CN101613796B - Method for separating metal elements of zinc-nickel-cadmium-containing materials - Google Patents
Method for separating metal elements of zinc-nickel-cadmium-containing materials Download PDFInfo
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- CN101613796B CN101613796B CN2008100481824A CN200810048182A CN101613796B CN 101613796 B CN101613796 B CN 101613796B CN 2008100481824 A CN2008100481824 A CN 2008100481824A CN 200810048182 A CN200810048182 A CN 200810048182A CN 101613796 B CN101613796 B CN 101613796B
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Abstract
The invention relates to a method for separating metal elements of zinc-nickel-cadmium-containing materials. The method comprises the following process steps that: (1) zinc-nickel-cadmium materials are crushed, damply milled and fed into a rotary kiln, and the residence time and calcination temperature of the materials are controlled; (2) after calcinations is over, by adopting water leaching, cadmium sulfate solution is obtained through filtration and washing, and filter residue contains nickel and zinc; and (3) the filter residue is dried, added with reducing agents, damply milled and fed into the rotary kiln; the residence time and reduction temperature of the materials are controlled; during reduction, zinc is first reduced to metallic zinc which volatilizes and enters dust collection equipment and has contact with oxygen to form zinc oxide; and after reduction is over, residue contains nickel, while zinc is deposited in the dust collection equipment as zinc oxide, thus the separation of nickel and zinc is realized. The method adopts the mature rotary kiln for calcinations and reduction, is simple in operation and steady in running during the entire treatment process, and is low in treatment cost, thereby providing a novel way for separating valuable metals from zinc-nickel-cadmium-containing materials, copper-zinc-containing ash and the like and having broad industrial application prospects.
Description
(1) technical field
The invention belongs to field of metallurgy, be specifically related to a kind of separation method of metal elements of zinc-nickel-cadmium-containing materials.
(2) background technology
In the whole nation and even external, zinc-nickel-cadmium-containing materials is distributed more widely, and quantity is bigger, complicated component, and main three kinds of major metal elements of zinc-nickel-cadmium-containing, and exist with oxide form, its value is higher.At present, from this material, separate three kinds of valuable metal elements, adopt full wet processing: acid system and alkaline process.The process of acid system is as follows: add sulfuric acid and leach, filter, obtain the mixing solutions of sulfur acid nickel, zinc sulfate and Cadmium Sulphate, adopt the zinc dust precipitation cadmium, but parcel zinc is serious in the Spongy Cadmium that displaces, and brings difficulty to subsequent disposal, and remaining single nickel salt is difficult to separate with the zinc sulfate mixture, general method of extraction separating nickel and the zinc of adopting, higher owing to zinc content, bring difficulty to operation.The employing alkaline process is handled, and its process is as follows: hydro-oxidation sodium leaches, zinc oxide and sodium hydroxide reaction, generate sodium zincate, and nickel oxide and Cadmium oxide do not react with sodium hydroxide, through filtering, realized that zinc separates with NI-G, adopted sulfuric acid to leach, filtered and contain the NI-G slag, obtain sulfur acid cadmium and single nickel salt mixing solutions, with the sodium sulphite precipitation, control pH value, can realize that NI-G separates, but reagent consumption is excessive, product Cadmium Sulfide market is less, be worth lowlyer, the entire treatment cost is bigger.
Because there is above technical problem in traditional acid system and alkaline process, cause in the zinc-nickel-cadmium-containing materials metallic element not to be fully used.
(3) summary of the invention
Purpose of the present invention just provides a kind of separation method of metal elements of zinc-nickel-cadmium-containing materials.That this method has is simple to operate, stable equipment operation, overhaul of the equipments is convenient, production efficiency is high, environmental friendliness, low cost and other advantages.
The present invention includes following steps:
A, zinc-nickel-cadmium material add zinc sulfate and moisten mill together through pulverizing, and the zinc sulfate consumption is 0.5～3.5% of a zinc-nickel-cadmium-containing materials weight, roasting, and maturing temperature is 300～900 ℃, roasting time is 1～5h;
After b, roasting finish, go out 60～90 ℃ of extraction temperatures, extraction time 1～5h with water logging; Filter, wash, get cadmium sulfate solution and nickeliferous and zinc filter residue;
C, filter residue oven dry add reductive agent bituminous coal, smokeless brown coal or coke, and the reductive agent consumption is 10～50% of a zinc-nickel-cadmium-containing materials weight; Mix thoroughly, the profit mill, roasting reduction, reduction temperature are 1000～1300 ℃, the recovery time is 1～4h;
After d, reduction finished, slag charge was nickeliferous, and zinc then is deposited in the dust collection device with the zinc oxide form, got nickel-containing material and material containing zinc respectively.
