CN1337360A - Method of preparing cobelt chloride with colbalt slag containing Fe and Mg - Google Patents
Method of preparing cobelt chloride with colbalt slag containing Fe and Mg Download PDFInfo
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- CN1337360A CN1337360A CN 00122064 CN00122064A CN1337360A CN 1337360 A CN1337360 A CN 1337360A CN 00122064 CN00122064 CN 00122064 CN 00122064 A CN00122064 A CN 00122064A CN 1337360 A CN1337360 A CN 1337360A
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Abstract
The production method of cobalt chloride by using cobalt slag containing iron and manganese includes the folloiwng steps: dissolivng cobalt slag in acid, when the acid-solution is reached to reaction end point, adding a proper quantity of oxidant, using needle ironstone precipitation method to treat reaction liquor to remove iron, adding permanganate to iron-removed filtrate to make Mn (II) being in reaction liquor be oxidated, and made into manganese dioxide, the recovery rate of manganese being in solution is greater than 98%, and recovery rate of manganese being in cobalt slag is greater than 85%, the adding dicarbonate in manganese-removed filtrate to obtain cobalt carbonate, and the recovery rate of cobalt is greater than 95%. The cobalt carbonate can be undergone the processes of hydrochloric acid dissolving, concentrating and crystallizing, and the purity of coblat chloride crystal is above 95%. It is specially applicable to prepare cobalt chloride by uisng cobalt slag produced by using low-pressure carbonylation to synthesize phenylacetic acid, and its by-product manganese dioxide can be used as resource.
Description
The invention relates to a method for preparing cobalt chloride from cobalt slag containing iron and manganese.
In the prior art, the method for preparing cobalt chloride from cobalt slag containing iron and manganese generally adopts a precipitation method or an extraction method. Dissolving iron-and manganese-containing cobalt slag acid, adding an oxidant to oxidize Fe (II) in the solution into Fe (III) when the reaction is close to the end point, precipitating and removing iron in the form of ferric hydroxide or jarosite salt, and then adopting different steps according to the used method. The precipitation method is that sodium sulfide solution is droppedinto the filtrate obtained after iron removal or hydrogen sulfide gas is introduced, the pH value of the solution is adjusted, cobalt is precipitated in the form of cobalt sulfide, the solution is filtered and separated, the filtrate is discarded, the cobalt sulfide is oxidized in acid by oxidant or directly oxidized and dissolved into soluble cobalt salt solution by oxidizing acid, sodium carbonate is added to form cobalt carbonate precipitate, the cobalt carbonate is dissolved in hydrochloric acid, and cobalt chloride crystal is obtained through concentration and crystallization. The extraction method is that extracting agent is added into the filtrate after iron removal to extract and separate manganese, cobalt is precipitated from water phase through carbonate, then hydrochloric acid is used for dissolving, and cobalt chloride crystal is obtained through concentration and crystallization. Both of the above methods have disadvantages. A precipitation method: (1) in the process of using sulfide to precipitate cobalt, hydrogen sulfide gas is discharged, and the operation environment is severe. The PH value is difficult to control in the cobalt precipitation process, and manganese sulfide is accompanied with precipitation, so that the cobalt and manganese are not completely separated. The produced cobalt sulfide has colloidal property, and is difficult to filter and separate, so that the cobalt sulfide cannot be produced normally. (2) The cobalt sulfide can be dissolved into soluble cobalt salt only by oxidizing in acid with an oxidant or directly oxidizing with an oxidizing acid, along with generation of polluting gases, and the method has the disadvantages of harsh reaction conditions, high equipment requirements and no contribution to industrial production. (3) When cobalt is precipitated from soluble cobalt salt by carbonate, basic cobalt carbonate with colloidal properties is generated, and the filtration and separation are difficult, so that the cobalt recovery rate is lower than 90%, and the purity of thecobalt product is also reduced. The extraction method is a new wet metal refining industry, and gradually develops from the atomic energy industry to the nonferrous metal refining and purification. Has the advantages of high speed, high selectivity and the like. It has the following disadvantages: (1) the extraction method must be carried out through three stages of extraction, washing and back extraction, and in order to carry out the extraction, an extractant and a solvent must be recycled, so that the process is complex, the cost is high, and the investment is large. The extraction and separation of nonferrous metals are still not perfect at present. (2) The extraction is generally carried out under the condition that the ion concentration in the solution is relatively low, and the concentration is higher in practical work, so that the separation cannot be fully carried out. The extraction method for refining and purifying is suitable for large-scale industrial production and is not convenient for medium and small-scale industrial production. The precipitation method and the extraction method have the following problems: (1) when the iron is precipitated in the form of ferric hydroxide, the ferric hydroxide is difficult to filter, other cations are absorbed more, and the cobalt loss is serious; the iron is precipitated in the form of jarosite, the time consumption is long, and a certain amount of alkali metal cations need to be supplemented. (2) The manganese is discharged as waste, so that the resource is wasted and the environment is polluted.
