CN105755281B - A kind of method based on self-propagating reaction processing zinc sulfide concentrates - Google Patents

A kind of method based on self-propagating reaction processing zinc sulfide concentrates Download PDF

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Publication number
CN105755281B
CN105755281B CN201610204724.7A CN201610204724A CN105755281B CN 105755281 B CN105755281 B CN 105755281B CN 201610204724 A CN201610204724 A CN 201610204724A CN 105755281 B CN105755281 B CN 105755281B
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zinc
reaction
self
leaching
sulfide concentrates
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CN105755281A (en
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殷晓飞
吴玉锋
李彬
章启军
谭哲
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Shaoguan Shengfa Renewable Resources Technology Co.,Ltd.
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Beijing University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B19/00—Obtaining zinc or zinc oxide
    • C22B19/02—Preliminary treatment of ores; Preliminary refining of zinc oxide
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B19/00—Obtaining zinc or zinc oxide
    • C22B19/20—Obtaining zinc otherwise than by distilling
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B19/00—Obtaining zinc or zinc oxide
    • C22B19/20—Obtaining zinc otherwise than by distilling
    • C22B19/24—Obtaining zinc otherwise than by distilling with leaching with alkaline solutions, e.g. ammonia
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/12—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Abstract

A kind of method based on self-propagating reaction processing zinc sulfide concentrates, belongs to technical field of non-ferrous metallurgy.It is related to the method using the green processing zinc sulfide concentrates that zinc oxide is prepared except sial self-propagating reaction flooding zinc vulcanized sodium impurity-removing precipitating zinc hydroxide calcining.It is characterized in that：Alkaline pretreatment removes sial impurity, the zinc sulfide concentrates powder after removal of impurities and sodium peroxide powder mixed compaction, is placed in high temperature resistant reaction vessel, triggers self-propagating reaction；Using water as the molten leaching reaction product of leaching agent, filtering obtains leaching liquid containing zinc；Using vulcanized sodium except lead, copper impurity, solution precipitation recovery Zn (OH) after purification2, ZnO products are prepared after calcining.The leaching rate of zinc of the present invention is up to 98%, obtains oxide powder and zinc and meets industrial production standard.Process of the present invention control is simple, and cost is cheap, and energy consumption is extremely low, and uncontaminated gases produce, and carbon emission is low, realizes efficient Rapid Leaching and extracts Zinc Content in Zinc Sulphide Concentrate.

Description

A kind of method based on self-propagating reaction processing zinc sulfide concentrates
Technical field
The invention belongs to technical field of non-ferrous metallurgy, at application self-propagating reaction green, quick, low energy consumption Reason zinc sulfide concentrates and the method for reclaiming extraction zinc oxide.
Background technology
The raw mineral materials of zinc is broadly divided into two kinds of sulphide ore and oxide ore, and zinc sulfide ore accounts for the overwhelming majority, and zinc oxide ore accounts for Few part.The main raw material of industrial production zinc is zinc sulfide concentrates in world wide at present, accounts for world's zinc abstraction raw material More than 90%.Zinc sulfide concentrates main component is generally w (Zn) 45~60%, w (S) 30~35%, w (Fe) 5~15%, w (Pb) 0.8~1.5%, w (Si) 0.2~2%, w (Cu) 0.01~1%, w (Al) 0.1~0.5%.The technique of zinc abstraction is substantially Firing method process and the major class of wet process two can be divided into, wherein zinc hydrometallurgy is the most important smelting process in the world today, and it is produced 85% or so of Liang Zhan worlds zinc total output.
Zinc concentrate is carried out oxidizing roasting first or baked with agglomeration by pyrometallurgy of zinc, the zinc sulphide in concentrate is changed into oxidation Zinc, sintering temperature need to be controlled more than 1000 DEG C, then with carbonaceous reduction by zinc oxide reduction into metallic zinc.It is main in the world at present Pyrometallurgy of zinc technique be mainly blast furnace zinc metallurgy (ISP methods), zinc vertical retorting, electrothermal way zinc metallurgy and horizontal retort zinc metallurgy.Horizontal retort zinc metallurgy (patent application 96216948.X) is zinc metallurgy method that is a kind of simple and falling behind, because high energy consumption, productivity ratio are low, is washed in a pan at present Eliminate.The too big subject matter of power consumption, zinc vertical retorting (patent application be present in electrothermal way (patent application 91107379.5) 02276554.9) the shortcomings of low single series production capacity, high energy consumption and working condition difference be present, both in factory of developing country still There are a small number of applications.Blast furnace zinc metallurgy (patent application 99232376.2) is most important pyrometallurgy of zinc method in the world, its yield Account for 13% or so of world's zinc total output.The technique is mainly baked with agglomeration by zinc concentrate, agglomerate reduction melting, zinc vapor condensing With 4 process compositions of crude zinc smelting.Blast furnace zinc metallurgy has sulfur dioxide, lead steam and dust to produce when baking with agglomeration, to ring Border pollutes, while pyrogenic process high energy consumption, blast furnace in melting in the presence of consumption smelter coke and clear up stove knot trouble, with Development, the increasingly strict of environmental requirement, the rise of coke price and the raising of zinc sulfide ore sorting technology of Zinc Hydrometallurgy Technology, Its development is seriously restricted.