Described material is a zinc-nickel-cadmium-containing materials.
Add additive zinc sulfate and moisten mill together when the zinc-nickel-cadmium material is pulverized, its effect is and the Cadmium oxide reaction that generation Cadmium Sulphate and zinc oxide by water logging, thereby make Cadmium oxide enter solution with the Cadmium Sulphate form, realize that cadmium separates with zinc.
Described reduction apparatus is a rotary kiln.
The present invention and sulfuric acid or sodium-hydroxide treatment relatively have simple to operate, stable equipment operation, overhaul of the equipments convenience, environmental friendliness, low cost and other advantages.Because the present invention adopts sophisticated rotary kiln baking and water logging to go out technology, avoided the cadmium dust pollution, adopt the rotary kiln reduction, the entire treatment process operation is simple and operate steadily, and additive is renewable, and the reductive agent source is wide, cheap, and the entire treatment cost is lower.Therefore, the present invention provides a kind of new method for realization valuable metals such as zinc-nickel-cadmium-containing materials or cupric zinc gray separate, and has the potential prospects for commercial application.
(4) description of drawings:
Fig. 1 is a technological process block-diagram of the present invention.
(5) embodiment;
Embodiment 1
1. the chemical ingredients of zinc-nickel-cadmium-containing materials is as follows: Cd 13.25～14.60%, Zn 25.01～26.88%, Ni 4.54～4.69%.
2. processing condition: zinc-nickel-cadmium-containing materials is through pulverizing, and material～0.074mm accounts for 80%, adds Zincomed, its consumption is 0.5% of a zinc-nickel-cadmium-containing materials weight, and the profit mill passes through screw feeder, enter rotary kiln, 300 ℃ of control material maturing temperatures, time 1h, after roasting finishes, adopt water logging to go out 60 ℃ of extraction temperatures, extraction time 1h is after leach finishing, after filtration and washing, obtain cadmium sulfate solution, the nickeliferous and zinc of filter residue.Filter residue is through oven dry, and adding smokeless brown coal amount is 10% of zinc-nickel-cadmium-containing materials weight, the profit mill, pass through screw feeder, enter rotary kiln, 1000 ℃ of control residence time of material 1h and reduction temperatures, zinc at first is reduced into metallic zinc in the reduction process, volatilize with gaseous state, enter harvest equipment and contact generation zinc oxide with oxygen, after reduction finished, slag was nickeliferous, zinc in dust collection device, so just realizes that nickel separates with zinc with deposition of zinc oxide.With this understanding, the cadmium yield is 97.68%, the zinc yield is 96.09%, the nickel yield is 97.73%.
Embodiment 2
1. the chemical ingredients of zinc-nickel-cadmium-containing materials is as follows: Cd 14.64～15.98%, Zn 26.77～28.01%, Ni 4.70～4.85%.
2. processing condition: zinc-nickel-cadmium-containing materials is through pulverizing, and material～0.074mm accounts for 80%, and adding the Zincomed amount is 3.5% of zinc-nickel-cadmium-containing materials weight, the profit mill by screw feeder, enters rotary kiln, 650 ℃ of control residence time of material 3h and maturing temperatures after roasting finishes, adopt water logging to go out, 70 ℃ of extraction temperatures, extraction time 3h is after leaching finishes, through filtering and washing, obtain cadmium sulfate solution, the nickeliferous and zinc of filter residue.Filter residue is through oven dry, and adding the bituminous coal amount is 40% of zinc-nickel-cadmium-containing materials weight, the profit mill, pass through spiral pusher, enter rotary kiln, 1250 ℃ of control residence time of material 3h and reduction temperatures, zinc at first is reduced into metallic zinc in the reduction process, volatilize with gaseous state, enter harvest equipment and contact generation zinc oxide with oxygen, after reduction finished, slag was nickeliferous, zinc in dust collection device, so just realizes that nickel separates with zinc with deposition of zinc oxide.With this understanding, the cadmium yield is 98.11%, the zinc yield is 97.55%, the nickel yield is 96.70%.
Embodiment 3
1. the chemical ingredients of zinc-nickel-cadmium-containing materials is as follows: Cd 14.81～14.90%, Zn 26.57～28.17%, Ni 4.60～4.74%.
