CN115216633A - Method for separating copper and arsenic from black copper sludge and directly solidifying arsenic - Google Patents
Method for separating copper and arsenic from black copper sludge and directly solidifying arsenic Download PDFInfo
- Publication number
- CN115216633A CN115216633A CN202211046059.5A CN202211046059A CN115216633A CN 115216633 A CN115216633 A CN 115216633A CN 202211046059 A CN202211046059 A CN 202211046059A CN 115216633 A CN115216633 A CN 115216633A
- Authority
- CN
- China
- Prior art keywords
- arsenic
- copper
- leaching
- black copper
- black
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000010949 copper Substances 0.000 title claims abstract description 204
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 189
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 187
- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 123
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims abstract description 119
- 238000000034 method Methods 0.000 title claims abstract description 67
- 239000010802 sludge Substances 0.000 title claims abstract description 54
- 238000002386 leaching Methods 0.000 claims abstract description 119
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000007788 liquid Substances 0.000 claims abstract description 40
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 37
- 230000008569 process Effects 0.000 claims abstract description 36
- 150000003839 salts Chemical class 0.000 claims abstract description 30
- 238000002156 mixing Methods 0.000 claims abstract description 26
- 238000000926 separation method Methods 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 16
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 11
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 11
- 238000005303 weighing Methods 0.000 claims abstract description 4
- UYZMAFWCKGTUMA-UHFFFAOYSA-K iron(3+);trioxido(oxo)-$l^{5}-arsane;dihydrate Chemical compound O.O.[Fe+3].[O-][As]([O-])([O-])=O UYZMAFWCKGTUMA-UHFFFAOYSA-K 0.000 claims description 30
- 150000001879 copper Chemical class 0.000 claims description 16
- 238000005868 electrolysis reaction Methods 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 8
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 8
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 claims description 6
- 239000011790 ferrous sulphate Substances 0.000 claims description 6
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 6
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 6
- KAEAMHPPLLJBKF-UHFFFAOYSA-N iron(3+) sulfide Chemical compound [S-2].[S-2].[S-2].[Fe+3].[Fe+3] KAEAMHPPLLJBKF-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000011268 mixed slurry Substances 0.000 claims description 3
- 230000008901 benefit Effects 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 51
- 239000000047 product Substances 0.000 description 40
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 33
- 239000002893 slag Substances 0.000 description 28
- 239000000203 mixture Substances 0.000 description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 16
- 238000007711 solidification Methods 0.000 description 16
- 230000008023 solidification Effects 0.000 description 15
- 238000003723 Smelting Methods 0.000 description 14
- 239000002994 raw material Substances 0.000 description 13
- 239000007853 buffer solution Substances 0.000 description 11
- 238000001514 detection method Methods 0.000 description 11
- 229910052745 lead Inorganic materials 0.000 description 11
- 238000002791 soaking Methods 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- 238000004458 analytical method Methods 0.000 description 10
- 231100000419 toxicity Toxicity 0.000 description 10
- 230000001988 toxicity Effects 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 238000001556 precipitation Methods 0.000 description 9
- 230000006872 improvement Effects 0.000 description 8
- 238000011084 recovery Methods 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- MHUWZNTUIIFHAS-XPWSMXQVSA-N 9-octadecenoic acid 1-[(phosphonoxy)methyl]-1,2-ethanediyl ester Chemical compound CCCCCCCC\C=C\CCCCCCCC(=O)OCC(COP(O)(O)=O)OC(=O)CCCCCCC\C=C\CCCCCCCC MHUWZNTUIIFHAS-XPWSMXQVSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- MKOYQDCOZXHZSO-UHFFFAOYSA-N [Cu].[Cu].[Cu].[As] Chemical compound [Cu].[Cu].[Cu].[As] MKOYQDCOZXHZSO-UHFFFAOYSA-N 0.000 description 2
- IKWTVSLWAPBBKU-UHFFFAOYSA-N a1010_sial Chemical compound O=[As]O[As]=O IKWTVSLWAPBBKU-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229960002594 arsenic trioxide Drugs 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000002920 hazardous waste Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000001698 pyrogenic effect Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 229940047047 sodium arsenate Drugs 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000001180 sulfating effect Effects 0.000 description 2
- RMBBSOLAGVEUSI-UHFFFAOYSA-H Calcium arsenate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-][As]([O-])([O-])=O.[O-][As]([O-])([O-])=O RMBBSOLAGVEUSI-UHFFFAOYSA-H 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- -1 and meanwhile Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 150000001495 arsenic compounds Chemical class 0.000 description 1
- 229910000413 arsenic oxide Inorganic materials 0.000 description 1
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229940103357 calcium arsenate Drugs 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229940093920 gynecological arsenic compound Drugs 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- BMWMWYBEJWFCJI-UHFFFAOYSA-K iron(3+);trioxido(oxo)-$l^{5}-arsane Chemical compound [Fe+3].[O-][As]([O-])([O-])=O BMWMWYBEJWFCJI-UHFFFAOYSA-K 0.000 description 1
- 238000010310 metallurgical process Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- CIWAOCMKRKRDME-UHFFFAOYSA-N tetrasodium dioxido-oxo-stibonatooxy-lambda5-stibane Chemical compound [Na+].[Na+].[Na+].[Na+].[O-][Sb]([O-])(=O)O[Sb]([O-])([O-])=O CIWAOCMKRKRDME-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- NSBGJRFJIJFMGW-UHFFFAOYSA-N trisodium;stiborate Chemical compound [Na+].[Na+].[Na+].[O-][Sb]([O-])([O-])=O NSBGJRFJIJFMGW-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
-
- 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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
-
- 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
- C22B15/0002—Preliminary treatment
- C22B15/001—Preliminary treatment with modification of the copper constituent
- C22B15/0013—Preliminary treatment with modification of the copper constituent by roasting
- C22B15/0017—Sulfating or sulfiding roasting
-
- 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
- C22B15/0065—Leaching or slurrying
- C22B15/0082—Leaching or slurrying with water
-
- 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
- C22B30/04—Obtaining arsenic
-
- 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
Abstract
The invention provides a method for separating copper and arsenic from black copper sludge and directly solidifying the arsenic, which is characterized by comprising the following steps of: step 1, weighing a certain amount of black copper mud, and uniformly mixing ferric salt or ferrous salt and the black copper mud according to a certain proportion to obtain a mixed material; step 2, placing the mixed material obtained in the step 1 in a muffle furnace for low-temperature roasting treatment to obtain a roasted product, and taking out the roasted product for later use after roasting is finished; step 3, adding water into the roasted product obtained in the step 2 for leaching, and then carrying out solid-liquid separation to obtain a leaching solution and leaching residues; and step 4, the leaching solution obtained in the step 3 is a copper sulfate solution, and the leaching residue is washed and dried to obtain arsenic-containing condensate. The technology of the invention greatly shortens the treatment process flow of the black copper mud, realizes the high-efficiency separation of arsenic and copper in the black copper mud and the harmless treatment of arsenic, and has the advantages of simple and convenient operation, high efficiency, environmental protection, high efficiency and good popularization and application prospect.
