CN111560518B - Treatment method of copper-containing molybdenum concentrate - Google Patents
Treatment method of copper-containing molybdenum concentrate Download PDFInfo
- Publication number
- CN111560518B CN111560518B CN202010621212.7A CN202010621212A CN111560518B CN 111560518 B CN111560518 B CN 111560518B CN 202010621212 A CN202010621212 A CN 202010621212A CN 111560518 B CN111560518 B CN 111560518B
- Authority
- CN
- China
- Prior art keywords
- leaching
- molybdenum
- copper
- content
- stage
- 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.)
- Active
Links
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 88
- 239000011733 molybdenum Substances 0.000 title claims abstract description 88
- 239000010949 copper Substances 0.000 title claims abstract description 71
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 65
- 239000012141 concentrate Substances 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title abstract description 40
- 238000002386 leaching Methods 0.000 claims abstract description 154
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000001301 oxygen Substances 0.000 claims abstract description 25
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 25
- 238000000926 separation method Methods 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 11
- 239000002893 slag Substances 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 6
- 239000011268 mixed slurry Substances 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims abstract description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 38
- 238000000605 extraction Methods 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 11
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 8
- 239000011609 ammonium molybdate Substances 0.000 claims description 8
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 8
- 229940010552 ammonium molybdate Drugs 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 7
- 238000003916 acid precipitation Methods 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000012074 organic phase Substances 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 239000008346 aqueous phase Substances 0.000 claims description 2
- 238000003672 processing method Methods 0.000 claims 7
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 3
- 239000011707 mineral Substances 0.000 abstract description 3
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 17
- 239000000706 filtrate Substances 0.000 description 13
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 229910052961 molybdenite Inorganic materials 0.000 description 9
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 8
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000004070 electrodeposition Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- WUUZKBJEUBFVMV-UHFFFAOYSA-N copper molybdenum Chemical compound [Cu].[Mo] WUUZKBJEUBFVMV-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000006864 oxidative decomposition reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910004619 Na2MoO4 Inorganic materials 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009854 hydrometallurgy Methods 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 2
- 239000011684 sodium molybdate Substances 0.000 description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229910003562 H2MoO4 Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 239000000374 eutectic mixture Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- -1 molybdate radical ions Chemical class 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010959 steel Substances 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
-
- 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
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/12—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline 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
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/34—Obtaining molybdenum
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Environmental & Geological Engineering (AREA)
- Geology (AREA)
- Geochemistry & Mineralogy (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
本发明涉及一种含铜钼精矿的处理方法，将含铜钼精矿磨细，获得矿粉；将矿粉与水按1:3‑5的质量比混合均匀，进行一段氧压浸出后，固液分离，获得第一浸出液和第一浸出渣；将第一浸出渣与水按1:6‑9的质量比混合均匀，进行二段氧压浸出后，固液分离，获得第二浸出液和第二浸出渣；对第二浸出渣进行碱浸处理，获得pH值为8‑10的矿浆；将第二浸出液与矿浆混合，反应，获得混合浆液；对混合浆液进行固液分离后，获得第三浸出渣和富含钼的第三浸出液。本发明的处理方法浸出率高，且酸得到有效利用。The invention relates to a method for treating copper-containing molybdenum concentrate. The copper-containing molybdenum concentrate is ground finely to obtain mineral powder; , solid-liquid separation to obtain the first leaching solution and the first leaching slag; the first leaching slag and water are uniformly mixed at a mass ratio of 1:6-9, and after the second-stage oxygen pressure leaching is performed, the solid-liquid separation is performed to obtain the second leaching solution and the second leaching slag; the second leaching slag is subjected to alkali leaching treatment to obtain ore pulp with a pH value of 8-10; the second leaching solution is mixed with the ore pulp and reacted to obtain a mixed slurry; after the mixed slurry is subjected to solid-liquid separation, the obtained The third leachate and the molybdenum-rich third leachate. The treatment method of the invention has a high leaching rate, and the acid is effectively utilized.