The invention aims to provide a method for preparing cobalt chloride from cobalt slag containing iron and manganese. Manganese is also recycled and overcomes the disadvantages. The process is easy to operate, has low cost and is more reasonable, and can be directly used for industrial production in medium and small factories. After the iron removal process is improved, the recovery rate of cobalt is obviously improved.
In order to achieve the aim, the invention adopts the solution that cobalt slag containing iron and manganese is dissolved by sulfuric acid, oxidant is added when the reaction end point is approached to ensure that Fe (II) in the solution is oxidized into Fe (III), and a new goethite precipitation-partial hydrolysis method developed by Australian electro-zinc company is adopted to remove iron by a spray iron precipitation process. Under the condition of controlling the pH value, Mn (II) in the permanganate oxidation solution is quantitatively converted into manganese dioxide, the manganese dioxide is separated out by centrifugation, sodium bicarbonate is added into the filtrate, cobalt is separated out in the form of cobalt carbonate, the cobalt carbonate is obtained by centrifugation, and the filtrate contains alkali metal sulfate and can be recycled. The cobalt carbonate is dissolved, concentrated and crystallized by hydrochloric acid to obtain cobalt chloride crystal.
The chemical reaction principle of the invention is as follows:
after the cobalt slag is dissolved by acid, oxidized and filtered, the components of the solution are cobalt sulfate, ferric sulfate, manganese sulfate and a small amount of sulfuric acid. The reaction formula of the iron precipitation is as follows:
quantitatively adding sulfuric acid with a certain concentration into a glass lining reactor, and slowly adding cobalt slag at a proper temperature under good stirring. The reaction is carried out under normal pressure, and a small amount of oxidant is added when the pH value of the reaction solution is close to 1.0. The concentration of the sulfuric acid is 10-85%, preferably 30-40%. The reaction temperature is controlled to be 85-105 ℃, and preferably 95 +/-2 ℃. The oxidant is a permanganate, manganese dioxide, chlorate or hypochlorite, preferably manganese dioxide. The pH value of the reaction end point is controlled to be 1.0-2.0, preferably 1.5. The reaction is completed within 4-5 hours, wherein the oxidation time is 1.0-1.5 hours, and the reaction can be stopped when no Fe (II) exists.
And (3) cooling the reaction liquid to obtain a black red reaction liquid, filtering the reaction liquid to remove filter residues, and removing iron from the filtrate. A certain amount of base solution is added in advance into a reactor with two sets of spraying devices, steam is introduced for heating, and filtrate and a neutralizing agent are sprayed into the base solution at a proper temperature and under good stirring, and the pH value is strictly controlled. The base solution is an aqueous solution of sulfuric acid having a pH of 2.0. The temperature in the reaction is 85-95 ℃, preferably 90 +/-2 ℃; the neutralizer is 10-30% sodium hydroxide or sodium carbonate solution, preferably 20% sodium hydroxide solution. The pH of the reaction solution is always controlled to 1.5 to 3.5, preferably 2.0 to 3.0. Stopping spraying and stirring for 10-15 minutes, and finishing the reaction. Cooling, centrifuging, and removing residue.