Zinc hydrometallurgy is also known as electrolysis zinc metallurgy, including the Whote-wet method zinc metallurgy of traditional conventional wet lay smelting process and new development Technique.Conventional wet zinc metallurgy is actually pyrogenic process-wet method combined flow (patent application 201410255424.2), its normal process Zinc concentrate " desulfurization with roasting technique-leaching-net liquid-electrodeposition ", fluidized bed roasting temperature need to unanimously be controlled with thermal process 1000 DEG C with On.The technique is substantially using dilute sulfuric acid as solvent solving zinc fired slags, is made in the zinc pass into solution as much as possible in zinc fired slags It is individual, solution of zinc sulfate is made, then purification and impurity removal is carried out to solution of zinc sulfate, metallic zinc then is parsed from scavenging solution midpoint, electricity Zinc and then founding are into zinc ingot metal.Whote-wet method smelt zinc be the direct weighting acid-hatching of young eggs (patent application 201210061603.3, 201210188719.3rd, 201110311519.8), roasting process is eliminated, temperature and oxygen pressure are controlled in autoclave pressure Under the conditions of, the sulphur in concentrate is converted into recovery of elemental sulfur, zinc and other part metals elements are dissolved in acidity in the form of an ion In solution, zinc lysate carries out impurity and purification, electrodeposition and founding again.Conventional wet lay can not avoid energy consumption caused by pyrogenic process roasting High, the problems such as sulfur-containing smoke gas is seriously polluted, although pressurized acid leaching method solves the problems such as waste gas, flue dust, but equally exist manipulation It is required that strict, old of high-tension apparatus is with high investment greatly, be difficult in adapt to high F, Cl raw material, is also easy to produce the problems such as sulphur caking.
Present invention employs self-propagating reaction technology, flooding zinc, prepares zinc oxide product.Avoid existing pyrogenic process wet method The problems such as high energy consumption, high cost, complex procedures such as the next high temperature of process bands, high pressure, peracid, self-propagating reaction speed is exceedingly fast, production Thing is stable, avoids the generation of the sulfur-bearing toxic gas such as sulfur dioxide, realizes cleanliness without any pollution, is leached using water, real Show normal temperature and pressure low cost Rapid Leaching, overcome environment, energy that zinc sulfide concentrates HTHP wet-leaching process bands are come The problems such as consumption, equipment, there is good environmental economical profit.The present invention has simple for process, and raw materials used and equipment is normal See and easily obtain and cheap, energy consumption is low, green non-pollution.
The content of the invention
The present invention seeks to the high energy consumption for solving to bring in existing wet method and pyrogenic process zinc metallurgical process, high cost, high investment, The problems such as high pollution, tediously long complex process.Therefore, the present invention be a kind of low power consuming is disclosed, pollution-free, technique is simple, cost is low The method that zinc sulfide concentrates are handled under honest and clean normal temperature and pressure conditionses.
The present invention it has been investigated that：Zinc sulphide in the case where being well mixed, passes through with suitable oxidant (sodium peroxide) Self-propagating reaction can be occurred after igniting, reaction generation is highly soluble in the zinc salt of water (or alkaline solution), and the sulphur of-divalent is from climing Prolong and sodium sulfate salt is converted into pyroreaction.Found according to more than, present invention process application self-propagating reaction technology, make oxidation also Original reaction is carried out by itself chemical energy, without external offer additional-energy, realizes low energy consumption, efficiently quick processing zinc sulphide essence Ore deposit, while the generation of SOx dusty gas is avoided, thoroughly solve fume treatment disposal and environmental pollution that existing roasting technology is brought Problem；Leaching agent is adopted water as, leaches zinc resource, realizes that zinc sulfide concentrates low-cost high-efficiency normal temperature and pressure low cost leaches, zinc Leaching rate is generally greater than 98%.