2. processing condition: zinc-nickel-cadmium-containing materials is through pulverizing, and material～0.074mm accounts for 80%, and adding the Zincomed amount is 2% of zinc-nickel-cadmium-containing materials weight, the profit mill by screw feeder, enters rotary kiln, 800 ℃ of control residence time of material 5h and maturing temperatures after roasting finishes, adopt water logging to go out, 80 ℃ of extraction temperatures, extraction time 2h is after leaching finishes, through filtering and washing, obtain cadmium sulfate solution, the nickeliferous and zinc of filter residue.Filter residue is through oven dry, and adding the coke amount is 30% of zinc-nickel-cadmium-containing materials weight, the profit mill, pass through screw feeder, enter rotary kiln, 1150 ℃ of control residence time of material 1h and reduction temperatures, zinc at first is reduced into metallic zinc in the reduction process, volatilize with gaseous state, enter dust collection device and contact generation zinc oxide with oxygen, after reduction finished, slag was nickeliferous, zinc in dust collection device, so just realizes that nickel separates with zinc with deposition of zinc oxide.With this understanding, the cadmium yield is 98.01%, the zinc yield is 97.27%, the nickel yield is 96.85%.
Embodiment 4
1. the chemical ingredients of zinc-nickel-cadmium-containing materials is as follows: Cd 15.01～16.23%, Zn 26.56～27.38%, Ni 4.75～4.87%.
2. processing condition: zinc-nickel-cadmium-containing materials is through pulverizing, and material～0.074mm accounts for 80%, and adding the Zincomed amount is 3.5% of zinc-nickel-cadmium-containing materials weight ratio, the profit mill by screw feeder, enters rotary kiln, 900 ℃ of control residence time of material 5h and maturing temperatures after roasting finishes, adopt water logging to go out, 90 ℃ of extraction temperatures, extraction time 5h is after leaching finishes, through filtering and washing, obtain cadmium sulfate solution, the nickeliferous and zinc of filter residue.Filter residue is through oven dry, and adding smokeless brown coal amount is 50% of zinc-nickel-cadmium-containing materials weight, the profit mill, pass through spiral pusher, enter rotary kiln, 1300 ℃ of control residence time of material 4h and reduction temperatures, zinc at first is reduced into metallic zinc in the reduction process, volatilize with gaseous state, enter dust collection device and contact generation zinc oxide with oxygen, after reduction finished, slag was nickeliferous, zinc in dust collection device, so just realizes that nickel separates with zinc with deposition of zinc oxide.With this understanding, the cadmium yield is 98.47%, the zinc yield is 97.82%, the nickel yield is 97.66%.
Claims (1)
1. the separation method of a metal elements of zinc-nickel-cadmium-containing materials, it is characterized in that may further comprise the steps: a, zinc-nickel-cadmium material are through pulverizing, add zinc sulfate and moisten mill together, the zinc sulfate consumption is the 0.5-3.5% of zinc-nickel-cadmium-containing materials weight, roasting, maturing temperature is 300～900 ℃, and roasting time is 1～5h; After b, roasting finish, go out 60～90 ℃ of extraction temperatures, extraction time 1～5h with water logging; Filter, wash, get cadmium sulfate solution and nickeliferous and zinc filter residue; C, filter residue oven dry add reductive agent bituminous coal, smokeless brown coal or coke, and the reductive agent consumption is 10～50% of a zinc-nickel-cadmium-containing materials weight; Mix thoroughly, the profit mill, roasting reduction, reduction temperature are 1000～1300 ℃, the recovery time is 1～4h; After d, reduction finished, slag was nickeliferous, and zinc then is deposited in the dust collection device with the zinc oxide form, got nickel-containing material and material containing zinc respectively.
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| CN2008100481824A CN101613796B (en) | 2008-06-24 | 2008-06-24 | Method for separating metal elements of zinc-nickel-cadmium-containing materials |
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| CN2008100481824A CN101613796B (en) | 2008-06-24 | 2008-06-24 | Method for separating metal elements of zinc-nickel-cadmium-containing materials |
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| CN101613796B true CN101613796B (en) | 2011-06-22 |
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| CN102031366B (en) * | 2010-12-15 | 2012-11-28 | 浙江海尚环境科技有限公司 | Extractive preparation method of high-purity zinc oxide |
| CN103695635B (en) * | 2013-12-13 | 2015-04-15 | 来宾华锡冶炼有限公司 | Method for treating high-iron and multi-metal zinc concentrate |
| CN105331821A (en) * | 2015-11-20 | 2016-02-17 | 金川集团股份有限公司 | Recycling method for nickel in nickel-cadmium-zinc slag |
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