CN110669946B - Extraction method of iron-rich and high-impurity copper leaching solution - Google Patents
Extraction method of iron-rich and high-impurity copper leaching solution Download PDFInfo
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- 238000000605 extraction Methods 0.000 title claims abstract description 145
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000010949 copper Substances 0.000 title claims abstract description 64
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 63
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 25
- 238000002386 leaching Methods 0.000 title claims abstract description 18
- 239000012535 impurity Substances 0.000 title claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 40
- 238000003860 storage Methods 0.000 claims abstract description 25
- 239000002253 acid Substances 0.000 claims abstract description 23
- 229910001437 manganese ion Inorganic materials 0.000 claims abstract description 13
- 238000005352 clarification Methods 0.000 claims description 35
- 239000012074 organic phase Substances 0.000 claims description 30
- 238000005406 washing Methods 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 19
- 238000000926 separation method Methods 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 11
- 239000012071 phase Substances 0.000 claims description 5
- 238000005086 pumping Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000008346 aqueous phase Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 20
- 238000004519 manufacturing process Methods 0.000 abstract description 18
- 239000000460 chlorine Substances 0.000 abstract description 7
- 229910052801 chlorine Inorganic materials 0.000 abstract description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 230000000630 rising effect Effects 0.000 abstract description 4
- -1 iron ions Chemical class 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000003085 diluting agent Substances 0.000 abstract description 2
- 238000009854 hydrometallurgy Methods 0.000 abstract description 2
- 238000005363 electrowinning Methods 0.000 abstract 2
- 238000004581 coalescence Methods 0.000 abstract 1
- 238000004070 electrodeposition Methods 0.000 description 17
- 239000000243 solution Substances 0.000 description 15
- 238000005516 engineering process Methods 0.000 description 6
- 238000004886 process control Methods 0.000 description 6
- 238000011112 process operation Methods 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 3
- 229910052947 chalcocite Inorganic materials 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052948 bornite Inorganic materials 0.000 description 2
- 229910052951 chalcopyrite Inorganic materials 0.000 description 2
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 description 2
- 239000012527 feed solution Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052683 pyrite Inorganic materials 0.000 description 2
- 239000011028 pyrite Substances 0.000 description 2
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 241000086254 Arnica montana Species 0.000 description 1
- 229910052934 alunite Inorganic materials 0.000 description 1
- 239000010424 alunite Substances 0.000 description 1
- MJLGNAGLHAQFHV-UHFFFAOYSA-N arsenopyrite Chemical compound [S-2].[Fe+3].[As-] MJLGNAGLHAQFHV-UHFFFAOYSA-N 0.000 description 1
- 229910052964 arsenopyrite Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- 229910001648 diaspore Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 229910052900 illite Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- KPZTWMNLAFDTGF-UHFFFAOYSA-D trialuminum;potassium;hexahydroxide;disulfate Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O KPZTWMNLAFDTGF-UHFFFAOYSA-D 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
-
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/02—Apparatus therefor
-
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
the invention belongs to the technical field of copper hydrometallurgy, and particularly relates to an extraction method of a copper leaching solution with high acid content, iron content and impurities content, which is implemented by adopting two series of extraction devices, wherein the extraction rate of the obtained copper can be controlled to be 65-85%, the consumption of copper acid per extraction electrowinning ton is about 180-300kg (effective control and reduction of acid consumption, further control of acidity rising of the whole storage yard), the consumption of an extracting agent is about 4kg, the consumption of a diluting agent is about 25kg, meanwhile, the stable control of each parameter index of the copper-rich liquid to be about 45-50 g/L, the content of chlorine and manganese ions is within 10ppm, the content of iron ions is 1.5-2.5 g/L, and the oil content is 5-10ppm through oil removing devices (ultrasonic oil removers or coalescence oil removers and the like), thereby being beneficial to the stable control and production of the subsequent electrowinning process.
Description
Technical Field
The invention belongs to the technical field of copper hydrometallurgy, and particularly relates to an extraction method of a high-acid-content, high-impurity copper leaching solution, which is mainly applied to the copper extraction process part of a copper sulfide ore (chalcocite, chalcopyrite, bornite, copper blue and the like) leaching solution.
