CN101709373A - Method and system for treating lead-zinc sulfide ores - Google Patents
Method and system for treating lead-zinc sulfide ores Download PDFInfo
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- CN101709373A CN101709373A CN200910223379A CN200910223379A CN101709373A CN 101709373 A CN101709373 A CN 101709373A CN 200910223379 A CN200910223379 A CN 200910223379A CN 200910223379 A CN200910223379 A CN 200910223379A CN 101709373 A CN101709373 A CN 101709373A
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Abstract
The invention discloses method and system for treating lead-zinc sulfide ores. The method comprises the following steps of: dressing the lead-zinc sulfide ores to obtain concentrate lead-zinc sulfide ores; fine grinding the concentrate lead-zinc sulfide ores and pulpifying the fine-grinded concentrate lead-zinc sulfide ores by using sulfuric acid; carrying out a first stage of oxygen pressure acid leaching on the pulpified concentrate lead-zinc sulfide ores; after solid-liquid separation of the serosity leached from the first stage, purifying and electrolyzing the leached solution from the first stage to obtain a metal zinc, and dressing the slag leached from the first stage to obtain a simple substance of sulfur and part of lead sulfate; carrying out a second stage of oxygen pressure acid leaching on the leached slag of the first stage and conducting solid-liquid separation on the serosity leached from the second stage; returning the leached liquid of the second stage into a first stage pressurizing leaching container, and dressing the sulfur from the leached slag of the second stage; and sending the zinc sulfate and the second stage leached slag in which the sulfur is dressed out to a pyrogenic process for zinc melting. The method remarkably improves recovery rate of the lead and the zinc without generating large quantities of mineral dressing wastewater which is difficulty to treat. The invention also discloses a treatment system of lead-zinc sulfide ores.
Description
Technical field
The invention belongs to technical field of non-ferrous metallurgy, more particularly, relate to a kind of treatment process of lead-zinc sulfide ore, relate to a kind of method of utilizing oxygen to press pickling process extracting zinc, lead and sulphur from lead-zinc sulfide ore especially, also relate to a kind of treatment system of lead-zinc sulfide ore simultaneously.
Background technology
Plumbous zinc resource major part in the world is the mixed concomitant sulphide ores, mid-term in 20th century, usually with airtight blast furnace as major equipment, utilize pyrometallurgical smelting technical finesse mixed lead zinc ore to come extracting zinc and lead, but this method energy consumption is big, and can produce a large amount of sulfurous gas in process of production, along with the increasingly stringent that current society requires environment, the energy, the use of this method has been subjected to very big restriction.
At present, the lead-zinc sulfide ore after normally will digging up mine carries out the differential flotation sorting, adds the zinc inhibitor earlier and selects lead ore concentrate, further selects zinc ore concentrate again, extracts zinc and lead then respectively from zinc ore concentrate and lead ore concentrate.Owing to contain the lead and the zinc of higher amount in zinc ore concentrate and the lead ore concentrate mutually, therefore zinc, the lead recovery of this method are low.In addition, in order reaching, to need to use a large amount of inhibitor, therefore to have produced and be difficult to the beneficiation wastewater recycled in a large number zinc ore in the lead-zinc sulfide ore and the isolating purpose of lead ore, this for low-grade refractory choosing to mix the ore deposit outstanding especially.
Summary of the invention
At the problems referred to above, the purpose of this invention is to provide that a kind of technology is simple, the rate of recovery is high and the treatment process of the lead-zinc sulfide ore of environmental protection.
Another object of the present invention provides a kind of treatment system of lead-zinc sulfide ore.
According to an aspect of the present invention, provide a kind of method of handling lead-zinc sulfide ore, comprised the steps:
(a) lead-zinc sulfide ore is carried out ore dressing to obtain the lead sulfide zinc ore concentrate;
(b) the lead sulfide zinc ore concentrate that obtains is carried out fine grinding and carries out pulp with the lead sulfide zinc ore concentrate of sulphuric acid soln after to fine grinding;
(c) the lead sulfide zinc ore concentrate after the pulp is joined first section pressurization leaching container and carry out the acidleach of first section oxygen pressure, first section leaching slurry carried out first section solid-liquid separation to obtain first section leach liquor and first section leached mud to obtain first section leaching slurry;
(d) to first section leach liquor purify, electrolysis obtains metallic zinc, and first section leached mud carried out ore dressing to select elemental sulfur and a part of lead sulfate;
(e) first section leached mud will selecting elemental sulfur and a part of lead sulfate joins second section pressurization and leaches container and carry out second section oxygen and press acidleach to obtain second section leaching slurry, and second section leaching slurry carried out second section solid-liquid separation to obtain second section leach liquor and second section leached mud;
(f) second section leach liquor turned back to first section pressurization and leach container, and second section leached mud carried out ore dressing to select elemental sulfur;
(g) send the pyrogenic process lead smelting together with described lead sulfate and second section leached mud selecting elemental sulfur.
According to an embodiment of the invention, the electrolysis waste solution of first section leach liquor of electrolysis is divided into two portions, turns back to first section pressurization leaching container and second section pressurization respectively and leaches in the container.
