CN1164775C - Ammonium salt liquid phase oxidation direct leaching method for nonferrous metal sulfide mineral - Google Patents
Ammonium salt liquid phase oxidation direct leaching method for nonferrous metal sulfide mineral Download PDFInfo
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- CN1164775C CN1164775C CNB01141555XA CN01141555A CN1164775C CN 1164775 C CN1164775 C CN 1164775C CN B01141555X A CNB01141555X A CN B01141555XA CN 01141555 A CN01141555 A CN 01141555A CN 1164775 C CN1164775 C CN 1164775C
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- leaching
- ammonium salt
- liquid
- phase oxidation
- nonferrous metal
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- 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 present invention relates to a direct ammonium salt liquid phase oxidation leaching method for nonferrous metal sulfide minerals. The present invention is characterized in that ammonium salt solution is adopted as a leaching agent; a liquid phase oxidation activating agent composed of surfactant-woody sodium sulfide or laurylsulfonic sodium dodecanesulphonate, liquid phase oxidation catalyst Cu<2+> and a sulfur extraction agent-ethylene tetrachloride is adopted to realize the quick leaching process of sulfide minerals in a gas liquid and solid three-phase reactor. Sulfur contained in various sulfides in mineral powder is converted into elementary sulfur and sulfuric acid radical; zinc, copper, nickel, copper, lead, cadmium, silver, etc. contained in various sulfides are converted into soluble salts to enter leaching liquid or remain in leaching dregs. The discharge of sulfur dioxide, hydrogen sulfide, nitrogen oxides and noxious gases containing arsenic, mercury, lead, etc. in traditional flows are eliminated. Baking systems, dust collection systems, acid preparation systems and three-waste processing systems do not need establishing after the present invention is adopted. The present invention shortens processes and construction period, and reduces total investment and production cost in large amplitude. The leaching method does not generate pollution sources, and belongs to an environmental-friendly clean production technology.
Description
Invention field
The present invention relates to the technical field of non-ferrous metal metallurgy, particularly a kind of ammonium salt liquid phase oxidation direct leaching method of nonferrous metal sulfide mineral.
Background technology
At present China's non-ferrous metal metallurgy technology is no matter be hydrometallurgy or pyrometallurgical smelting, and concentrate generally all will pass through roasting, and noxious gas emission such as sulfurous gas is in atmosphere in a large number in the roasting process, and contaminate environment is destroyed ecotope.Existing technical process is to the grade of raw material, and the requirement of foreign matter content is very harsh, need carry out strict batching before smelting.Along with the continuous consumption of resource, the continuous dilution of mineral reserve, existing technology will be more and more incompatible to this.So the technology that sulphide ores directly leaches without roasting is subjected to increasing attention.
Fonseca has proposed chalcopyrite (CuFeS
2) ammonia leaching method (US3967957).Adopt pure oxygen, service temperature is 150 ℃.The leaching of zink sulphide is more much more difficult than other metal sulfide, and this patent does not relate to the leaching of zink sulphide;
Arbiter etc. (United States Patent (USP) 4,331,635) have proposed to leach with the mixing solutions of ammonium sulfate and ammonia the sulphide ores of copper, nickel, zinc, adopt pure oxygen, require power of agitator up to 2.76kw/m
3Feed liquid, several leacher serial operations.But bad to the zinc sulphide leaching effect, behind the leaching 5h, the leaching yield of zinc only reaches 70%, and leach liquor contains only 40～50g/L of zinc, causes the significant wastage of Mineral resources;
Satchell, Jr. (United States Patent (USP) 4,165,264) has proposed to leach cupric sulfide with ammonium nitrate, does not also relate to the leaching of other nonferrous metal sulfide mineral.
Summary of the invention
Flow process is tediously long when the objective of the invention is to overcome present smelting nonferrous metal sulfide mineral, equipment is complicated and huge, investment cost is high and roasting process requires very defective such as harshness to grade, the foreign matter content of raw material, provide a kind of novel method that is applicable to that sulphide ores leaches, i.e. the ammonium salt liquid phase oxidation direct leaching method of nonferrous metal sulfide mineral.