Background
Copper is an important nonferrous metal and is widely applied to industry, engineering technology and process. With the development of economy, the global demand of copper increases year by year, however, the mining grade of copper ore is gradually reduced, the amount of refractory ore is increased, and the problem of environmental pollution caused by pyrometallurgical copper smelting is solved. With the development of wet smelting technology, the gradual maturity and industrial application of leaching-extraction-electrodeposition technology, compared with the traditional pyrometallurgical copper smelting technology, the technology has the unique advantages of investment saving, low cost and avoidance of emission of sulfur dioxide and As particularly in the aspect of environmental protection, and the biological wet leaching copper extraction technology is more and more emphasized and widely applied.
Domestic large-scale biological wet-process copper extraction mines mainly comprise arnica and dexing copper ores, and international large-scale biological wet-process copper ores comprise Quebrad Blanca and Escion in Chile, Carneaia (Cananea) in Mexico, Montany copper ores in Myanmar and the like.
The Burma Mongolia copper ore mainly comprises chalcocite, a small amount of chalcopyrite, arsenopyrite, bornite and oxidation state (copper), the ore grade is about 0.5%, the pyrite content is 13-14%, gangue ore mainly comprises quartz with the content being close to 50%, and sericite, illite, kaolinite, diaspore, alunite and the like are contained in the gangue ore, the main process of the project is mining, crushing and stacking, biological heap leaching, extracting and electrodepositing, the zero emission standard is strictly executed, and the internal circulation of all solution systems is realized. Because the annual evaporation capacity of the Mongolian tile raising area is larger than the rainfall, the copper ore project needs to be supplemented with water from the Qingdun river nearby every year in millions, and the unique climatic conditions create good external environment for zero emission and internal circulation of all solutions in the system.
due to the unique ore characteristics and process characteristics of the project, the copper concentration of feed liquid is in a range of 3-7 g/L through continuous oxidation leaching of chalcocite, pyrite and the like along with the continuous production, and can be adjusted through the production, but the iron concentration in the leaching liquid is continuously increased, wherein the acid concentration (sulfuric acid) is increased to 14 g/L from 3 g/L, the iron concentration is increased to 35 g/L from 2 g/L at the beginning of the project, and the trend is continuously increased, impurity ions are continuously accumulated, Cl ions are currently increased to 3-3.5 g/L, Mn ions are increased to 0.5-1 g/L, TDS (total dissolved solids) is increased to 200 g/L from 10 g/L.
It is well known that the copper extraction process is essentially H +And Cu 2+The exchange process of (1) extracting the copper ions from the low-acid feed solution by the extractant under the condition of low acid, and then back-extracting the copper ions from the loaded organic phase into the copper-rich solution by the high-acid electric barren solution, so-called 'low-acid extraction and high-acid back extraction', thereby realizing the transfer of copper. It is known that extraction becomes relatively difficult as the acidity of the feed solution continues to increase. The copper-iron selectivity is also one of the key factors of the performance of the extracting agent and the extraction separation, and the copper-iron separation effect of the extraction process gradually becomes worse along with the continuous increase of the iron concentration in the feed liquid, namely, the iron extraction amount is increased while the copper is extracted, so that the iron transfer amount entering the electrodeposition through extraction is increased The increase of the concentration of iron ions can cause the reduction of the electro-deposition efficiency, thereby increasing the power consumption cost, and the increase of the open circuit of the electric barren solution in the production can cause the increase of the reagent cost. Although Mn and Cl ions can not be transferred through chemical transfer, the physical entrainment mode is unavoidable, the corrosion of chloride ions to stainless steel is very large, the concentration of the chloride ions in the electrolytic solution is strictly controlled to be lower than 30ppm in production, otherwise, the stainless steel is subjected to pitting corrosion, so that a cathode plate is damaged, and cathode copper is difficult to strip; after the content of manganese ions in the electrolyte is too high, on one hand, anode corrosion can be caused, the service life of an anode plate is shortened, and on the other hand, the extractant can be subjected to oxidative degradation, so that the extractant is ineffective and extremely harmful. The increase of TDS content can cause the viscosity of the solution to increase, thereby leading to difficult phase separation of the feed liquid and the organic phase and influencing the production.