According to an embodiment of the invention, adopt the bulk flotation method that described lead-zinc sulfide ore is carried out ore dressing, to obtain the lead sulfide zinc ore concentrate.Further, can also carry out re-selection process to the lead sulfide zinc ore concentrate that obtains after the bulk flotation, to obtain the lead sulfide zinc ore concentrate that lead ore concentrate and lead content reduce, wherein lead ore concentrate send the pyrogenic process lead smelting with lead sulfate and second section leached mud selecting elemental sulfur.
According to an embodiment of the invention, granularity is higher than 98% less than 320 purpose particle ratios in the described lead sulfide zinc ore concentrate after the fine grinding.
According to an embodiment of the invention, it is that concentration at sulphuric acid soln is that 60-80g/l, oxygen pressure are that 0.8-1.0MPa, temperature are to carry out under 145-155 ℃ the condition that first section oxygen is pressed acidleach.
According to an embodiment of the invention, it is that concentration at sulphuric acid soln is that 90-130g/l, oxygen pressure are that 1.0-1.2MPa, temperature are to carry out under 150-160 ℃ the condition that second section oxygen is pressed acidleach.
According to an embodiment of the invention, first section oxygen press the consumption of sulphuric acid soln in the acidleach be lead sulfide zinc ore concentrate weight 3-6 doubly, and second section oxygen press the consumption of sulphuric acid soln in the acidleach be first section leached mud weight after selecting elemental sulfur and a part of lead sulfate 3-5 doubly.
The method according to this invention can directly be carried out oxygen to the mixing sulfuration lead and zinc concentrate that ore dressing obtains and press pickling process to handle, with extracting zinc and lead.Compared with prior art, need not to elect behind zinc ore concentrate and the lead ore concentrate again lead sulfide zinc ore concentrate branch as extracting zinc and lead respectively, thereby eliminated zinc and plumbous loss problem in the separation treatment process, significantly improved zinc, the plumbous rate of recovery, wherein the Qian rate of recovery is higher than 98%.This method technology is simple, has avoided the use of inhibitor, therefore can not produce a large amount of reluctant beneficiation wastewaters, and is friendly more to environment.
In addition, method of the present invention is after oxygen is pressed pickling process in first section pressurization leaching container to the lead sulfide zinc ore concentrate, be not directly the first section leached mud that obtains to be carried out pyrometallurgical smelting to refine plumbous, in container carried out secondary oxygen pressure acidleach processing but first section leached mud leached second section pressurization under certain condition, and second section leach liquor returned first section pressurization leach container and utilize again, improved zinc, the plumbous rate of recovery thus.In addition, in the method for the invention, elemental sulfur and part of sulfuric acid lead are selected the interference of element sulphur in the time of not only can reducing by second section oxygen pressure acidleach in the leached mud that first section oxygen pressure acidleach processing obtained, and reduced the inventory of subsequent disposal, thereby reduced energy consumption.
According to a further aspect in the invention, also provide a kind of treatment system of lead-zinc sulfide ore, this system comprises:
First section ore-dressing plant, described first section ore-dressing plant are used for lead-zinc sulfide ore is carried out ore dressing to obtain the lead sulfide zinc ore concentrate;
Container is leached in first section pressurization, and described first section pressurization leaching container is used to hold with the lead sulfide zinc ore concentrate after the sulphuric acid soln pulp and carries out first section oxygen and press acidleach;
First section leaching slurry that first section equipment for separating liquid from solid, described first section equipment for separating liquid from solid are used for leaching the container discharge from described first section pressurization carries out solid-liquid separation, to obtain first section leach liquor and first section leached mud;
Electrolyzer, described electrolyzer is used for the zinc that electrolytic deposition goes out first section leach liquor, and the electrolysis waste solution that produces is divided into two portions, turns back to respectively that container is leached in first section pressurization and second section pressurization leached in the container;
Second section ore-dressing plant, described second section ore-dressing plant are used for first section leached mud carried out ore dressing to select elemental sulfur and a part of lead sulfate;
Container is leached in second section pressurization, and described second section pressurization leached container and be used to hold and select first section leached mud behind elemental sulfur and a part of lead sulfate and carry out second section oxygen and press acidleach to obtain second section leaching slurry;
Second section equipment for separating liquid from solid, described second section equipment for separating liquid from solid are used for second section leaching slurry carried out solid-liquid separation to obtain second section leach liquor and second section leached mud;
The 3rd section ore-dressing plant, described the 3rd section ore-dressing plant is used for second section leached mud carried out ore dressing to select elemental sulfur;
Pyrometallurgical smelting of lead device, described pyrometallurgical smelting of lead device are used for described lead sulfate and the lead smelting of selecting second section leached mud of elemental sulfur are gone out.
According to one embodiment of the present invention, described first section ore-dressing plant is hybrid flotation machine.Further, after described hybrid flotation machine, also be provided with gravity concentrator, be used for the lead sulfide zinc ore concentrate that obtains through hybrid flotation machine bulk flotation is carried out re-selection process, to obtain the lead sulfide zinc ore concentrate that lead ore concentrate and lead content reduce; Described lead ore concentrate send the pyrometallurgical smelting of lead device to carry out the pyrogenic process lead smelting with lead sulfate and second section leached mud selecting elemental sulfur.