Embodiment of the present invention are as follows:
The ammonium salt liquid phase oxidation direct leaching method of nonferrous metal sulfide mineral provided by the invention, its processing step is as follows:
(1) grinds also surface active nonferrous metal sulfide mineral mineral aggregate
After the proportioning that adds 0.2～2kg surfactant by nonferrous metal sulfide mineral mineral aggregate per ton mixed nonferrous metal sulfide mineral mineral aggregate and surfactant, wearing into granularity was 100-350 purpose breeze;
(2) preparation ammonium salt leaching agent
Leaching agent is an ammonium salt solution, and the ammonium concentration in this solution is 2.0mol/L to 4.0mol/L;
(3) size mixing
The ammonium salt leaching agent of breeze that step (1) is obtained and step (2) preparation and liquid-phase oxidation catalyst and sulfur extraction agent fully stir into slurries, in the slurries, the concentration of liquid-phase oxidation catalyst is 0.1～0.5mol/L, sulfur extraction agent and water be in a ratio of 1: 5～50, the liquid-solid ratio of these slurries is 5～10: 1;
(4) leach
The slurries that step (3) is obtained are transported to leach in the reactor and leach, its leaching condition is: feed pure oxygen or air oxidant earlier, its oxygen partial pressure is adjusted to 1～2MPa, heat temperature raising while stirring then, and keep reactor temperature between 90～145 ℃, leach after 1～6 hour, stop heating and stirring, finish the leaching operation;
(5) liquid, the solid separation
When temperature is reduced to 100 ℃ in leaching reactor, filter and separate, obtain containing the leach liquor and the leached mud of nonferrous metal ion leaching leaching feed liquid in the reactor;
(6) to leached mud wash, drying and desulfurization
With the acidic solution washing leached mud of 50 ℃ pH=2～3, and carry out centrifuging, slag washing liquid is mixed with the ammonium salt leaching agent in order to recycling through replenishing ammonium salt; Adopt dry distillation, hot filter method or extraction process to reclaim wherein contained sulphur after the leached mud drying.
Described surfactant is wooden sodium sulfonate or sodium laurylsulfonate; Described liquid-phase oxidation catalyst is for containing Cu
2+Mantoquita; Described sulfur extraction agent be zellon or with the mixture of kerosene; Described ammonium salt is ammonium chloride, ammonium sulfate or ammonium nitrate; Leaching reactor is the gas-liquid-solid phase reaction device.
The ammonium salt liquid phase oxidation direct leaching method of this nonferrous metal sulfide mineral provided by the invention has following characteristics:
(1) do not need drying, roasting, relieving haperacidity, the dust collecting system of concentrate; Do not need Waelz kiln, equipment does not have other harsh requirement except that anticorrosion; Reduce investment outlay, save floor occupying area, shorten and found the factory the duration;
(2) non-ferrous metal leaching yield can reach 70～97%;
(3) by direct leaching the sulphur major part in the sulfide is converted into sulphur, is convenient to storage and transportation, produce and be not subjected to the restriction in calcining process and sulfuric acid market;
(4) use by liquid-phase oxidation catalyst Cu
2+, the liquid-phase oxidation activator formed of surfactant wooden sodium sulfonate (or sodium laurylsulfonate), sulfur extraction agent zellon, leaching velocity is improved, extraction time is short; And the liquid-phase oxidation activator can be recycled;
(5) leaching plant is simple in structure, and is easy to operate; Facility investment is low and solve anticorrosion problem easily;
(6) mineral aggregate can adopt qualified concentrate containing, also can adopt underproof complicated ore, low-grade concentrate, all restrictions that do not exist fluidized bed roasting that mineral aggregate is formed;
(7) technological operation of the present invention is simple, grasps easily;
(8) the invention belongs to cleaning procedure, the shopwork condition is good, and process is not discharged and contained SO
2, H
2S, NO
x, cadmium, lead, arsenic, the gas of dust does not have toxic liquid discharge, non-environmental-pollution yet;
The present invention can directly handle the sulphide ores of elements such as containing zinc, copper, nickel, cobalt, lead, cadmium, silver, comprises low-grade and the multielement complicated sulfuration mine; The content height of arsenic, mercury, iron does not influence the leaching of main metal yet, therefore can realize the comprehensive recovery of resource.