Disclosure of Invention
The invention aims to provide an extraction method of a copper leaching solution with high ferric oxide content and high impurity content, which can economically and efficiently realize copper extraction, well control impurity transfer, create good production conditions for electrodeposition, simultaneously give consideration to the control requirement of ferric oxide rising in a heap leaching process, and realize systematic optimization production of heap leaching, extraction and electrodeposition. The specific technical scheme is as follows;
A method for extracting a copper leaching solution with high acid iron and high impurity content adopts two series-parallel extraction devices, wherein the extraction devices comprise five mixed extraction clarification chambers of back extraction, parallel connection, two extractions, one extraction and washing which are sequentially connected, and also comprise a copper-rich liquid oil separation tank, a raffinate oil separation tank, a loaded organic phase storage tank, a washing water storage tank and an organic entrainment pump; wherein the parallel mixed extraction clarification chamber is provided with a feed liquid inlet and a feed liquid outlet, the first extraction mixed extraction clarification chamber is provided with a feed liquid inlet, and the second extraction mixed extraction clarification chamber is provided with a feed liquid outlet; one end of the copper-rich liquid oil-separating groove is connected with the back extraction mixing extraction clarifying chamber, and the other end is connected with copper-rich liquid oil removing equipment; the raffinate oil-separating tank is respectively connected with the parallel mixed extraction clarifying chamber and the two extraction mixed extraction clarifying chambers; one end of the loaded organic phase storage tank is connected with the back extraction mixing extraction clarifying chamber, and the other end is connected with the washing mixing extraction clarifying chamber; the washing water storage tank is connected with the washing mixing extraction clarification chamber, and the organic entrainment pump is respectively connected with the second extraction mixing extraction clarification chamber, the first extraction mixing extraction clarification chamber and the loaded organic phase storage tank;
The specific extraction method is as follows;
After one part of feed liquid passes through the parallel mixed extraction clarification chamber, raffinate is directly discharged to enter a raffinate oil separation tank; the other part enters from a first extraction mixed extraction clarifying chamber, first-stage mixed extraction clarification separation is carried out, then the other part enters into a second extraction mixed extraction clarifying chamber for secondary mixed extraction clarification separation, and raffinate is discharged to enter a raffinate oil-separating groove; the raffinate generated in the two parts is discharged outside after oil separation by a raffinate oil separation tank and returned to a storage yard for circular leaching;
The loaded organic phase is subjected to back extraction and decoppering by a back extraction mixed extraction clarification chamber, then is subjected to flow direction of a parallel connection, secondary extraction and primary extraction mixed extraction clarification chamber to realize step-by-step extraction, then enters a washing mixed extraction clarification chamber to be washed with the organic phase, and the washed loaded organic phase flows into a loaded organic phase storage tank and is subjected to next back extraction circulation; and continuously pumping the washing water accumulated in the washing water storage tank or part of the organic phase carried with the washing water to an organic phase overflow port of the first extraction or second extraction mixed extraction clarification chamber through an organic carrying pump at the bottom of the loaded organic phase storage tank, so that the washing water carried with the organic phase is further controlled to enter back extraction.
Preferably, the mixing extraction clarification chambers are all three-stage mixing stirring, the mixing time is at least 3 minutes, and the clarification time is 7-8 minutes.
Preferably, the back extraction, parallel connection, secondary extraction and primary extraction mixed extraction clarification chambers are continuous in organic phase, and the phase ratio is 1.5-2.0, and the washing mixed extraction clarification chambers are continuous in water phase, and the phase ratio is 1.1.