Description
Technical Field
One or more embodiments of the specification relate to the technical field of metallurgical process hazardous waste recycling treatment, and in particular relates to a method for separating copper and arsenic from black copper sludge and directly solidifying the arsenic.
Background
In the process of electrolytic refining of copper, the electrolyte is purified and decoppered, impurities such As As, sb, bi and the like in the electrolyte are continuously accumulated and then are separated out from a cathode together with Cu to generate a gray black silt-like mixture, namely black copper mud, the main phase of which is Cu 3 As、Cu 2 As, and the like. If the copper is returned to a smelting system, a large amount of arsenic, antimony and bismuth are easy to circulate in a closed circuit in the copper smelting system, the direct recovery rate of metal and the subsequent quality of electrolytic copper are seriously influenced, the energy consumption is increased, and the health of workers is harmed. Therefore, the black copper sludge needs to be subjected to open-circuit treatment, so that the copper and arsenic resources are recycled, and good economic benefit and environmental benefit are obtained.
The traditional treatment method of the black copper mud comprises a pyrogenic process and a wet process, wherein the pyrogenic process has the defects of high investment, poor field operation environment and low recovery rate of valuable metals, and meanwhile, arsenic volatilizes in the form of arsenic trioxide during roasting to generate toxic gas to pollute the environment, so enterprises adopting the processes to recover arsenic mainly adopt hazardous waste treatment enterprises, and copper smelting enterprises rarely adopt the processes. The wet dearsenification process for black copper mud mainly includes acid leaching process and alkali leaching process, in which the acid leaching process utilizes sulfuric acid solution to leach black copper mud and prepare copper sulfate and As 2 O 3 Sodium arsenate, sodium antimonate, sodium pyroantimonate and other products, but the problems of serious corrosion to equipment, high cost of arsenic products, complex flow and the like exist; the alkaline leaching method utilizes sodium hydroxide to carry out alkaline oxidation leaching on the black copper mudArsenic is converted into sodium arsenate, and then the crude product As is prepared through causticization, acid decomposition and reduction crystallization processes 2 O 3 The process for treating the black copper sludge has certain advantages, but the metal recovery rate is low and the reagent consumption is large.
In the prior art, CN113862464A discloses a method for recovering copper and scattered metals in black copper sludge, and the method adopts a sulfating roasting-water leaching-acid leaching-solidification arsenic precipitation process to recover copper from the black copper sludge and stably solidify arsenic, but the method has the disadvantages of high acid consumption, high equipment corrosion prevention requirement, long process flow and high cost. CN110643815A discloses a method for harmlessly treating arsenic in black copper sludge, which converts the arsenic into storable calcium arsenate and scorodite through procedures of acid oxidation and acid leaching, arsenic neutralization and arsenic precipitation, scorodite solidification and arsenic precipitation and the like, but the process is also complicated, the reagent consumption is large, the cost is high, and the comprehensive recovery effect is poor; CN110643815B discloses a black copper mud recycling harmless treatment method, which adopts an oxidation leaching-back extraction electrodeposition-arsenic precipitation and arsenic fixation process to recycle and harmlessly treat black copper mud, but the method needs high-cost and difficult-control autoclave equipment to operate, and the subsequent process needs ferric sulfate and hydrogen peroxide to completely separate copper and arsenic, so that a large amount of reagents are consumed, the operation step of arsenic precipitation treatment is long, and the industrial application of enterprises is inconvenient.
In view of the above, the present application provides a method for separating copper and arsenic from black copper sludge and directly solidifying the arsenic, so as to solve the above-mentioned problems.
Disclosure of Invention
The present invention has been made to solve the problems occurring in the prior art, and an object of one or more embodiments of the present invention is to provide a method for manufacturing a copper-containing material having a short process flow, a low cost, a high leaching rate of copper, and a stable arsenic condensate.
The invention adopts ferric salt or ferrous salt as additive, and converts the copper arsenide in the black copper sludge into ferric arsenate by oxidizing roasting pretreatment process, i.e. arsenic component is solidified in the form of scorodite precipitation (can be safely stockpiled), and copper component is fed into solution in the form of soluble copper sulfate, and the obtained copper sulfate solution can be used for producing copper salt product or can be directly returned to copper electrolysis system for cyclic utilization, so as to achieve the high-efficiency separation and recovery of copper/arsenic and the harmless treatment of arsenic.