Embodiment
Further describe the present invention below in conjunction with embodiment:
Because the direct leaching of zink sulphide more is difficult to carry out than other sulphide ores, so following direct leaching with zinc ore concentrate is an example.
Embodiment 1
The zinc ore concentrate moiety is as shown in table 1;
Table 1 zinc ore concentrate moiety (%)
Zn SiO
2 Pb Al
2O
3 Fe Cu Mg S As
50 2.65 3 0.62 7 0.8 0.35 31 2.05
Mn Ca Cd Ni Co Ag Au
0.14 0.02 0.45 0.01 ＜0.001 500g/t 2.12g/t
Use the stainless steel of 1.5L to leach reactor, inside reactor is provided with frp lining with anticorrosion, and the electric stove wire heating is with electric thermo-couple temperature controller controlled temperature; Use magnetic stirrer; Use the oxygen cylinder supply oxygen.
Its processing step is:
(1) grinds also surface active zinc ore concentrate mineral aggregate
After 120g zinc ore concentrate mineral aggregate and 0.024g surfactant mixed, wearing into granularity was 100 purpose breezes;
(2) preparation 600ml ammonium salt leaching agent
The ammonium salt leaching agent is ammonium chloride (but also ammonium sulfate or ammonium nitrate) solution, and in this ammonium salt solution, its ammonium concentration is 2.0mol/L;
(3) size mixing
The ammonium salt leaching agent and the liquid-phase oxidation catalyst Cu of breeze that step (1) is obtained and step (2) preparation
2+Solution and sulfur extraction agent zellon fully stir into slurries.In the slurries, liquid-phase oxidation catalyst Cu
2+Concentration be 0.1mol/L, sulfur extraction agent zellon and water be in a ratio of 1: 50, the liquid-solid ratio of these slurries is 5;
(4) leach
The slurries that step (3) is obtained are transported to leach in the reactor and leach, its leaching condition is: feed pure oxygen earlier and make oxygenant, the control oxygen partial pressure is 0.2MPa, energising heats up while stirring then, and keep reactor temperature about 90 ℃, leach after 3 hours powered-down, stop to stir, finish the leaching operation;
(5) liquid, the solid separation
Leaching feed liquid in the leaching reactor to filter and to separate, is obtained containing the leach liquor and the leached mud of nonferrous metal ion;
(6) to leached mud wash, drying and desulfurization
With the acidic solution washing leached mud of 50 ℃ pH=2～3, and carry out centrifuging, slag washing liquid is mixed with the ammonium salt leaching agent in order to recycling through replenishing ammonium salt; Adopt dry distillation, hot filter method or extraction process to reclaim wherein contained sulphur after the leached mud drying;
The leaching result of present embodiment is as shown in table 2.
Table 2 zinc, silver, the leaching yield of copper
Test sequence number 12345
The leaching yield of zinc (%) 75.0 71.0 73.0 73.0 75.0
The leaching yield (%) 76.0 74.0 72.0 74.0 76.0 of silver
The leaching yield of copper (%) 69.0 67.0 70.0 64.0 72.0
Embodiment 2
The effective volume that leaches reactor is 8m
3, being steel plate structure, inner lining glass fiber reinforced plastic is anticorrosion, uses steam heating, and the control oxygen partial pressure is 1～2, and the delivery rate of oxygen is controlled by metering valve.