The filtrate is added into a reactor with a spraying device, and the neutralizer is sprayed while adding the permanganate solid or solution under good stirring. The reaction is carried out at normal temperature. The pH of the reaction solution is always controlled to 1.5-2.5, preferably 2.0. The permanganate used is potassium or sodium. The neutralizer is 10-30% sodium hydroxide solution, preferably 20% solution. The presence or absence of Mn (II) in the reaction solution is detected by a conventional method, and if the presence or absence of Mn (II) in the reaction solution is detected, the reaction is stopped. Centrifugally separating, washing with water, and obtaining a filter cake of high-purity manganese dioxide. The purity of the dried manganese-containing solution is over 97 percent, and the recovery rate of manganese in the solution is over 98 percent. The recovery rate of manganese in the cobalt slag is more than 85 percent.
To the above filtrate, 15% sodium bicarbonate solution or ground sodium bicarbonate powder was slowly added with good stirring. The reaction is carried out at normal temperature, and the reaction is stopped when the pH value of the reaction solution reaches 8.5-9.0. And (4) centrifugally separating, and washing a filter cake for multiple times by using deionized water until no sulfate ions are detected. The recovery rate of cobalt is more than 95%. The filtrate is alkalescent solution containing alkali metal sulfate, and is easy to treat.
And slowly adding the cobalt carbonate filter cake into industrial hydrochloric acid under good stirring, reacting at normal temperature, and stopping the reaction when the pH value of the reaction liquid rises to 3.5-4.0. Filtering the solution, concentrating to density of 1.50, cooling, and crystallizing to obtain cobalt chloride crystal. Washing the crystal with a small amount of deionized water, drying in the shade, measuring the purity of the crystal to be more than 98%, and circularly crystallizing the mother liquor.
The present invention is clearly superior and unique to the prior art. The oxidant used in aciddissolution can be a substance generated in the reaction process, so that the raw materials are saved. The iron precipitation adopts goethite precipitation-partial hydrolysis method, the speed is high, the adsorption quantity to other cations is small, the precipitation filtration performance is good, and the concentration of residual iron in the solution is less than 0.05 g/L, which is incomparable with other methods. The particular feature is that the manganese is not discharged as waste, but is converted to high purity manganese dioxide of considerable utility value, with the manganese in the solution being converted almost quantitatively to manganese dioxide. The cobalt precipitation adopts sodium bicarbonate, and because of small alkalinity, basic cobalt carbonate with colloid property can not be formed, but cobalt carbonate which is easy to filter and wash can not be lost, the recovery rate is more than 95 percent, and the purity of the crystallized cobalt chloride crystal is more than 98 percent. The method has no waste gas pollution, and the discharged wastewater is an alkalescent aqueous solution containing alkali metal sulfate, is easy to treat and almost has no pollution to the environment.
The invention relates to a method for preparing cobalt chloride from cobalt slag containing iron and manganese and simultaneously producing high-purity manganese dioxide as a byproduct. It is especially suitable for preparing cobalt chloride from cobalt slag containing iron and manganese in the synthesis of phenylacetic acid by low-pressure carbonylation, so that cobalt can be recycled. Manganese dioxide can be used for preparing permanganate and the like. Solves the problem of manganese pollution in the prior method.
The best embodiment of the invention is as follows:
the cobalt slag containing iron and manganese is the cobalt slag for synthesizing phenylacetic acid bylow-pressure carbonylation. The analysis shows that the alloy contains 12.10 percent of manganese, 4.40 percent of iron, 6.25 percent of cobalt and a small amount of sodium phenylacetate and other impurities.
Adding 200 liters of 35% sulfuric acid into a 500 liter enamel glass reaction kettle with a stirrer and a thermometer, heating to 95 +/-2 ℃ under stirring, slowly adding 200 kilograms of cobalt slag, adding after 1.5-2.0 hours, sampling to measure the pH value of the solution, adding a small amount of manganese dioxide oxidant when the pH value is close to 1.0, sampling to detect whether Fe (II) exists in the reaction solution, supplementing manganese dioxide if so, adding 1.50 kilograms of manganese dioxide in the whole process, and stopping the reaction when the sampling detects that Fe (II) does not exist. The oxidation time is 1.0-1.5 hours, and the whole reaction is completed in 4-5 hours.
The reaction solution was cooled, centrifuged to remove insoluble impurities and the upper oily layer was discarded. And (5) carrying out iron removal treatment on the filtrate. Adding 100 kg of sulfuric acid aqueous solution with the pH value of 2 into a 1000-liter stainless steel reactor with a stirrer, a thermometer, a pH meter and two sets of spraying devices, introducing steam for heating and stirring, respectively dropwise adding the filtrate and 20% of sodium hydroxide solution through the spraying devices when the temperature reaches 90 +/-2 ℃, keeping the temperature, always controlling the pH value of the reaction solution to be 2-3, and continuously reacting for 0.5 hour after the dropwise adding is finished within 2 hours. Cooling, centrifuging, discarding filter cake, and using filtrate for next treatment.
The above filtrate was added to a 1000 liter stainless steel reactor equipped with a stirrer, a thermometer, a PH meter and a spray device, finely ground potassium permanganate and 20% sodium hydroxide solution were added with good stirring, the PH of the reaction solution was controlled at 2.0, and the reaction was carried out at normal temperature. Sampling to detect the existence of Mn (II), stopping feeding when no Mn (II) exists, continuing stirring for 0.5 hour, and strictly controlling the pH value. After the reaction, centrifugal separation, filter cake washed three times with deionized water, dried and weighed as 56.30 kg, the recovery rate of manganese in the solution was determined by analysis to be 98.72%, 1.50 kg added as oxidant was subtracted, and the recovery rate of manganese in cobalt residue was 85.89%. The purity of manganese dioxide was 97.60%. The filtrate is used for the next step of treatment.
And (3) adding the filtrate into a 1000-liter reactor with a stirrer, slowly adding a 15% sodium bicarbonate solution under good stirring, reacting at normal temperature, stopping adding the sodium bicarbonate solution when the pH value of the reaction solution is increased to 8.5-9.0, and stirring for 0.5 hour. And (4) centrifugally separating, washing the filter cake with deionized water for many times until no sulfate ions exist, and obtaining 30.38 kilograms of cobalt carbonate with the water content of 21.00 percent. The recovery of cobalt was 95.23%.
Slowly adding the cobalt carbonate filter cake into industrial hydrochloric acid under the condition of good stirring, reacting at normal temperature, stopping adding the filter cake when the pH value of the reaction liquid rises to 3.5-4.0, continuously stirring for 0.5 hour, filtering the reaction liquid, concentrating to the density of 1.50, cooling, crystallizing, washing crystals with a small amount of deionized water, drying in the shade, measuring the purity of the cobalt chloride crystals to be 98.50%, and circularly crystallizing the mother liquid.
Claims (7)
1. A method for preparing cobalt chloride from cobalt slag containing iron and manganese. The present invention features that cobalt slag containing Fe and Mn is dissolved in acid, proper amount of oxidant is added near the end of reaction to oxidize Fe (II) into Fe (III), the filtrate is filtered to obtain filtrate, which is precipitated with goethite precipitation process to eliminate Fe and then centrifugally separated, permanganate and Mn (II) are quantitatively oxidized into manganese dioxide, centrifugally separated, sodium bicarbonate is added into the filtrate to obtain cobalt carbonate, which is centrifugally separated to obtain cobalt carbonate crystal after hydrochloric acid dissolution, concentration and crystallization.
2. The method of claim 1, wherein the acid is sulfuric acid with a concentration of 10-85%. The reaction temperature is controlled to be 85-105 ℃, and the pH value at the end of the reaction is 1.0-2.0.
3. The method according to claim 1, wherein the oxidizing agent added to the acid solution near the end of the reaction is a permanganate, manganese dioxide, chlorate or hypochlorite.
4. The method of claim 1, wherein the iron is removed by goethite precipitation-partial hydrolysis precipitation, the reaction temperature is 85-95 ℃, and the pH value of the reaction solution is controlled to be 1.5-3.5 by spraying sodium hydroxide or sodium carbonate neutralizer.
5. The method according to claim 1, wherein Mn (II) in the solution is oxidized to manganese dioxide, and potassium permanganate or sodium permanganate is used as the oxidizing agent. The reaction is carried out at normal temperature. And spraying a sodiumhydroxide neutralizing agent, and controlling the pH value of the reaction solution to be 1.5-2.5.
6. The method of claim 1, wherein sodium bicarbonate is used as a precipitant to produce cobalt carbonate, the reaction is carried out at room temperature, and the pH value at the end of the reaction is 8.5-9.0.
7. The method of claim 1, wherein the cobalt carbonate is slowly added to the industrial hydrochloric acid, the reaction is carried out at room temperature, the reaction is carried out at a final pH of 3.5 to 4.0, and the solution is cooled and crystallized to obtain cobalt chloride crystals when the solution is concentrated to a density of 1.50.
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| CN 00122064 CN1337360A (en) | 2000-08-15 | 2000-08-15 | Method of preparing cobelt chloride with colbalt slag containing Fe and Mg |
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| CN 00122064 CN1337360A (en) | 2000-08-15 | 2000-08-15 | Method of preparing cobelt chloride with colbalt slag containing Fe and Mg |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101774651B (en) * | 2010-01-11 | 2011-09-21 | 广东光华科技股份有限公司 | Method for preparing reagent cobalt chloride hexahydrate |
| CN103290214A (en) * | 2013-05-28 | 2013-09-11 | 中国恩菲工程技术有限公司 | Method for depositing iron from ferruginous zinc sulfate solution |
| CN103305692A (en) * | 2013-05-28 | 2013-09-18 | 中国恩菲工程技术有限公司 | Leaching method of zinc sulfide concentrate |
| CN103911510A (en) * | 2014-04-28 | 2014-07-09 | 德清县立荣金属粉末有限公司 | Method for purifying and removing iron, aluminum and silicon in superimposition manner |
| CN107858509A (en) * | 2017-11-13 | 2018-03-30 | 中国恩菲工程技术有限公司 | The device of iron removaling in hydrometallurgy iron-containing liquor |
| CN108060303A (en) * | 2017-11-13 | 2018-05-22 | 中国恩菲工程技术有限公司 | The method that iron is removed in hydrometallurgy iron-containing liquor |
| CN112359225A (en) * | 2020-11-12 | 2021-02-12 | 格林美（江苏）钴业股份有限公司 | Selective leaching process of rough cobalt hydroxide ore |
| CN114196826A (en) * | 2020-09-17 | 2022-03-18 | 常宁市华兴冶化实业有限责任公司 | Method for recovering and producing cobalt sulfate heptahydrate from cobalt slag |
| CN114438334A (en) * | 2022-02-10 | 2022-05-06 | 刘云派 | Green cobalt slag recovery process |
-
2000
- 2000-08-15 CN CN 00122064 patent/CN1337360A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101774651B (en) * | 2010-01-11 | 2011-09-21 | 广东光华科技股份有限公司 | Method for preparing reagent cobalt chloride hexahydrate |
| CN103290214A (en) * | 2013-05-28 | 2013-09-11 | 中国恩菲工程技术有限公司 | Method for depositing iron from ferruginous zinc sulfate solution |
| CN103305692A (en) * | 2013-05-28 | 2013-09-18 | 中国恩菲工程技术有限公司 | Leaching method of zinc sulfide concentrate |
| CN103911510A (en) * | 2014-04-28 | 2014-07-09 | 德清县立荣金属粉末有限公司 | Method for purifying and removing iron, aluminum and silicon in superimposition manner |
| CN107858509A (en) * | 2017-11-13 | 2018-03-30 | 中国恩菲工程技术有限公司 | The device of iron removaling in hydrometallurgy iron-containing liquor |
| CN108060303A (en) * | 2017-11-13 | 2018-05-22 | 中国恩菲工程技术有限公司 | The method that iron is removed in hydrometallurgy iron-containing liquor |
| CN114196826A (en) * | 2020-09-17 | 2022-03-18 | 常宁市华兴冶化实业有限责任公司 | Method for recovering and producing cobalt sulfate heptahydrate from cobalt slag |
| CN112359225A (en) * | 2020-11-12 | 2021-02-12 | 格林美（江苏）钴业股份有限公司 | Selective leaching process of rough cobalt hydroxide ore |
| CN114438334A (en) * | 2022-02-10 | 2022-05-06 | 刘云派 | Green cobalt slag recovery process |
| CN114438334B (en) * | 2022-02-10 | 2024-01-16 | 刘云派 | Recovery process of green cobalt slag |
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