Description
Technical Field
The invention relates to a method for treating copper-containing molybdenum concentrate, and belongs to the field of hydrometallurgy.
Background
Molybdenum is widely used as an important rare metal in industrial fields such as steel, catalysts, pigments and the like. The average molybdenum content in the earth's crust is only 1.11g/t, copper-molybdenum ore is one of the main sources of metallic molybdenum, usually present in porphyry-type copper ores and skarn-type copper deposits, and nearly half of the molybdenum yield is derived from the associated recovery of copper-molybdenum ore, so that the molybdenum concentrate usually contains copper. At present, the direct oxidation roasting-ammonia leaching-acid precipitation process is mainly adopted for industrially treating molybdenum concentrate (molybdenite), the principle flow is that the molybdenum concentrate is converted into molybdenum trioxide which is easy to be leached by ammonia water through oxidation roasting, and the leaching solution is purified and subjected to acid precipitation to produce ammonium molybdate. The roasting of the molybdenum concentrate generally adopts a multi-hearth furnace, a fluidized bed roaster, a rotary kiln, a reverberatory furnace and the like. In the direct oxidation roasting process of molybdenite, the roasting product molybdenum trioxide is easy to sublime and lose due to overhigh temperature, and the molybdenum trioxide and associated metal molybdate generate eutectic mixtures to sinter materials to influence the product desulfurization and low SO content2The concentrated flue gas is difficult to be used for preparing acid, thereby polluting the environment and causing the volatilization loss of the associated rhenium element. Therefore, an environment-friendly, efficient and economical smelting technology is urgently needed to replace the existing smelting technology.
The whole hydrometallurgy can fundamentally avoid harmful gas SO2The metal recovery rate is greatly improved compared with the traditional method, associated metal rhenium can be comprehensively recovered, low-grade and complex molybdenite can be processed, and continuous production and automation of the leaching process are easy to realize. At present, more molybdenite hydrometallurgical methods are formed, and are generally divided into atmospheric pressure oxidative decomposition and high pressure oxidative decomposition. The atmospheric oxidative decomposition mainly comprises nitric acid or nitrate oxidative decomposition, sodium hypochlorite leaching, electrooxidation leaching, biological oxidation leaching and the like, and the processes have the defects of high oxidant consumption and sewage water consumptionLarge treatment difficulty, chlorine pollution or low leaching efficiency and the like.
The high-pressure oxidation decomposition of the molybdenum concentrate mainly comprises a pressure alkaline leaching method and a pressure oxidation method. The pressure alkaline leaching method adopts Na2CO3And alkaline reagents such as NaOH and the like are used for leaching the molybdenum concentrate, the process has the disadvantages of high alkali consumption and high auxiliary production cost. The pressure oxidation method comprises adding a certain amount of water, leaching under oxygen pressure, and adding MoS2Conversion to MoO3And then the subsequent alkaline leaching process is carried out. Chinese patent CN101323915B proposes that finely ground molybdenum-nickel ore is subjected to oxygen pressure water leaching to obtain leaching solution containing molybdenum and nickel and leaching residue containing molybdenum oxide, the leaching solution is subjected to extraction separation of molybdenum and nickel to produce nickel salt and ammonium molybdate or molybdenum trioxide, and the molybdenum in the leaching residue is subjected to normal pressure alkaline leaching, purification and acid precipitation to recover ammonium molybdate. Chinese patent CN106477630B is to perform oxygen pressure water leaching on molybdenite, after liquid-solid separation, the leaching solution is sent to an ion exchange method or an extraction process to recover molybdate radical ions, and leaching residues are subjected to ammonia leaching, filtering and crystallization to obtain an ammonium molybdate product. U.S. Pat. No. 4, 8753591, 2 also uses oxygen pressure water leaching, leaching residue normal pressure alkali leaching, mixed acid leaching and molybdenum extraction to treat molybdenite.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for treating copper-molybdenum-containing concentrate, which is used for efficiently leaching copper and molybdenum.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a method for treating copper-containing molybdenum concentrate comprises the following steps:
s1, grinding the copper-molybdenum-containing concentrate to obtain mineral powder;
wherein, in the copper-containing molybdenum concentrate, the content of Mo is 25-35 wt%, further 27-33 wt%, and the content of Cu is 5-9 wt%, further 5.2-8.5 wt%;
s2, uniformly mixing the mineral powder obtained in the step S1 and water according to the mass ratio of 1:3-5 (further 1:3.2-4.8), carrying out primary oxygen pressure leaching, and carrying out solid-liquid separation to obtain a first leaching solution and first leaching residues;
wherein, during the first-stage oxygen pressure leaching, the temperature is controlled to be 110-150 ℃, further 120-140 ℃, the total pressure is 0.6-1.0MPa, further 0.7-0.9MPa, the leaching time is 1-3h, further 1.2-2.8 h; in the first leaching solution, the copper content is 12-30g/L, and the sulfuric acid concentration is less than 25 g/L;
s3, uniformly mixing the first leaching residue obtained in the step S2 and water according to the mass ratio of 1:6-9 (further 1:7-8), carrying out two-stage oxygen pressure leaching, and then carrying out solid-liquid separation to obtain a second leaching solution and a second leaching residue;
wherein, during the two-stage oxygen pressure leaching, the temperature is controlled to be 210-230 ℃, further to be 215-225 ℃, the total pressure is 2.5-3.5MPa, further to be 2.7-3.2MPa, the leaching time is 2-4h, further to be 2.5-3.5 h; in the second leaching solution, the content of molybdenum is 3-20g/L, and the concentration of sulfuric acid is less than 100 g/L;
s4, performing alkaline leaching treatment on the second leaching residue obtained in the step S3 to obtain ore pulp with the pH value of 8-10;
s5, mixing the second leaching solution obtained in the step S3 with the ore pulp obtained in the step S4, reacting, and adjusting acid by using the second leaching solution to obtain mixed slurry;
and S6, carrying out solid-liquid separation on the mixed slurry obtained in the step S5 to obtain third leaching slag and a third leaching solution rich in molybdenum.
Wherein, in the third leaching solution, the content of molybdenum is 20-40g/L, and the concentration of sulfuric acid is less than 40 g/L; further, in S1, the copper-containing molybdenum concentrate was ground to D90<30 μm. The applicant repeatedly researches and discovers that the grinding degree can meet the requirement of high-efficiency leaching without greatly increasing the cost and the grinding time.
Further, in S2, the first leaching solution contains 15-25 g/L of copper and 15-23g/L of sulfuric acid.
Further, after S2, copper in the first leachate is recovered by extraction. Optionally, the concentration of the extracting agent is 15% -30%, and the ratio (O/A) is 0.25/1-2.5/1. Copper electrodeposition waste liquid is used as a stripping agent, and the phase ratio (O/A) is 1: 1-3: 1.
Further, in S3, the content of molybdenum in the second leaching solution is 4-16g/L, and the concentration of sulfuric acid is 80-98 g/L.
Further, in S4, in the alkaline leaching treatment, the leaching temperature is controlled to be 20-80 ℃, further 25-75 ℃, the liquid-solid mass ratio is 1-3:1, further 1.2-2.8:1, and the leaching time is 2-4 hours, further 2.2-3.5 hours. Atmospheric leaching is preferred.
Further, in S4, when the alkaline leaching is performed, the leachate contains one or more of sodium carbonate, sodium hydroxide, and ammonia water.
Further, in S6, the content of molybdenum in the third leaching solution is 25-38g/L, and the concentration of sulfuric acid is 25-35 g/L.
Further, after S6, molybdenum in the third leach solution is recovered by extraction to obtain an aqueous phase and a molybdenum-rich organic phase. Optionally, the organic phase is a conventional process solvent.
