CN1022578C

CN1022578C - Treatment and use of waste residue and waste liq. from Cd-Ni cell

Info

Publication number: CN1022578C
Application number: CN89105850A
Authority: CN
Inventors: 于秀兰; 杨家玲; 王金英
Original assignee: Individual
Current assignee: Individual
Priority date: 1989-12-30
Filing date: 1989-12-30
Publication date: 1993-10-27
Anticipated expiration: 2004-12-30
Also published as: CN1053092A

Abstract

The present invention relates to the treatment and the use of waste residue and waste liquid from cadmium-nickel cells, which belongs to environmental protection and waste recovery. A process comprises the following steps: (1) the waste residue of the cells is pulverized and dried; (2) the waste residue of the cells is roasted and converted into oxides; (3) the oxides are dipped by acid, the cadmium is converted into cadmium ions under the condition of the pH value between 4.5 and 5.5, and nickel and iron still remain in the settlement residue; (4) the cadmium ions are converted into cadmium carbonate precipitate and recovered; (5) the settlement residue is treated by acid, and the nickel and the iron are converted into nickel ions and iron ions under the condition of the pH value less than 2. Subsequently, the pH value of the solution is regulated to 3.5 to 5 so as to remove the iron hydroxide precipitate, and finally, the nickel is recovered by nickel salt.

Description

Treatment and use of waste residue and waste liq. from Cd-Ni cell

The present invention relates to environment protection, relate in particular to the processing and the utilization that contain cadmium, nickel trade waste.

Because cadmium nickel battery excellent property, of many uses, its demand grows with each passing day.Correspondingly, the cadmium nickel battery waste residue is also increasing, and heavy-metal pollution water source and soil that these are harmful to HUMAN HEALTH are endangering existent environment of people directly or indirectly, and it is administered has become the current important topic that needs to be resolved hurrily.Some industrially developed country have carried out research already and have put into practice this problem, it is documented, and U.S., moral, day, Soviet Union and China, the main methods of present employing is as follows.The U.S.: based on hydrogen-metal smelting method, pyrometallurgical smelting method, high temperature distillation under vacuum, the advantage of these methods is that pollution-free generation, raw material are easy to get, and its weak point is that technical qualification require height, equipment is complicated, processing cost is higher.West Germany: based on the step-by-step replacement precipitation separation, this method with aluminium powder cementation cadmium, is used aluminium powder cementation nickel earlier again behind the cadmium separation, and the advantage of this method is pollution-free.Equipment is simple, shortcoming be big with the aluminium amount, cost is high and the condition of separation by displacement is difficult to grasp.Japan: based on electrolytic process, the advantage of this method is pollution-free, and reaction end is controlled easily, and shortcoming is that current consumption is big, and isolating cadmium, nickel purity are difficult to guarantee.The Soviet Union: based on ion exchange method, promptly use the nickel ion in diazanyl-dicarboxyl acid type ion-exchanger adsorbent solution, cadmium, nickel are separated, and this method only should be used for dilute solution, then must have the drawback that exchange capacity is excessive, the regeneration period is too short to nickel, the cadmium salt soln of high density.

Several cadmiums-nickel waste residue treatment process that China adopts at present is as follows: (one) ammonium salt leaching method: earlier with cadmium-nickel waste residue roasting, separate, reclaim with ammonium nitrate solution classification leaching again, and the low and non-secondary pollution of this method cost, but its rate of recovery only is 20～30%.(2) a sulfuration bed electrolytic process: with the metal shot copper is negative electrode, makes metal ion in cathodic reduction, but makes difficulty because of granular negative electrode, still fails to drop into industrial applications.(3) organic reagent extraction process: cadmium-nickel waste residue is got with acidleach, and with the extraction of N-503 reagent, water carries out back extraction to containing the cadmium organic phase more then; Organic phase in raffinate adds the form recovery nickel of sodium hydroxide with nickel hydroxide.This method rate of recovery can reach more than 99%, but costs an arm and a leg, and is not suitable for industrial applications.(4) sulfurization-precipitation method: cadmium-nickel waste residue with the acid dissolving, is fed hydrogen sulfide Cadmium Sulfide is separated out, and concentrating filter liquor, cooling make nickel ion with NiSO ₄6H ₂The O crystal is separated out, and this method separation rate height and cost are low, but H ₂S breath malodor, atmosphere pollution.

The improvement processing method of the cadmium nickel battery waste residue that the present invention aims to provide a kind of pollution-free generation, equipment is simple, easy and simple to handle, with low cost, the rate of recovery is high, the recovery product purity is high.

The treatment process of cadmium nickel battery waste residue of the present invention is made up of following steps:

1. pulverize, drying: with cadmium-nickel refuse battery mechanical disintegration powdered, oven dry then.

2. roasting, make into oxide compound:, make into oxide compound with 1. gained powder roasting in atmosphere of step.Its reaction is as follows:

3. with leaching, isolate cadmium: with step 2. the gained powdered oxide leach with dilute acid soln, and the pH value of this solution is controlled between 4.5～5.5, make Cadmium oxide be converted into cadmium ion and enter solution, and nickel and impurity iron are still stayed in the sediment, react as follows:

Then with known technology with sediment and solution separating.