In view of the above, one or more embodiments of the present disclosure provide a method for separating copper and arsenic from black copper sludge and directly solidifying the arsenic, comprising the steps of:
step 2, placing the mixed material obtained in the step 1 in a muffle furnace for low-temperature roasting treatment to obtain a roasted product, and taking out the roasted product for later use after roasting is finished;
step 3, adding water into the roasted product obtained in the step 2 for leaching, and then carrying out solid-liquid separation to obtain a leaching solution and leaching residues;
and 4, washing and drying leaching residues to obtain arsenic-containing condensate, wherein the leaching solution obtained in the step 3 is a copper sulfate solution.
Preferably, the ferric salt or ferrous salt mixed with the black copper mud in the step 1 is one or more of ferric sulfate, ferrous sulfate, ferric sulfide and ferrous sulfide.
More preferably, the black copper mud and the ferric salt or the ferrous salt are uniformly mixed according to the molar ratio of As/Fe elements, wherein the molar ratio of As/Fe elements is 1:1.1 to 1:2.5.
preferably, the roasting temperature of the mixed material in the step 2 in the roasting process is 150-550 ℃.
More preferably, the roasting time in the roasting process of the mixed material in the step 2 is 0.5 to 8h.
Preferably, in the step 3, the roasted product is soaked in water at 20-90 ℃ for 1-4h in the water leaching process, and then solid-liquid separation is carried out when the temperature is not completely cooled, so as to obtain leachate and filter residue.
More preferably, during the water addition reaction in the step 3, the mixed slurry is stirred and leached, and the stirring speed is 100-300rpm.
More preferably, the solid-to-liquid ratio of the roasted product to water in the step 3 is 1g.
More preferably, the leaching solution in the step 4 is a copper sulfate solution, can be used for producing copper salt products, or can be directly combined with a production solution of a copper electrolysis system for conventional treatment; and 4, washing and drying the leached residues in the step 4 to obtain arsenic-containing condensate which is scorodite capable of being safely stockpiled.
As can be seen from the above, the present invention includes the following advantageous effects:
1. the invention adopts ferric salt or ferrous salt additive to carry out roasting-water leaching treatment on the black copper mud, which is different from sulfating roasting-water leaching-acid leaching-solidified arsenic precipitation processes, oxidation acid leaching-solidified arsenic precipitation processes, alkali leaching-solidified arsenic precipitation processes reported in the previous patents.
2. According to the invention, the arsenic solidification rate can reach 99.9% at most, the arsenic-containing condensate (scorodite) is stable in property, the stability of the obtained scorodite is analyzed according to GB5085.3-2007, the arsenic concentration in the toxic leachate can reach 1.12mg/L at most, the leaching concentration of the arsenic is less than the limit value (5 mg/L) of the standard, the scorodite can be safely stockpiled, and the problem of arsenic harm which troubles the industry is effectively solved.
3. The leaching rate of copper in the invention can reach 96% at most, and the leaching solution can be used for producing copper salt products, or can be directly combined with the production solution of a copper electrolysis system for conventional treatment.
4. The roasting technical scheme of the invention belongs to low-temperature roasting, is different from the roasting process reported in the previous patent, and effectively avoids the loss of arsenic in the form of gaseous arsenic oxide. In addition, the invention adopts the ferric salt or ferrous salt raw materials which are cheap and easy to obtain, has low cost, short process flow, simple operation, strong controllability and stable arsenic condensate property, and is suitable for industrial popularization.
Drawings
In order to more clearly illustrate one or more embodiments or prior art solutions of the present specification, the drawings that are needed in the description of the embodiments or prior art will be briefly described below, it is obvious that the drawings in the description below are only one or more embodiments of the present specification, and that other drawings may be obtained by those skilled in the art without inventive effort.
FIG. 1 is a schematic process flow diagram of the present invention.
FIG. 2 is a schematic diagram of XRD analysis results of arsenic-containing leaching residues obtained in the embodiment of the invention.
Detailed Description
To make the objects, technical solutions and advantages of the present disclosure more apparent, the present disclosure is further described in detail below with reference to specific embodiments.
Referring to fig. 1-2, in an embodiment of the present invention, a method for separating copper and arsenic from black copper sludge and directly solidifying the arsenic includes the following steps:
s1, weighing a certain amount of black copper mud, and uniformly mixing ferric salt or ferrous salt and the black copper mud according to a certain proportion to obtain a mixed material;
s2, placing the mixed material obtained in the step S1 in a muffle furnace for low-temperature roasting treatment to obtain a roasted product, and taking out the roasted product for later use after roasting is finished;
step S3, adding water into the roasted product obtained in the step S2 for leaching, and then carrying out solid-liquid separation to obtain a leaching solution and leaching residues;
and S4, the leaching solution obtained in the step S3 is a copper sulfate solution, and the leaching residues are washed and dried to obtain arsenic-containing condensate.
The working principle of the method for separating copper and arsenic from black copper sludge and directly curing arsenic in the embodiment of the invention is that under the aerobic roasting condition, a ferrous salt Fe (II) additive is easily oxidized into a Fe (III) or ferric salt additive by air, and low-valence arsenic compounds such as copper arsenide compounds in black copper sludge can be oxidized into FeAsO 4 I.e. arsenic components can be fixed in the slag in the form of scorodite precipitates, while copper components in the black copper sludge are oxidized to Cu 2+ And the arsenic and the copper in the black copper mud can be efficiently separated and the arsenic can be solidified by the solution by utilizing the chemical properties.