A kind of method based on self-propagating reaction processing zinc sulfide concentrates of the present invention is as follows：
Step 1：Pretreatment removes sial
Zinc sulfide concentrates powder after sorting is soaked into removal of impurities in alkaline solution of sodium hydroxide, to remove in zinc sulfide concentrates A small amount of impurity silicon, aluminium etc.；Filtered after reaction, filter residue is rinsed with alkali lye, to reclaim sial etc., residue collection is dried to be used filtrate In subsequent handling；
Leaching condition is：9.5~11.5, solid-to-liquid ratio is controlled 1 for leachate pH controls:20~1:100 (g/mL), reaction 30~80 DEG C of temperature, 1~4h of reaction time.
Step 2：Self-propagating reaction
Fine grinding is crushed after pretreated zinc sulfide concentrates powder is fully dried, it is then that miberal powder and peroxidating sodium powder is abundant It is uniformly mixed, is compacted, is placed in high temperature resistant reaction vessel；Using chemic ignition, combustion wave igniting or local heating methods In one or more ignite and trigger self-propagating reaction, react once igniting with the spontaneous progress of the waveshape that burns, without providing Additional-energy, until reaction terminates；
Particularly, zinc sulfide concentrates powder and sodium peroxide mass ratio are 1:0.5~1:5, it is desirable to carried out in dry environment Material mixes and compacting process.
ZnS+Na2O2→NaxZnOy+Na2SO4
Step 3：Leach
Be placed in after being reacted in step 2 after product cooling in alkali resistance reaction vessel, using water or sodium hydroxide solution as Leaching agent carries out the leaching of zinc, and leaching process is stirred continuously；Leachate is filtered, and is obtained impure filtrate and is rinsed with alkali lye and is filtered Slag A, washing lotion are incorporated to leachate and leached, and filter wash slag A is reclaimed for reclaiming other metals；
Leaching condition is：Reaction product is controlled 1 with water by solid-to-liquid ratio:20~1:100g/mL, extraction temperature 20~80 DEG C, 0.5~2h of extraction time.Particularly, sodium hydroxide mass concentration in leaching process leachate can be controlled by adding NaOH For 0.1~5%, to ensure that the high-efficiency dissolution of zinc leaches；
Leach reaction equation is as follows：
NaxZnOy+H2O→Na2Zn(OH)4+NaOH
Step 4：Purification and impurity removal
The major impurity ion contained in impure filtrate in step 3 is Pb (OH)4 2-、Na+、SO4 2-And a small amount of Cu (OH)4 2-, Na+And SO4 2-Extraction on follow-up zinc does not influence, therefore this step removal of impurities object is plumbic acid radical ion.To step Vulcanized sodium is added in impure filtrate in three, heating stirring, lead and copper in solution is fully precipitated with sulphided form, is realized The separation of impurity element；Filtered after the completion of precipitation, obtain filter residue B and the filtrate containing zinc, filter residue B is washed with being reclaimed after hot water injection Liquid is incorporated in the filtrate containing zinc；
Deposition condition：Lead is controlled 1 with vulcanized sodium mass ratio in solution:1~1:2,50~80 DEG C of precipitation temperature, during precipitation Between 1~4h.
Step 5：Recovery prepares zinc oxide
Zn (OH) in the filtrate containing zinc in step 4 containing high concentration4 2-, by adding acid for adjusting pH to make zinc for 9~11 With Zn (OH)2Form fully precipitates, impurity element Na+And SO4 2-Stay in filtrate, filtered filtration residue calcining recovery prepares ZnO powder End, filtrate prepare sodium sulphate for recovery.
The present invention has advantages below：
1st, because invention employs self-propagating reaction technology, the zinc sulphide in zinc sulfide concentrates is made to occur certainly with sodium peroxide Sprawling reaction, without providing additional-energy, reaction speed is exceedingly fast, overcome high temperature, high pressure that existing pyrogenic process wet processing brings, The problems such as high energy consumptions such as peracid, high cost, complex procedures.And high temperature caused by self-propagating reaction can realize heat recovery, Realize zinc sulfide concentrates low energy consumption, Quick Pretreatment.
2nd, because the present invention uses self-propagating reaction, reaction product is stable, and element sulphur is converted into sulfate, avoided The generation of the sulfur-bearing toxic gas such as sulfur dioxide, realizes cleanliness without any pollution.Zinc is converted into zincic acid sodium salt, can direct applicable industry Leached with water, realize normal temperature and pressure low cost Rapid Leaching, overcome zinc sulfide concentrates HTHP wet-leaching work The problems such as environment that skill is brought, energy consumption, equipment, there is good environmental economical profit.