Its processing step is as follows;
(1) grinds also surface active nonferrous metal sulfide mineral mineral aggregate
After the sodium laurylsulfonate of 0.9 ton of zinc ore concentrate and 1Kg mixed, wearing into granularity was 200-350 purpose breeze;
(2) preparation ammonium salt leaching agent
Earlier with 6m
3Clear water add surge tank, add ammonium sulfate (also can add ammonium nitrate or ammonium chloride) again and stir, the ammonium concentration in this solution is 3.5mol/L;
(3) size mixing
The ammonium salt leaching agent and the liquid-phase oxidation catalyst Cu of breeze that step (1) is obtained and step (2) preparation
2+Solution and sulfur extraction agent zellon fully stir into slurries.In the slurries, contain Cu
2+Concentration be 0.5mol/L, zellon sulfur extraction agent and water be in a ratio of 1: 20, the liquid-solid ratio of these slurries is 7.5: 1;
(4) leach
The slurries that step (3) is obtained are transported to leach in the reactor and leach, its leaching condition is: feed pure oxygen or air oxidant earlier, its oxygen partial pressure is adjusted to 1.5MPa, feeding steam then while stirring heats up, and keep reactor temperature about 130 ℃, leach after 5 hours steam off, stop to stir, finish the leaching operation;
(5) liquid, the solid separation
When temperature is reduced to 100 ℃ in leaching reactor, the leaching feed liquid in the leaching reactor to filter and to separate, is obtained containing the leach liquor and the leached mud of nonferrous metal ion;
(6) to leached mud wash, drying and desulfurization
With the acidic solution washing leached mud of 50 ℃ pH=2～3, and carry out centrifuging, slag washing liquid is mixed with the ammonium salt leaching agent in order to recycling through replenishing ammonium salt; Adopt dry distillation, hot filter method or extraction process to reclaim wherein contained sulphur after the leached mud drying.
Leach liquor volume 5.8m
3, the leach liquor zinc concentration is 72.2g/L, leached mud washing water volume 2m
3, the washing water zinc concentration is 2g/L, and calculating leaching yield with the leach liquor zinc content is 93.9%, and leached mud weighs 0.27 ton (butt), contains zinc 15.3%, and calculating leaching yield with the leached mud zinc content is 90.82%.
Embodiment 3
The leaching reactor that uses is with embodiment 1.
Its processing step is:
Its processing step is as follows:
(1) grinds also surface active nonferrous metal sulfide mineral mineral aggregate
After the sodium laurylsulfonate of 120g zinc ore concentrate mineral aggregate and 0.24g mixed, wearing into granularity was 350 purpose breezes;
(2) preparation 1200ml ammonium salt leaching agent
With embodiment 1, but the ammonium concentration in this solution is 4.0mol/L;
(3) size mixing
The ammonium salt leaching agent and the Cu of breeze that step (1) is obtained and step (2) preparation
2+Solution and zellon fully stir into slurries.In the slurries, Cu
2+Concentration be 0.6mol/L, zellon 240ml, the liquid-solid ratio of these slurries is 10: 1;
(4) leach
The slurries that step (3) is obtained are transported to leach in the reactor and leach, its leaching condition is: feed pure oxygen or air oxidant earlier, its oxygen partial pressure is adjusted to 2MPa, the heat temperature raising of switching on while stirring then, and keep reactor temperature about 145 ℃, leach after 1 hour steam off, stop to stir, finish the leaching operation;
(5) liquid, the solid separation
When temperature is reduced to 100 ℃ in leaching reactor, the leaching feed liquid in the leaching reactor to filter and to separate, is obtained containing the leach liquor and the leached mud of nonferrous metal ion;
(6) to leached mud wash, drying and desulfurization
With the acidic solution washing leached mud of 50 ℃ pH=2～3, and carry out centrifuging, slag washing liquid is mixed with the ammonium salt leaching agent in order to recycling through replenishing ammonium salt; Adopt dry distillation, hot filter method or extraction process to reclaim wherein contained sulphur after the leached mud drying.
