CN104789771B - Complicated copper-lead zinc-silver bulk concentrate valuable metal separation method - Google Patents
Complicated copper-lead zinc-silver bulk concentrate valuable metal separation method Download PDFInfo
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Abstract
The present invention relates to a kind of complicated copper-lead zinc-silver bulk concentrate valuable metal separation method, belong to metal separation and recovery technology field.The inventive method includes the separation of thermal activation, Oxidation Leaching, copper, lead, silver and zinc and displacement copper and the big step of heavy zinc four, and the inventive method practicality is wide, it is adaptable to the separation of various Complex metal bulk concentrates；The realization of present invention process, so that this polymetallic ore need to only mix choosing, it is not required to sorting, so cause that bargh does not need screening installation and sorting place etc., reduce investment about 30% and reduce production cost 20%, reduce the waste of mineral resources, recovery rate in ore-dressing improves more than 25%, cycle time 1/3rd, personnel reduce 1/3rd, power consumption reduces 1/3rd.Meanwhile, the present invention is small with investment than current technique both domestic and external, and with short production cycle, recovery rate of valuable metals is high, it is easy to popularization and application.
Description
Technical field
The invention belongs to metal separation and recovery technology field, and in particular to a kind of complicated valuable gold of copper-lead zinc-silver bulk concentrate
Category novel method for separating.
Background technology
The ground such as China Sichuan, Xinjiang, Yunnan Three River Region, the domestic Mekong River valley storage in the billows Yangtze river basin and Laos of Burma
The polymetallic ore of substantial amounts of copper-lead zinc-silver is hidden, the comprehensive utilization in such multi-metal complex mineral deposit there are two kinds of process routes, it is a kind of
It is sorting torpedo, i.e., selects lead concentrate, zinc concentrate and copper concentrate respectively by ore dressing, then process to extract lead, zinc and copper respectively.
The difficult point of this technique is ore dressing.Because sorting is difficult, not only recovery rate in ore-dressing is low, and Er Qieqian, zinc and copper are mutually containing height, concentrate matter
Amount is poor.Such as Sichuan white jade sips village's copper mine, and the situation of the glutinous military copper mine in Lincang demonstrates this point.
Another process route is that process integration is controlled in choosing, and ore dressing is not sorted, and only selects bulk concentrate, then with controlling golden means
Treatment bulk concentrate.Its advantage is that recovery rate in ore-dressing is increased substantially, and ore-dressing practice is simple.This kind of process route problem is
The activation of copper, lead, zinc and silver-colored bulk concentrate.The complicated many metal mineral intergrowth storage numbers of copper-lead zinc-silver are big, and valuable metal is wide in variety, separates
Technology difficulty is big, and separation method current situation has following several both at home and abroad at present：
1st, wet separation technique
1. potassium cloride
Some slightly solubility metal sulfides are leached under the conditions of acid chloride solution, can be molten with the complex ion form of chlorine
Go out, such as [PbCl4 -]2-、[ZnCl4 -]2-Deng.This provides thermodynamics base for acid chloride solution Selectively leaching metal sulfide
Plinth.Conventional potassium cloride agent is hydrochloric acid, villaumite and chlorine etc..
South jiangxi scalds level ground copper-lead zinc composite sulfuration ore deposit, in 105 DEG C of temperature, solid-to-liquid ratio 1:4, Fe3+Under conditions of 192 grams/t of concentration
Leach 3 hours, the leaching rate of copper, lead and zinc is respectively 99.5%, 98.6% and 99.6%, and sulphur is rich in elementary sulfur or pyrite form
In combining in slag.
But during due to potassium cloride polymetallic ore, exist with ZnCl2It is more difficult that solution produces electric zinc, with PbCl2For raw material system
Take metallic lead technological process more long, leach and the linking of follow-up electrodeposition process on it is more difficult, the presence of chlorion is to environment and sets
The problems such as requiring higher.Therefore, the industrial implementation of the method is more difficult.