According to one embodiment of the present invention, the concentration that the sulphuric acid soln in the container is leached in described first section pressurization is that 60-80g/l, oxygen pressure are that 0.8-1.0MPa, temperature are 145-155 ℃.
According to one embodiment of the present invention, the concentration that the sulphuric acid soln in the container is leached in described second section pressurization is that 90-130g/l, oxygen pressure are that 1.0-1.2MPa, temperature are 150-160 ℃.
System of the present invention can be used in lead-zinc sulfide ore is carried out ore dressing, and the mixing that will obtain sulfuration lead and zinc concentrate directly carries out two step oxygen and press acidleach to handle extracting zinc and lead, can realize higher lead, zinc recovery.
Description of drawings
Above-mentioned and/or additional aspect of the present invention and advantage are from obviously and easily understanding becoming the description of embodiment below in conjunction with accompanying drawing, wherein:
Fig. 1 is the process flow figure according to the lead-zinc sulfide ore of the embodiment of the invention.
Fig. 2 is the treatment system synoptic diagram according to the lead-zinc sulfide ore of the embodiment of the invention.
Fig. 3 is according to continuous horizontal type autoclave synoptic diagram in the lead-zinc sulfide ore treatment system of the embodiment of the invention.
Embodiment
Describe embodiments of the invention below in detail, the example of described embodiment is shown in the drawings, and wherein identical from start to finish or similar label is represented identical or similar elements or the element with identical or similar functions.Below by the embodiment that is described with reference to the drawings is exemplary, only is used to explain the present invention, and can not be interpreted as limitation of the present invention.
Specify treatment process below with reference to Fig. 1 according to the lead-zinc sulfide ore of the embodiment of the invention.
As shown in Figure 1, at first, adopt the bulk flotation method to carry out flotation beneficiation lead-zinc sulfide ore fine grinding, screening back, obtain the lead sulfide zinc ore concentrate.The complicated component of lead-zinc sulfide ore, Zn that wherein contains and Pb mainly exist with the form of sulfide.The grade of most of lead-zinc sulfide ore is all lower, and Zn and Pb total content can be brought up to its total content more than the 40wt% by bulk flotation about 5wt%, thereby can put forward the efficient of high oxygen pressure acidleach.What the lead sulfide zinc ore concentrate was carried out that bulk flotation adopts is technology well known in the art, therefore is not described in detail here.
Then, the lead sulfide zinc ore concentrate that bulk flotation is obtained carries out fine grinding, particularly, becomes granularity to be higher than 98% less than 320 purpose particle ratios the fine grinding of lead sulfide zinc ore concentrate, breeze, acid solution and oxygen are fully contacted, improved the rate of oxidation and the oxidation ratio of zinc sulphide and lead sulfide.After the lead sulfide zinc ore concentrate pulp of sulphuric acid soln after, in first section pressurized acid leaching container, carry out first section oxygen and press acidleach to handle fine grinding.
The pressurized acid leaching container can be various withstand high temperatures and strong acid corrosive autoclave, in the present invention, because treatment process carries out continuously, considers the operation ease and the use properties of equipment simultaneously, preferably adopts the continuous horizontal type autoclave.
In the various factors of decision oxidizing reaction speed and oxidation ratio, the most key is sulphuric acid soln concentration and consumption, oxygen pressure and temperature of reaction.Adopt concentration to modulate the slip that first section oxygen is pressed acidleach for the 60-80g/l sulphuric acid soln in the present embodiment, consumption is 3-6 a times of described lead sulfide zinc ore concentrate weight, and also promptly the liquid-solid body ratio of first section slurry is 3-6: 1; The control oxygen pressure is that 0.8-1.0MPa, temperature are 145-155 ℃ in first section oxygen pressure acidleach process.After reaction is carried out 40-100 minute, zinc sulphide more than 70% and lead sulfide in the breeze can be converted into zinc sulfate and lead sulfate, at this moment just the first section leaching slurry that obtains can be carried out first section solid-liquid separation, the section of winning leach liquor and first section leached mud.In liquid-solid lock out operation, can adopt thickener that leaching slurry is carried out dense washing, to be separated into first section leach liquor and first section leached mud.
Press in the acidleach process at oxygen, redox reaction takes place between zinc sulphide in the lead-zinc sulfide ore powder and lead sulfide and sulfuric acid, the oxygen, zinc sulphide wherein is converted into water-soluble zinc sulfate, and lead sulfide is converted into the lead sulfate that is insoluble to acid, and element sulphur is then separated out with the form of simple substance.The reaction equation of this redox processes is as follows:
2ZnS+2H
2SO
4+O
2→2ZnSO
4+2H
2O+2S↓
2PbS+2H
2SO
4+O
2→2PbSO
4↓+2H
2O+2S↓
The water-soluble salt ZnSO that mainly contains object element zinc in first section leach liquor
4, adopt electrolytic process that zinc is separated out, obtain the simple substance zinc product.In order to ensure obtaining highly purified simple substance zinc product, before electrolysis, can adopt technology well known in the art earlier with first section purification of leaching liquor, remove such as iron, cadmium, copper, cobalt, nickel.The main component of first section leached mud is PbSO
4And elemental sulfur, and unconverted zinc sulphide and lead sulfide adopt and knownly select sulphur technology and select lead sulfate technology that elemental sulfur and a part of lead sulfate are selected.So not only can reduce the interference of leached mud being carried out second section oxygen element sulphur when pressing acidleach, and reduce the inventory of subsequent disposal, thereby reduce energy consumption.