The chemical reaction equation of the above principle is:
（1）4Cu 3 As+4Fe 2 (SO 4 ) 3 +11O 2 =4FeAsO 4 +12CuSO 4 +2Fe 2 O 3 ；
（2）2Cu 3 As+6FeSO 4 +7O 2 =2FeAsO 4 +6CuSO 4 +2Fe 2 O 3 ；
（3）2Cu 3 As+6FeS+19O 2 =2FeAsO 4 +6CuSO 4 +2Fe 2 O 3 ；
（4）4Cu 3 As+4Fe 2 S 3 +35O 2 =4FeAsO 4 +12CuSO 4 +2Fe 2 O 3 。
the invention adopts the ferric salt or ferrous salt roasting-water leaching process to carry out resource and harmless treatment on the black copper mud, realizes the high-efficiency separation of Cu and As in the black copper mud and the harmless treatment of arsenic, obtains copper-containing filtrate (copper sulfate solution), and arsenic is in the most stable scorodite form (FeAsO solution) 4 ·2H 2 O) solidifies in the slag. The method provided by the invention can obviously improve the leaching rate of copper and the arsenic fixation rate in the black copper sludge, and experimental results show that when the method provided by the invention is used for treating the black copper sludge, the copper leaching rate respectively reaches over 96 percent, and the arsenic fixation rate reaches 99.9 percent. In addition, the method adopts ferric salt or ferrous salt for low-temperature roasting, does not need the high-temperature (more than 700 ℃) condition selected by the traditional roasting method, and reduces the energy consumption. The technology of the invention greatly shortens the black copper sludge treatment process flow, and has the advantages of simple operation, high efficiency, environmental protection, high efficiency and good popularization and application prospect.
As an improvement of the above scheme, the ferric salt or ferrous salt mixed with the black copper mud in step S1 is one or more of ferric sulfate, ferrous sulfate, ferric sulfide and ferrous sulfide.
As an improvement scheme of the scheme, the black copper mud and ferric salt or ferrous salt are uniformly mixed according to the molar ratio of As/Fe elements, wherein the molar ratio of As/Fe elements is 1:1.1 to 1:2.5.
as an improvement scheme of the scheme, the roasting temperature in the roasting process of the mixed material in the step S2 is 150-550 ℃.
As an improvement scheme of the scheme, the roasting time in the roasting process of the mixed material in the step S2 is 0.5 to 8h.
As an improvement of the scheme, in the step S3, the roasted product is soaked in water at 20-90 ℃ for 1-4h in the water leaching process, and then solid-liquid separation is performed when the temperature is not completely cooled, so as to obtain leachate and filter residue.
As an improvement of the above scheme, in the water leaching process in the step S3, the mixed slurry is subjected to agitation leaching at a stirring speed of 100-300rpm.
As a modified scheme of the scheme, the solid-to-liquid ratio of the roasted product to water in the step S3 is 1g; more preferably, the solid-to-liquid ratio of the roast product to water is: 1g, 5-9 mL.
As an improvement scheme of the scheme, the leaching solution in the step 4 is a copper sulfate solution, can be used for producing copper salt products, or can be directly combined with a production solution of a copper electrolysis system for conventional treatment; and 4, washing and drying the leached residues in the step 4 to obtain arsenic-containing condensate which is scorodite capable of being safely stockpiled.
To make the objects, technical solutions and advantages of the present disclosure more apparent, the present disclosure will be described in further detail with reference to specific embodiments. The present invention is further illustrated by the following examples, while the present invention is not limited to the following embodiments.
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention. The main components (by mass) of the black copper mud raw material are not particularly described, and are 20 to 70wt% of Cu, 5 to 40wt% of As, 0.5 to 5wt% of Bi, 0.5 to 7wt% of Sb, 0.1 to 4.5wt% of Pb, and 0.5 to 1.5wt% of ni, but the technical scheme of the present invention is not limited to the black copper mud used only in the content of the substance.
Example 1
Taking black copper sludge of a certain copper smelting plant in China As an example, the raw material components in the black copper sludge are Cu 31.565%, as 10.687%, bi1.567%, ni 0.874%, sb 0.267% and Pb 0.101%, and the black copper sludge is treated by the following steps:
(1) Roasting ferric salt or ferrous salt: taking 15g of black copper mud, uniformly mixing the black copper mud and ferric sulfate according to the molar ratio of As/Fe of 1.5, placing the mixture in a muffle furnace, roasting for 3 hours at the temperature of 300 ℃, and opening a furnace door to cool roasting slag to the required temperature after roasting;
(2) And (3) calcine water leaching: and (3) uniformly mixing the obtained roasted product with water according to a liquid-solid ratio of 8 (mL/g) to 1, soaking in water at the temperature of 80 ℃ for 1.5h, and carrying out solid-liquid separation while the mixture is hot to obtain leaching slag and leaching liquid. The leaching residue is washed and dried to obtain stable arsenic-containing condensate (scorodite), the leaching solution can be used for producing copper salt products, or can be directly combined with the production solution of a copper electrolysis system for conventional treatment;
(3) Analyzing and detecting: the detection shows that the arsenic solidification rate in the step (2) is 94.3 percent, and the copper leaching rate is 92.7 percent; after leaching the leaching residue by TCLP acetic acid buffer solution, the arsenic concentration of the liquid is 2.14 (mg/L) and is lower than 5 (mg/L) in reference to GB5085.3-2007 toxicity analysis, the requirement of GB5085.3-2007 is met, and scorodite can be stockpiled and treated.
Example 2
Taking black copper sludge of a certain copper smelting plant in China As an example, the raw material components in the black copper sludge are Cu 31.565%, as 10.687%, bi1.567%, ni 0.874%, sb 0.267% and Pb 0.101%, and the black copper sludge is treated by the following steps:
(1) Roasting ferric salt or ferrous salt: taking 15g of black copper mud, uniformly mixing the black copper mud and ferric sulfate according to the molar ratio of As to Fe of 1.9, placing the mixture into a muffle furnace, roasting for 0.5h at the temperature of 550 ℃, and opening a furnace door to cool roasting slag to the required temperature after roasting;
(2) And (3) calcine water leaching: and uniformly mixing the obtained roasted product with water according to a liquid-solid ratio of 8 (mL/g), soaking in water at 60 ℃ for 1h, and carrying out solid-liquid separation while the mixture is hot to obtain leaching slag and a leaching solution. The leaching residue is washed and dried to obtain stable arsenic-containing condensate (scorodite), the leaching solution can be used for producing copper salt products, or can be directly combined with the production solution of a copper electrolysis system for conventional treatment;
(3) Analyzing and detecting: the detection shows that the arsenic solidification rate in the step (2) is 99.9 percent, and the copper leaching rate is 95.9 percent; after leaching residues are leached by TCLP acetic acid buffer solution, the arsenic concentration of liquid is 1.12 (mg/L) and is lower than 5 (mg/L) in reference to GB5085.3-2007 toxicity analysis, the requirements of GB5085.3-2007 are met, and scorodite can be stockpiled.