3rd, it is leaching agent that the present invention, which is leached using water, and cost is extremely low, and leaching efficiency is high, and equipment requirement is low, green non-pollution. The purer liquid of alkaline leaching containing zinc can be obtained after separation, impurity removal, after precipitation high efficiente callback prepare zinc oxide product, realize it is low into Zinc resource in this high efficiente callback zinc sulfide concentrates.
4th, technique of the invention can be directed to all kinds zinc sulfide concentrates, and zinc content in zinc sulfide concentrates is required compared with Low, zinc sulfide concentrates of the Zn content higher than 40% can be applied to this technique, have wide range of applications.The present invention has technique letter Single easy, raw materials used and equipment is all relatively common and cheap, and energy consumption is extremely low, green non-pollution.
Brief description of the drawings
Fig. 1 represents a kind of flow chart of the method based on self-propagating reaction processing zinc sulfide concentrates.
Embodiment
With reference to embodiment, the present invention will be further described, but the present invention is not limited to following examples.
Embodiment 1
Zinc sulfide concentrates powder after sorting is soaked into removal of impurities in the alkaline solution of sodium hydroxide that pH value is 13, solid-to-liquid ratio is 1:100 (g/mL), 30 DEG C, reaction time 4h of reaction temperature, to remove impurity silicon, aluminium.Filtered after reaction, rinsed and filtered with alkali lye Slag, filtrate is fully dried to reclaim sial etc., after residue collection and broken fine grinding.Fine grinding miberal powder and sodium peroxide are pressed into quality Than 1:4 are thoroughly mixed uniformly, compacting, are placed in high temperature resistant reaction vessel, are triggered using the chemistry to drip method of igniting from climing Prolong reaction.It is placed in after reaction product cooling in alkali resistance reaction vessel, using 0.5% sodium hydroxide solution as leaching agent Leaching Zinc, Solid-to-liquid ratio is 1:20 (g/mL), 80 DEG C of extraction temperature, extraction time 1.2h.Leachate is filtered, and is rinsed filter residue with alkali lye, is washed Liquid is incorporated to leachate, and filter residue is reclaimed for reclaiming other metals.Add vulcanized sodium in containing zinc lixiviating solution, lead and copper in solution Quality is controlled 1 with vulcanized sodium mass ratio:1.5,60 DEG C of stirring precipitation 3h, make lead and copper in solution fully heavy with sulphided form Form sediment.Filtered after the completion of precipitation, filter residue is incorporated in filtrate with hot water injection, washing lotion, filter residue recovery.Being leached containing zinc after regulation purification Liquid pH is 10.2, makes zinc ion with Zn (OH)2Form fully precipitates, after filtering calcining prepare ZnO powder, filtrate, which is used to reclaim, makes Standby sodium sulphate.The rate of recovery of zinc is 98.8%.
Embodiment 2
Zinc sulfide concentrates powder after sorting is soaked into removal of impurities, solid-to-liquid ratio in the alkaline solution of sodium hydroxide that pH value is 12.5 For 1:90 (g/mL), 35 DEG C, reaction time 3.5h of reaction temperature, to remove impurity silicon, aluminium.Filter after reaction, rinsed with alkali lye Filter residue, filtrate is fully dried to reclaim sial etc., after residue collection and broken fine grinding.Fine grinding miberal powder and sodium peroxide are pressed into matter Measure ratio 1:5 are thoroughly mixed uniformly, compacting, are placed in high temperature resistant reaction vessel, are lighted a fire using microwave and trigger self-propagating reaction. It is placed in after reaction product cooling in alkali resistance reaction vessel, using 1% sodium hydroxide solution as leaching agent Leaching Zinc, solid-to-liquid ratio 1: 25 (g/mL), 65 DEG C of extraction temperature, extraction time 2h.Leachate is filtered, and rinses filter residue with alkali lye, washing lotion is incorporated to leaching Liquid, filter residue are reclaimed for reclaiming other metals.Add vulcanized sodium in containing zinc lixiviating solution, the quality and vulcanization of lead and copper in solution Sodium mass ratio is controlled 1:1.7,55 DEG C of stirring precipitation 4h, make lead and copper in solution fully be precipitated with sulphided form.Precipitate Into rear filtering, filter residue is incorporated in filtrate with hot water injection, washing lotion, filter residue recovery.The pH of leaching liquid containing zinc after regulation purification is 11, Make zinc ion with Zn (OH)2Form fully precipitates, after filtering calcining prepare ZnO powder, filtrate prepares sodium sulphate for recovery.Zinc The rate of recovery be 98.3%.