2. sulfating roasting Selectively leaching
Multi-metal sulfide with a temperature of, carries out sulfating roasting in atmosphere in appropriate atmosphere, makes iron main transition
Into Fe2O3, and copper zinc etc. is transformed into sulfate, realizes selective sulfate roasting, gained calcining is leached with dilute sulfuric acid again, is reached
The purpose of Selectively leaching.Such as with 2% Na2SO4Make additive, lh is calcined at 550 DEG C, be then with weight fraction to calcining
9.5% H2SO4As leaching agent, 30min is leached under conditions of being 2.5 in liquid-solid ratio, copper, zinc leaching rate are respectively 95% and
90%。
But first it is calcined the operation for leaching afterwards because baking acid immersion technique is used so that the tediously long leaching rate of integrated artistic flow
It is low, equipment operating maintenance cost improve, and calcining process output low concentration SO2There is more difficult recovery and heavy-polluted in gas
Shortcoming, the need for being unfavorable for that current smelter carries out green production.
3. alkaline leaching
The country uses vulcanised ore concentrate ammonia soaking technology：In NH4 +Concentration is 300g/L, and oxidant SN22 concentration is 60kg/t, is urged
It is 0.12kg/t to change AN31 consumptions, and liquid-solid ratio is stirring at normal temperature 4h under conditions of 5, and the leaching rate of copper is up to 80.25%.
The characteristics of having leaching process selectivity strong using alkaline leaching technique.But for existing technique, effectively
There are some problems in the linking for solving subsequent technique, and ammonia presence working environment and natural environment it is also proposed it is higher
Requirement.
4. direct weighting acidic leaching
The direct acid-hatching of young eggs is that a kind of to use acid be leaching agent（Sulfuric acid etc.）, oxygen directly soaks under a certain pressure for oxidant
The method for going out bulk concentrate.Its key reaction formula is：
The pressurized acid leaching technique that have studied copper-lead zinc-silver polymetallic sulfide concentrate such as strong is thanked gram by Kunming University of Science and Technology, in temperature
145 ~ 150 DEG C, granularity of concentrate<50 μm, initial acid H2SO4 150g/t, gross pressure 1.5MPa（Partial pressure of oxygen 1.1MPa）, leach
Time 2h, by liquid-solid ratio processed 8:1, under mixing speed 800r/min, Zn leaching rates>99%, Cu leaching rate>91%th, Pb, Fe leaching rate
More than 95%, more than 98% pb, Ag enter leached mud.
Using direct weighting acidleach, its leach liquid energy and it is existing neutralize leach and electrodeposition procedure connection, leached mud then with
Existing pyrometallurgical smelting procedure connection, realizes the comprehensive reutilization of Cu, Zn, Pb, Ag, S etc. in multi-metal sulfide.But exist
It is following not enough：
（1）Using one section of Leaching way, extract technology is long, it is desirable to temperature higher, pressure and sulfuric acid concentration（Such as require temperature
Spend more than 140 DEG C, more than pressure 1.1MPa, acidity more than 150g/L）, leachate containing acid it is higher, need to take measures reduce sulphur
Acid concentration, is beneficial to follow-up stripping process；There is technique at present using two sections of counterflow leachings, i.e., using one section of pressurized acid leaching leachate
Raw ore is leached, then carries out the mode of pressurized acid leaching to one section of leached mud again to improve acid-utilising rate, reduce the acid of leachate
Degree, the Zn in rich leachate2+。
（2）The technique that leaching agent is done using villaumite, Cl-Although presence can improve sulphur permeability of the membrane, beneficial to mineral
Oxidation dissolution so that direct weighting acidleach process can be carried out under relatively low temperature, acidity and pressure, but Cl-Presence can be right
Follow-up electrodeposition brings influence, can also heavy corrosion metallurgical equipment.
（3）To obtain preferable leaching rate, the leaching rate of copper is especially improved, it is necessary to carry out Ultra-fine grinding, cause mill
Ore deposit energy consumption increases.
（4）In course of reaction, the elementary sulfur of system generation can be covered on mineral particle surface, hinder solvent to be moved to surface
Move and product is by diffusion into the surface to bulk solution, influence reaction is carried out.Need using the good desulfurizing agent of low cost, effect or de-
Sulphur method is aoxidized and leaching efficiency to improve.