Example 3
Taking black copper mud of a certain copper smelting plant in China As an example, the raw material components in the black copper mud are Cu 31.565%, as 10.687%, bi1.567%, ni 0.874%, sb 0.267% and Pb 0.101%, and the black copper mud is treated by the following steps:
(1) Roasting ferric salt or ferrous salt: taking 15g of black copper mud, uniformly mixing the black copper mud and ferrous sulfate according to the molar ratio of As/Fe of 1 to 2.5, placing the mixture in a muffle furnace, roasting for 2.5 hours at the temperature of 400 ℃, and opening a furnace door to cool roasting slag to the required temperature after roasting;
(2) And (3) calcine water leaching: and (3) uniformly mixing the obtained roasted product with water according to a liquid-solid ratio of 6 (mL/g), soaking in water at 50 ℃ for 2 hours, and carrying out solid-liquid separation while the mixture is hot to obtain leaching slag and leaching liquid. The leaching residue is washed and dried to obtain stable arsenic-containing condensate (scorodite), and the leaching solution can be used for producing copper salt products or can be directly combined with production solution of a copper electrolysis system for conventional treatment;
(3) Analyzing and detecting: the detection shows that the arsenic solidification rate in the step (2) is 98.2 percent, and the copper leaching rate is 92.6 percent; after leaching residues are leached by TCLP acetic acid buffer solution, the arsenic concentration of liquid is 1.96 (mg/L) and is lower than 5 (mg/L) in reference to GB5085.3-2007 toxicity analysis, the requirements of GB5085.3-2007 are met, and scorodite can be stockpiled.
Example 4
Taking black copper sludge of a certain copper smelting plant in China As an example, the raw material components in the black copper sludge are Cu 31.565%, as 10.687%, bi1.567%, ni 0.874%, sb 0.267% and Pb 0.101%, and the black copper sludge is treated by the following steps:
(1) Roasting ferric salt or ferrous salt: taking 15g of black copper mud, uniformly mixing the black copper mud and ferrous sulfide according to the molar ratio of As/Fe of 1.1, placing the mixture in a muffle furnace, roasting for 8 hours at the temperature of 150 ℃, and opening a furnace door to cool roasting slag to the required temperature after roasting;
(2) And (3) calcine water leaching: and uniformly mixing the obtained roasted product with water according to a liquid-solid ratio of 9 (mL/g), soaking in water at 90 ℃ for 4h, and carrying out solid-liquid separation while the mixture is hot to obtain leaching slag and a leaching solution. The leaching residue is washed and dried to obtain stable arsenic-containing condensate (scorodite), the leaching solution can be used for producing copper salt products, or can be directly combined with the production solution of a copper electrolysis system for conventional treatment;
(3) Analyzing and detecting: the detection shows that the arsenic solidification rate in the step (2) is 94.9 percent, and the copper leaching rate is 91.2 percent; after leaching the leaching residue by TCLP acetic acid buffer solution, the arsenic concentration of the liquid is 2.19 (mg/L) and is lower than 5 (mg/L) in reference to GB5085.3-2007 toxicity analysis, the requirement of GB5085.3-2007 is met, and scorodite can be stockpiled and treated.
Example 5
Taking black copper mud of a certain copper smelting plant in China As an example, the raw material components in the black copper mud are Cu 31.565%, as 10.687%, bi1.567%, ni 0.874%, sb 0.267% and Pb 0.101%, and the black copper mud is treated by the following steps:
(1) Roasting ferric salt or ferrous salt: taking 15g of black copper mud, uniformly mixing the black copper mud and iron sulfide according to the molar ratio of As to Fe of 1.7, placing the mixture into a muffle furnace, roasting for 4 hours at the temperature of 400 ℃, and opening a furnace door to cool roasting slag to the required temperature after roasting and sintering;
(2) And (3) calcine water leaching: and (3) uniformly mixing the obtained roasted product with water according to a liquid-solid ratio of 7 (mL/g), soaking in water at 20 ℃ for 3 hours, and carrying out solid-liquid separation while the roasted product is hot to obtain leaching slag and leaching liquid. The leaching residue is washed and dried to obtain stable arsenic-containing condensate (scorodite), the leaching solution can be used for producing copper salt products, or can be directly combined with the production solution of a copper electrolysis system for conventional treatment;
(3) Analyzing and detecting: the detection shows that the arsenic solidification rate in the step (2) is 97.1 percent, and the copper leaching rate is 94.2 percent; after leaching the leaching residue by TCLP acetic acid buffer solution, the arsenic concentration of the liquid is 1.99 (mg/L) and is lower than 5 (mg/L) in reference to GB5085.3-2007 toxicity analysis, the requirement of GB5085.3-2007 is met, and scorodite can be stockpiled and treated.
