CN1361295A - Direct zinc sulfide concentrate leaching-out process with coupled synergic leaching-out and solvent extraction and separation - Google Patents
Direct zinc sulfide concentrate leaching-out process with coupled synergic leaching-out and solvent extraction and separation Download PDFInfo
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Abstract
The present invention belongs to the field of non-ferrous metal smelting technology and is the direct zinc sulfide concentrate leaching-out process with coupled synergic leaching-out and solvent extraction and separation inside one identical plant. The organic phase and water constitute both leaching agent and extracting agent of several products. The back washing of the loaded organic phase and the preparation of material are combined. The present invention has a main metal leaching out rate up to 95% and can realize the comprehensive recovery of resource.
Description
The invention belongs to the technical field of non-ferrous metal smelting, and particularly relates to a method for directly leaching zinc sulfide concentrate by coupling synergistic leaching and synergistic solvent extraction separation.
The traditional process is innovated, a new operation mode is developed, the process flow is simplified, high-efficiency engineering equipment is adopted, and the solution of industrial pollution is an important research subject of the current reaction and mass transfer separation in the production process. The nonferrous metal resources in China are mainly complex sulfide ores containing accompanying multiple elements, the existing smelting process basically adopts a sulfide ore roasting acid making process, and the process flow is long, equipment is complex and huge, and the investment cost is high. The roasting process has very strict requirements on the grade and the impurity content of the raw materials, and strict burdening is required before smelting.Along with the continuous consumption of resources, the contradiction between the poor adaptability of the existing process to mineral aggregates and the continuous poor hematization of mineral reserves can be more and more prominent. Most importantly, a large amount of SO is generated in the roasting process of the sulphide ore2And dust containing mercury, arsenic, cadmium and lead oxides seriously threatens the health of human beings, especially SO2The acid rain is easy to cause harm when the water is discharged into the atmosphere.
The direct leaching of sulphide ores without roasting is a research and development direction. Over the 40 years, a great deal of research has been done by the scientists and scientists, developing the oxygen pressure method, the ammonia pressure method, the ferric chloride method, the cupric chloride method, the manganese dioxide oxidation leaching in hydrochloric acid solution and other technologies. Such as Anderson; corby g.; krys; leo e.; harrison; kevin d. in us patent 5096486 it is proposed to leach sulphide ores with sulphuric acid-sodium sulphate; chlorination leaching of sulphide ores is proposed in us patent 4206623 to Au Robert w; paul, Pemsler J; litchfield john k in us patent 3950487 proposes a process for the extractive separation of copper and nickel from ammonia leach pulp. However, it is very rare that these methods are industrially applied.
The invention aims to overcome the defects of long flow, complex and huge equipment, high investment cost, severe requirements on the grade and impurity content of raw materials in the roasting process and the like in the preparation of zinc sulfide concentrate, and provides a method for directly leaching zinc sulfide concentrate by coupling synergistic leaching and synergistic solvent extraction separation, which is suitable for the all-wet smelting of zinc sulfide concentrate and also suitable for the all-wet smelting of other non-ferrous metal sulfide ores.
The present invention for the first time proposes a modern mode of operation of a coupled process of synergistic leaching and synergistic solvent extraction separation, unlike the direct leaching and solvent-in-slurry extraction (SIP) mentioned earlier.
The invention uses surface active agents such as sodium dodecyl sulfate, animal glue or water-soluble silicate to carry out hydrophilic treatment on the surface of mineral particles; sulfuric acid-nitric acid mixed acid or ferric chloride-hydrochloric acid solution is used as a leaching agent, 2-diethylhexyl phosphoric acid (P204) or naphthenic acid (HA) is used as an iron extracting agent, and tetrachloroethylene is used as a sulfur extracting agent, so that the rapid leaching process of the sulfide ore is realized. The sulfur contained in the mineral powder is converted into elemental sulfur, and the Zn, Cu, Cd and the like contained in the mineral powder are converted into soluble salts to enter the leaching solution. The process comprises the following steps:
(1) milling and surface modification
And grinding the zinc concentrate to enable the granularity of the zinc concentrate to be larger than 200 meshes. In the grinding process, surfactants such as sodium dodecyl sulfate, animal glue or water-soluble silicate are added to treat the surface of the ore particles, so that the surface of the ore particles is changed from lipophilicity to hydrophilicity, the minerals are not agglomerated in the leaching process, the contact between the minerals and the leaching agent is facilitated, and the loss of an organic phase in slag discharge is reduced. The addition amount of the surfactant is 0.2-2 kg/ton of ore.