Then, first section leached mud selecting elemental sulfur and part of sulfuric acid lead sent second section pressurization leach and carry out second section oxygen pressure acidleach processing in the container.Press in the acidleach process at second section oxygen of present embodiment, employing concentration is that the sulphuric acid soln of 90-130g/l is modulated the slip that first section oxygen is pressed acidleach, and consumption is 3-5 a times of described lead sulfide zinc ore concentrate weight, and the liquid-solid body that also is second section slurry is than being 3-5: 1; The control oxygen pressure is that 1.0-1.2MPa, temperature are 150-160 ℃ in second section oxygen pressure acidleach process.
In circulation technology, the electrolysis waste solution that first section leach liquor of electrolysis obtains is divided into two portions, a part turns back to first section pressurization leaching container and is used for pulp lead sulfide zinc ore concentrate, and another part turns back to second section pressurization leaching container and is used for first section leached mud that elemental sulfur and part of sulfuric acid lead are selected in pulp.
Press in the acidleach process at second section oxygen, after reaction is carried out 40-100 minute, zinc sulphide in the lead-zinc sulfide ore slag and lead sulfide substantially fully are converted into zinc sulfate and lead sulfate, at this moment just the second section leaching slurry that obtains second section solid-liquid separation be can be carried out, second section leach liquor and second section leached mud got.Second section leach liquor returned first section oxygen press acidleach to go out recycle in the process, and from second section leached mud, select elemental sulfur, select that main component is a lead sulfate in second section slag behind the sulphur.Here, only press the difference of acidleach and first section to make an explanation to second section oxygen, other are unspecified be construed as identical with first segment process.
At last, the lead sulfate of selecting second section leached mud of elemental sulfur and selecting from first section leached mud is merged, adopt the lead smelting in the material after known pyrometallurgical smelting of lead technology will merge to go out.
Further, can before solid-liquid separation, carry out flash distillation to the slurries of discharging and handle, and wherein part moisture steams, thereby help follow-up solid-liquid separation operation with the working pressure of reduction from the slurries of high pressure vessel discharge from high pressure vessel.
In another embodiment of the present invention, different with above-described embodiment is, the lead sulfide zinc ore concentrate that bulk flotation is obtained further adopts known gravity separation technology to handle, and lead sulfide zinc ore concentrate branch is elected as the lead sulfide zinc ore concentrate of lead ore concentrate and lead content reduction.The weight ratio of Zn: Pb is greater than 1.5 in the lead sulfide zinc ore concentrate that lead content that re-selection process obtains reduces, and the total content of Zn and Pb is greater than 40wt%.Select the inventory that the part lead ore concentrate has reduced subsequent disposal earlier, thereby reduced energy consumption.Send the pyrogenic process lead smelting to obtain lead after at last lead ore concentrate that sub-elects and the lead sulfate of selecting from first section leached mud and second section leached mud selecting elemental sulfur being mixed.
Below with reference to Fig. 2 and Fig. 3 the treatment system according to the lead-zinc sulfide ore of the embodiment of the invention is described in detail.
As shown in Figure 2, in an embodiment of the treatment system of lead-zinc sulfide ore of the present invention, this system comprises: first section ore-dressing plant 1, first section pressurization are leached container 2, first section equipment for separating liquid from solid 3, electrolyzer 4, second section ore-dressing plant 5, second section pressurization and are leached container 6, second section equipment for separating liquid from solid 7, the 3rd section ore-dressing plant 8, pyrometallurgical smelting of lead device 9, first section flash drum 10 and second section flash drum 11.
Particularly, first section ore-dressing plant 1 is used for lead-zinc sulfide ore is carried out ore dressing to obtain the lead sulfide zinc ore concentrate, can select known hybrid flotation machine at plumbous zinc ore for use.After hybrid flotation machine, can also further be provided with gravity concentrator, further divide the lead sulfide zinc ore concentrate of electing lead ore concentrate and lead content reduction as with the lead sulfide zinc ore concentrate that flotation is obtained.