4. reclaim cadmium: 3. add the soluble carbon hydrochlorate or feed carbonic acid gas in the solution of gained in step, cadmium ion is separated out with the cadmium carbonate precipitation, its reaction is as follows:

To precipitate cadmium carbonate and solution separating, reclaim, and perhaps the cadmium carbonate high-temperature roasting be become Cadmium oxide to reclaim, or be converted into other required compounds.

5. deironing, reclaim nickel: when iron concentration is not high, 3. add mineral acid commonly used in the sediment of gained in step, to pH value of solution less than 2, make nickel, ferriferous oxide be converted into nickel ion and iron ion and enter solution, its reaction down:

After discarding insoluble sludge, pH value of solution is adjusted to 3.5～5, make iron ion become the ironic hydroxide precipitation, and nickel ion still is retained in the solution, will precipitate and solution separating with known technology, its reaction is as follows:

When iron concentration is very high, very easy formation colloidal ironic hydroxide, so should and blast under the conditions of air in heating, it is 3～4.5 that pH slowly is adjusted to pH less than 2 solution, and iron ion is separated out with the double salt form of granulous iron, for example:

To contain solution concentration, the cooling of nickel salt, the nickel salt that will contain crystal water is separated out, is reclaimed.

Embodiment and effect:

Example 1, get cadmium, nickel content and be respectively 31.2% and 9.6% cadmium nickel battery residue, by above-mentioned art breading, cadmium reclaims with the Cadmium oxide form, and its purity is 98.3%, and the rate of recovery is 89%; Nickel reclaims with the nickelous nitrate form, and its purity is 98.1%, and the rate of recovery is 83.1%.

Example 2, get example 1 sample, adopt same process, just change acid into hydrochloric acid or sulfuric acid, and reclaim nickel with the form of nickelous chloride or single nickel salt, its rate of recovery is all identical substantially with product purity as a result, proves that the acid relation of its rate of recovery and use is little, and key is condition control.

Example 3, get cadmium, nickel content and be respectively 5.76%, 47.1% sample, handle with same process and reclaim result: the rate of recovery 88.5% of cadmium, the rate of recovery 81% of nickel.What confirm this technology is stable aspect the rate of recovery.Additional disclosure, the above-mentioned rate of recovery does not comprise the nickel salt in the reusable mother liquor.

Cadmium nickel battery waste residue recovery processing technique of the present invention and equipment are all very simple, and reagent source is wide, and is with low cost, and rate of recovery height, reclaim the product purity height, and the value of promoting the use of is arranged.

For the improvement of ickel-cadmium cell waste liquid, then directly 3., the pH of solution is transferred to 4.5～5.5, so that cadmium ion is separated with the sediment nickel iron compound from step.Below reclaim the technology of cadmium and deironing recovery nickel and step 4., step is 5. identical.

Claims

1, a kind of improvement of ickel-cadmium cell waste residue and liquid and utilize method, it is characterized in that this method is made up of following steps: powdered oxide or battery waste liquid that (1) makes the battery waste residue leach with dilute acid soln, and the pH value of this solution is controlled between 4.5～5.5, make Cadmium oxide be converted into cadmium ion and enter solution, nickel and iron contamination are still stayed in the precipitation, then with sediment and solution separating; (2) in the solution of step (1) gained, add soluble carbon hydrochlorate or feeding carbonic acid gas, cadmium ion is settled out with cadmium carbonate, cadmium carbonate and solution separating are reclaimed; (3) nickel is reclaimed in deironing, in the sediment of step (1) gained, add mineral acid commonly used, to pH value of solution less than 2, make nickel, ferriferous oxide be converted into nickel ion and iron ion and enter solution, discard insoluble sludge after, pH value of solution is adjusted to 3.5～5, make iron ion become the ironic hydroxide precipitation, and nickel ion still is retained in the solution, will precipitate and solution separating, to contain solution concentration, the cooling of nickel salt, the nickel salt that will contain crystal water is separated out, is reclaimed.

2, the improvement of ickel-cadmium cell waste residue and liquid according to claim 1 and utilize method is characterized in that: before the leaching step, the battery waste residue is broken into powder and oven dry earlier, and roasting makes into oxide compound in atmosphere then.

3, the improvement of ickel-cadmium cell waste residue and liquid according to claim 1 and utilize method is characterized in that: by the cadmium carbonate that reclaims in the step (2), can become Cadmium oxide to reclaim or be converted into other cadmic compound to reclaim through high-temperature roasting.

4, ickel-cadmium cell waste residue and liquid according to claim 1 has improvement and utilizes method, it is characterized in that: in the deferrization process of step (3), when iron concentration is very big, should and blast under the air conditions in heating, pH overflow less than 2 solution to be adjusted to pH slowly be 3～4.5, iron ion is separated out with the double salt form of granulous iron.