Embodiment 3
Zinc sulfide concentrates powder after sorting is soaked into removal of impurities, solid-to-liquid ratio in the alkaline solution of sodium hydroxide that pH value is 11.8 For 1:85 (g/mL), 40 DEG C, reaction time 3h of reaction temperature, to remove impurity silicon, aluminium.Filtered after reaction, rinsed and filtered with alkali lye Slag, filtrate is fully dried to reclaim sial etc., after residue collection and broken fine grinding.Fine grinding miberal powder and sodium peroxide are pressed into quality Than 1:4.5 are thoroughly mixed uniformly, compacting, are placed in high temperature resistant reaction vessel, are heated using electric hot plate and trigger self- propagating anti- Should.It is placed in after reaction product cooling in alkali resistance reaction vessel, using water as leaching agent Leaching Zinc, solid-to-liquid ratio 1:30 (g/mL), 50 DEG C of extraction temperature, extraction time 1.8h.Leachate is filtered, and rinses filter residue with alkali lye, washing lotion is incorporated to leachate, and filter residue returns Receive for reclaiming other metals.Add vulcanized sodium in containing zinc lixiviating solution, the quality of lead and copper and vulcanized sodium mass ratio in solution Control is 1:1.5,50 DEG C of stirring precipitation 3.5h, make lead and copper in solution fully be precipitated with sulphided form.Mistake after the completion of precipitation Filter, filter residue are incorporated in filtrate with hot water injection, washing lotion, filter residue recovery.The pH of leaching liquid containing zinc after regulation purification is 10.5, makes zinc Ion is with Zn (OH)2Form fully precipitates, after filtering calcining prepare ZnO powder, filtrate prepares sodium sulphate for recovery.Zinc returns Yield is 97.5%.
Embodiment 4
Zinc sulfide concentrates powder after sorting is soaked into removal of impurities, solid-to-liquid ratio in the alkaline solution of sodium hydroxide that pH value is 11.3 For 1:75 (g/mL), 45 DEG C, reaction time 2.5h of reaction temperature, to remove impurity silicon, aluminium.Filter after reaction, rinsed with alkali lye Filter residue, filtrate is fully dried to reclaim sial etc., after residue collection and broken fine grinding.Fine grinding miberal powder and sodium peroxide are pressed into matter Measure ratio 1:3.5 are thoroughly mixed uniformly, compacting, are placed in high temperature resistant reaction vessel, trigger self- propagating anti-using laser ignition Should.It is placed in after reaction product cooling in alkali resistance reaction vessel, using 1% sodium hydroxide solution as leaching agent Leaching Zinc, solid-to-liquid ratio For 1:40 (g/mL), 40 DEG C of extraction temperature, extraction time 0.8h.Leachate is filtered, and rinses filter residue with alkali lye, washing lotion is incorporated to Leachate, filter residue are reclaimed for reclaiming other metals.Add vulcanized sodium in containing zinc lixiviating solution, in solution the quality of lead and copper with Vulcanized sodium mass ratio is controlled 1:1.3,60 DEG C of stirring precipitation 3h, make lead and copper in solution fully be precipitated with sulphided form.It is heavy Filtered after the completion of shallow lake, filter residue is incorporated in filtrate with hot water injection, washing lotion, filter residue recovery.The pH of leaching liquid containing zinc after regulation purification For 9.3, make zinc ion with Zn (OH)2Form fully precipitates, after filtering calcining prepare ZnO powder, filtrate prepares sulphur for recovery Sour sodium.The rate of recovery of zinc is 99.2%.
Embodiment 5
Zinc sulfide concentrates powder after sorting is soaked into removal of impurities, solid-to-liquid ratio in the alkaline solution of sodium hydroxide that pH value is 10.7 For 1:60 (g/mL), 55 DEG C, reaction time 2h of reaction temperature, to remove impurity silicon, aluminium.Filtered after reaction, rinsed and filtered with alkali lye Slag, filtrate is fully dried to reclaim sial etc., after residue collection and broken fine grinding.Fine grinding miberal powder and sodium peroxide are pressed into quality Than 1:2.5 are thoroughly mixed uniformly, compacting, are placed in high temperature resistant reaction vessel, and method initiation is ignited certainly using the chemistry to drip Sprawling reaction.It is placed in alkali resistance reaction vessel after reaction product cooling, is leached by leaching agent of 1.5% sodium hydroxide solution Zinc, solid-to-liquid ratio 1:50 (g/mL), 35 DEG C of extraction temperature, extraction time 0.5h.Leachate is filtered, and is rinsed and filtered with alkali lye Slag, washing lotion are incorporated to leachate, and filter residue is reclaimed for reclaiming other metals.Add vulcanized sodium in containing zinc lixiviating solution, lead in solution Controlled with the quality of copper with vulcanized sodium mass ratio 1:1,65 DEG C of stirring precipitation 2.5h, makes in solution lead and copper with sulphided form Fully precipitation.Filtered after the completion of precipitation, filter residue is incorporated in filtrate with hot water injection, washing lotion, filter residue recovery.Containing after regulation purification Zinc leaching liquid pH is 9.3, makes zinc ion with Zn (OH)2Form fully precipitates, after filtering calcining prepare ZnO powder, filtrate is used for Recovery prepares sodium sulphate.The rate of recovery of zinc is 98.2%.