Preferably, the electric barren solution of the washing, mixing, extracting and clarifying chamber has the open circuit amount of 3-5m 3The electric deposit enters the washing water with the external discharge capacity of 25-35m 3The water is replenished with fresh water of the same cubic meter,
preferably, the acidity of the washing water in the washing water storage tank is controlled to be 18-22 g/L, and the concentration of chloride ions is controlled to be below 90 mg/L.
preferably, the concentration of copper in the feed liquid is 3-7 g/L, the concentration of acid is 8-24 g/L, the concentration of iron is 15-55 g/L, the concentration of chlorine and manganese ions is 2-4 g/L, the concentration of TDS is 50-400 g/L, and the concentration of the extractant is 18-35 wt%.
Preferably, the thickness of the organic phase in the mixed extraction and clarification chamber is maintained between 300 and 350 mm.
Preferably, the liquid level of the copper-rich liquid oil separation tank is 2-2.1 m, the liquid level of the raffinate oil separation tank is 1.9-2 m, the storage tank for the loaded organic phase is more than or equal to 1 m, and the storage tank for the washing water is 1.6 m.
The invention has the beneficial effects that:
1. the high-efficiency extraction of copper in the high-impurity copper leaching solution of ferric oxide is realized (the extraction rate is 65-85%), the transmission of iron, chlorine and manganese ions is strictly controlled, and the electric pregnant solution generated by extraction (the parameter indexes of the copper-rich solution are stably controlled to be about 45-50 g/L of copper concentration, within 10ppm of chlorine and manganese ions, 1.5-2.5 g/L of iron ions and 5-10ppm of oil content) can be directly used for the production of high-purity cathode copper electrodeposition;
2. The consumption of copper acid for producing ton is only about 180-300kg, the unit consumption of the extracting agent and the diluting agent is lower, the production cost is low, meanwhile, the effective control of the acid consumption also reduces the acid which is leached out by returning to a stock dump, and the rising of the acidity of the stock dump is controlled to a certain extent;
3. The process is simple to operate, the index control stability is good, and process production fluctuation caused by phase continuity and instability can not occur.
4. the process has strong adaptability to the feed liquid, wide range, 3-7 g/L of copper concentration, 8-24 g/L of acid concentration, 15-55 g/L of iron concentration, 2-4 g/L of chlorine and manganese ions and 50-400 g/L of TDS, compared with the three-extraction-one-reaction and two-extraction-two-reaction processes under the same design scale, feed liquid concentration and flow rate, the copper transmission yield of the two-series combined process can reach 1.2 times of that of the two-series combined process, the index control is good, and the large-scale industrial stable production can be realized.
5. The invention adopts a two-series one-time extraction method, realizes the high-efficiency extraction of feed liquid copper, controls the transfer of impurities, creates safe and stable qualified electro-deposition liquid for electro-deposition, simultaneously considers the control requirement of iron rising in the heap leaching process, and realizes the system optimization production.
Drawings
FIG. 1 is a schematic view of two series of parallel extraction process equipment according to the present invention;
Detailed Description
The invention is further described with reference to the following figures and specific embodiments.
Example 1
referring to FIG. 1, the iron-rich and high-impurity feed liquid treated by the invention contains 3.6 g/L of copper, 8.5 g/L of acid, 15 g/L of iron, 2 g/L of chloride ions, 0.3 g/L of manganese ions, 50 g/L of TDS and 18% of extractant;
Two series and parallel processes are adopted to extract copper for extraction production, and qualified electro-deposition liquid for electro-deposition is obtained. The specific process operations, process control conditions and experimental results are shown in table 1.
Table 1: the operating conditions and experimental results of example 1.
Example 2.
referring to fig. 1, the treated high-acid-iron-content high-impurity feed liquid contains 4.3 g/L of copper, 10.8 g/L of acid, 20 g/L of iron, 2.5 g/L of chloride ions, 0.4 g/L of manganese ions and 100 g/L of TDS, the concentration of an extracting agent is 19.5%, two series of processes are adopted to extract copper for extraction production, and qualified electrolyte for electrodeposition is obtained, and specific process operation, process control conditions and experimental results are shown in table 2.