(2) Preparation of the leachant
The leaching agent can be a sulfuric acid-nitric acid mixed acid system, a ferric chloride-hydrochloric acid solution system or other direct leaching systems. In a sulfuric acid-nitric acid mixed acid system, a leaching agent can be prepared by using waste electrolyte and supplemented sulfuric acid, the sulfuric acid concentration is 1-3 mol/L at the beginning of leaching, and the nitric acid concentration is 0.1-2 mol/L; in the ferric chloride-hydrochloric acid solution system, the concentration of ferric chloride is 1-3 mol/L, and the concentration of hydrochloric acid is 0.5-2 mol/L.
(3) Preparation of the synergistic extractant (organic phase)
And adding a proper amount of diluent to prepare the synergistic extractant according to the molar ratio of the iron extracting agent to the sulfur extracting agent being 1: 1-3.
The iron extracting agent is 2-diethyl hexyl phosphoric acid or naphthenic acid; the sulfur extracting agent is tetrachloroethylene; the diluent is kerosene.
(4) Mixing the slurry
And mixing the leaching agent and the mineral powder subjected to surface hydrophilic treatment according to the solid-liquid ratio of 1: 4-10, and conveying the mixture to a size mixing tank for uniformly stirring. The size mixing tank is a mechanical stirring tank.
(5) Leaching-extraction
Is finished in a leaching-extracting integrated reactor. The leaching-extraction integrated reactor comprises a stirring system, an oxygen supply system, a temperature control system, an organic phase circulation system and a sampling analysis system. Wherein the organic phase circulating system comprises a mixing clarifier arranged in the leaching-extracting integrated reactor, a cooling sulfur precipitation tank arranged outside the reactor, a sulfur filter, a hydrolysis back-extraction tank, an iron oxide powder filter and a circulating pump. The operating conditions were:
and (2) conveying the slurry in the slurry mixing tank into a leaching-extraction integrated reactor, forming a synergistic leaching agent by an organic phase and a water phase, and adding the synergistic leaching agent (the organic phase) according to the ratio of O/A (1: 5-20) of the organic phase to the water phase. Stirring to mix the liquid, solid and oil in the reactor evenly; introducing steam to raise the temperature and maintaining the temperature inside the reactor at 70-95 deg.c; maintaining normal pressure operation; the leaching time is 1-4 hours, and the leaching operation is stopped when the leaching rate reaches the leaching index (generally more than 85%).
(6) Separation of oil from liquid and solid
And after leaching, filtering the feed liquid in the reactor, and separating the loaded organic phase, the leaching residue and the leaching liquid.
(7) Washing of leached residue
And (3) washing the leaching slag containingiron, lead, calcium, silicon and the like by using clear water with the pH value of 2-3, centrifugally filtering, returning the washing liquid to prepare a leaching solution, and conveying the leaching slag to a slag yard for stacking.
(8) Purification of leach liquors and product preparation
The leachate contains ions of metals such as zinc, copper, cadmium, cobalt, nickel and the like, and contains trace iron and manganese. In the purification process, goethite is adopted for removing iron.
Heating the feed liquid in an iron removing tank to raise the temperature, maintaining the temperature at about 70-95 ℃, adding potassium permanganate, and removing trace ferrous iron in the feed liquid to obtain goethite. Manganese is also removed simultaneously. Filtering to remove iron and manganese slag, and conveying the filtrate to a copper and cadmium removing tank.
And (3) replacing the copper and the cadmium in a copper and cadmium removing tank by using zinc powder, removing the copper and the cadmium, and stirring for 0.5-2 hours at the temperature of 40-60 ℃. Filtering to remove copper and cadmium residues, and conveying the filtrate to a cobalt and nickel removing tank.