First section pressurization leached container 2 and is used to hold with the lead sulfide zinc ore concentrate after the sulphuric acid soln pulp and carries out the acidleach of first section oxygen pressure.Press in the acidleach process at oxygen, the first section concentration that leaches the sulphuric acid soln in the container of pressurizeing is that 60-80g/l, oxygen pressure are that 0.8-1.0MPa, temperature are 145-155 ℃.The pressurized acid leaching container can be various withstand high temperatures and strong acid corrosive autoclave, preferred continuous horizontal type autoclave, for example the polytetrafluoroethyllining lining stainless steel continuous horizontal type autoclave of adopting among the present invention.As shown in Figure 3, be provided with 2 dividing plates 100 and 101 in the described continuous horizontal type autoclave, will be separated into 3 chambers in the still, the top of each chamber be communicate so that slip can pass through.In order to make slip and oxygen thorough mixing that reaction is advantageously carried out, in each chamber, be provided with a blade agitators, shown in 201 among Fig. 3,202 and 203.Bottom at autoclave is provided with oxygen inlet, in the bottom of each chamber an oxygen inlet 204,205 and 206 is set respectively specifically.The benefit that oxygen inlet is arranged on the bottom is and can also can plays the dispersed with stirring effect to slip under the impingement flow effect of oxygen so that oxygen enters the back fully to be disperseed apace slip from the bottom of autoclave, can improve the efficient of oxidizing reaction.In addition, on autoclave, also be provided with well heater 200, be used for the reaction mass of autoclave is heated, can adopt steam heating, electrically heated or high-temperature flue gas type of heating.The oxygen inlet 204,205 and 206 of autoclave bottom is connected with the oxygen supply source by pipeline respectively, by pipeline pressurised oxygen is fed in the autoclave.
First section equipment for separating liquid from solid 3 is used for and will carries out solid-liquid separation from first section leaching slurry that first section pressurization leaching container 2 discharged, to obtain first section leach liquor and first section leached mud; Equipment for separating liquid from solid can be selected thickener particularly, by the solid-liquid separation of dense washing realization to leaching slurry.
Electrolyzer 4 is used for the zinc that electrolytic deposition goes out first section leach liquor, and the electrolysis waste solution that produces is divided into two portions, turns back to first section pressurization leaching container 2 and second section pressurization respectively and leaches in the container 6.The device of electro deposited zinc can adopt known technology, therefore omits the detailed description to this device.
Second section ore-dressing plant 5 is used for first section leached mud carried out ore dressing to select elemental sulfur and a part of lead sulfate.The ore-dressing plant of selecting sulphur and lead sulfate can obtain by prior art, therefore omits its detailed description.
Second section pressurization leached first section leached mud that container 6 is used to hold select elemental sulfur and a part of lead sulfate and pressed acidleach to obtain second section leaching slurry to carry out second section oxygen; Second section pressurization leaching container is identical with first section, therefore omits its description.Press in the acidleach process at oxygen, the second section concentration that leaches the sulphuric acid soln in the container of pressurizeing is that 90-130g/l, oxygen pressure are that 1.0-1.2MPa, temperature are 150-160 ℃.
Second section equipment for separating liquid from solid 7 is used for second section leaching slurry carried out solid-liquid separation to obtain second section leach liquor and second section leached mud; Equipment for separating liquid from solid can be selected thickener particularly, by the solid-liquid separation of dense washing realization to leaching slurry.
The 3rd section ore-dressing plant 8 is used for second section leached mud carried out ore dressing to select elemental sulfur, can adopt the various existing sulphur machines that select, and therefore no longer is described in detail.
Pyrometallurgical smelting of lead device 9 is used for described lead sulfate and the plumbous pyrometallurgical smelting of selecting second section leached mud of elemental sulfur are gone out.
Below by specific embodiment the present invention is made more detailed description.
(lead content is 2.6wt% to get lead-zinc sulfide ore, zinc content is 4.0wt%), after fine grinding, the screening, adopt the bulk flotation method that lead-zinc sulfide ore is carried out ore dressing, (lead content is 15.0wt% to obtain the lead sulfide zinc ore concentrate, zinc content is 37.5wt%), it is 100% breeze less than 320 purpose particles that its fine grinding is become granularity.It is the sulphuric acid soln of 78g/l to the breeze weight concentration that breeze after fine grinding adds 3 times, fully stirs and makes the breeze pulp, and slip is injected first section continuous horizontal type autoclave.Aerating oxygen in autoclave is warming up to 150 ℃, and for maintaining 1.0MPa, the rotating speed of agitator is 220 rev/mins in the autoclave with the oxygen pressure in the reaction process.Finish reaction after 45 minutes, reacted slurries are discharged, carry out dense washing, the section of winning leach liquor and first section leached mud after handling by the flash drum flash distillation.After first section purification of leaching liquor removed wherein iron, cadmium, copper, cobalt, nickel, adopt electrolytic process with in the leach liquor with ZnSO
4The zinc that form exists is separated out, and obtains simple substance Zn.Sulphur in first section leached mud and part of sulfuric acid lead are selected.
Will be in first section leached mud after the ore dressing add in second section continuous horizontal type autoclave, adding 3 times is that the sulphuric acid soln of 120g/l is made second section slip to the leached mud weight concentration.Aerating oxygen in autoclave, and be warming up to 150 ℃, for maintaining 1.0MPa, the rotating speed of agitator is 230 rev/mins in the autoclave with the oxygen pressure in the reaction process.Finish reaction after 40 minutes, reacted slurries are discharged, carry out dense washing after handling by the flash drum flash distillation, get second section leach liquor and second section leached mud.Sulphur in second section leached mud is selected, and the object element of selecting in the residue behind the elemental sulfur mainly is with PbSO
4The lead that form exists, the lead sulfate of pressing the acidleach process to obtain itself and first section oxygen merges, and adopts then the material of pyrometallurgical smelting of lead technology after merging and melts out lead, obtains simple substance lead product.Wherein, second section leach liquor, and the part in the electrolysis waste solution that produces of first section leach liquor of electrolysis returns and is used to prepare first section slip, another part electrolysis waste solution returns and is used to prepare second section slip.In the present embodiment, the leaching yield of zinc is 98.9%, and the plumbous rate of recovery is 98.6%, and the transformation efficiency of element sulphur is 72.5%.