2nd, bioleaching process
The Microorganism Leaching technology of metal sulfide is study hotspot in recent years, to the intractable complexity of conventional art
Ore（Such as the monometallic ore deposit and many metal composite ore deposits of various combined forms）, low-grade unbalanced-ore, abandoned mine etc., with Bioleaching work
Skill treatment have pollution less, condition of work is gentle, flow is short, low cost, small investment the features such as.Bacterial leaching mechanism is using thin
Some components are aoxidized or reduced during the oxidation of bacterium itself or reproducibility make mineral, and then with solvable or precipitation form and the original
Matter is separated；Or by the metabolite of bacterium（Organic acid, inorganic acid and ferric ion）Reacted with mineral, made useful
Component enters solution.
There is preferable cost advantage using bioleaching process, but it is long for the work period, and leaching rate is low, biocoene
It is not enough by the big grade of Environmental Factors, in addition it is also necessary to further to strengthen studying and being able to effectively solve.At present, to Complicated Copper,
Lead, the separating technology of zinc-silver concentrate are not reported.
In sum：1. potassium cloride is used, the presence of chlorion not only can bring influence to the linking of subsequent technique, and
And corrosive equipment is gone back, pollute environment；2. same alkaline leaching also can bring influence to the connecting of subsequent technique, and ammonia
In the presence of also all proposing high requirement to working environment and natural environment；3. then there is technological process using baking acid immersion long, be calcined
The low concentration SO of operation output2The weakness of the more difficult recovery of gas；4. then have that the work period is long, leaching rate using Bioleaching
Low, biocoene is by the drawback such as Environmental Factors are big.5. use direct weighting acid leaching process, it is desirable to temperature higher, pressure,
Sulfuric acid concentration, and require that the sulphur of generation can be covered on mineral surface, influence to be carried out to reaction.
Therefore, for complex multi-metal the characteristics of, it is many metals for the treatment of to develop efficient bulk concentrate clean metallurgical technology
The breach of complicated sulfuration mine.And have broad application prospects.From technique the characteristics of for, how to realize more friendly to environment
Good, separation condition is gentleer, such as relatively low extraction temperature, relatively low leaching pressure and relatively low leaching agent sulfuric acid concentration, is
The target of Future Development.
The content of the invention
The invention aims to solve the deficiencies in the prior art, there is provided a kind of complicated copper-lead zinc-silver bulk concentrate is valuable
Metal separation method, the method copper leaching rate >=99%, zinc leaching rate >=98.5%, lead silver entrance enrichment slag, accumulation rate >=99%,
The advanced level of domestic and international technique is reached
The technical solution adopted by the present invention is as follows：
Unless there are specified otherwise, percentage sign of the invention is all mass percent.
Solid-to-liquid ratio（W/V）It is the ratio of the volume (ml) of the quality (g) and liquid of solid.
A kind of complicated copper-lead zinc-silver bulk concentrate valuable metal separation method, comprises the following steps：
Step（1）, thermal activation：Rotary kiln is heated to 300-650 DEG C, concentrate and sulphur-fixing agent is slowly added into, then constant temperature
Thermal activation 3.5-4.5h, the quality of the addition of sulphur-fixing agent is the 20-50% of the quality of sulphur in concentrate, obtains the flue gas containing zinc oxide
With activation concentrate；
The gas that described flue gas is obtained after gathering dust first is passed through first order scavenging solution and carries out first order spray cleaning, then leads to
Enter and carry out second level spray cleaning in the scavenging solution of the second level, the gas of the purification for obtaining is directly discharged in air；To I and II
Liquid after purification spray adds NaOH untill precipitation is not produced（Precipitation is mainly hydroxide, such as calcium hydroxide, hydrogen-oxygen
Change ferrous iron etc.）, filter, filtrate condensing crystallizing, sodium sulfite solid is obtained, sodium sulfite solid after drying, take out by packaging；Should
Purifying step is referred to as " one washes two absorptions "；
Described first order scavenging solution is the aqueous sodium carbonate that mass concentration is 40%, and second level scavenging solution is that quality is dense
Spend the sodium hydrate aqueous solution for 40%；Gathering dust, receive is zinc oxide fumes；
Step（2）, Oxidation Leaching：Step（1）The activation concentrate for obtaining in dissolution kettle, is added after being milled to 200 mesh