Example 6
Taking black copper sludge of a certain copper smelting plant in China As an example, the raw material components in the black copper sludge are Cu 31.565%, as 10.687%, bi1.567%, ni 0.874%, sb 0.267% and Pb 0.101%, and the black copper sludge is treated by the following steps:
(1) Roasting ferric salt or ferrous salt: taking 15g of black copper mud, uniformly mixing the black copper mud and ferric sulfate according to the molar ratio of As to Fe of 1:2.1, placing the mixture into a muffle furnace, roasting for 3.5 hours at the temperature of 350 ℃, and opening a furnace door to cool roasting slag to the required temperature after roasting;
(2) And (3) calcine water leaching: and uniformly mixing the obtained roasted product with water according to a liquid-solid ratio of 8 (mL/g), soaking in water at 40 ℃ for 1h, and carrying out solid-liquid separation while the mixture is hot to obtain leaching slag and a leaching solution. The leaching residue is washed and dried to obtain stable arsenic-containing condensate (scorodite), the leaching solution can be used for producing copper salt products, or can be directly combined with the production solution of a copper electrolysis system for conventional treatment;
(3) Analyzing and detecting: the detection shows that the arsenic solidification rate in the step (2) is 96.7 percent, and the copper leaching rate is 93.5 percent; after leaching residues are leached by TCLP acetic acid buffer solution, the arsenic concentration of liquid is 2.07 (mg/L) and is lower than 5 (mg/L) in reference to GB5085.3-2007 toxicity analysis, the requirement of GB5085.3-2007 is met, and scorodite can be stockpiled and treated.
Example 7
Taking black copper sludge of a certain copper smelting plant in China As an example, the raw material components in the black copper sludge are Cu 31.565%, as 10.687%, bi1.567%, ni 0.874%, sb 0.267% and Pb 0.101%, and the black copper sludge is treated by the following steps:
(1) Roasting ferric salt or ferrous salt: taking 15g of black copper mud, uniformly mixing the black copper mud and ferrous sulfate according to the molar ratio of As/Fe of 1 to 2.2, placing the mixture in a muffle furnace, roasting for 2.5 hours at the temperature of 500 ℃, and opening a furnace door to cool roasting slag to the required temperature after roasting;
(2) And (3) calcine water leaching: and (3) uniformly mixing the obtained roasted product with water according to a liquid-solid ratio of 5 (mL/g) to 1, soaking in water at 40 ℃ for 2.5h, and carrying out solid-liquid separation while the mixture is hot to obtain leaching slag and leaching liquid. The leaching residue is washed and dried to obtain stable arsenic-containing condensate (scorodite), and the leaching solution can be used for producing copper salt products or can be directly combined with production solution of a copper electrolysis system for conventional treatment;
(3) Analyzing and detecting: the detection shows that the arsenic solidification rate in the step (2) is 99.6 percent, and the copper leaching rate is 93.2 percent; after leaching the leaching residue by TCLP acetic acid buffer solution, the arsenic concentration of the liquid is 1.91 (mg/L) and is lower than 5 (mg/L) in reference to GB5085.3-2007 toxicity analysis, the requirement of GB5085.3-2007 is met, and scorodite can be stockpiled and treated.
Example 8
Taking black copper sludge of a certain copper smelting plant in China As an example, the raw material components in the black copper sludge are Cu 31.565%, as 10.687%, bi1.567%, ni 0.874%, sb 0.267% and Pb 0.101%, and the black copper sludge is treated by the following steps:
(1) Roasting ferric salt or ferrous salt: taking 15g of black copper mud, uniformly mixing the black copper mud and ferric sulfide according to the molar ratio of As/Fe of 1.3, placing the mixture in a muffle furnace, roasting for 6 hours at the temperature of 250 ℃, and opening a furnace door to cool roasting slag to the required temperature after roasting;
(2) And (3) calcine water leaching: and uniformly mixing the obtained roasted product with water according to a liquid-solid ratio of 9 (mL/g), soaking in water at 50 ℃ for 4h, and carrying out solid-liquid separation while the mixture is hot to obtain leaching slag and a leaching solution. The leaching residue is washed and dried to obtain stable arsenic-containing condensate (scorodite), the leaching solution can be used for producing copper salt products, or can be directly combined with the production solution of a copper electrolysis system for conventional treatment;
(3) Analyzing and detecting: the detection shows that the arsenic solidification rate in the step (2) is 95.6 percent, and the copper leaching rate is 92.3 percent; after leaching the leaching residue by TCLP acetic acid buffer solution, the arsenic concentration of the liquid is 2.0 (mg/L) and is lower than 5 (mg/L) in reference to GB5085.3-2007 toxicity analysis, the requirement of GB5085.3-2007 is met, and scorodite can be stockpiled and treated.
Comparative example 1
Taking black copper sludge of a certain copper smelting plant in China As an example, the raw material components in the black copper sludge are Cu 31.565%, as 10.687%, bi1.567%, ni 0.874%, sb 0.267% and Pb 0.101%, and the black copper sludge is treated by the following steps:
(1) Roasting ferric salt or ferrous salt: taking 15g of black copper mud, uniformly mixing the black copper mud and ferric sulfate according to the molar ratio of As/Fe of 1 to 0.7, placing the mixture in a muffle furnace, roasting for 3 hours at the temperature of 300 ℃, and opening a furnace door to cool roasting slag to the required temperature after roasting;
(2) And (3) calcine water leaching: and (3) uniformly mixing the obtained roasted product with water according to a liquid-solid ratio of 8 (mL/g) to 1, soaking in water at the temperature of 80 ℃ for 1.5h, and carrying out solid-liquid separation while the mixture is hot to obtain leaching slag and leaching liquid. Washing and drying leached residues to obtain arsenic-containing condensate (scorodite), and retreating the leached solution to be used as a copper salt product or directly combining the leached solution with a production solution of a copper electrolysis system for conventional treatment;
(3) Analyzing and detecting: detection shows that the arsenic solidification rate in the step (2) is 14.7 percent, and the copper leaching rate is 58.5 percent; compared with the embodiment 1, the reason is that the addition amount of the ferric salt or the ferrous salt is less, the roasting reaction is incomplete, and the arsenic solidification rate is reduced; after leaching residues are leached by TCLP acetic acid buffer solution, the arsenic concentration of liquid is 147.27 (mg/L) and is far higher than 5 (mg/L) in the toxicity analysis of GB5085.3-2007, the requirement of GB5085.3-2007 is not met, and the arsenic-containing condensate (leaching residues) can not be stockpiled.