The leaching result such as the table 3 of present embodiment
Table 3 zinc, silver, the leaching yield of copper
Test sequence number 12345
The leaching yield of zinc (%) 95.2 91.2 93.7 93.9 95.2
The leaching yield (%) 96.2 94.1 92.8 94.7 96.4 of silver
The leaching yield of copper (%) 89.4 87.3 90.4 84.8 92.2
Claims (5)
1. the ammonium salt liquid phase oxidation direct leaching method of a nonferrous metal sulfide mineral, its processing step is as follows:
(1) grinds also surface active nonferrous metal sulfide mineral mineral aggregate
After the proportioning that adds 0.2～2kg surfactant by nonferrous metal sulfide mineral mineral aggregate per ton mixed nonferrous metal sulfide mineral mineral aggregate and surfactant, wearing into granularity was 100-350 purpose breeze;
(2) preparation ammonium salt leaching agent
Described leaching agent is ammonium chloride solution, ammoniumsulphate soln or ammonium nitrate solution, and the ammonium concentration in the solution is 2.0mol/L to 4.0mol/L;
(3) size mixing
The ammonium salt leaching agent of breeze that step (1) is obtained and step (2) preparation and liquid-phase oxidation catalyst and sulfur extraction agent fully stir into slurries, in the slurries, the concentration of liquid-phase oxidation catalyst is 0.1～0.5mol/L, sulfur extraction agent and water be in a ratio of 1: 5～50, the liquid-solid ratio of these slurries is 5～10: 1;
(4) leach
The slurries that step (3) is obtained are transported to leach in the reactor and leach, its leaching condition is: feed pure oxygen or air oxidant earlier, its oxygen partial pressure is adjusted to 1～2MPa, heat temperature raising while stirring then, and keep reactor temperature between 90～145 ℃, leach after 1～6 hour, stop heating and stirring, finish the leaching operation;
(5) liquid, the solid separation
When temperature is reduced to 100 ℃ in leaching reactor, filter and separate, obtain containing the leach liquor and the leached mud of nonferrous metal ion leaching leaching feed liquid in the reactor;
(6) to leached mud wash, drying and desulfurization
With the acidic solution washing leached mud of 50 ℃ pH=2～3, and carry out centrifuging, slag washing liquid is mixed with the ammonium salt leaching agent in order to recycling through replenishing ammonium salt; Adopt dry distillation, hot filter method or extraction process to reclaim wherein contained sulphur after the leached mud drying.
2. by the ammonium salt liquid phase oxidation direct leaching method of the described nonferrous metal sulfide mineral of claim 1, it is characterized in that: described surfactant is wooden sodium sulfonate or sodium laurylsulfonate.
3. by the ammonium salt liquid phase oxidation direct leaching method of the described nonferrous metal sulfide mineral of claim 1, it is characterized in that: described liquid-phase oxidation catalyst is for containing Cu
2+Mantoquita.
4. by the ammonium salt liquid phase oxidation direct leaching method of the described nonferrous metal sulfide mineral of claim 1, it is characterized in that: described sulfur extraction agent is a zellon.
5. by the ammonium salt liquid phase oxidation direct leaching method of the described nonferrous metal sulfide mineral of claim 1, it is characterized in that: described leaching reactor is the gas-liquid-solid phase reaction device.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB01141555XA CN1164775C (en) | 2001-10-15 | 2001-10-15 | Ammonium salt liquid phase oxidation direct leaching method for nonferrous metal sulfide mineral |
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| CNB01141555XA CN1164775C (en) | 2001-10-15 | 2001-10-15 | Ammonium salt liquid phase oxidation direct leaching method for nonferrous metal sulfide mineral |
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| CN1164775C true CN1164775C (en) | 2004-09-01 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101215637B (en) * | 2008-01-11 | 2010-06-02 | 昆明理工大学 | Method for eluting nickel from nickel-carrying activated carbon by cleanser essence |
| CN104928467A (en) * | 2015-06-30 | 2015-09-23 | 中南大学 | Method for leaching zinc in oxidation-sulfidation mixed zinc ore through ammonium chloride solution at high temperature and oxygen pressure |
| CN108315571A (en) * | 2018-01-17 | 2018-07-24 | 中国瑞林工程技术有限公司 | A kind for the treatment of process of Containing Sulfur arsenic material |
| CN109825700B (en) * | 2019-03-18 | 2020-07-17 | 中国科学院过程工程研究所 | Method for selectively extracting valuable metals from nickel sulfide concentrate at low temperature and normal pressure |
| CN110273064A (en) * | 2019-04-23 | 2019-09-24 | 国家电投黄河上游水电开发有限责任公司 | A kind of method that mechanical activation strengthens Nickel Sulfide Leaching at Atmospheric Pressure nickel |
| CN113981217B (en) * | 2021-11-01 | 2024-02-09 | 昆明理工大学 | Method for selectively separating copper, zinc and iron in low-grade complex chalcopyrite |
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