To in sulfur-bearing aqueous acid, the weight/mass percentage composition of sulfuric acid is 15% in the aqueous solution, activates concentrate and sulfur-bearing aqueous acid
Solid-to-liquid ratio be 1：3, when being then heated to more than 85 DEG C with steam, addition is oxidizing, and the consumption of oxidant is activating essence
1.1-1.2 times of the quality of sulphur in ore deposit, then azeotropic 3-4h, then through filtering, obtains leached mud and leachate；
Step（3）, the separation of copper, lead, silver and zinc：Step（2）After the leached mud for obtaining is washed with water to neutrality, contained
The slag of lead and silver, the leaded and silver-colored slag enters traditional lead silver recovery technique or directly take-away；Cleaning solution is back to step
（2）Oxidation Leaching process section, sulfur-bearing aqueous acid is configured to together with the concentrated sulfuric acid, for Oxidation Leaching；
To step（2）Manganese dioxide to Fe is added in the leachate for obtaining2+It is fully oxidized to Fe3+Afterwards, sulfuric acid to pH is added
It is 1.5, be then hydrolyzed removing Fe3+（Use conventional methods and be hydrolyzed）, filter, obtain filter residue and the filtrate of iron content
（Filtrate is the mixed solution of copper sulphate and zinc sulfate）；Filter residue is directly taken out or is separately used it for anything else；
Step（4）, replace copper and heavy zinc：To step（3）Iron is added to enter line replacement in the filtrate for obtaining, the addition of iron is
The 1.2-1.3 mass of copper content times in filtrate, filtering obtains filtrate and filter residue；It is 7 that filter residue is washed with water to pH, obtains blister copper
Powder；Blister copper powder is taken out；Cleaning solution is back to step（2）Oxidation Leaching process section, sulfur acid is configured to together with the concentrated sulfuric acid
The aqueous solution, for Oxidation Leaching；The conventional electrowinning zinc electrodeposition of filtrate feeding obtains zinc product.
It is further preferred that described step（1）Rotary kiln heating uses heated by gas mode.
It is further preferred that step（1）Described sulphur-fixing agent is NaOH, calcium hydroxide, magnesium hydroxide or hydrogen-oxygen
Change iron.
It is further preferred that step（2）Described oxidant is appointing in hydrogen peroxide, sodium chlorate, bleaching powder and air
The combination of two kinds of meaning, the ratio between composition is not required.
Compared with prior art, its advantage is the present invention：
1st, activation is warmed in this use so that the lattice structure of copper mineral is distorted in concentrate, or due to ore deposit
" Fe and S is aoxidized thing surface portion so that the Cu-Fe-S keys or Cu-S keys of stabilization become unstable so that the metal life in concentrate
Into the material that other are easily leached, due to this technique heat activation temperature<Carried out at 650 DEG C, sulphur, zinc, lead volatility amount are reduced, flue gas warp
Gather dust, " one washes two absorptions " has not only purified waste gas, and scavenging solution generates sodium sulfite as by-product sale through treatment,
Produce very big economic benefit.The presence of sulphur serves combustion-supporting in concentrate, has saved fuel, reduces energy consumption.
2nd, this project is using Oxidation Leaching under low-temperature atmosphere-pressure, and the atmosphere than being leached under traditional HTHP is gentleer,
And produce safer, only equipment investment cost reduces more than 3 times.
3rd, practicality of the present invention is wide, it is adaptable to which the separation of various Complex metal bulk concentrates includes copper concentrate, lead concentrate, zinc essence
The copper-contained materials such as ore deposit, and new change is brought to the floatation process that complicated copper-lead zinc-silver answers metallic ore.Past is to this ore deposit
Flotation, general to be selected using first mixing, rear sorting process, the realization of present invention process so that this polymetallic ore need to only mix choosing,
Just it is not required to sorting.So so that bargh does not need screening installation and sorting place etc., reduce investment about 30% and reduce
Production cost 20%, reduces the waste of mineral resources, recovery rate in ore-dressing improves more than 25%, cycle time 1/3rd, people
Member reduces 1/3rd, and power consumption reduces 1/3rd.
4th, the present invention meets country, saves related industry development policies and encourages direction.Project implementation is Complicated Copper from now on
The ore dressing of Pb-Zn-Ag ore and its corresponding concentrate valuable metal hydrometallurgy process for separating and recovering open a new technological approaches,
The technological progress of industry is promoted, improve the aspects such as comprehensive resource utilization rate all has great economic implications.