In a cobalt and nickel removing tank, removing cobalt and nickel by replacing with zinc powder, and stirring for 0.5-2 hours at 40-70 ℃. Filtering to remove cobalt and nickel residues, and conveying the filtrate to a purified solution storage tank to obtain a purified zinc-containing solution.
The step (6) is followed by a loaded organic phase stripping regeneration step:
a. cooling and sulfur precipitation: continuously pumping out part of the organic phase from the reactor to a cooling sulfur precipitation tank in the leaching process, and slowly cooling to obtain needle-shaped crystal sulfur; rapidly cooling and violently stirring, and cooling to normal temperature-40 ℃ to obtain micro sulfur powder larger than 200 meshes; and (4) filtering and separating.
b. And washing the cooled and sulfur-precipitated organic phase with deionized water for several times, and conveying the organic phase into a hydrolysis stripping tank for hydrolysis and iron precipitation. The pH was adjusted to about 1.9 with ammonia. Adding deionized water according to the ratio of organic phase to water O/A of 1: 0.5-2, 1-10g L-1The temperature of the hydrolysis reduction back extraction is controlled to be 100-200 ℃, the time is about 0.5-2 hours, and the mixture is cooled to normal temperature and pressure and then filtered and separated. The morphology of the precipitated iron oxide product depends on the operating temperature, pressure, stirring strength and the type of additive. Vigorous stirring produces fine iron oxide powder. Adding reducer will produce magnetic ferroferric oxide.
The reducing agent is sodium sulfite, sodium thiosulfate or sulfur dioxide and the like.
c. The regenerated organic phase is recycled to the reactor. The back extraction regeneration of the loaded organic phase can also be completed once after the leaching is finished.
Regeneration of the catalyst and lixiviant of the invention
In sulfuric acid-nitric acid systems, the catalyst NO2Regeneration is obtained by continuously oxidizing the generated NO with oxygen or air. The sulfuric acid is regenerated during zinc sulfate electrodeposition. In the ferric chloride-hydrochloric acid system, zinc in the leachate is extracted and separated by a solvent, and ferrous iron is oxidized by air or an electrolytic method to regenerate ferric chloride.
The essence of the coupling process proposed by the present inventionis that the direct leaching-extraction separation of solid raw materials (such as refractory sulphide ores) is carried out simultaneously in an integrated unit. The organic phase can form a synergistic leaching agent with the water phase to leach materials, and is a synergistic extraction agent of various leaching products. The material is continuously leached by the synergistic leaching agent, and the products (such as sulfur and metal complex ions) are immediately extracted by the organic phase. And (3) carrying out decantation liquid-solid separation, purifying and impurity removal and back extraction regeneration on the loaded organic phase, and returning the regenerated organic phase to the integrated device.
The whole process of the invention consists of a plurality of systems. Namely a leaching system consisting of a feeding system, an oxygen supply system, a leaching reactor and a filter; an organic phase/slurry phase separation system; an organic phase cooling and sulfur precipitating system; a hydrolysis back-extraction iron-precipitation system; and (4) a deep purification system.
In a sulfuric acid-nitric acid system, the initial concentration of sulfuric acid is 1-3 mol/L and the initial concentration of nitric acid is 0.1-2 mol/L at the beginning of leaching (in a ferric chloride-hydrochloric acid system, the initial concentrations of ferric trichloride and hydrochloric acid are 1-3 mol/L and 0.5-2 mol/L respectively).
Taking a sulfuric acid-nitric acid system as an example, and combining the attached drawings. Firstly, the mineral powder is ground to more than 90 percent of the mineral powder which can pass through a standard sieve of 200 meshes. The activating agent is added in the grinding process, and after the surface of the ore particles is treated by the surfactant, the lipophilicity is changed into the hydrophilicity, so that the minerals cannot agglomerate in the leaching process, the contact between the minerals and the leaching agent is facilitated, and the loss of an organic phase in slag discharge is reduced. And (3) conveying the ground mineral powder into a size mixing tank 19, adding the prepared leaching agent, and uniformly stirring for size mixing. The prepared slurry is then transferred to the reactor 4 via the feed valve 18 and the ceramic mortar pump 17 and the extractant is added. The solid-liquid ratio is 1: 4-8; the ratio of O/A of the organic phase to the aqueous phase is 1: 5 to 20, and the ratio of 2-diethylhexylphosphoric acid (or naphthenic acid) to tetrachloroethylene in the extractant is 1: 1 to 3.