Table 2: the operating conditions and experimental results of example 2.
Example 3.
referring to fig. 1, the treated high-acid-iron-content high-impurity feed liquid contains 5.8 g/L of copper, 12.5 g/L of acid, 30 g/L of iron, 2.2 g/L of chloride ions, 0.5 g/L of manganese ions, 21% of extractant and 160 g/L of TDS, two series and parallel processes are adopted to extract copper for extraction production, and qualified electrolyte for electrodeposition is obtained, and the specific process operation, process control conditions and experimental results are shown in table 3.
Table 3: the operating conditions and experimental results of example 3.
Example 4.
referring to fig. 1, the treated high-acid-iron-content high-impurity feed liquid contains 6.6 g/L of copper, 12.5 g/L of acid, 35 g/L of iron, 3.5 g/L of chloride ions and 0.8 g/L of manganese ions, the concentration of an extracting agent is 23 percent and the TDS is 200 g/L, two series of processes are adopted to extract copper for extraction production, and qualified electrolyte for electrodeposition is obtained, and the specific process operation, process control conditions and experimental results are shown in table 4.
Table 4: the operating conditions and experimental results of example 4.
Example 5.
referring to fig. 1, the treated high-acid-iron-content high-impurity feed liquid contains 6.8 g/L of copper, 20 g/L of acid, 40 g/L of iron, 3.8 g/L of chloride ions, 1.5 g/L of manganese ions, 30% of extractant and 280 g/L of TDS, two series of processes are adopted to extract copper for extraction production, and qualified electro-deposition liquid for electro-deposition is obtained, and the specific process operation, process control conditions and experimental results are shown in table 5.
Table 5: the operating conditions and experimental results of example 5.
Example 6.
referring to fig. 1, the treated high-acid-iron-content high-impurity feed liquid contains 7.2 g/L of copper, 24 g/L of acid, 52 g/L of iron, 3.8 g/L of chloride ions, 3.2 g/L of manganese ions, 35% of extractant and 380% of TDS380 g/L, two series of processes are adopted to extract copper for extraction production, and qualified electro-deposition liquid for electro-deposition is obtained, and the specific process operation, process control conditions and experimental results are shown in table 6.
Table 6: the operating conditions and experimental results of example 6.
Claims (7)
1. The extraction method of the copper leaching solution with high acid iron and high impurity content is characterized in that two series-parallel extraction devices are adopted for extraction, and the extraction device comprises five mixed extraction clarification chambers of back extraction, parallel connection, two extraction, one extraction and washing which are sequentially connected, and also comprises a copper-rich liquid oil separation tank, a raffinate oil separation tank, a loaded organic phase storage tank, a washing water storage tank and an organic entrainment pump; the parallel mixed extraction clarifying chamber is provided with a feed liquid inlet and a feed liquid outlet, the first extraction mixed extraction clarifying chamber is provided with a feed liquid inlet, and the second extraction mixed extraction clarifying chamber is provided with a feed liquid outlet; one end of the copper-rich liquid oil-separating groove is connected with the back extraction mixing extraction clarifying chamber, and the other end is connected with copper-rich liquid oil removing equipment; the raffinate oil-separating tank is respectively connected with the parallel mixed extraction clarifying chamber and the two extraction mixed extraction clarifying chambers; one end of the loaded organic phase storage tank is connected with the back extraction mixing extraction clarifying chamber, and the other end is connected with the washing mixing extraction clarifying chamber; the washing water storage tank is connected with the washing mixing extraction clarification chamber, and the organic entrainment pump is respectively connected with the second extraction mixing extraction clarification chamber, the first extraction mixing extraction clarification chamber and the loaded organic phase storage tank;
The specific extraction method is as follows;
After one part of feed liquid passes through the parallel mixed extraction clarification chamber, raffinate is directly discharged to enter a raffinate oil separation tank; the other part enters from a first extraction mixed extraction clarifying chamber, first-stage mixed extraction clarification separation is carried out, then the other part enters into a second extraction mixed extraction clarifying chamber for secondary mixed extraction clarification separation, and raffinate is discharged to enter a raffinate oil-separating groove; the raffinate generated in the two parts is discharged outside after oil separation by a raffinate oil separation tank and returned to a storage yard for circular leaching;
The loaded organic phase is subjected to back extraction and decoppering by a back extraction mixed extraction clarification chamber, then is subjected to flow direction of a parallel connection, secondary extraction and primary extraction mixed extraction clarification chamber to realize step-by-step extraction, then enters a washing mixed extraction clarification chamber to be washed with the organic phase, and the washed loaded organic phase flows into a loaded organic phase storage tank and is subjected to next back extraction circulation; and continuously pumping the washing water accumulated in the washing water storage tank or part of the organic phase carried with the washing water to an organic phase overflow port of the first extraction or second extraction mixed extraction clarification chamber through an organic carrying pump at the bottom of the loaded organic phase storage tank, so that the washing water carried with the organic phase is further controlled to enter back extraction.