Comparative example 2
Taking black copper mud of a certain copper smelting plant in China As an example, the raw material components in the black copper mud are Cu 31.565%, as 10.687%, bi1.567%, ni 0.874%, sb 0.267% and Pb 0.101%, and the black copper mud is treated by the following steps:
(1) Roasting ferric salt or ferrous salt: taking 15g of black copper mud, uniformly mixing the black copper mud and ferrous sulfate according to the molar ratio of As/Fe of 1.9, placing the mixture in a muffle furnace, roasting for 0.5h at the temperature of 650 ℃, and opening a furnace door to cool roasting slag to the required temperature after roasting;
(2) And (3) calcine water leaching: and uniformly mixing the obtained roasted product with water according to a liquid-solid ratio of 8 (mL/g), soaking in water at 60 ℃ for 1h, and carrying out solid-liquid separation while the mixture is hot to obtain leaching slag and a leaching solution. Washing and drying the leached slag to obtain arsenic-containing condensate (scorodite), and treating the leached liquid to produce copper salt product or directly combining the leached liquid with the production solution of a copper electrolysis system for conventional treatment;
(3) Analyzing and detecting: the detection shows that the arsenic solidification rate in the step (2) is 12.7 percent, and the copper leaching rate is 68.9 percent; compared with the embodiment 2, the arsenic curing rate is reduced due to the fact that the roasting temperature of ferric salt or ferrous salt is high, a large amount of arsenic volatilizes, the arsenic concentration of the leached residues is 124.71 (mg/L) and is far higher than 5 (mg/L) by referring to GB5085.3-2007 after the leached residues are leached by TCLP acetic acid buffer solution, the requirement of GB5085.3-2007 is not met, and the arsenic-containing cured materials (the leached residues) cannot be stockpiled.
Comparative example 3
Taking black copper sludge of a certain copper smelting plant in China As an example, the raw material components in the black copper sludge are Cu 31.565%, as 10.687%, bi1.567%, ni 0.874%, sb 0.267% and Pb 0.101%, and the black copper sludge is treated by the following steps:
(1) Roasting ferric salt or ferrous salt: taking 15g of black copper mud, uniformly mixing the black copper mud and ferrous sulfide according to the molar ratio of As/Fe of 1 to 2.5, placing the mixture in a muffle furnace, roasting for 2.5 hours at the temperature of 120 ℃, and opening a furnace door to cool roasting slag to the required temperature after roasting;
(2) And (3) calcine water leaching: and (3) uniformly mixing the obtained roasted product with water according to a liquid-solid ratio of 6 (mL/g), soaking in water at 50 ℃ for 2 hours, and carrying out solid-liquid separation while the mixture is hot to obtain leaching slag and leaching liquid. Washing and drying leached residues to obtain arsenic-containing condensate (scorodite), and retreating the leached solution to be used as a copper salt product or directly combining the leached solution with a production solution of a copper electrolysis system for conventional treatment;
(3) Analyzing and detecting: the detection shows that the arsenic solidification rate in the step (2) is 9.4 percent, and the copper leaching rate is 43.7 percent; compared with the example 3, the reason is that the roasting temperature of the ferric salt or ferrous salt is too low, only a small part of the ferric salt or ferrous salt participates in the reaction, the reaction is not thorough enough, so that the arsenic solidification rate is reduced, the arsenic concentration of the leached slag is 183.9 (mg/L) and far higher than 5 (mg/L) in the toxicity analysis of the liquid by referring to GB5085.3-2007 after the leached slag is leached by the TCLP acetic acid buffer solution, the requirement of GB5085.3-2007 is not met, and the arsenic-containing condensate (the leached slag) cannot be stockpiled.
It is intended that the one or more embodiments of the present specification embrace all such alternatives, modifications and variations as fall within the broad scope of the appended claims. Therefore, any omissions, modifications, substitutions, improvements, and the like that may be made without departing from the spirit or scope of the disclosure are intended to be included within the scope of the disclosure.
Claims (9)
1. A method for separating copper and arsenic from black copper sludge and directly solidifying the arsenic is characterized by comprising the following steps:
step 1, weighing a certain amount of black copper mud, and uniformly mixing ferric salt or ferrous salt and the black copper mud according to a certain proportion to obtain a mixed material;
step 2, placing the mixed material obtained in the step 1 in a muffle furnace for low-temperature roasting treatment to obtain a roasted product, and taking out the roasted product for later use after roasting is finished;
step 3, adding water into the roasted product obtained in the step 2 for leaching, and then carrying out solid-liquid separation to obtain a leaching solution and leaching residues;
and 4, washing and drying leaching residues to obtain arsenic-containing condensate, wherein the leaching solution obtained in the step 3 is a copper sulfate solution.
2. The method for separating copper and arsenic from black copper sludge and directly solidifying arsenic according to claim 1, wherein the ferric salt or ferrous salt mixed with the black copper sludge in the step 1 is one or more of ferric sulfate, ferrous sulfate, ferric sulfide and ferrous sulfide.
3. The method for separating copper and arsenic from black copper sludge and directly solidifying arsenic according to claim 2, wherein the black copper sludge and the ferric or ferrous salt are uniformly mixed in terms of molar ratio of As/Fe elements, the molar ratio of As/Fe elements is 1:1.1 to 1:2.5.
4. the method for separating copper and arsenic from black copper sludge and directly solidifying arsenic as claimed in claim 1, wherein the roasting temperature of the mixed material in the step 2 is 150 ℃ to 550 ℃.
5. The method for separating copper and arsenic from black copper sludge and directly curing arsenic as claimed in claim 4, wherein the baking time of the mixed material in the step 2 is 0.5 to 8h in the baking process.