Embodiment 6
Zinc sulfide concentrates powder after sorting is soaked into removal of impurities in the alkaline solution of sodium hydroxide that pH value is 10, solid-to-liquid ratio is 1:50 (g/mL), 60 DEG C, reaction time 1.5h of reaction temperature, to remove impurity silicon, aluminium.Filtered after reaction, rinsed and filtered with alkali lye Slag, filtrate is fully dried to reclaim sial etc., after residue collection and broken fine grinding.Fine grinding miberal powder and sodium peroxide are pressed into quality Than 1:3 are thoroughly mixed uniformly, compacting, are placed in high temperature resistant reaction vessel, are triggered using combustion wave igniting method of igniting from climing Prolong reaction.It is placed in after reaction product cooling in alkali resistance reaction vessel, using 2% sodium hydroxide solution as leaching agent Leaching Zinc, Gu Liquor ratio is 1:60 (g/mL), 75 DEG C of extraction temperature, extraction time 1h.Leachate is filtered, and rinses filter residue with alkali lye, washing lotion is simultaneously Enter leachate, filter residue is reclaimed for reclaiming other metals.Add vulcanized sodium in containing zinc lixiviating solution, the quality of lead and copper in solution Controlled with vulcanized sodium mass ratio 1:2,55 DEG C of stirring precipitation 2.5h, make lead and copper in solution fully be precipitated with sulphided form. Filtered after the completion of precipitation, filter residue is incorporated in filtrate with hot water injection, washing lotion, filter residue recovery.Leaching liquid containing zinc after regulation purification PH is 11, makes zinc ion with Zn (OH)2Form fully precipitates, after filtering calcining prepare ZnO powder, filtrate prepares sulphur for recovery Sour sodium.The rate of recovery of zinc is 97.3%.
Embodiment 7
Zinc sulfide concentrates powder after sorting is soaked into removal of impurities, solid-to-liquid ratio in the alkaline solution of sodium hydroxide that pH value is 9.8 For 1:40 (g/mL), 70 DEG C, reaction time 1h of reaction temperature, to remove impurity silicon, aluminium.Filtered after reaction, rinsed and filtered with alkali lye Slag, filtrate is fully dried to reclaim sial etc., after residue collection and broken fine grinding.Fine grinding miberal powder and sodium peroxide are pressed into quality Than 1:2 are thoroughly mixed uniformly, compacting, are placed in high temperature resistant reaction vessel, are heated using microwave and trigger self-propagating reaction.Instead Product is answered to be placed in after cooling down in alkali resistance reaction vessel, using 1.5% sodium hydroxide solution as leaching agent Leaching Zinc, solid-to-liquid ratio 1: 75 (g/mL), 20 DEG C of extraction temperature, extraction time 1.5h.Leachate is filtered, and rinses filter residue with alkali lye, washing lotion is incorporated to leaching Liquid, filter residue are reclaimed for reclaiming other metals.Add vulcanized sodium in containing zinc lixiviating solution, the quality and vulcanization of lead and copper in solution Sodium mass ratio is controlled 1:1.5,60 DEG C of stirring precipitation 2h, make lead and copper in solution fully be precipitated with sulphided form.Precipitate Into rear filtering, filter residue is incorporated in filtrate with hot water injection, washing lotion, filter residue recovery.Adjusting the pH of leaching liquid containing zinc after purification is 10.7, make zinc ion with Zn (OH)2Form fully precipitates, after filtering calcining prepare ZnO powder, filtrate prepares sulfuric acid for recovery Sodium.The rate of recovery of zinc is 98.6%.