Further, the organic phase is back-extracted by ammonia water, and then is subjected to acid precipitation and crystallization to obtain ammonium molybdate.
The process principle of the invention is as follows:
2CuFeS2+H2SO4+8.5O2＝2CuSO4+Fe2(SO4)3+H2O
Cu2S+2.5O2+H2SO4＝2CuSO4+H2O
MoS2+4.5O2+2H2O＝MoO3+2H2SO4
MoS2+4.5O2+3H2O＝H2MoO4+2H2SO4
MoO3+Na2CO3＝Na2MoO4+CO2
MoO3+2NaOH＝Na2MoO4+H2O
when the applicant conducts leaching research on the copper-containing molybdenum concentrate (with the Mo content of 25-35 wt% and the Cu content of 5-9 wt%) by using CN101323915B, CN106477630B and US8753591B2, the final leaching rate of molybdenum is not higher than 60%, the expected result of the related technology cannot be obtained, and the conversion rate of molybdenum is sharply reduced along with the increase of the copper content in the raw material. For example, when the copper content is 5.5%, the molybdenum conversion is 54.51%; when the copper grade is 7.1 percent, the conversion rate of molybdenum is 45.81 percent; when the copper grade is 8.5%, the molybdenum conversion is 28.5%. Therefore, the copper in the molybdenum concentrate has obvious inhibition effect on the conversion of the molybdenum sulfide into the molybdenum oxide.
Compared with the prior art, the invention has the following beneficial effects:
(1) because the copper content in the molybdenum concentrate has a great inhibiting effect on the efficiency of converting molybdenum sulfide into molybdenum oxide, the invention adopts a two-stage oxygen pressure leaching process, the first stage leaches out copper under a mild condition, the first stage leaches out copper by extraction, and the copper and the molybdenum in the molybdenum concentrate are separated and recovered by one process. The molybdenum sulfide is converted into molybdenum oxide by the first-stage leaching residue under the strengthened condition, so that the subsequent alkaline leaching under normal pressure is facilitated, and the final molybdenum leaching rate can reach more than 98%.
(2) Because the first stage of oxygen pressure leaching has mild condition, the leachate has low acid content and does not need neutralization, and copper extraction can be directly carried out. The alkaline leaching filtrate is mixed with the second-stage leaching solution with higher acid content, so that the technical effect of reducing acid can be achieved, the efficient extraction of molybdenum is facilitated, and the problem of post-treatment of acid is solved.
(3) The lime can be used for neutralizing the molybdenum raffinate, so that a gypsum product is obtained, and the additional value of the product is increased.
Drawings
Fig. 1 is a process flow diagram of a method of treatment of copper-containing molybdenum concentrate according to the invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, rather than all embodiments, and all other embodiments obtained by those skilled in the art without any creative work based on the embodiments of the present invention belong to the protection scope of the present invention.
Example 1
In this example, the treatment method of the copper-containing molybdenum concentrate is as follows:
(1) 100g of copper-containing molybdenum concentrate (containing 27.5 wt% of Mo, 5.5 wt% of Cu and 24.6 wt% of S) was ground until D90 was <30 μm.
(2) Uniformly mixing the finely ground molybdenum concentrate and water according to a ratio of 1:3.2, adding the mixture into an autoclave to perform primary oxygen pressure leaching under the leaching conditions of 135 ℃ and a total pressure of 0.7Mpa for 1.5 hours. The liquid-solid separation obtains a first stage copper-containing filtrate (copper 16.9g/L, sulfuric acid 18.4g/L) and a first stage leaching residue (copper 0.11 wt%), and the leaching rate of copper is 98.16 wt%.
(3) And (3) extracting copper from the first-stage copper-containing filtrate by adopting 25% of extractant and 75% of kerosene (v/v) in a ratio of (O/A) to (1: 1), performing two-stage extraction, wherein the raffinate contains 0.15g/L of copper, and the copper extraction rate is 99.11 wt%. Copper back extraction adopts copper electrodeposition waste liquid, the ratio (O/A) is 1.5:1, three-stage back extraction is carried out, and back extraction liquid is sent to copper electrodeposition.
(4) And (3) uniformly mixing the first-stage leaching residue obtained in the step (2) with water according to a ratio of 1:8, adding the mixture into an autoclave for second-stage oxygen pressure leaching, wherein the leaching conditions are 220 ℃, the total pressure is 3.0MPa, and the leaching time is 2.5 hours. And (3) carrying out liquid-solid separation to obtain a second-stage leaching solution and second-stage leaching residues, wherein the second-stage leaching solution contains 6.8g/L of molybdenum and 94.2g/L of sulfuric acid. The second-stage leaching residue contains 31.56 wt% of molybdenum, wherein the molybdenum oxide accounts for 99.30 wt% of the total amount of the molybdenum.
(5) Adopting Na as the second-stage leaching residue obtained in the step (4)2CO3Leaching for 2.2h at 30 deg.C and liquid-solid ratio of 2:1 under normal pressure. The alkaline leaching solution contains 157.0g/L of molybdenum and has a pH value of 8. The alkaline leaching residue contains 1.03 wt% of molybdenum, and the leaching rate of the molybdenum is 99.50 wt%.
(6) And (5) uniformly stirring the second-stage filtrate obtained in the step (4) and the ore pulp obtained in the step (5), adjusting acid, and performing liquid-solid separation to obtain filtrate and filter residue. The filtrate contains 30.8g/L of molybdenum and 30.2g/L of sulfuric acid. The filter residue contains 0.4 wt% of molybdenum.
(7) And (4) separating molybdenum from the filtrate obtained in the step (6) by adopting a conventional process solvent extraction method, wherein a molybdenum back extraction solution is ammonia water, and then performing acid precipitation and crystallization to prepare an ammonium molybdate product.
Comparative example 1
For the raw material in example 1, the molybdenum concentrate is directly leached by using the process conditions of the second stage leaching in the step (4) in example 1 without a first stage copper leaching process, and the experimental results are shown in table 1.
Table 1 comparative example 1 oxygen pressure leach results
The oxygen pressure leaching residue was subjected to alkaline leaching under atmospheric pressure under the process conditions of step (5) in example 1, and the results are shown in Table 2.
Table 2 comparative example 1 results of alkaline leaching under atmospheric pressure
As can be seen from Table 1, the molybdenum oxide in the leaching residue accounts for a low proportion of the total molybdenum content, mainly because the copper in the concentrate influences the MoS in the oxygen pressure leaching process2Conversion to MoO3The conversion of (a). Therefore, the leaching rate of molybdenum resulting in the alkaline leaching under atmospheric pressure in table 2 was low.
Example 2
In this example, the treatment method of the copper-containing molybdenum concentrate is as follows:
(1) 100g of copper-containing molybdenum concentrate (containing 32.2 wt% of Mo, 7.1 wt% of Cu and 25.1 wt% of S25 wt%) was ground until D90 was <30 μm.
(2) Uniformly mixing the finely ground molybdenum concentrate and water according to a ratio of 1:4, adding the mixture into an autoclave to perform primary oxygen pressure leaching under the leaching conditions of 140 ℃ and a total pressure of 0.9Mpa for 2.5 hours. The liquid-solid separation obtains a first stage copper-containing filtrate (copper 17.5g/L, sulfuric acid 21.5g/L) and a first stage leaching residue (copper 0.08 wt%), and the leaching rate of copper is 98.98 wt%.
(3) And extracting copper from the first-stage copper-containing filtrate by adopting 25% of extractant and 75% of kerosene (v/v) in a ratio (O/A) of 1:1, performing two-stage extraction, wherein the copper content of raffinate is 0.12g/L, and the copper extraction rate is 99.32 wt%. Copper back extraction adopts copper electrodeposition waste liquid, the ratio (O/A) is 1.5:1, three-stage back extraction is carried out, and back extraction liquid is sent to copper electrodeposition.