6. The method for separating copper and arsenic from black copper sludge and directly solidifying arsenic according to claim 1, wherein the roasted product in the step 3 is soaked in water at 20-90 ℃ for 1-4h, and then solid-liquid separation is carried out when the temperature is not completely cooled, so as to obtain leachate and filter residue.
7. The method for separating copper and arsenic from black copper sludge and directly solidifying arsenic as claimed in claim 6, wherein the step 3 of leaching with water is performed by stirring the mixed slurry at a stirring speed of 100-300rpm.
8. The method for separating copper and arsenic from black copper sludge and directly solidifying arsenic according to claim 6, wherein the solid-to-liquid ratio of the roasted product to water in the step 3 is 1 g.
9. The method for separating copper and arsenic from black copper sludge and directly solidifying arsenic as claimed in claim 6, wherein the leaching solution in step 4 is copper sulfate solution, which can be used for producing copper salt products, or can be directly combined with the production solution of copper electrolysis system for conventional treatment; and 4, washing and drying the leaching residue in the step 4 to obtain arsenic-containing condensate which is scorodite capable of being safely stockpiled.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211046059.5A CN115216633B (en) | 2022-08-30 | 2022-08-30 | Method for separating copper, arsenic and directly solidifying arsenic from black copper mud |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211046059.5A CN115216633B (en) | 2022-08-30 | 2022-08-30 | Method for separating copper, arsenic and directly solidifying arsenic from black copper mud |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115216633A true CN115216633A (en) | 2022-10-21 |
| CN115216633B CN115216633B (en) | 2024-03-08 |
Family
ID=83617105
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211046059.5A Active CN115216633B (en) | 2022-08-30 | 2022-08-30 | Method for separating copper, arsenic and directly solidifying arsenic from black copper mud |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115216633B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116177589A (en) * | 2023-02-15 | 2023-05-30 | 西北矿冶研究院 | Method for preparing electroplating-grade copper sulfate from black copper sludge |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE569586A (en) * | ||||
| US5762891A (en) * | 1996-02-27 | 1998-06-09 | Hazen Research, Inc. | Process for stabilization of arsenic |
| JP2002192167A (en) * | 2000-12-28 | 2002-07-10 | Mitsui Mining & Smelting Co Ltd | METHOD FOR TREATING Se AND As-CONTAINING WASTEWATER |
| CN1904094A (en) * | 2006-08-03 | 2007-01-31 | 山东国大黄金股份有限公司 | Method of extracting gold and silver from arsenic containing aurin ore |
-
2022
- 2022-08-30 CN CN202211046059.5A patent/CN115216633B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE569586A (en) * | ||||
| US5762891A (en) * | 1996-02-27 | 1998-06-09 | Hazen Research, Inc. | Process for stabilization of arsenic |
| JP2002192167A (en) * | 2000-12-28 | 2002-07-10 | Mitsui Mining & Smelting Co Ltd | METHOD FOR TREATING Se AND As-CONTAINING WASTEWATER |
| CN1904094A (en) * | 2006-08-03 | 2007-01-31 | 山东国大黄金股份有限公司 | Method of extracting gold and silver from arsenic containing aurin ore |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116177589A (en) * | 2023-02-15 | 2023-05-30 | 西北矿冶研究院 | Method for preparing electroplating-grade copper sulfate from black copper sludge |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115216633B (en) | 2024-03-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102443701B (en) | Clean metallurgic comprehensive utilization method of iron vitriol slags | |
| CN113684368A (en) | Method for co-processing arsenic sulfide slag and arsenic-containing smoke dust in copper smelting | |
| CN104928478B (en) | A kind of method of electroplating sludge comprehensively recovering valuable metal | |
| CN101817553B (en) | Method for treating arsenic-containing smoke dust | |
| CN101519727A (en) | Method for treating zinc smelting by-products | |
| CN104946903A (en) | Method for recovering metal resource from zinc calcine through reduction roasting-leaching-zinc sinking | |
| CN105129839A (en) | Method for producing micron-grade zinc oxide with high fluorine and chlorine crude zinc oxide as raw material | |
| CN106636656A (en) | Method for recovering valuable metal from copper smelting white smoke | |
| CN111647754A (en) | Comprehensive utilization method of zinc-containing dust and sludge in steel plant | |
| CN109055719A (en) | A method of recycling valuable metal from selenic acid mud | |
| CN113862464B (en) | Method for recovering copper and scattered metal in black copper sludge | |
| CN102925701A (en) | Method using wet alkaline process of cobalt-nickel (Co-Ni) residue containing arsenic to prepare arsenate | |
| CN110172583B (en) | Method for efficiently treating arsenic-containing soot in reduction mode | |
| CN115216633B (en) | Method for separating copper, arsenic and directly solidifying arsenic from black copper mud | |
| CN107058750A (en) | Germanic Bellamya aeruginosa comprehensive recycling process | |
| CN101817554A (en) | Method for synthesizing calcium arsenate by oxygen pressure conversion | |
| CN102002597B (en) | Method for comprehensively recovering valuable metals from low-grade tellurium slag | |
| CN106636657B (en) | A method of containing the pre- dearsenification of arsenic smoke dust | |
| CN102828033A (en) | Method for recycling electrolytic zinc acid leaching slag | |
| CN114558440B (en) | High-efficiency zinc extraction coupling pulp flue gas desulfurization carbon fixation process by high-chlorine zinc gray ammonia-ammonium sulfate method | |
| CN102863009B (en) | Method of using low-grade zinc oxide ore to produce high-purity zinc oxide | |
| CN109055764A (en) | A kind of comprehensive recovering process of the low zinc material of high chlorine | |
| CN108913892A (en) | A method of the comprehensively recovering valuable metal from the pickle liquor of cupric | |
| CN112111647B (en) | Method for pre-treating gold leaching by using gold ore calcine or roasting cyanidation tailings | |
| CN108063295A (en) | The method that lithium is extracted in the clinker generated from pyrogenic process recycling lithium battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |