CN100999371A - Treatment method of nickel cadmium calcium battery mud - Google Patents
Treatment method of nickel cadmium calcium battery mud Download PDFInfo
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- CN100999371A CN100999371A CN 200710019572 CN200710019572A CN100999371A CN 100999371 A CN100999371 A CN 100999371A CN 200710019572 CN200710019572 CN 200710019572 CN 200710019572 A CN200710019572 A CN 200710019572A CN 100999371 A CN100999371 A CN 100999371A
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Abstract
This invention relates to a Nickel-cadmium batteries sludge treatment methods, including the following steps: a. through acidification to remove calcium and iron, get calcium sulfate; b. Ni and Cd separation, get cadmium sulfide products; C. sediment of nickel , gain carbonic nickel, carbonic nickel through calcination to obtain nickel oxide product, and the filtrate through concentration and evaporation to gain sodium sulfate products. The advantages of this invention is to recover the nickel, Cd and calcium from the nickel-cadmium batteries calcium in the battery production process, and the production process pollution-free, with high social and economic benefits.
Description
Technical Field
The invention relates to an environment-friendly recovery method of waste metal, in particular to an environment-friendly recovery and utilization method for treating nickel-cadmium-calcium battery sludge generated after a battery production enterprise produces a nickel-cadmium-containing battery.
Background
Most of the power sources for portable electronic products in use today use rechargeable nickel-cadmium or nickel-hydrogen batteries, and these battery companies produce large amounts of sludge (such as tin-free batteries) containing cadmium, nickel, etc. which are harmful to the environment during their production. The components of the sludge comprise 50-70% of water, 3-4% of nickel, 6-9% of cadmium and 8-15% of calcium, silicon, iron and the like. If the sludge generated in the production process is not effectively treated, the environment is seriously polluted.
Disclosure of Invention
The invention aims at resource utilization and pollution prevention and control, and provides a method for treating nickel-cadmium-calcium battery sludge, which can perform environment-friendly treatment on battery sludge which is a highly pollution source generated in the production process of battery production enterprises, and can convert the sludge into nickel and cadmium products with economic value after treatment.
The technical scheme for realizing the purpose is as follows:
the treatment method of the nickel-cadmium-calcium battery sludge comprises the following steps:
a, acidifying to remove calcium and iron, mixing battery sludge and water to obtain slurry, slowly adding sulfuric acid and stirring until the pH value is 3-4, slowly adding hydrogen peroxide until the iron content in the solution meets the requirement, heating to 70-85 ℃, filtering, washing filter residues with water until the washing solution is neutral, and drying the filter residues to obtain an iron-containing calcium sulfate product;
b, separating cadmium and nickel, adding the filtrate obtained in the step a into a cadmium precipitation tank, introducing hydrogen sulfide and adding sodium sulfide according to the cadmium content, wherein the hydrogen sulfide is added to react with cadmium sulfate to generate dilute sulfuric acid until the pH value of the solution is 1-1.5, cadmium sulfide does not react with sulfuric acid in the acid, and sodium sulfide reacts with cadmium sulfate to generate cadmium sulfide precipitation at the pH value. Fully stirring for 1-5 hours, filtering after the reaction is finished, washing off the nickel-containing solution attached to the filter residue by using water, and drying the filter residue to obtain a cadmium sulfide product;
and c, depositing nickel, heating the filtrate obtained after cadmium separation in the step b to 65-80 ℃, slowly adding a sodium carbonate saturated solution until the pH value of the reaction solution is 7.5-8.5, stirring for 1-5 hours, heating to 70-85 ℃, filtering, washing the filter residue with water until sulfate ions in the washing liquid meet the requirements, and drying the filter residue to obtain a nickel carbonate product.
The filtration in the steps a, b and c is vacuum filtration.
And c, continuously stirring for 10-50 minutes after the pH value of the solution is 3-4 before adding hydrogen peroxide in the step a.
And c, adding a washing solution (containing cadmium and nickel ions) obtained after washing the filter residue with water in the step a into a cadmium precipitation cylinder together with the filtrate as a mixture in the step b.
And c, before the calcium carbonate saturated solution is added, sodium fluoride is added into the filtrate after cadmium separation to react with calciumions remained in the solution to generate calcium fluoride precipitate, and then the calcium fluoride precipitate is filtered.
Furthermore, the nickel carbonate product obtained after the step c is calcined for 1-3 hours at the temperature of 450-550 ℃, then taken out, and ground into fine particles as required to obtain the nickel oxide product.
And c, evaporating and concentrating the filtrate obtained after the step c for multiple times to obtain a sodium sulfate product.
The principle of the technical scheme is as follows: nickel and cadmium in the battery sludge mainly exist in the form of nickel and cadmium hydroxides, nickel-cadmium hydroxide and sulfuric acid react to generate nickel sulfate (42, 30 ℃) and cadmium sulfate (77, 30 ℃), calcium ions generate calcium sulfate (0.1, 30 ℃) with higher solubility, all nickel and cadmium enter the solution through solid-liquid separation, and filter residues are dried and dehydrated to obtain calcium sulfate hemihydrate with better coagulability, which can be used as a cement additive; the stability of cadmium nickel to sulfide is greatly different (the stability of cadmium sulfide formation under standard conditions is 2.5X 10 times that of nickel sulfide8Double), thereby effectively separating nickel and cadmium by the principle and preparing the nickel and cadmium products which are well sold in the market.
The main chemical reaction equations related to the technical scheme and the technical measures are as follows:
Ni(OH)2+H2SO4→NiSO4+H2O
Cd(OH)2+H2SO4→CdSO4+H2O
Ca2+SO4- 2-→CaSO4↓
Fe2++H2O2→Fe2O3·xH2O↓
CdSO4+H2S→CdS+H2SO4(the reaction can adjust the pH to 1-1.5)
CdSO4+Na2S→CdS↓+H2SO4(pH value below 1.5)
Ca2++NaF→CaF2↓
NiSO4+Na2CO3→NiCO3↓+Na2SO4
The invention has the advantages that the nickel, cadmium and calcium of the nickel-cadmium-calcium battery sludge generated in the battery production process can be recycled, and the production process has no environmental pollution and has higher social and economic benefits.
Detailed Description
The following are specific embodiments of the present invention:
mixing battery sludge and water according to a ratio of 1: 1 to prepare slurry, slowly adding sulfuric acid and fully stirring until the pH value is 3, continuously stirring for 30 minutes, slowly adding hydrogen peroxide to remove iron in the solution until the iron content in the solution meets the requirement, generating nickel sulfate and cadmium sulfate by hydroxide of nickel and cadmium in the reaction process, generating calcium sulfate precipitate, heating the reaction product to 80 ℃, performing vacuum filtration, washing the filter residue with water until the washing liquid is neutral, and if the cadmium content in the filter residue can be lower than 0.005% after the filter residue is strictly washed with water, drying the filter residue to obtain an iron-containing calcium sulfate product which can be used as a cement additive.
Adding the solution containing nickel and cadmium ions of the filtrate and the water-washed filter residue into a cadmium precipitation tank, introducing hydrogen sulfide according to the cadmium content, and adding sodium sulfide, wherein the hydrogen sulfide is added to react with cadmium sulfate to generate dilute sulfuric acid until the pH value of the solution is 1, cadmium sulfide does not react with sulfuric acid in the acidity, and simultaneously, sodium sulfide reacts with cadmium sulfate to generate cadmium sulfide precipitate at the pH value. Fully stirring for 3 hours, carrying out vacuum filtration after the reaction is finished, washing off the nickel-containing solution attached to the filter residue by using water, and drying the filter residue to obtain the cadmium sulfide product. Excessive hydrogen sulfide escaping in the reaction process can be collected and used in another cadmium precipitation cylinder.
Heating the nickel-containing filtrate after cadmium separation to 70 ℃, adding sodium fluoride to react with residual calcium ions in the solution to generate calcium fluoride precipitate, filtering the calcium fluoride precipitate, then slowly adding a sodium carbonate saturated solution into the filtrate until the pH value of the reaction solution is 8, stirring for 3 hours, heating to 75 ℃, carrying out vacuum filtration, washing the filter residue with water until sulfate ions in the washing solution meet the requirements, and drying the filter residue to obtain a nickel carbonate product.
Or calcining the nickel carbonate product at 500 ℃ for 2 hours, taking out, grinding and sieving according to requirements to obtain the nickel oxide product.
The final filtrate (mainly sodium sulfate solution) is concentrated by evaporation several times to recover sodium sulfate, which is used as a base material for detergents.
Claims (7)
1. The method for treating the nickel-cadmium-calcium battery sludge is characterized by comprising the following steps: the method comprises the following steps of a, removing calcium and iron by acidification, mixing battery sludge and water to form slurry, slowly adding sulfuric acid and stirring until the pH value is 3-4, slowly adding hydrogen peroxide until the iron content in the solution meets the requirement, heating to 70-85 ℃, filtering, washing filter residue with water until the washing liquid is neutral, and drying the filter residue to obtain an iron-containing calcium sulfate product; b, cadmium and nickel separation, namely adding the filtrate obtained in the step a into a cadmium precipitation tank, introducing hydrogen sulfide and adding sodium sulfide according to the cadmium content until the pH value of the solution is 1-1.5, fully stirring for 1-5 hours, filtering after the reaction is finished, washing the nickel-containing solution attached to the filter residue with water, and drying the filter residue to obtain a cadmium sulfide product; and c, depositing nickel, heating the filtrate obtained after cadmium separation in the step b to 65-80 ℃, slowly adding a sodium carbonate saturated solution until the pH value of the reaction solution is 7.5-8.5, stirring for 1-5 hours, heating to 70-85 ℃, filtering, washing the filter residue with water until sulfate ions in the washing liquid meet the requirements, and drying the filter residue to obtain a nickel carbonate product.
2. The method for treating nickel cadmium calcium battery sludge accordingto claim 1, characterized in that: and the filtration in the steps a, b and c is vacuum filtration.
3. The method for treating nickel cadmium calcium battery sludge according to claim 1, characterized in that: and in the step a, the solution is continuously stirred for 10 to 50 minutes after the pH value is 3 to 4 before hydrogen peroxide is added.
4. The method for treating nickel cadmium calcium battery sludge according to claim 1, characterized in that: and b, adding a washing solution (containing cadmium and nickel ions) obtained by washing the filter residue with water in the step a into a cadmium precipitation cylinder together with the filtrate as a mixture in the step b.
5. The method for treating nickel cadmium calcium battery sludge according to claim 1, characterized in that: and c, before adding the calcium carbonate saturated solution, adding sodium fluoride into the filtrate after cadmium separation to react with calcium ions remained in the solution to generate calcium fluoride precipitate, and filtering the calcium fluoride precipitate.
6. The method for treating nickel cadmium calcium battery sludge according to any one of claims 1 to 5, wherein the method comprises the following steps: and c, calcining the nickel carbonate product obtained after the step c at the temperature of 450-550 ℃ for 1-3 hours, taking out the nickel carbonate product, and grinding the nickel carbonate product as required to obtain the nickel oxide product.
7. The method for treating nickel cadmium calcium battery sludge according to any one of claims 1 to 5, wherein the method comprises the following steps: andc, evaporating and concentrating the filtrate obtained after the step c for multiple times to obtain a sodium sulfate product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100195724A CN100471803C (en) | 2007-01-15 | 2007-01-15 | Treatment method of nickel cadmium calcium battery mud |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100195724A CN100471803C (en) | 2007-01-15 | 2007-01-15 | Treatment method of nickel cadmium calcium battery mud |
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| Publication Number | Publication Date |
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| CN100999371A true CN100999371A (en) | 2007-07-18 |
| CN100471803C CN100471803C (en) | 2009-03-25 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102503054A (en) * | 2011-11-02 | 2012-06-20 | 长沙华清泰污泥处理科技有限公司 | Textile dyeing sludge processing method for removing heavy metal and dehydrating |
| CN106044724A (en) * | 2016-07-22 | 2016-10-26 | 包头锐博新能源材料有限公司 | Sulfuric acid systemcadmium removal method |
| CN112359224A (en) * | 2020-11-11 | 2021-02-12 | 吉林吉恩镍业股份有限公司 | Method for purifying cadmium-containing nickel-cobalt solution to remove cadmium |
-
2007
- 2007-01-15 CN CNB2007100195724A patent/CN100471803C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102503054A (en) * | 2011-11-02 | 2012-06-20 | 长沙华清泰污泥处理科技有限公司 | Textile dyeing sludge processing method for removing heavy metal and dehydrating |
| CN106044724A (en) * | 2016-07-22 | 2016-10-26 | 包头锐博新能源材料有限公司 | Sulfuric acid systemcadmium removal method |
| CN112359224A (en) * | 2020-11-11 | 2021-02-12 | 吉林吉恩镍业股份有限公司 | Method for purifying cadmium-containing nickel-cobalt solution to remove cadmium |
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| Publication number | Publication date |
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| CN100471803C (en) | 2009-03-25 |
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