Embodiment 8
Zinc sulfide concentrates powder after sorting is soaked into removal of impurities, solid-to-liquid ratio in the alkaline solution of sodium hydroxide that pH value is 9.5 For 1:30 (g/mL), 80 DEG C, reaction time 1h of reaction temperature, to remove impurity silicon, aluminium.Filtered after reaction, rinsed and filtered with alkali lye Slag, filtrate is fully dried to reclaim sial etc., after residue collection and broken fine grinding.Fine grinding miberal powder and sodium peroxide are pressed into quality Than 1:1.5 are thoroughly mixed uniformly, compacting, are placed in high temperature resistant reaction vessel, initiation self-propagating reaction is lighted using thermal explosion. It is placed in after reaction product cooling in alkali resistance reaction vessel, using 2% sodium hydroxide solution as leaching agent Leaching Zinc, solid-to-liquid ratio 1: 95 (g/mL), 25 DEG C of extraction temperature, extraction time 1h.Leachate is filtered, and rinses filter residue with alkali lye, washing lotion is incorporated to leaching Liquid, filter residue are reclaimed for reclaiming other metals.Add vulcanized sodium in containing zinc lixiviating solution, the quality and vulcanization of lead and copper in solution Sodium mass ratio is controlled 1:1.8,75 DEG C of stirring precipitation 1h, make lead and copper in solution fully be precipitated with sulphided form.Precipitate Into rear filtering, filter residue is incorporated in filtrate with hot water injection, washing lotion, filter residue recovery.Adjusting the pH of leaching liquid containing zinc after purification is 9.5, make zinc ion with Zn (OH)2Form fully precipitates, after filtering calcining prepare ZnO powder, filtrate prepares sulfuric acid for recovery Sodium.The rate of recovery of zinc is 99.0%.
Embodiment 9
Zinc sulfide concentrates powder after sorting is soaked into removal of impurities in the alkaline solution of sodium hydroxide that pH value is 9, solid-to-liquid ratio is 1:20 (g/mL), 85 DEG C, reaction time 2.4h of reaction temperature, to remove impurity silicon, aluminium.Filtered after reaction, rinsed and filtered with alkali lye Slag, filtrate is fully dried to reclaim sial etc., after residue collection and broken fine grinding.Fine grinding miberal powder and sodium peroxide are pressed into quality Than 1:0.5 is thoroughly mixed uniformly, compacting, is placed in high temperature resistant reaction vessel, triggers self- propagating anti-using laser spots pyrogenic process Should.It is placed in after reaction product cooling in alkali resistance reaction vessel, using 5% sodium hydroxide solution as leaching agent Leaching Zinc, solid-to-liquid ratio For 1:80 (g/mL), 45 DEG C of extraction temperature, extraction time 2h.Leachate is filtered, and rinses filter residue with alkali lye, washing lotion is incorporated to leaching Go out liquid, filter residue is reclaimed for reclaiming other metals.Add vulcanized sodium in containing zinc lixiviating solution, the quality and sulphur of lead and copper in solution Change the control of sodium mass ratio 1:1.6,70 DEG C of stirring precipitation 1.5h, make lead and copper in solution fully be precipitated with sulphided form.It is heavy Filtered after the completion of shallow lake, filter residue is incorporated in filtrate with hot water injection, washing lotion, filter residue recovery.The pH of leaching liquid containing zinc after regulation purification For 9.3, make zinc ion with Zn (OH)2Form fully precipitates, after filtering calcining prepare ZnO powder, filtrate prepares sulphur for recovery Sour sodium.The rate of recovery of zinc is 98.9%.
Embodiment 10
Zinc sulfide concentrates powder after sorting is soaked into removal of impurities in the alkaline solution of sodium hydroxide that pH value is 12, solid-to-liquid ratio is 1:10 (g/mL), 90 DEG C, reaction time 1.8h of reaction temperature, to remove impurity silicon, aluminium.Filtered after reaction, rinsed and filtered with alkali lye Slag, filtrate is fully dried to reclaim sial etc., after residue collection and broken fine grinding.Fine grinding miberal powder and sodium peroxide are pressed into quality Than 1:2 are thoroughly mixed uniformly, compacting, are placed in high temperature resistant reaction vessel, are triggered using the chemistry to drip method of igniting from climing Prolong reaction.It is placed in after reaction product cooling in alkali resistance reaction vessel, using 0.1% sodium hydroxide solution as leaching agent Leaching Zinc, Solid-to-liquid ratio is 1:100 (g/mL), 70 DEG C of extraction temperature, extraction time 2h.Leachate is filtered, and is rinsed filter residue with alkali lye, is washed Liquid is incorporated to leachate, and filter residue is reclaimed for reclaiming other metals.Add vulcanized sodium in containing zinc lixiviating solution, lead and copper in solution Quality is controlled 1 with vulcanized sodium mass ratio:1.5,80 DEG C of stirring precipitation 1h, make lead and copper in solution fully heavy with sulphided form Form sediment.Filtered after the completion of precipitation, filter residue is incorporated in filtrate with hot water injection, washing lotion, filter residue recovery.Being leached containing zinc after regulation purification Liquid pH is 9, makes zinc ion with Zn (OH)2Form fully precipitates, after filtering calcining prepare ZnO powder, filtrate, which is used to reclaim, to be prepared Sodium sulphate.The rate of recovery of zinc is 97.8%.

Claims (7)

  1. A kind of 1. method based on self-propagating reaction processing zinc sulfide concentrates, it is characterised in that zinc sulphide and suitable oxidant In the case of well mixed self-propagating reaction can occur after igniting for sodium peroxide, and reaction generation is highly soluble in water or alkalescence The zinc salt of solution, and the sulphur of-divalent is converted into sulfate in self propagating high temperature reaction；Comprise the following steps：
    Step 1：Pretreatment removes sial
    Zinc sulfide concentrates powder after sorting is soaked into removal of impurities in alkaline solution of sodium hydroxide, it is a small amount of in zinc sulfide concentrates to remove Include silicon, the impurity of aluminium；Filtered after reaction, filter residue is rinsed with alkali lye, to reclaim sial, residue collection is dried to be used for filtrate Subsequent handling；
    Step 2：Self-propagating reaction
    Fine grinding is crushed after pretreated zinc sulfide concentrates powder is fully dried, is then sufficiently stirred miberal powder and peroxidating sodium powder It is well mixed, compacting, it is placed in high temperature resistant reaction vessel；Ignite and trigger self-propagating reaction, react once igniting with combustion wave The spontaneous progress of form, without providing additional-energy, until reaction terminates；
    Step 3：Leach
    It will be placed in after being reacted in step 2 after product cooling in alkali resistance reaction vessel, leaching is used as using water or sodium hydroxide solution Agent carries out the leaching of zinc, and leaching process is stirred continuously；Leachate is filtered, and is obtained impure filtrate and is rinsed filter residue A with alkali lye, Washing lotion is incorporated to leachate and leached, and filter wash slag A is reclaimed for reclaiming other metals；
    Step 4：Purification and impurity removal
    Vulcanized sodium is added in impure filtrate into step 3, heating stirring, lead and copper in solution is filled with sulphided form Fractional precipitation, realize the separation of impurity element；Filtered after the completion of precipitation, obtain filter residue B and the filtrate containing zinc, filter residue B is rushed with hot water Reclaimed after washing, washing lotion is incorporated in the filtrate containing zinc；
    Step 5：Recovery prepares zinc oxide
    Zn (OH) in the filtrate containing zinc in step 4 containing high concentration4 2-, by adding acid for adjusting pH to make zinc for 9~11 with Zn (OH)2Form fully precipitates, impurity element Na+And SO4 2-Stay in filtrate, filtered filtration residue calcining recovery prepares ZnO powder, filters Liquid prepares sodium sulphate for recovery.
  2. 2. according to a kind of method that zinc sulfide concentrates are handled based on self-propagating reaction described in claim 1, it is characterised in that step Rapid one：Pretreatment removes sial, and immersion removal of impurities condition is：9.5~11.5, solid-to-liquid ratio is controlled 1 for leachate pH controls:20~1: 100g/mL, 30~80 DEG C of reaction temperature, 1~4h of reaction time.
  3. 3. according to a kind of method that zinc sulfide concentrates are handled based on self-propagating reaction described in claim 1, it is characterised in that step Rapid curing zinc concentrate powder is 1 with sodium peroxide mass ratio:0.5~1:5, it is desirable to material mixing and pressure are carried out in dry environment Real process.
  4. 4. according to a kind of method that zinc sulfide concentrates are handled based on self-propagating reaction described in claim 1, it is characterised in that step Rapid three leaching condition is：Reaction product is controlled 1 with water by solid-to-liquid ratio:20~1:100g/mL, 20~80 DEG C of extraction temperature, leaching Go out 0.5~2h of time.
  5. 5. according to a kind of method that zinc sulfide concentrates are handled based on self-propagating reaction described in claim 1, it is characterised in that step Rapid three by adding NaOH to control in leaching process leachate sodium hydroxide mass concentration be 0.1~5%, to ensure the efficient of zinc Dissolving is leached.
  6. 6. according to a kind of method that zinc sulfide concentrates are handled based on self-propagating reaction described in claim 1, it is characterised in that step Rapid four deposition condition：Lead is controlled 1 with vulcanized sodium mass ratio in solution:1~1:2,50~80 DEG C of precipitation temperature, the sedimentation time 1 ~4h.
  7. 7. according to a kind of method that zinc sulfide concentrates are handled based on self-propagating reaction described in claim 1, it is characterised in that adopt Initiation is ignited with the one or more in chemic ignition, combustion wave igniting, laser ignition, thermal explosion igniting or microwave ignition method certainly Sprawling reaction.
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