CN101550485B - Oxidative pressure acid leaching method for processing purified waste residue in zinc hydrometallurgy process - Google Patents

Oxidative pressure acid leaching method for processing purified waste residue in zinc hydrometallurgy process Download PDF

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CN101550485B
CN101550485B CN2008101032610A CN200810103261A CN101550485B CN 101550485 B CN101550485 B CN 101550485B CN 2008101032610 A CN2008101032610 A CN 2008101032610A CN 200810103261 A CN200810103261 A CN 200810103261A CN 101550485 B CN101550485 B CN 101550485B
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zinc
waste residue
purified waste
zinc hydrometallurgy
copper
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CN2008101032610A
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Chinese (zh)
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CN101550485A (en
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张广积
韩宝玲
方兆珩
杨超
禹耕之
毛在砂
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中国科学院过程工程研究所
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Abstract

The invention relates to an oxidative pressure acid leaching method for processing the purified waste residue generated in the zinc hydrometallurgy process. The method comprises the following steps: the copper-cadmium residue generated during the copper-cadmium removal and the nickel-cobalt residue generated during the nickel-cobalt removal is replaced, i.e., the waste residue from the purification of zinc is leached with sulfuric acid in an acid-resistant high pressure autoclave under the condition that the high-pressure oxygen is introduced in. Compared with the commonly-used direct acid solution method, the method has the advantages of high leaching rate, high processing speed, no poisonous and harmful gas and iron removal during the leaching process, and the like, can obviously improve the prior process conditions, reduce the pollution and the production cost and also provides a new method for processing the other waste residues containing heavy metal.

Description

Oxidative pressure acid leaching method for processing purified waste residue in zinc hydrometallurgy process

Technical field

Heavy metal in the purification slag that the present invention relates to produce in the oxygen pressure acidleach solving zinc wet smelting process, be specially adapted to dissolve and reclaim copper-cadmium slag, the nickel cobalt slag that produces in the zinc hydrometallurgy, can also be applied to dissolve electron wastes, other heavy metal melting waste slags of containing heavy metal.

Background technology

The zinc wet smelting process is mainly leached by the sulfuric acid of mineral baked for producing calcining, calcining and several steps such as leach liquor electrodeposition production metallic zinc is formed, since in the employed zinc sulfide ore often association other metals such as copper, cadmium, cobalt etc. are arranged, therefore outer these foreign ions that also contain dezincify in the leach liquor, be carrying out smoothly of metallic zinc electrolytic deposition process after guaranteeing, need before electrodeposition, carry out removal of impurities leach liquor.Existing impurity-removing method is to adopt zinc dust precipitation, and displacement generally is divided into two sections, and first section displacement mainly is the copper removal cadmium, and the waste residue of generation is called copper-cadmium slag, and second section displacement purpose is to remove the nickel and the cobalt of trace, and the waste residue of generation is called nickel cobalt slag.Metals such as the cinder ladle containing metal zinc that displacement purge produces, copper, cadmium, cobalt, iron can be used as metals such as raw material production copper, cadmium, cobalt, and reclaim zinc wherein.

Treatment process at this class slag is to use earlier sulfuric acid dissolution at present, make and dissolve in vitriolic metallic zinc, cadmium, the cobalt dissolving enters solution, by means such as cementations different metal separation and Extraction is wherein come out then, because metallic copper is insoluble to dilute sulphuric acid, metallic copper is retained in the slag, handles by pyrometallurgical smelting.In this process, the sulfuric acid leaching that zinc purifies slag is a committed step, but there is significant disadvantages in existing direct dilute sulphuric acid dissolution method, at first owing to can produce a large amount of hydrogen in the process of sulfuric acid dissolution metal, the inflammable and explosive characteristic of hydrogen makes operating process very dangerous, also can generate hypertoxic gas hydrogen arsenide and stibine with this understanding and be mixed in elements such as arsenic in the slag, antimony, the serious harm workers ' health, and environment worked the mischief; Secondly since slag store up that part metals copper is oxidized into cupric oxide in the process, can be entered in the leach liquor by sulfuric acid dissolution, not only make the treating processes of leach liquor complicated more, and the metallic copper content in the slag reduced, influence pyrogenic attack efficient; Owing in the sulfuric acid leaching process, the iron in the slag also can enter solution in addition, so the necessary deironing of leach liquor, has increased treatment step.

It is to leach the metal waste residue with sulfuric acid under high pressure oxygen existence condition that oxygen is pressed pickling process, because the oxygenizement of high pressure oxygen, in leaching process, do not produce hydrogen and other toxic gases, and the whole heavy metals that comprise metallic copper are dissolved in the solution fast, and the iron in the leach liquor is oxidized to ferric iron, forms precipitation under heating condition, from solution, remove easily, reduce follow-up deironing burden, do not contain in the leached mud of formation and easily be dissolved with malicious heavy metal element, directly landfill disposal.All metals extract by wet method in the oxygen pressure acidleach zinc replacement slag technology, have cancelled the pyrogenic attack step, have simplified flow process.To sum up, utilize oxygen to press pickling process to handle the purification slag that produces in the zinc wet smelting process, have advantages such as processing efficiency height, process cost are low, simple and easy to do, non-secondary pollution.

Aspect the processing of zinc replacement slag, domestic report is more, generally take direct method of pickling, carrying out selectivity by controlling acidity leaches, tend in the leaching process produce hypertoxic arsine gas, have patent to adopt the method for interpolation oxygenant to strengthen and leach (Chinese patent, application number 99115282.4), but need in operating process, add the strong oxidizer Sodium Persulfate, increase that operation steps, flow process are long, the cobalt rate of recovery is low.Only there is the equipment patent (United States Patent (USP), application number 94101927.6) of a small amount of employing pyrogenic attack technology external hydrometallurgy slag processing aspect at present.Press processing hydrometallurgy waste residue technical elements at oxygen, have with this patent and similarly handle copper anode mud patent (Chinese patent, application number 200510011022.9), but handle the waste residue different in kind with the oxygen platen press.

Summary of the invention

Purpose of the present invention provides a kind of oxygen is pressed the valency heavy metal in the pickling process leaching zinc hydrometallurgy purified waste residue technology of utilizing, and this technology has advantages such as processing efficiency height, process cost are low, simple and easy to do, non-secondary pollution.

For achieving the above object, the present invention takes following design: zinc is purified the ground-slag comminution size mixing after thin, add in the acidproof autoclave, air tight condition adds a certain amount of sulfuric acid down, feed high pressure oxygen or pressurized air then, heating makes valuable metal dissolvings such as zinc in the waste residue, copper, cadmium, cobalt under high pressure oxygen and vitriolic acting in conjunction, high pressure oxygen and heating condition make the oxidation of divalent that leaches in the slag to be trivalent and hydrolysis precipitation takes place, and removes from leach liquor.

A kind of technology of oxidative pressure acid leaching method for processing purified waste residue in zinc hydrometallurgy process, it is characterized in that: zinc hydrometallurgy purified waste residue contains copper, zinc, cadmium, cobalt and iron, be difficult to be dissolved in fully dilute sulphuric acid, be divided into two kinds, a kind of is one section copper-cadmium slag that purifies generation, and another kind is two sections and purifies the nickel cobalt slags that produce; Technology mainly by fine grinding size mixing, pressure oxidation sulfuric acid dissolution two portions form, concrete steps are: (1) fine grinding is sized mixing the stage, and zinc hydrometallurgy purified waste residue is milled to-100 orders, and adds water and size mixing; (2) the pressure oxidation sulfuric acid dissolution stage, zinc hydrometallurgy purified waste residue after sizing mixing is added in the reactor, add sulfuric acid, in reactor, charge into high pressure oxygen, improve temperature, valuable metal is dissolved fully, the oxidized formation precipitation of iron, described reactor adopts acidproof autoclave, and the initial gauge pressure in inflation back is 0.1-1.0MPa, temperature is controlled at 85~140 ℃, and the reaction times was controlled at 1-3 hour.

Former slip concentration is 100-400g/L, uses sulfuric acid concentration to be 200-500g/L, and the control final pH is 0.

Zinc hydrometallurgy purified waste residue is the copper-cadmium slag that is produced by zinc dust precipitation copper cadmium in the zinc wet smelting process.

Zinc hydrometallurgy purified waste residue is the nickel cobalt slag that is produced by zinc dust precipitation nickel cobalt in the zinc wet smelting process.

High pressure oxygen is filled in institute in the step (2) replace with pressurized air.

Realize that step of the present invention is: (1) with waste residue pulverizing, fine grinding, size mixing to solids concn be 100-400g/L; (2) material after will sizing mixing adds in the autoclave, adds the sulfuric acid of 200g/L-500g/L, and controlled temperature is at 85-140 ℃, and pH is 0; (3) feed high pressure oxygen or pressurized air, adjusting pressure is gauge pressure 0.1-1.0MPa, leaches discharging after 1-3 hour; (4) carry out solid-liquid separation, zinc, copper, cadmium, cobalt total content remaining in the leached mud are lower than 0.5%, and impurity iron content is lower than 0.1g/L in the solution.

Zinc purifies slag oxygen and presses the main chemical reactions formula in the leaching process as follows:

2Zn+2H 2SO 4+O 2→2ZnSO 4+2H 2O

2Cd+2H 2SO 4+O 2→2CdSO 4+2H 2O

2Co+2H 2SO 4+O 2→2CoSO 4+H 2O

4FeSO 4+O 2+2H 2SO 4→2Fe 2(SO 4) 3+2H 2O

Beneficial effect of the present invention is: purify slag because adopt oxygen to press pickling process to handle hydrometallurgy zinc, can accelerate the leaching velocity of metals such as zinc in the slag, cadmium, cobalt, improve leaching yield; Owing in autoclave, adopt oxidation acid leaching, do not produce dangerous obnoxious flavour such as hydrogen and hydrogen arsenide and stibine etc. in the leaching process substantially, reduced the injury of operational danger and obnoxious flavour to the workman; The oxidized formation ferric iron of ferrous iron in the leach liquor, and the formation of hydrolysis at high temperature precipitation are removed from leach liquor, have reduced the deironing burden in the leach liquor treating processes; The effect of oxygen can make that metallic copper is directly entered leach liquor by sulfuric acid dissolution in the copper-cadmium slag, has reduced the step of Treatment of Copper slag.Adopt oxygen to press and leach to replace existing direct pickling process that treatment scheme is simplified, reduce facility investment, reduce and pollute, improve metal recovery rate.

Description of drawings:

Fig. 1 is the process flow diagram of oxidative pressure acid leaching method for processing purified waste residue in zinc hydrometallurgy process of the present invention.

Wherein: the A purified waste residue B ball mill C pond of sizing mixing

The acidproof autoclave E of D industrial sulphuric acid F tonnage oxygen

Specific embodiment

Embodiment 1: the copper-cadmium slag that produces in the zinc hydrometallurgy scavenging process, cupric 10%, cadmium 15%, zinc 20%, cobalt 0.1%, iron 6%.

With block slag fragmentation, be milled to-100 orders, add water and size mixing, add in the 2L lining titanium autoclave, add 300g/L sulfuric acid, airtight; Feeding industrial oxygen to gauge pressure is 0.4MPa, stirs and is warming up to 120 ℃, insulation reaction 120min.

The leaching yield of copper, zinc, cadmium is all more than 99.5%, and copper content remaining in the slag is less than 0.2%, and iron level is lower than 0.1g/L in the leach liquor, can directly carry out the valuable metal separation and Extraction without deironing.

Embodiment 2: the nickel cobalt slag that produces in the hydrometallurgy scavenging process, and contain zinc 40%, cadmium and cobalt and be 0.1%, iron is 6%.

With the slag fragmentation, levigate extremely-100 orders add water and size mixing, and add in the 2L lining titanium autoclave, add 300g/L sulfuric acid, and are airtight; Feeding industrial oxygen to gauge pressure is 0.4MPa, stirs and is warming up to 120 ℃, insulation reaction 120min.

The leaching yield of zinc, cadmium, cobalt is all more than 99.9%, and remaining zinc cadmium cobalt heavy metal total content is less than 0.1% in the slag, and iron level is lower than 0.1g/L in the leach liquor, can directly carry out the valuable metal separation and Extraction without deironing.

Embodiment 3: the copper-cadmium slag that produces in the zinc hydrometallurgy scavenging process, cupric 11%, cadmium 12%, zinc 26%, iron 7%.

With block slag fragmentation, be milled to-100 orders, add water and size mixing, add in the 2L lining titanium autoclave, add 300g/L sulfuric acid, airtight; Feeding industrial oxygen to gauge pressure is 0.2MPa, stirs and is warming up to 130 ℃, insulation reaction 150min.The leaching yield of copper, zinc, cadmium is all more than 99.5%, and extraneous copper content is less than 0.1% in the slag, and iron level is lower than 0.1g/L in the leach liquor.

