfide slag.
The application of the invention is not limited to the resource treatment of the copper-removing of the waste acid in the copper smelting industry, and can be used for the waste acid treatment in the non-ferrous metal smelting industry, such as the waste acid treatment with higher copper content in the smelting industries of copper, lead, zinc and the like.
The technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. It is clear that the described embodiments are only a part of the embodiments of the invention, not all embodiments, merely intended to illustrate the invention and in no way limit it. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A treatment method of copper smelting complex waste acid comprises the following steps:
s10, adding scrap iron into the selenium-removed liquid to perform a displacement reaction to obtain a copper precipitate and a first reaction liquid; wherein, the solution after selenium removal contains 10.71g/l of copper, 3.87g/l of arsenic and 11.27kg/m of scrap iron 3 Contaminated acid;
s20, carrying out filter pressing treatment on the first reaction solution to obtain sponge copper and copper precipitation solution;
s30, mixing the copper-precipitated solution with the beneficiation wastewater to obtain low-copper-content waste acid; wherein the beneficiation wastewater contains 3.31g/l of copper and 2.68g/l of arsenic;
s40, adding sodium sulfide into the low-copper-content waste acid, and then performing filter pressing treatment to obtain copper sulfide slag and a liquid after copper sulfide removal; wherein the adding amount of sodium sulfide is 7.67kg/m 3 Contaminated acid;
s50, adding the copper sulfide removal solution intoSulfuric acid and sodium sulfide to obtain arsenic sulfide slag; wherein the adding amount of sodium sulfide is 7.67kg/m 3 And (4) contaminated acid.
The processing capacity of the scrap iron and the copper deposit is 80m 3 D, the reaction efficiency in step S40 is 6 to 8m 3 The reaction efficiency in step S50 is 15 to 18m 3 The obtained sponge copper contains 46.92% of copper, 3.9% of bismuth and 14.55% of tellurium; the copper content of the copper sulfide slag is 30.23%, the arsenic content of the copper sulfide slag is 9.91%, and the copper recovery rate reaches 99.23%.
Comparative example 1
A treatment method of copper smelting complex waste acid comprises the following steps:
s10, adding scrap iron into the selenium-removed liquid to perform a displacement reaction to obtain a copper precipitate and a first reaction liquid; wherein, the solution after selenium removal contains 11.27g/l of copper, 5.05g/l of arsenic and 14.71kg/m of iron filings 3 Contaminated acid;
s20, performing filter pressing treatment on the first reacted liquid to obtain sponge copper and a copper-deposition liquid; wherein the beneficiation wastewater contains 2.03g/l of copper and 3.26g/l of arsenic;
s30, mixing the copper-precipitated solution with the beneficiation wastewater to obtain low-copper-content waste acid;
s40, adding sodium sulfide into the low-copper-content waste acid, and then performing filter pressing treatment to obtain copper sulfide slag and a liquid after copper sulfide removal; wherein the adding amount of sodium sulfide is 8.07kg/m 3 And (4) waste acid.
The processing capacity of the scrap iron and the copper deposit is 80m 3 D, the reaction efficiency in step S40 is 6 to 8m 3 The obtained sponge copper contains 43.51 percent of copper, 2.01 percent of bismuth and 16.23 percent of tellurium; the copper content of the copper sulfide slag is 29.86%, the arsenic content of the copper sulfide slag is 9.81%, and the copper recovery rate reaches 99.21%.
Comparative example 2
A treatment method of complex waste acid in copper smelting is characterized in that the waste acid is mixed with mineral processing wastewater after selenium removal, wherein when the copper content of the mixed waste acid is 15.51g/l and the arsenic content of the mixed waste acid is 3.42g/l, copper is removed by adopting an original first-stage vulcanization reaction. The adding amount of the sodium sulfide is 19.81kg/m 3 And (4) waste acid.
The copper content of the copper sulfide slag is 28.63%, the arsenic content of the copper sulfide slag is 4.98%, and the copper recovery rate reaches 92.19%.
In conclusion, the invention discloses a treatment method and a system for copper smelting complex waste acid, wherein the complex waste acid comprises a selenium-removed solution and mineral processing wastewater, and the method comprises the following steps: adding scrap iron into the selenium-removed liquid to perform a displacement reaction to obtain copper precipitate and a first reaction liquid; carrying out filter pressing treatment on the first reaction solution to obtain sponge copper and copper precipitation solution; mixing the copper-precipitated solution with the beneficiation wastewater to obtain low-copper-content waste acid; adding a vulcanizing agent into the low-copper-content waste acid, and then performing filter pressing treatment to obtain copper sulfide slag and a liquid after copper sulfide removal; and adding sulfuric acid and a vulcanizing agent into the liquid after copper sulfide and decoppering to obtain arsenic sulfide slag. According to the invention, on the basis of the existing process for treating the copper smelting waste acid by primary vulcanization, the selenium-removed liquid in the copper smelting complex waste acid is used as the high-copper-content waste acid, so that the process for replacing copper deposition by scrap iron is added, the recovery rate of copper in the copper smelting complex waste acid can be greatly improved, and the consumption of vulcanizing agents in the subsequent vulcanization treatment can be reduced, thereby reducing the cost; and then mixing the copper-precipitated solution with the beneficiation wastewater to obtain low-copper-content waste acid, and performing two-stage vulcanization treatment on the low-copper-content waste acid, so that the recovery rate of copper can be effectively improved, and the copper content of arsenic sulfide slag can be reduced. The invention treats the complex waste acid in copper smelting by adopting the process of scrap iron replacement and two-stage vulcanization treatment, has simple process, higher copper metal recovery rate, low copper content in arsenic sulfide slag and reduced operation cost.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A treatment method of complex waste acid in copper smelting comprises selenium-removed liquid and mineral processing wastewater, and is characterized by comprising the following steps:
adding scrap iron into the selenium-removed liquid to perform a displacement reaction, and filtering to obtain a copper precipitate and a liquid after the first reaction;
carrying out filter pressing treatment on the first reaction solution to obtain sponge copper and copper precipitation solution;
mixing the copper-precipitated solution with the beneficiation wastewater to obtain low-copper-content waste acid;
adding a vulcanizing agent into the low-copper-content waste acid, and then performing filter pressing treatment to obtain copper sulfide slag and a liquid after copper sulfide removal;
and adding sulfuric acid and a vulcanizing agent into the liquid after copper sulfide and decoppering to obtain arsenic sulfide slag.
2. The method for treating the complex waste acid from copper smelting according to claim 1, wherein the copper ion concentration in the selenium-removed solution is 8-15 g/L, and the arsenic ion concentration in the selenium-removed solution is 2-5 g/L.
3. The method for treating the copper smelting complex waste acid according to claim 1, wherein the concentration of copper ions in the beneficiation wastewater is 2-4 g/L, and the concentration of arsenic ions in the beneficiation wastewater is 2-4 g/L.
4. The method for treating the copper smelting complex waste acid according to claim 1, wherein the addition amount of the iron filings is every m 3 11-15 kg of scrap iron is added into the selenium-removed liquid, and the mass percentage of iron in the scrap iron is not lower than 80%.
5. The method for treating the copper smelting complex waste acid according to claim 1, wherein the concentration of copper ions in the copper precipitation solution is 2-4 g/L.
6. The method for treating the copper smelting complex waste acid according to the claim 1, wherein the vulcanizing agent is one or more of sodium sulfide, sodium hydrosulfide, potassium sulfide, barium sulfide and hydrogen sulfide.
7. The method for treating the copper smelting complex waste acid according to claim 1, wherein in the step of adding the vulcanizing agent into the low copper containing waste acid, the adding amount of the vulcanizing agent is every m 3 7-9 kg of vulcanizing agent is added into the low-copper-content waste acid.
8. The method for treating the copper smelting complex waste acid according to claim 1, characterized by further comprising the following steps after the step of obtaining the spongy copper and the copper precipitation solution:
and (3) treating the sponge copper in a pyrogenic process system, and respectively recovering copper, tellurium and bismuth.
9. The method for treating the copper smelting complex waste acid according to claim 1, characterized by further comprising the following steps after the step of obtaining copper sulfide slag and liquid after copper sulfide removal:
and (3) placing the copper sulfide slag in a pyrogenic process system for treatment, and recovering copper.
10. The utility model provides a processing system of complicated dirty acid is smelted to copper, its characterized in that includes and still includes second plate frame filter press by the cistern, first spent acid storage tank, vulcanization reaction tank, dense pond, second spent acid storage tank after the replacement groove, middle groove, first plate frame filter press, the heavy copper that connect gradually through the pipeline, second plate frame filter press with dense pond passes through the pipe connection.
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