2. The extraction method according to claim 1, wherein the mixing extraction clarification chambers are three-stage mixing stirring, the mixing time is at least 3 minutes, and the clarification time is 7-8 minutes.
3. The extraction method according to claim 1, wherein the back extraction, parallel connection, secondary extraction and primary extraction mixed extraction clarification chamber is continuous in organic phase, and the washing mixed extraction clarification chamber is continuous in aqueous phase, and the phase ratio is 1.1, compared with 1.5-2.0.
4. the extraction method according to claim 1, wherein the washing water acidity of the washing water storage tank is controlled to be 18-22 g/L, and the chloride ion concentration is controlled to be below 90 mg/L.
5. the extraction method according to claim 1, wherein the feed liquid contains 3-7 g/L of copper, 8-24 g/L of acid, 15-55 g/L of iron, 2-4 g/L of chloride and manganese ions, 50-400 g/L of TDS and 18-35 wt% of extractant.
6. The extraction process according to claim 1, wherein the thickness of the organic phase in the mixed extraction and clarification chamber is maintained between 300 and 350 mm.
7. The extraction process according to claim 1, wherein the copper-rich liquid sump level is 2-2.1 m, the raffinate sump level is 1.9-2 m, the loaded organic phase storage tank is 1 m or more, and the wash water storage tank is 1.6 m.
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| US5758255A (en) * | 1996-08-19 | 1998-05-26 | Nalco Chemical Company | Opposite phase entrainment reduction in solvent extraction/electrowinning circuits by addition of water soluble cationic polymers |
| CN2294095Y (en) * | 1997-04-30 | 1998-10-14 | 张荣华 | Supercritical fluid extraction reaction device |
| CN100390308C (en) * | 2003-04-16 | 2008-05-28 | 科宁公司 | Interlaced series parallel configuration for metal solvent extraction plants |
| CN101094929A (en) * | 2004-12-03 | 2007-12-26 | 科宁知识产权管理有限公司 | Processes for recovering metals from ores using organic solvent extraction and aqueous stripping at selected temperature differentials |
| CN200951330Y (en) * | 2005-12-22 | 2007-09-26 | 北京方正稀土科技研究所有限公司 | A circulating organic phase storage tank for extraction and separation with stable liquid level |
| US9169533B2 (en) * | 2011-12-20 | 2015-10-27 | Freeport Minerals Corporation | System and method including multi-circuit solution extraction for recovery of metal values from metal-bearing materials |
| CN102743896B (en) * | 2012-06-21 | 2014-07-30 | 中国科学院过程工程研究所 | Tower-type mixing and clarification extraction device with multiple gas stripping sections and extraction method therefor |
| CN102776369A (en) * | 2012-07-30 | 2012-11-14 | 云南迪庆矿业开发有限责任公司 | Iron removing method in process for extracting-electrowinning copper metal by using high-iron and low-copper material liquid |
| CN104451191A (en) * | 2014-12-03 | 2015-03-25 | 紫金矿业集团股份有限公司 | Dilution extraction process capable of improving copper recovery rate |
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