Claims (5)

1. the technology of oxidative pressure acid leaching method for processing purified waste residue in zinc hydrometallurgy process, it is characterized in that: zinc hydrometallurgy purified waste residue contains copper, zinc, cadmium, cobalt and iron, be difficult to be dissolved in fully dilute sulphuric acid, be divided into two kinds, a kind of is one section copper-cadmium slag that purifies generation, and another kind is two sections and purifies the nickel cobalt slags that produce; Technology mainly by fine grinding size mixing, pressure oxidation sulfuric acid dissolution two portions form, concrete steps are: (1) fine grinding is sized mixing the stage, and zinc hydrometallurgy purified waste residue is milled to-100 orders, and adds water and size mixing; (2) the pressure oxidation sulfuric acid dissolution stage, zinc hydrometallurgy purified waste residue after sizing mixing is added in the reactor, add sulfuric acid, in reactor, charge into high pressure oxygen, improve temperature, valuable metal is dissolved fully, the oxidized formation precipitation of iron, described reactor adopts acidproof autoclave, and the initial gauge pressure in inflation back is 0.1-1.0MPa, temperature is controlled at 85~140 ℃, and the reaction times was controlled at 1-3 hour.
2. the technology of oxidative pressure acid leaching method for processing purified waste residue in zinc hydrometallurgy process according to claim 1, it is characterized in that: former slip concentration is 100-400g/L, uses sulfuric acid concentration to be 200-500g/L, the control final pH is 0.
3. the technology of oxidative pressure acid leaching method for processing purified waste residue in zinc hydrometallurgy process according to claim 1 is characterized in that: zinc hydrometallurgy purified waste residue is the copper-cadmium slag that is produced by zinc dust precipitation copper cadmium in the zinc wet smelting process.
4. the technology of oxidative pressure acid leaching method for processing purified waste residue in zinc hydrometallurgy process according to claim 1 is characterized in that: zinc hydrometallurgy purified waste residue is the nickel cobalt slag that is produced by zinc dust precipitation nickel cobalt in the zinc wet smelting process.
5. the technology of oxidative pressure acid leaching method for processing purified waste residue in zinc hydrometallurgy process according to claim 1 is characterized in that: high pressure oxygen is filled in institute in the step (2) replace with pressurized air.
CN2008101032610A 2008-04-02 2008-04-02 Oxidative pressure acid leaching method for processing purified waste residue in zinc hydrometallurgy process CN101550485B (en)

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CN101994008B (en) * 2010-11-11 2012-07-04 西北矿冶研究院 Novel process for separating zinc and cobalt from nickel and cobalt slag from zinc smelting and purification
CN102492849A (en) * 2011-12-28 2012-06-13 株洲冶炼集团股份有限公司 Wet treatment method of cadmium slag
CN102876903A (en) * 2012-10-08 2013-01-16 来宾华锡冶炼有限公司 Direct acidity oxygen pressure leaching treatment method of crude tin copper removal residues
CN104911349A (en) * 2015-04-29 2015-09-16 云南锡业股份有限公司 Method for one segment leaching recovery of valuable metals in zinc system copper cadmium slag
CN105039739A (en) * 2015-08-12 2015-11-11 葫芦岛锌业股份有限公司 Method for comprehensively recovering cobalt and zinc from purified cobalt residues of zinc hydrometallurgy
CN105087949A (en) * 2015-08-26 2015-11-25 昆明理工大学 Method for selectively leaching cobalt, nickel and copper in converting slag of converter
CN105400960A (en) * 2015-11-20 2016-03-16 金川集团股份有限公司 Method for pressurizing cobalt-rich copper matte to leach out nickel and cobalt and remove iron
CN105771602A (en) * 2016-04-25 2016-07-20 云南煜锜环保科技有限公司 Strong-oxidation absorption purification process for arsenic hydride containing waste gas
CN105950875A (en) * 2016-05-09 2016-09-21 钟庆文 Processing method for purified cobalt residues of zinc and manganese hydrometallurgy
CN105821216A (en) * 2016-05-23 2016-08-03 西部矿业股份有限公司 Method for leaching zinc from purification copper, cadmium, cobalt and nickel slag of zinc hydrometallurgy
CN106868295B (en) * 2016-12-27 2018-07-31 河南豫光锌业有限公司 The starting method of hematite process iron removal system in a kind of Zinc hydrometallurgy process
CN107287432B (en) * 2017-06-23 2019-11-29 贵州省兴安环保科技有限公司 A method of recycling zinc, copper, cadmium from the copper-cadmium slag of zinc hydrometallurgy
CN107619945A (en) * 2017-09-12 2018-01-23 贵州省冶金科学研究室 A kind of method that high cobalt Zinc residue removes cobalt
CN108048659B (en) * 2017-11-22 2020-02-14 深圳市中金岭南有色金属股份有限公司丹霞冶炼厂 Leaching method of zinc replacement slag
CN108929954A (en) * 2018-05-31 2018-12-04 西北矿冶研究院 A method of the high efficiente callback zinc from zinc leaching residue
CN109439916A (en) * 2018-11-26 2019-03-08 云南锡业研究院有限公司 A kind of method of the wet-treating containing cadmium fumes

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