(lead content is 5.1wt% to get lead-zinc sulfide ore, zinc content is 8.4wt%), after fine grinding, the screening, adopt the bulk flotation method that lead-zinc sulfide ore is carried out ore dressing, (lead content is 18.3wt% to obtain the lead sulfide zinc ore concentrate, zinc content is 39.5wt%), it is 98.5% breeze less than 320 purpose particle ratios that its fine grinding is become granularity.It is the sulphuric acid soln of 65g/l that breeze after fine grinding adds 5 times of concentration to breeze weight, fully stirs and makes the breeze pulp, and slip is injected first section continuous horizontal type autoclave.Aerating oxygen in autoclave is warming up to 145 ℃, and for maintaining 0.8MPa, the rotating speed of agitator is 230 rev/mins in the autoclave with the oxygen pressure in the reaction process.Finish reaction after 60 minutes, reacted slurries are discharged, carry out dense washing, the section of winning leach liquor and first section leached mud after handling by the flash drum flash distillation.After first section purification of leaching liquor removed wherein iron, cadmium, copper, cobalt, nickel, adopt electrolytic process with in the leach liquor with ZnSO
4The zinc that form exists is separated out, and obtains simple substance Zn.Sulphur in first section leached mud and part of sulfuric acid lead are selected.
Make second section slip with adding in second section continuous horizontal type autoclave, add 5 times of concentration the sulphuric acid soln that is 130g/l in first section leached mud after the ore dressing to leached mud weight.Aerating oxygen in autoclave, and be warming up to 160 ℃, for maintaining 1.2MPa, the rotating speed of agitator is 230 rev/mins in the autoclave with the oxygen pressure in the reaction process.Finish reaction after 50 minutes, reacted slurries are discharged, carry out dense washing after handling by the flash drum flash distillation, get second section leach liquor and second section leached mud.Sulphur in second section leached mud is selected, and the object element of selecting in the residue behind the elemental sulfur mainly is with PbSO
4The lead that form exists, the lead sulfate of pressing the acidleach process to obtain itself and first section oxygen merges, and adopts then the material of pyrometallurgical smelting of lead technology after merging and melts out lead, obtains simple substance lead product.Wherein, second section leach liquor, and the part in the electrolysis waste solution that produces of first section leach liquor of electrolysis returns and is used to prepare first section slip, another part electrolysis waste solution returns and is used to prepare second section slip.In the present embodiment, the leaching yield of zinc is 98.4%, and the plumbous rate of recovery is 98.0%, and the transformation efficiency of element sulphur is 75.8%.
(lead content is 7.9wt% to get lead-zinc sulfide ore, zinc content is 15.6wt%), after fine grinding, the screening, adopt the bulk flotation method that lead-zinc sulfide ore is carried out ore dressing, (lead content is 19.5wt% to obtain the lead sulfide zinc ore concentrate, zinc content is 39.6wt%), (weight ratio of Zn: Pb is greater than 1.5 to elect lead sulfide zinc ore concentrate branch as lead content low lead sulfide zinc ore concentrate by gravity separation technology again, and the total content of Zn and Pb element is greater than 40wt%) and lead ore concentrate (lead content is 10.2wt%, and zinc content is 42.5wt%).It is to be 98.7% breeze less than 320 purpose particle ratios that its fine grinding is become granularity.Breeze after the fine grinding is joined in first section surge tank, is the sulphuric acid soln of 70g/l to wherein adding 6 times of concentration to breeze weight, fully stirs and makes the breeze pulp, and slip is injected first section continuous horizontal type autoclave.Aerating oxygen in autoclave is warming up to 145 ℃, and for maintaining 0.8MPa, the rotating speed of agitator is 240 rev/mins in the autoclave with the oxygen pressure in the reaction process.Finish reaction after 60 minutes, reacted slurries are discharged, carry out dense washing, the section of winning leach liquor and first section leached mud after handling by the flash drum flash distillation.After first section purification of leaching liquor removed wherein iron, cadmium, copper, cobalt, nickel, adopt electrolytic process with in first section leach liquor with ZnSO
4The zinc that form exists is separated out, and obtains simple substance Zn.Sulphur in first section leached mud and part of sulfuric acid lead are selected.
First section leached mud after the ore dressing added in second section continuous horizontal type autoclave, and the sulphuric acid soln that to add 4 times of concentration to leached mud weight be 90g/l is made second section slip.Aerating oxygen in autoclave, and be warming up to 160 ℃, for maintaining 1.2MPa, the rotating speed of agitator is 250 rev/mins in the autoclave with the oxygen pressure in the reaction process.Finish reaction after 60 minutes, reacted slurries are discharged, carry out dense washing after handling by the flash drum flash distillation, get second section leach liquor and second section leached mud.Sulphur in second section leached mud is selected, and the object element of selecting in the residue behind the elemental sulfur mainly is with PbSO
4The lead that form exists, the lead sulfate of pressing the acidleach process to obtain itself and first section oxygen merges, and the lead ore concentrate that gravity treatment is obtained with merge thing and mix, adopt pyrometallurgical smelting of lead technology from the material after the merging, to melt out lead then, obtain simple substance lead product.Wherein, second section leach liquor, and the part in the electrolysis waste solution that produces of first section leach liquor of electrolysis returns and is used to prepare first section slip, another part electrolysis waste solution returns and is used to prepare second section slip.In the present embodiment, the leaching yield of zinc is 99.5%, and the plumbous rate of recovery is 98.2%, and the transformation efficiency of element sulphur is 78.3%.
Method of the present invention is the lead sulfide zinc ore concentrate that ore dressing obtains directly to be carried out oxygen press acidleach to handle, need not to elect behind zinc ore concentrate and the lead ore concentrate again its branch as extracting zinc and lead respectively, thereby zinc and plumbous loss problem in the separation treatment process have been eliminated, zinc, the plumbous rate of recovery have been significantly improved, wherein the rate of recovery of zinc reaches more than 98%, also avoid the use of inhibitor simultaneously, therefore can not produce a large amount of reluctant beneficiation wastewaters.In addition, present method is abundant to the oxidation of lead-zinc sulfide ore powder, can not produce SO substantially
2, friendly more to environment.In addition, method of the present invention adopts two-stage process that the lead sulfide zinc ore concentrate is carried out oxygen and presses acidleach to handle, press pickling process to compare with one section oxygen, can be under same raw material consumption amount situation, the lead-zinc powder is carried out oxidation more fully, improved the zinc and the plumbous rate of recovery thus.And the electrolysis waste solution that first section leach liquor of second section leach liquor and electrolysis produces returned in the circulation technology utilize again, and entire treatment technology carries out continuously, improved zinc, the plumbous rate of recovery thus.
Although illustrated and described embodiments of the invention, for the ordinary skill in the art, be appreciated that without departing from the principles and spirit of the present invention and can carry out multiple variation, modification, replacement and modification to these embodiment, scope of the present invention is limited by claims and equivalent thereof.
Claims (17)
1. the treatment process of a lead-zinc sulfide ore comprises the steps:
(a) lead-zinc sulfide ore is carried out ore dressing to obtain the lead sulfide zinc ore concentrate;
(b) the lead sulfide zinc ore concentrate that obtains is carried out fine grinding and carries out pulp with the lead sulfide zinc ore concentrate of sulphuric acid soln after to fine grinding;
(c) the lead sulfide zinc ore concentrate after the pulp is joined first section pressurization leaching container and carry out the acidleach of first section oxygen pressure, first section leaching slurry carried out first section solid-liquid separation to obtain first section leach liquor and first section leached mud to obtain first section leaching slurry;
(d) to first section leach liquor purify, electrolysis obtains metallic zinc, and first section leached mud carried out ore dressing to select elemental sulfur and a part of lead sulfate;
(e) first section leached mud will selecting elemental sulfur and a part of lead sulfate joins second section pressurization and leaches container and carry out second section oxygen and press acidleach to obtain second section leaching slurry, and second section leaching slurry carried out second section solid-liquid separation to obtain second section leach liquor and second section leached mud;
(f) second section leach liquor turned back to first section pressurization and leach container, and second section leached mud carried out ore dressing to select elemental sulfur;
(g) send the pyrogenic process lead smelting together with described lead sulfate and second section leached mud selecting elemental sulfur.
2. the treatment process of lead-zinc sulfide ore according to claim 1, wherein, the electrolysis waste solution of first section leach liquor of electrolysis is divided into two portions, turns back to respectively that container is leached in first section pressurization and second section pressurization leached in the container.
3. the treatment process of lead-zinc sulfide ore according to claim 1 wherein, adopts the bulk flotation method that described lead-zinc sulfide ore is carried out ore dressing.
4. the treatment process of lead-zinc sulfide ore according to claim 3 comprises that further the described lead sulfide zinc ore concentrate to obtaining after the bulk flotation carries out re-selection process, to obtain the lead sulfide zinc ore concentrate that lead ore concentrate and lead content reduce.
5. the treatment process of lead-zinc sulfide ore according to claim 4, wherein, described lead ore concentrate send the pyrogenic process lead smelting with lead sulfate and second section leached mud selecting elemental sulfur.
6. the treatment process of lead-zinc sulfide ore according to claim 4, wherein, the weight ratio of Zn: Pb is greater than 1.5 in the lead sulfide zinc ore concentrate that described lead content reduces, and the total content of Zn and Pb is greater than 40wt%.
7. the treatment process of lead-zinc sulfide ore according to claim 1, wherein, granularity is higher than 98% less than 320 purpose particle ratios in the described lead sulfide zinc ore concentrate after the fine grinding.
8. the treatment process of lead-zinc sulfide ore according to claim 1, wherein, it is that concentration at sulphuric acid soln is that 60-80g/l, oxygen pressure are that 0.8-1.0MPa, temperature are to carry out under 145-155 ℃ the condition that first section oxygen is pressed acidleach.
9. the treatment process of lead-zinc sulfide ore according to claim 1, wherein, it is that concentration at sulphuric acid soln is that 90-130g/l, oxygen pressure are that 1.0-1.2MPa, temperature are to carry out under 150-160 ℃ the condition that second section oxygen is pressed acidleach.
10. the treatment process of lead-zinc sulfide ore according to claim 1, wherein, first section oxygen press the consumption of sulphuric acid soln in the acidleach be lead sulfide zinc ore concentrate weight 3-6 doubly, and second section oxygen press the consumption of sulphuric acid soln in the acidleach be first section leached mud weight after selecting elemental sulfur and a part of lead sulfate 3-5 doubly.
11. the treatment process of lead-zinc sulfide ore according to claim 1, wherein, it is 40-100 minute that first section oxygen is pressed the reaction times of acidleach, and it is 40-100 minute that second section oxygen is pressed the reaction times of acidleach.
12. the treatment system of a lead-zinc sulfide ore, this system comprises:
First section ore-dressing plant, described first section ore-dressing plant are used for lead-zinc sulfide ore is carried out ore dressing to obtain the lead sulfide zinc ore concentrate;
Container is leached in first section pressurization, and described first section pressurization leaching container is used to hold with the lead sulfide zinc ore concentrate after the sulphuric acid soln pulp and carries out first section oxygen and press acidleach;
First section leaching slurry that first section equipment for separating liquid from solid, described first section equipment for separating liquid from solid are used for leaching the container discharge from described first section pressurization carries out solid-liquid separation, to obtain first section leach liquor and first section leached mud;
Electrolyzer, described electrolyzer is used for the zinc that electrolytic deposition goes out first section leach liquor, and the electrolysis waste solution that produces is divided into two portions, turns back to respectively that container is leached in first section pressurization and second section pressurization leached in the container;
Second section ore-dressing plant, described second section ore-dressing plant are used for first section leached mud carried out ore dressing to select elemental sulfur and a part of lead sulfate;
Container is leached in second section pressurization, and described second section pressurization leached container and be used to hold and select first section leached mud behind elemental sulfur and a part of lead sulfate and carry out second section oxygen and press acidleach to obtain second section leaching slurry;
Second section equipment for separating liquid from solid, described second section equipment for separating liquid from solid are used for second section leaching slurry carried out solid-liquid separation to obtain second section leach liquor and second section leached mud;
The 3rd section ore-dressing plant, described the 3rd section ore-dressing plant is used for second section leached mud carried out ore dressing to select elemental sulfur;
Pyrometallurgical smelting of lead device, described pyrometallurgical smelting of lead device are used for described lead sulfate and the lead smelting of selecting second section leached mud of elemental sulfur are gone out.
13. the treatment system of lead-zinc sulfide ore according to claim 12, wherein, described first section ore-dressing plant is hybrid flotation machine.
14. the treatment system of lead-zinc sulfide ore according to claim 13, wherein, after described hybrid flotation machine, further also be provided with gravity concentrator, described gravity concentrator is used for the lead sulfide zinc ore concentrate that obtains through described hybrid flotation machine bulk flotation is carried out re-selection process, to obtain the lead sulfide zinc ore concentrate that lead ore concentrate and lead content reduce.
15. the treatment system of lead-zinc sulfide ore according to claim 12, wherein, the concentration that sulphuric acid soln in the container is leached in described first section pressurization is that 60-80g/l, oxygen pressure are that 0.8-1.0MPa, temperature are 145-155 ℃, and the concentration that sulphuric acid soln in the container is leached in described second section pressurization is that 90-130g/l, oxygen pressure are that 1.0-1.2MPa, temperature are 150-160 ℃.
16. the treatment system of lead-zinc sulfide ore according to claim 12, wherein, container is leached in described first section pressurization and second section pressurization leaching container is multicell continuous horizontal type autoclave.
17. the treatment system of lead-zinc sulfide ore according to claim 12, described system further comprises partition member, described partition member is used for that container is leached in described first section pressurization and second section pressurization leaching container is divided into a plurality of chambers, wherein respectively accommodates at least one agitator in each chamber.
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| CN102534205A (en) * | 2012-03-09 | 2012-07-04 | 云南冶金集团股份有限公司 | Method for processing lead-zinc mixed concentrate by using oxidative pressure acid leaching in zinc hydrometallurgy |
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| CN105618777A (en) * | 2016-01-02 | 2016-06-01 | 红河学院 | Method for preparing metal lead powder through vacuum carbothermal reduction |
| CN105603186A (en) * | 2016-01-24 | 2016-05-25 | 李家元 | Technology for efficiently and selectively separating zinc in zinc sulfide concentrate |
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| CN108130431A (en) * | 2017-12-04 | 2018-06-08 | 云南驰宏资源综合利用有限公司 | A kind of richness germanium zinc concentrate oxygen leaching inhibits the method that germanium leaches |
| CN108130431B (en) * | 2017-12-04 | 2019-09-20 | 云南驰宏资源综合利用有限公司 | A kind of method that richness germanium zinc concentrate oxygen leaching inhibits germanium to leach |
| CN113846214A (en) * | 2021-09-16 | 2021-12-28 | 昆明理工大学 | Method for treating zinc-containing material in zinc hydrometallurgy production |
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