(4) And (3) uniformly mixing the first-stage leaching residue obtained in the step (2) with water according to a ratio of 1:7, adding the mixture into an autoclave for second-stage oxygen pressure leaching, wherein the leaching conditions are 225 ℃, the total pressure is 3.2MPa, and the leaching time is 3.5 hours. And (3) carrying out liquid-solid separation to obtain a second-stage leaching solution and second-stage leaching residues, wherein the second-stage leaching solution contains 7.5g/L of molybdenum and 97.8g/L of sulfuric acid. The second-stage leaching residue contains 38.56 wt% of molybdenum, wherein the molybdenum oxide accounts for 99.50 wt% of the total molybdenum.
(5) And (4) leaching the second-stage leaching residue obtained in the step (4) by using NaOH for 3 hours at the leaching temperature of 75 ℃, the liquid-solid ratio of 2.8:1 and the normal pressure. The alkaline leaching solution contains 128.4g/L of molybdenum and has a pH value of 9.5. The alkaline leaching residue contains 0.33 wt% of molybdenum, and the leaching rate of the molybdenum is 99.90 wt%.
(6) And (5) uniformly stirring the second-stage filtrate obtained in the step (4) and the ore pulp obtained in the step (5), adjusting acid, and performing liquid-solid separation to obtain filtrate and filter residue. The filtrate contained 37.6g/L of molybdenum and 33.8g/L of sulfuric acid. The filter residue contains 0.42 wt% of molybdenum.
(7) And (4) separating molybdenum from the filtrate obtained in the step (6) by adopting a conventional process solvent extraction method, wherein a molybdenum back extraction solution is ammonia water, and then performing acid precipitation and crystallization to prepare an ammonium molybdate product.
Comparative example 2
For the raw material in example 2, the molybdenum concentrate was directly leached by the process conditions of the second stage leaching in step (4) in example 2 without a first stage copper leaching process, and the experimental results are shown in table 3.
Table 3 comparative example 2 oxygen pressure leach results
The oxygen pressure leaching residue was subjected to alkaline leaching under atmospheric pressure under the process conditions of step (5) in example 2, and the results are shown in Table 4.
Table 4 comparative example 2 results of alkaline leaching at atmospheric pressure
Similarly, it can be seen from table 3 that the molybdenum oxide in the leaching residue accounts for a low proportion of the total molybdenum content, mainly because the copper in the concentrate affects MoS in the oxygen pressure leaching process2Conversion to MoO3The conversion of (a). Therefore, the leaching rate of molybdenum resulting in the alkaline leaching under atmospheric pressure in Table 4 was low.
The foregoing examples are set forth to illustrate the present invention more clearly and are not to be construed as limiting the scope of the invention, which is defined in the appended claims to which the invention pertains, as modified in all equivalent forms, by those skilled in the art after reading the present invention.
Claims (7)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010621212.7A CN111560518B (en) | 2020-07-01 | 2020-07-01 | Treatment method of copper-containing molybdenum concentrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010621212.7A CN111560518B (en) | 2020-07-01 | 2020-07-01 | Treatment method of copper-containing molybdenum concentrate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111560518A CN111560518A (en) | 2020-08-21 |
| CN111560518B true CN111560518B (en) | 2022-01-28 |
Family
ID=72075406
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010621212.7A Active CN111560518B (en) | 2020-07-01 | 2020-07-01 | Treatment method of copper-containing molybdenum concentrate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111560518B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112174209B (en) * | 2020-09-17 | 2022-09-30 | 成都虹波钼业有限责任公司 | Green molybdenum smelting ion exchange process |
| CN114164349A (en) * | 2022-02-11 | 2022-03-11 | 矿冶科技集团有限公司 | Method for removing impurities from molybdenum ore with high copper content and performing closed circulation on solution |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101956070A (en) * | 2010-07-07 | 2011-01-26 | 紫金矿业集团股份有限公司 | Recovery method of molybdenum concentrates |
| CA2912940C (en) * | 2014-11-26 | 2021-09-14 | Keith Stuart Liddell | Treatment process for extraction of precious, base and rare elements |
| CN104846216B (en) * | 2015-04-27 | 2017-08-04 | 北京矿冶研究总院 | Treatment method of complex copper-molybdenum ore |
| CN105907992B (en) * | 2016-06-28 | 2018-08-31 | 西北有色金属研究院 | A kind of method that pressure oxidation detaches molybdenum, copper and rhenium in Low Grade Molybdenum Concentrates |
| CN106477630B (en) * | 2016-10-18 | 2018-03-02 | 中国科学院过程工程研究所 | A kind of method of oxygen pressure water seaoning processing molybdenite coproduction ammonium molybdate and sulfuric acid |
| CL2018003101A1 (en) * | 2018-10-30 | 2018-12-14 | Molibdenos Y Metales S A | Process for the selective removal of copper compounds and other impurities with respect to molybdenum and rhenium, from molybdenite concentrates. |
| CN109252049B (en) * | 2018-11-16 | 2020-09-29 | 王水平 | Process method for treating molybdenum-removing slag of tungsten product and recovering molybdenum and copper by alkaline leaching method |
-
2020
- 2020-07-01 CN CN202010621212.7A patent/CN111560518B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN111560518A (en) | 2020-08-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104178642B (en) | A method for separating zinc and iron in zinc leaching slag | |
| WO2019146619A1 (en) | Method for producing high-purity scandium oxide | |
| CN110184482B (en) | A kind of leaching process of germanium-containing secondary zinc oxide powder | |
| CN110066920B (en) | Method for selectively leaching and separating vanadium and iron from stone coal vanadium ore | |
| CN108707748B (en) | Method for purifying stone coal pickle liquor and recovering aluminum, potassium and iron | |
| CN105271632A (en) | Comprehensive recovery method for electroplating sludge | |
| CN102994747A (en) | Technology for recovering metallic copper from high-lead copper matte | |
| CN112609078B (en) | Copper anode mud treatment process | |
| CN115427592A (en) | Recovery of vanadium from slag material | |
| CN110117723A (en) | A kind of richness germanium zinc oxide fumes leaching method | |
| CN111004917A (en) | Process for comprehensively recovering arsenic sulfide slag | |
| CN111560518B (en) | Treatment method of copper-containing molybdenum concentrate | |
| CN113846214A (en) | A kind of processing method of zinc-containing material in the production of zinc hydrometallurgy | |
| CN108588425B (en) | Treatment method of cobalt-nickel metallurgy wastewater slag | |
| US11879165B2 (en) | Process for recovering vanadium in the form of iron vanadate from a gasifier slag | |
| CN115029562B (en) | A method for separating copper and germanium during hydrometallurgical zinc smelting | |
| CN110983040A (en) | Method for precipitating vanadium in acidic vanadium-rich solution without ammonia | |
| CN117758080A (en) | Method for extracting scandium by combining titanium white waste acid and alkali precipitation waste residue | |
| CN107352581B (en) | A kind of method that antimony cigarette ash pressure reduction prepares arsenic trioxide | |
| CN105886797A (en) | Method for preparing sponge indium from polymetallic sulfide material | |
| CN110629043B (en) | Bismuth extraction method based on phase transformation of bismuth sulfide ore | |
| JP7347083B2 (en) | Manufacturing method of high purity scandium oxide | |
| CN108862382B (en) | Method for extracting high-purity vanadium pentoxide from lead vanadium ore | |
| JP7347085B2 (en) | Manufacturing method of high purity scandium oxide | |
| JP7380030B2 (en) | Manufacturing method of high purity scandium oxide |
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 |