5th, the present invention is small with investment than current technique both domestic and external, and with short production cycle, recovery rate of valuable metals is high, by
In leaching carried out under low-temperature atmosphere-pressure, therefore production atmosphere milder, it is easier to realize industrialization.Copper leaching rate >=99%, zinc
Leaching rate >=98.5%, lead silver enter enrichment slag, accumulation rate >=99%.Therefore, the technology of the present invention feasible route, new technology reaches
The advanced level of domestic and international technique.
6th, the purified all recyclings of production waste water that the present invention is produced, accomplish zero-emission.The generation waste gas warp of production
Gather dust, secondary purification, i.e. " one washes two absorptions " can not only produce valuable byproduct.And waste gas is accomplished into qualified discharge.This
Project realization, greatly reduces energy consumption, therefore be environment-friendly type, energy-saving project.
Specific embodiment
With reference to embodiment, the present invention is described in further detail.
It will be understood to those of skill in the art that the following example is merely to illustrate the present invention, and should not be regarded as limiting this hair
Bright scope.In the examples where no specific technique or condition is specified, according to the technology or condition described by document in the art
Or carried out according to product description.Agents useful for same or the unreceipted production firm person of instrument, being can be by buying what is obtained
Conventional products.
Embodiment 1
A kind of complicated copper-lead zinc-silver bulk concentrate valuable metal separation method, comprises the following steps：
Step（1）, thermal activation：Rotary kiln is slowly added into concentrate and sulphur-fixing agent, then using heated by gas to 650 DEG C
Constant temperature thermal activation 4.5h, the quality of the addition of sulphur-fixing agent is 50% of the quality of sulphur in concentrate, obtains the flue gas containing zinc oxide and work
Change concentrate；
The gas that described flue gas is obtained after gathering dust first is passed through first order scavenging solution and carries out first order spray cleaning, then leads to
Enter and carry out second level spray cleaning in the scavenging solution of the second level, the gas of the purification for obtaining is directly discharged in air；To I and II
Liquid after purification spray adds NaOH untill precipitation is not produced（Precipitation is mainly hydroxide, such as calcium hydroxide, hydrogen-oxygen
Change ferrous iron etc.）, filter, filtrate condensing crystallizing, sodium sulfite solid is obtained, sodium sulfite solid after drying, take out by packaging；
Described first order scavenging solution is the aqueous sodium carbonate that mass concentration is 40%, and second level scavenging solution is that quality is dense
Spend the sodium hydrate aqueous solution for 40%；Gathering dust, receive is zinc oxide fumes；
Step（2）, Oxidation Leaching：Step（1）The activation concentrate for obtaining in dissolution kettle, is added after being milled to 200 mesh
To in sulfur-bearing aqueous acid, the weight/mass percentage composition of sulfuric acid is 15% in the aqueous solution, activates concentrate and sulfur-bearing aqueous acid
Solid-to-liquid ratio be 1：3, when being then heated to more than 85 DEG C with steam, addition is oxidizing, and the consumption of oxidant is activating essence
1.2 times of the quality of sulphur in ore deposit, then azeotropic 4h, then through filtering, obtains leached mud and leachate；
Step（3）, the separation of copper, lead, silver and zinc：Step（2）After the leached mud for obtaining is washed with water to neutrality, contained
The slag of lead and silver, the leaded and silver-colored slag enters traditional lead silver recovery technique or directly take-away；Cleaning solution is back to step
（2）Oxidation Leaching process section, sulfur-bearing aqueous acid is configured to together with the concentrated sulfuric acid, for Oxidation Leaching；
To step（2）Manganese dioxide to Fe is added in the leachate for obtaining2+It is fully oxidized to Fe3+Afterwards, sulfuric acid to pH is added
It is 1.5, be then hydrolyzed removing Fe3+（Use conventional methods and be hydrolyzed）, filter, obtain filter residue and the filtrate of iron content
（Filtrate is the mixed solution of copper sulphate and zinc sulfate）；Filter residue is directly taken out or is separately used it for anything else；
Step（4）, replace copper and heavy zinc：To step（3）Iron is added to enter line replacement in the filtrate for obtaining, the addition of iron is
1.3 mass of copper content times in filtrate, filtering obtains filtrate and filter residue；It is 7 that filter residue is washed with water to pH, obtains blister copper powder；Slightly
Copper powder is taken out；Cleaning solution is back to step（2）Oxidation Leaching process section, the water-soluble of sulfur acid is configured to together with the concentrated sulfuric acid
Liquid, for Oxidation Leaching；The conventional electrowinning zinc electrodeposition of filtrate feeding obtains zinc product.
Step in the present embodiment（1）Described sulphur-fixing agent is NaOH.Step（2）Described oxidant be hydrogen peroxide and
The combination of sodium chlorate.
Embodiment 2
A kind of complicated copper-lead zinc-silver bulk concentrate valuable metal separation method, comprises the following steps：
Step（1）, thermal activation：Rotary kiln is slowly added into concentrate and sulphur-fixing agent, then using heated by gas to 300 DEG C
Constant temperature thermal activation 3.5h, the quality of the addition of sulphur-fixing agent is 20% of the quality of sulphur in concentrate, obtains the flue gas containing zinc oxide and work
Change concentrate；
The gas that described flue gas is obtained after gathering dust first is passed through first order scavenging solution and carries out first order spray cleaning, then leads to
Enter and carry out second level spray cleaning in the scavenging solution of the second level, the gas of the purification for obtaining is directly discharged in air；To I and II
Liquid after purification spray adds NaOH untill precipitation is not produced（Precipitation is mainly hydroxide, such as calcium hydroxide, hydrogen-oxygen
Change ferrous iron etc.）, filter, filtrate condensing crystallizing, sodium sulfite solid is obtained, sodium sulfite solid after drying, take out by packaging；
Described first order scavenging solution is the aqueous sodium carbonate that mass concentration is 40%, and second level scavenging solution is that quality is dense
Spend the sodium hydrate aqueous solution for 40%；Gathering dust, receive is zinc oxide fumes；
Step（2）, Oxidation Leaching：Step（1）The activation concentrate for obtaining in dissolution kettle, is added after being milled to 200 mesh
To in sulfur-bearing aqueous acid, the weight/mass percentage composition of sulfuric acid is 15% in the aqueous solution, activates concentrate and sulfur-bearing aqueous acid
Solid-to-liquid ratio be 1：3, when being then heated to more than 85 DEG C with steam, addition is oxidizing, and the consumption of oxidant is activating essence
1.1 times of the quality of sulphur in ore deposit, then azeotropic 3h, then through filtering, obtains leached mud and leachate；
Step（3）, the separation of copper, lead, silver and zinc：Step（2）After the leached mud for obtaining is washed with water to neutrality, contained
The slag of lead and silver, the leaded and silver-colored slag enters traditional lead silver recovery technique or directly take-away；Cleaning solution is back to step
（2）Oxidation Leaching process section, sulfur-bearing aqueous acid is configured to together with the concentrated sulfuric acid, for Oxidation Leaching；
To step（2）Manganese dioxide to Fe is added in the leachate for obtaining2+It is fully oxidized to Fe3+Afterwards, sulfuric acid to pH is added
It is 1.5, be then hydrolyzed removing Fe3+（Use conventional methods and be hydrolyzed）, filter, obtain filter residue and the filtrate of iron content
（Filtrate is the mixed solution of copper sulphate and zinc sulfate）；Filter residue is directly taken out or is separately used it for anything else；
Step（4）, replace copper and heavy zinc：To step（3）Iron is added to enter line replacement in the filtrate for obtaining, the addition of iron is
1.2 mass of copper content times in filtrate, filtering obtains filtrate and filter residue；It is 7 that filter residue is washed with water to pH, obtains blister copper powder；Slightly
Copper powder is taken out；Cleaning solution is back to step（2）Oxidation Leaching process section, the water-soluble of sulfur acid is configured to together with the concentrated sulfuric acid
Liquid, for Oxidation Leaching；The conventional electrowinning zinc electrodeposition of filtrate feeding obtains zinc product.
Step in the present embodiment（1）Described sulphur-fixing agent is calcium hydroxide.Step（2）Described oxidant be hydrogen peroxide and
The combination of bleaching powder.
Embodiment 3
A kind of complicated copper-lead zinc-silver bulk concentrate valuable metal separation method, comprises the following steps：
Step（1）, thermal activation：Rotary kiln is slowly added into concentrate and sulphur-fixing agent, then using heated by gas to 500 DEG C
Constant temperature thermal activation 4h, the quality of the addition of sulphur-fixing agent is 30% of the quality of sulphur in concentrate, obtains the flue gas containing zinc oxide and activation
Concentrate；
The gas that described flue gas is obtained after gathering dust first is passed through first order scavenging solution and carries out first order spray cleaning, then leads to
Enter and carry out second level spray cleaning in the scavenging solution of the second level, the gas of the purification for obtaining is directly discharged in air；To I and II
Liquid after purification spray adds NaOH untill precipitation is not produced（Precipitation is mainly hydroxide, such as calcium hydroxide, hydrogen-oxygen
Change ferrous iron etc.）, filter, filtrate condensing crystallizing, sodium sulfite solid is obtained, sodium sulfite solid after drying, take out by packaging；
Described first order scavenging solution is the aqueous sodium carbonate that mass concentration is 40%, and second level scavenging solution is that quality is dense
Spend the sodium hydrate aqueous solution for 40%；Gathering dust, receive is zinc oxide fumes；
Step（2）, Oxidation Leaching：Step（1）The activation concentrate for obtaining in dissolution kettle, is added after being milled to 200 mesh
To in sulfur-bearing aqueous acid, the weight/mass percentage composition of sulfuric acid is 15% in the aqueous solution, activates concentrate and sulfur-bearing aqueous acid
Solid-to-liquid ratio be 1：3, when being then heated to more than 85 DEG C with steam, addition is oxidizing, and the consumption of oxidant is activating essence
1.12 times of the quality of sulphur in ore deposit, then azeotropic 3.6h, then through filtering, obtains leached mud and leachate；
Step（3）, the separation of copper, lead, silver and zinc：Step（2）After the leached mud for obtaining is washed with water to neutrality, contained
The slag of lead and silver, the leaded and silver-colored slag enters traditional lead silver recovery technique or directly take-away；Cleaning solution is back to step
（2）Oxidation Leaching process section, sulfur-bearing aqueous acid is configured to together with the concentrated sulfuric acid, for Oxidation Leaching；
To step（2）Manganese dioxide to Fe is added in the leachate for obtaining2+It is fully oxidized to Fe3+Afterwards, sulfuric acid to pH is added
It is 1.5, be then hydrolyzed removing Fe3+（Use conventional methods and be hydrolyzed）, filter, obtain filter residue and the filtrate of iron content
（Filtrate is the mixed solution of copper sulphate and zinc sulfate）；Filter residue is directly taken out or is separately used it for anything else；
Step（4）, replace copper and heavy zinc：To step（3）Iron is added to enter line replacement in the filtrate for obtaining, the addition of iron is
1.25 mass of copper content times in filtrate, filtering obtains filtrate and filter residue；It is 7 that filter residue is washed with water to pH, obtains blister copper powder；
Blister copper powder is taken out；Cleaning solution is back to step（2）Oxidation Leaching process section, the water-soluble of sulfur acid is configured to together with the concentrated sulfuric acid
Liquid, for Oxidation Leaching；The conventional electrowinning zinc electrodeposition of filtrate feeding obtains zinc product.
Step in the present embodiment（1）Described sulphur-fixing agent is magnesium hydroxide.Step（2）Described oxidant be hydrogen peroxide and
Combination in air.
Embodiment 4
Embodiment 4 is with the difference of embodiment 3：Step（1）Described sulphur-fixing agent is iron hydroxide.Step（2）It is described
Oxidant be the combination of sodium chlorate and bleaching powder.
Embodiment 5
Embodiment 5 is step with the difference of embodiment 3（2）Described oxidant is the combination of sodium chlorate and air.
Embodiment 6
Embodiment 5 is step with the difference of embodiment 3（2）Described oxidant is the combination of bleaching powder and air.
General principle of the invention, principal character and advantages of the present invention has been shown and described above.The technology of the industry
Personnel it should be appreciated that the present invention is not limited to the above embodiments, simply explanation described in above-described embodiment and specification this
The principle of invention, without departing from the spirit and scope of the present invention, various changes and modifications of the present invention are possible, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appending claims and its
Equivalent thereof.