The steam valve 2 is opened. Introducing steam to raise the temperature, and maintaining the temperature in the reactor to be 70-95 ℃ by a temperature controller 7. Stirring is performed by the stirrer 3.
Under the above conditions, sulfide such as ZnS in the ore is oxidized to So、Zn2+. The basic reactions that occur during leaching are as follows:
sulfide such as ZnS in ore being coated with NO3 -(NO2)+Oxidation to So。HNO3(NO2) Is itself reduced to NO. The basic reactions that occur during leaching are as follows:
in the leaching and extraction integrated device, the synergistic leaching agent consists of an organic phase and an aqueous phase, the organic phase is also an effective leaching agent of materials (reaction 11) besides the aqueous phase (reaction 1-9), the leaching agent and the materials are simultaneously placed in a leaching tank and stirred, and the materials are leached by the synergistic leaching agent.
The organic phase consists of more than two organic solvents and allows simultaneous extraction of multiple leaching products (reactions 10, 11).
The extraction agent and the additive strip the surface inert film (reaction 11), promote the surface to be continuously updated, strengthen the effect of the leaching process, and shorten the time of leaching and extraction separation from the current 6-8 h to 1-4 h.
Sulfur is produced as elemental sulfur and sulfate radical, and SO is completely eliminated in the leaching process2、H2S、NOx、As2O3And discharging mercury vapor.
The regeneration of the loaded organic phase is coupled with the preparation process of the ultrafine powder material, namely, the high-purity sulfur powder with more than 200 meshes is prepared by separating the loaded organic phase through cooling back extraction, then the fine ferric oxide powder is prepared by separating the loaded organic phase through hydrothermal back extraction, and the organic phase is regenerated. The reaction is as follows:
the synergistic extractant adopted by the invention meets the requirements of good leaching performance, extraction performance and back extraction performance and good oxidation resistance.
Stripping the inert film on the surface of the solid particles as much as possible by extraction and an activating agent, and promoting surface renewal to strengthen leaching; inhibiting the infiltration of oil on the surface of the material particles to enhance leaching and reduce the loss of organic phase.
The amount of oxygen supplied to the leaching reactor is such as to ensure that the ZnS is sufficiently oxidised.
The leaching is carried out at the temperature of 70-95 ℃, and compared with the operation condition of 130-190 ℃, the leaching method can save energy and improve the operation safety.
The leaching time is generally 1 to 4 hours. When the zinc content of the leached slag is lower than 5 percent, the operation of the leached slag is stopped, and liquid-solid separation is carried out by using liquid-solid separation equipment 7.
The filtrate contains ions of metals such as zinc, copper, cadmium, cobalt, nickel and the like, and contains trace iron and manganese.
And (3) washing the leached slag containing iron, lead, calcium, silicon and the like by using clear water with the pH value of 2-3 at 50 ℃, centrifugally filtering, returning the washing liquid to prepare a leaching solution, and conveying the leached slag to a slag yard for stacking.
By adopting the invention, the direct leaching of the sulfide ore can accelerate the leaching process. The leaching system is suitable for treating sulfide ore containing zinc, copper, lead and other elements, and can be used for treating low-grade and multi-element complex sulfide ore. The leaching of the main metal is not influenced by the high content of arsenic, mercury, lead, cadmium and iron, and the leaching rate of the main metal can reach more than 95 percent. Therefore, comprehensive recovery of resources can be realized.
In the purification process, goethite is adopted for removing iron. The feed liquid in the iron removing groove 10 is heated to raise the temperature, the temperature is maintained at about 90 ℃, potassium permanganate is added, and trace ferrous iron in the feed liquid is removed as goethite. Manganese is also removed simultaneously.
The coupling process provided by the invention has an extremely attractive application prospect in the fields of chemical engineering and wet metallurgy, and has the characteristics that the traditional process cannot have:
(1) a synergistic leaching agent consisting of an organic phase and a water phase simultaneously leaches materials; the synergistic extractant consisting of more than two organic solvents is used for simultaneously extracting and separating a plurality of leaching products.
(2) The leaching and mass transfer separation are simultaneously completed in the same reactor, the alkalinity of the materials is utilized to neutralize the acidity of the extracting agent, the acid generated in the extraction is utilized to leach the solid materials, the consumption of the alkali and the acid is reduced simultaneously, and the flow can be greatly simplified.
(3) The leaching process is carried out in a closed container, the temperature is higher, the stirring is violent, and the improvement of the mass transfer rate and the extraction balance are facilitated.
(4) The organic phase continuouslyextracts and separates solid matters (such as sulfur and salts of impurity elements) generated in the leaching process, so that the exposure of the surfaces of material particles is facilitated, the diffusion is enhanced, and the leaching driving force is increased.
(5) The regeneration process of the loaded organic phase is combined with the preparation of the superfine powder material. Sulfur is produced as high quality sulfur powder, and Fe in the organic phase is loaded3+By hydrolytic stripping, the iron can be relatively pure Fe2O3And (4) precipitating to produce the magnetic material.
(6) Absence of SO2And the iron slag causes environmental pollution, and the process is a clean process.
By adopting the invention, the direct leaching of the sulphide ore can accelerate the leaching process. The leaching system is suitable for treating sulfide ore containing zinc, copper, lead and other elements, and can be used for treating low-grade and multi-element complex sulfide ore. The leaching of the main metal is not influenced by the high content of arsenic, mercury, lead, cadmium and iron, and the leaching rate of the main metal can reach more than 95 percent, so that the comprehensive recovery of resources can be realized.
The technical solution of the present invention is further described below with reference to the following embodiments and the accompanying drawings.
FIG. 1 is a schematic diagram of the connection of leaching process equipment according to the invention;
FIG. 2 is a schematic process flow diagram of the present invention.
Reference numbers in the figures:
1. steam pipeline 2, steam valve 3, stirrer 4, leaching reactor 5 and pressure gauge
6. Exhaust valve 7, thermometer controller 8, oxygen (air) storage tank
9. Air inlet valve 10, flowmeter 11, discharge valve 12, mixing and clarifying chamber 13, cooling sulfur precipitation tank
14. Filter 15, hydrolysis back extraction tank 16, filter 17, feeding pump
18. Feed valve 19. size mixing tank
Example 1
The zinc concentrate used contained 50% zinc. Weighing 10g of the powder, and grinding the powder to ensure that the granularity of the powder is more than 200 meshes; adding 0.2g of sodium dodecyl sulfate surfactant to treat the surface of the ore particles in the grinding process to change the lipophilicity of the surface of the ore particles into the hydrophilicity, so that the ore cannot be agglomerated in the leaching process, and placing the treated ore particles in a reactor;
the leaching agent is FeCl3-an HCl system. Weighing FeCl3.2H2Pouring 30g of O into a beaker, adding 30ml of hydrochloric acid, adding water to dilute to 100ml, and pouring into a reactor;
adding naphthenic acid and tetrachloroethylene in the molar ratio of 1 to 3 into one container, and adding proper amount of kerosene to compound synergistic extractant. Weighing 20ml of prepared synergistic extractant (organic phase) and pouring into a reactor, and stirring by using a magnetic stirrer to uniformly mix liquid, solid and oil phases in the reactor; electrifying and heating up, and maintaining the temperature in the reactor at 85 ℃; the leaching time is 3 hours;
after leaching, filtering the feed liquid in the reactor, and separating a loaded organic phase, leaching residues and a leaching solution; and washing the leaching residue with 40ml of clear water with the pH value of 2-3. The organic phase load, the leaching residue (dry basis), the leaching liquid and the slag washing liquid are respectively 19.3ml, 4.2g, 91ml and 40 ml. The total zinc content in the leaching solution and the slag washing solution is detected to be 4.8g by an EDTA titration method, and the leaching rate of the zinc is 96.00 percent. Example 2
Placing the loaded organic phase obtained in the example 1 in a cooling sulfur precipitation tank, naturally cooling to normal temperature to obtain needle-shaped crystal sulfur, and filtering and separating;
washing the filtered and separated organic phase with purified water for several times, conveying the organic phase into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, adding 20ml of purified water, and adjusting the pH value of the material to 1.9 by using ammonia water; 0.5g of sodium thiosulfate was added. The reactor was closed. Stirring vigorously by using a magnetic stirrer, and controlling the temperature of hydrolysis reduction back extraction to be 160 ℃ by using a constant-temperature oil bath for 1 hour; cooling to normal temperature, and filtering and separating; the precipitate is washed and dried to obtain the product. The product has iron content of 95.36%, particle size of about 0.1 μm, magnetism, and Fe content by X-ray diffraction analysis3O4。
Example 3
The organic phase obtained in example 2 is washed and regenerated with hydrochloric acid and clean water and recycled. The operating conditions for each cycle were the same as in example 1. As shown in Table 1, it can be seen that the effect of recycling tetrachloroethylene for a plurality of times on the leaching rate is small.
TABLE 1 recoveryand reuse of tetrachloroethylene
Number of cycles 01234
Leaching rate (%) 96.0095.2893.9694.8894.18 of zinc
Example 4
Adding the leachate obtained in example 1 into a 200ml glass reaction kettle, placing the glass reaction kettle into a constant-temperature water bath, stirring by using a magnetic stirrer, adding potassium permanganate, electrifying, heating, stabilizing the temperature at about 90 ℃ for 1h, and filtering to remove iron-manganese slag while the temperature is hot. Pouring the filtrate back into a glass reaction kettle, stabilizing the temperature at 60 ℃, adding 0.1g of zinc powder, stirring for 1h, and filtering the feed liquid in the kettle to remove copper and cadmium residues. Pouring the filtrate back into a glass reaction kettle, stabilizing the temperature at about 70 ℃, adding 0.1g of zinc powder, stirring for 1 hour, and filtering the feed liquid in the kettle to remove cobalt and nickel residues. The filtrate composition is shown in table 2.
TABLE 2 composition of the purification solutions
Element Zn
The content (g/l) is 60
Element Cu Cd Fe (Mn) Co Ni Ce As Sb
The content (mg/l) is not more than 0.41 to 2 not more than 53 to 43 to 41 to 211
The recovery rate of zinc is more than 95%.
Claims (9)
1. A method for directly leaching zinc sulfide concentrate by coupling synergistic leaching and synergistic solvent extraction separation is characterized in that: the method comprises the following steps:
(1) milling and surface modification
Grinding the zinc concentrate to make the granularity of the zinc concentrate larger than-200 meshes; adding a surfactant to treat the surface of the mineral particles in the grinding process to change the lipophilicity of the surface of the mineral particles into the hydrophilicity; the addition amount of the surfactant is 0.2-2 kg/ton ore;
(2) preparation of the leachant
The leaching agent is a sulfuric acid-nitric acid mixed acid system or a ferric chloride-hydrochloric acid solution system; in a sulfuric acid-nitric acid mixed acid system, the sulfuric acid concentration is 1-3 mol/L and the nitric acid concentration is 0.1-2 mol/L at the beginning of leaching; in an iron chloride-hydrochloric acid solution system, the concentration of iron chloride is 1-3 mol/L, and the concentration of hydrochloric acid is 0.5-2 mol/L;
(3) preparation of synergistic extractant
Adding appropriate amount of diluent kerosene to prepare a synergistic extractant according to the mol ratio of the iron extraction agent 2-diethylhexyl phosphoric acid or naphthenic acid to the sulfur extraction agent tetrachloroethylene being 1: 1-3;
(4) mixing the slurry
Mixing the leaching agent and the mineral powder subjected to surface hydrophilic treatment according to the solid-liquid ratio of 1: 4-10, and conveying the mixture to a size mixing tank for uniformly stirring;
(5) leaching-extraction
Conveying the slurry in the slurry mixing tank into a leaching-extraction integrated reactor, forming a synergistic leaching agent by an organic phase and a water phase, adding the synergistic leaching agent according to the ratio of O/A (oxygen/oxygen) to water phase of 1: 5-20, and stirring to uniformly mix liquid, solid and oil phases in the reactor; introducing steam to raise the temperature and maintaining the temperature inside the reactor at 70-95 deg.c; stopping the leaching operation when the leaching rate reaches the leaching index;
(6) separation of oil from liquid and solid
After leaching, filtering the feed liquid in the reactor, and separating a loaded organic phase, leaching residues and a leaching solution;
(7) washing of leached residue
The leaching residue contains iron, lead, calcium or silicon elements, the leaching residue is washed by clear water with the pH value of 2-3, filtering is carried out, and the washing liquid is returned to prepare a leaching agent;
(8) purification of leach liquors and product preparation
The leaching solution contains zinc, copper, cadmium, cobalt, nickel, iron and manganese metal ions;
heating the feed liquid, adding potassium permanganate, removing iron and manganese;
adding zinc powder, and removing copper and cadmium by replacement;
and further adding zinc powder, removing cobalt and nickel by replacement, and filtering to obtain a purified zinc-containing solution.
2. A process of direct leaching of zinc sulphide concentrate coupled with synergistic leaching and synergistic solvent extraction separation according to claim 1, characterised in that: the surfactant is sodium dodecyl sulfate, animal glue or water-soluble silicate.
3. A process of direct leaching of zinc sulphide concentrate coupled with synergistic leaching and synergistic solvent extraction separation according to claim 1, characterised in that: the temperature of adding potassium permanganate in the step (8) is70-95 ℃.
4. A process of direct leaching of zinc sulphide concentrate coupled with synergistic leaching and synergistic solvent extraction separation according to claim 1, characterised in that: the process condition of the step (8) for removing copper and cadmium by replacement is that the mixture is stirred for 0.5 to 2 hours at the temperature of between 40 and 60 ℃.
5. A process of direct leaching of zinc sulphide concentrate coupled with synergistic leaching and synergistic solvent extraction separation according to claim 1, characterised in that: the process condition of the step (8) for removing cobalt and nickel by replacement is that the mixture is stirred for 0.5 to 2 hours at the temperature of between 40 and 70 ℃.
6. A process of direct leaching of zinc sulphide concentrate coupled with synergistic leaching and synergistic solvent extraction separation according to claim 1, characterised in that: the organic phase and the water phase form a synergistic leaching agent to simultaneously leach materials in an integrated device.
7. A process of direct leaching of zinc sulphide concentrate coupled with synergistic leaching and synergistic solvent extraction separation according to claim 1, characterised in that: the step (6) is followed by a loaded organic phase stripping regeneration step:
a. cooling and sulfur precipitation: extracting part of organic phase from the reactor to a cooling sulfur precipitation tank in the leaching process, and slowly cooling to obtain needle-shaped crystal sulfur; rapidly cooling and violently stirring to obtain fine sulfur powder of more than 200 meshes; cooling to normal temperature-40 ℃, and filtering and separating;
b. washing the filtered and separated organic phase with deionized water for several times, and conveying the organic phase into a hydrolysis stripping tank for hydrolysis and iron precipitation; ammonia water is used for size mixing, and the pH value is 1.7-2.1; adding deionized water according to the ratio of organic phase to aqueous phase O/A being 1: 0.5-2, and then adding 1-10 gL-1The temperature of the hydrolysis reduction back extraction is controlled to be 100-200 ℃, the time is about 0.5-2 hours, and the reducing agent is vigorously stirred to generate fine iron oxide powder; adding a reducing agent to generate magnetic ferroferric oxide; cooling to normal temperature and normal pressure, and filtering and separating;
c. the filtered organic phase is recycled to the reactor.
8. A method of direct leaching of zinc sulphide concentrate coupled with synergistic leaching and synergistic solvent extraction separation according to claim 7, characterised in that: the reducing agent is sodium sulfite, sodium thiosulfate or sulfur dioxide.
9. A method of direct leaching of zinc sulphide concentrate coupled with synergistic leaching and synergistic solvent extraction separation according to claim 7, characterised in that: the step (5) maintains normal pressure operation; the time is 1-4 hours.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1303231C (en) * | 2002-08-24 | 2007-03-07 | 祥云县飞龙实业有限责任公司 | Zinc sulfide concentrate calcines and zinc ide ore combined leaching process |
| CN101886170A (en) * | 2010-06-29 | 2010-11-17 | 白银先达科技服务有限责任公司 | Production process for isolating fluorine and chlorine by acid extraction during electrolytic zinc production |
| CN102206758A (en) * | 2011-05-06 | 2011-10-05 | 西昌宏鑫实业有限公司 | Method and equipment for wet extraction of zinc, cadmium and copper from zinc-containing waste residue |
| CN103740930A (en) * | 2014-01-16 | 2014-04-23 | 昆明理工大学 | Thiosulfate gold extraction method taking alkyl trimethyl quaternary ammonium salt as additive |
| CN103757208A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching manganese carbonate ore |
| CN103805784A (en) * | 2014-03-03 | 2014-05-21 | 北京工业大学 | Synergistic extraction system for recovering and extracting platinum through extraction method |
| CN104831062A (en) * | 2015-03-26 | 2015-08-12 | 武汉钢铁(集团)公司 | A method of extracting valuable elements by utilization of sulfur concentrate |
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2000
- 2000-12-27 CN CNB001362852A patent/CN1133752C/en not_active Expired - Fee Related
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1303231C (en) * | 2002-08-24 | 2007-03-07 | 祥云县飞龙实业有限责任公司 | Zinc sulfide concentrate calcines and zinc ide ore combined leaching process |
| CN101886170A (en) * | 2010-06-29 | 2010-11-17 | 白银先达科技服务有限责任公司 | Production process for isolating fluorine and chlorine by acid extraction during electrolytic zinc production |
| CN102206758A (en) * | 2011-05-06 | 2011-10-05 | 西昌宏鑫实业有限公司 | Method and equipment for wet extraction of zinc, cadmium and copper from zinc-containing waste residue |
| CN103757208A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching manganese carbonate ore |
| CN103757208B (en) * | 2013-12-29 | 2015-11-25 | 四川师范大学 | The leaching method of manganese carbonate ore |
| CN103740930B (en) * | 2014-01-16 | 2015-11-04 | 昆明理工大学 | A kind of take alkyl trimethyl quaternary ammonium salt as the thiosulfate gold extracting method of additive |
| CN103740930A (en) * | 2014-01-16 | 2014-04-23 | 昆明理工大学 | Thiosulfate gold extraction method taking alkyl trimethyl quaternary ammonium salt as additive |
| CN103805784B (en) * | 2014-03-03 | 2016-01-13 | 北京工业大学 | A kind of synergistic extraction method of fetching receipts platinum based on Recovery by Solvent Extraction Methold |
| CN103805784A (en) * | 2014-03-03 | 2014-05-21 | 北京工业大学 | Synergistic extraction system for recovering and extracting platinum through extraction method |
| CN104831062A (en) * | 2015-03-26 | 2015-08-12 | 武汉钢铁(集团)公司 | A method of extracting valuable elements by utilization of sulfur concentrate |
| CN110684903A (en) * | 2019-11-07 | 2020-01-14 | 郑州大学 | Method for enhancing dissolution of valuable metals in oil-contaminated cylinder liner honing waste based on electronic motion |
| CN110684903B (en) * | 2019-11-07 | 2021-06-25 | 郑州大学 | Method for enhancing dissolution of valuable metals in oil-contaminated cylinder liner honing waste based on electronic motion |
| CN114752768A (en) * | 2022-04-02 | 2022-07-15 | 中国科学院过程工程研究所 | Method for recovering metal molybdenum in waste hydrogenation catalyst through leaching and extraction integration |
| CN115261635A (en) * | 2022-08-01 | 2022-11-01 | 西安矿源有色冶金研究院有限公司 | Comprehensive recycling method of high-grade multi-element gold concentrate |
| CN115261635B (en) * | 2022-08-01 | 2024-01-16 | 西安矿源有色冶金研究院有限公司 | Comprehensive recycling method for high-grade multi-element gold concentrate |
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