Claims (1)
1. a kind of complicated copper-lead zinc-silver bulk concentrate valuable metal separation method, it is characterised in that comprise the following steps：
Step（1）, thermal activation：Rotary kiln is heated to 300-650 DEG C, concentrate and sulphur-fixing agent is slowly added into, then constant temperature heating is lived
Change 3.5-4.5h, the quality of the addition of sulphur-fixing agent is the 20-50% of the quality of sulphur in concentrate, obtains the flue gas containing zinc oxide and work
Change concentrate；The rotary kiln heating uses heated by gas；Described sulphur-fixing agent be NaOH, calcium hydroxide, magnesium hydroxide or
Iron hydroxide；
The gas that described flue gas is obtained after gathering dust first is passed through first order scavenging solution and carries out first order spray cleaning, then is passed through
Second level spray cleaning is carried out in secondary purification liquid, the gas of the purification for obtaining is directly discharged in air；Purified to I and II
Liquid after spray adds NaOH untill precipitation is not produced, and filtering, filtrate condensing crystallizing obtains sodium sulfite solid；
Described first order scavenging solution is the aqueous sodium carbonate that mass concentration is 40%, and second level scavenging solution is for mass concentration
40% sodium hydrate aqueous solution；
Step（2）, Oxidation Leaching：Step（1）The activation concentrate for obtaining is added to the water-soluble of sulfur acid after being milled to 200 mesh
In liquid, the weight/mass percentage composition of sulfuric acid is 15% in the aqueous solution, and activation concentrate is 1 with the solid-to-liquid ratio of sulfur-bearing aqueous acid：3,
When being then heated to more than 85 DEG C with steam, addition is oxidizing, and the consumption of oxidant is the quality for activating sulphur in concentrate
1.1-1.2 times, then azeotropic 3-4h, then through filtering, obtains leached mud and leachate；Described oxidant is hydrogen peroxide, chlorine
Any two kinds in sour sodium, bleaching powder and air of combination；
Step（3）, the separation of copper, lead, silver and zinc：Step（2）After the leached mud for obtaining is washed with water to neutrality, obtain it is leaded and
The slag of silver；Cleaning solution is back to step（2）Oxidation Leaching process section, sulfur-bearing aqueous acid is configured to together with the concentrated sulfuric acid,
For Oxidation Leaching；
To step（2）Manganese dioxide to Fe is added in the leachate for obtaining2+It is fully oxidized to Fe3+Afterwards, the sulfuric acid is added to be to pH
1.5, be then hydrolyzed removing Fe3+, filter, obtain filter residue and the filtrate of iron content；
Step（4）, replace copper and heavy zinc：To step（3）Iron is added to enter line replacement in the filtrate for obtaining, the addition of iron is filtrate
The 1.2-1.3 mass of middle copper content times, filtering, obtains filtrate and filter residue；It is 7 that filter residue is washed with water to pH, obtains blister copper powder；Wash
Wash liquid and be back to step（2）Oxidation Leaching process section, sulfur-bearing aqueous acid is configured to together with the concentrated sulfuric acid, for aoxidize soak
Go out；The conventional electrowinning zinc electrodeposition of filtrate feeding obtains zinc product.
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| CN107723460B (en) * | 2017-10-23 | 2019-03-19 | 湖南华信稀贵科技股份有限公司 | A kind of smelting process of complex lead-zinc copper mine |
| CN115232979B (en) * | 2022-08-16 | 2024-04-05 | 深圳市中金岭南有色金属股份有限公司 | Method for preparing zinc sulfate and recycling copper by bioleaching low-grade copper-zinc sulfide ore |
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| GB9309144D0 (en) * | 1993-05-04 | 1993-06-16 | Sherritt Gordon Ltd | Recovery of metals from sulphidic material |
| CN1266908A (en) * | 1999-03-14 | 2000-09-20 | 龙诗明 | Process for separating metallurgical materials of Zn, Cu, Cd and Pb by wet method and its application |
| US6835230B2 (en) * | 2001-03-28 | 2004-12-28 | Dowa Mining Co., Ltd. | Method for leaching zinc concentrate |
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| CN102703694A (en) * | 2012-06-15 | 2012-10-03 | 广西金山铟锗冶金化工有限公司 | Method for treating low-grade zinc oxide ores by wet method |
| CN104278149A (en) * | 2013-07-12 | 2015-01-14 | 无锡成博科技发展有限公司 | Hydrometallurgy process of copper-lead-zinc symbiotic collective concentrate |
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