CN105905951B - A kind of efficient method for removing nitrate anion impurity in cobalt sulfate solution - Google Patents
A kind of efficient method for removing nitrate anion impurity in cobalt sulfate solution Download PDFInfo
- Publication number
- CN105905951B CN105905951B CN201610402437.7A CN201610402437A CN105905951B CN 105905951 B CN105905951 B CN 105905951B CN 201610402437 A CN201610402437 A CN 201610402437A CN 105905951 B CN105905951 B CN 105905951B
- Authority
- CN
- China
- Prior art keywords
- solution
- nitrate anion
- cobalt sulfate
- sulfate solution
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/10—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention provides a kind of efficient method for removing nitrate anion impurity in cobalt sulfate solution, this method is that pH value≤2.5 of crude product cobalt sulfate solution are first adjusted using dilute sulfuric acid, 40% formalin of 0.4 0.5 times of nitrate anion quality is added in cobalt sulfate solution again, reacted at 75 85 DEG C, then the remaining formaldehyde of dereaction is removed with 30% hydrogen peroxide of 1.4 1.5 times of formaldehyde amounts, then high-purity Cobalt monosulfate heptahydrate is obtained through filtering, concentration, crystallisation by cooling.The impurity-removing method of the present invention, it is easy to operate, production procedure is short, process conditions are gentle and easily controllable, course of reaction is produced except purpose product, gas and water, no other impurities, can effectively remove nitrate anion impurity, the six cobalt sulfate hydrate product nitrate anion impurity contents obtained can reach less than 0.02%, meet the use requirement of the industries such as electronic information, battery, catalysis, analysis test.
Description
Technical field
The present invention relates to a kind of removing method of impurity, more particularly in a kind of metal salt solution nitrate anion impurity removing
Method, specifically relates to a kind of efficient method for removing nitrate anion impurity in cobalt sulfate solution.
Background technology
Cobalt monosulfate heptahydrate is a kind of rose monoclinic system crystal, and take on a red color powder after dehydration, is dissolved in water and methanol,
It is slightly soluble in ethanol.Cobaltous sulfate is mainly used in ceramic glaze and paint drier in the past, is also used for plating, alkaline battery, production and contains
Cobalt pigment and other cobalt products, are additionally operable to catalyst, analytical reagent, tire adhesive and lithopone additive etc.；In recent years, sulphur
Sour cobalt is widely used as the raw material of secondary battery positive electrode material, with wide market prospects, but nitrate anion in cobaltous sulfate
Presence to be used for performance impact very big, to ensure its performance, the industry such as domestic electronics, battery is to nitric acid in cobaltous sulfate
The control of root impurity is generally less than 0.05%, and internationally renowned brand Merck ＆ Co., Inc. is even more to require nitrate radical content≤0.01%.
The common preparation method of cobaltous sulfate mainly has：(1) nitration mixture cobalt method, by the mixed of metallic cobalt piece vitriolization and nitric acid
Close in acid, with boiling is steam heated to, through concentration, crystallization, separation mother liquor after reaction, cobaltous sulfate is made；(2) wet-leaching is extracted
Method, as raw materials recovery cobalt resource, cobaltous sulfate product is gone out by Oxidation Leaching, purification by liquid extraction containing cobalt ore, leftover containing cobalt；Due to
Method (1) needs to use nitric acid to dissolve metallic cobalt plate, therefore inevitably introduces nitric acid and nitrate impurity；And method
（2）Usually leached, separated using solvent kerosene extraction using sulfuric acid oxidation, because these auxiliary material purity are not high, nitrate anion is miscellaneous
Matter can accumulate residual, and it is complicated to add raw material sources, containing the presence for also having nitrate in cobalt ore, leftover containing cobalt, therefore the method is obtained
The cobalt sulfate solution nitrate radical content arrived is also higher, can reach 0.5% or even more than 1%.
For the impurities removal of cobaltous sulfate product, it is that the metal how removed in cobalt sulfate solution is miscellaneous to study at present more
The Chinese patent of matter, such as Patent No. ZL201110101859, entitled " preparation method of cobaltous sulfate ", describes cobalt leachate
Impurity-removing method, this method is that the impurity element such as manganese, iron, arsenic in cobaltous sulfate leachate is removed using oxidation precipitation, passes through fluorine
Change precipitation and remove the impurity elements such as calcium, magnesium again, the patent can only remove metal impurities, for how to remove nitrate anion impurity not
Refer to；Patent No. ZL201280059603, entitled " manufacture method of cobaltous sulfate " Chinese patent, are described by making
The method that the cobalt sulfate solution of high concentration is obtained with the solvent extraction of acid organic extractant, but this method also simply go deliming,
The metal impurities such as magnesium, sodium, can not remove nitrate anion therein.For how to remove the nitrate anion impurity in cobalt sulfate solution,
Current method is usually nitrate anion is deposited in crystalline mother solution using crystallization, recrystallization, but the rear product of mother liquor time
In nitrate radical content it is higher, do not reach at all electronic information, battery, catalysis, analysis test etc. industry use requirement.
The content of the invention
To overcome the problem of above is present, nitrate anion in cobalt sulfate solution is efficiently removed it is an object of the invention to provide a kind of
The method of impurity, the cobaltous sulfate obtained by this method, its nitrate radical content can reach less than 0.02%.
Method to realize nitrate anion impurity in object above, efficient removing cobalt sulfate solution of the invention, includes successively
Following steps：
(1) a certain amount of crude product cobalt sulfate solution is taken, dilute sulfuric acid is added and adjusts its pH value≤2.5, heat and make solution temperature
Degree is maintained at 75-85 DEG C, under conditions of stirring, and mass concentration is added by several times and is reacted for 40% formalin, was reacted
Journey solution has faint yellow gas to produce, and when formalin is added and is observed there is no during gas generation, continues at 75-85 DEG C
Insulation reaction more than 60 minutes；
(2) step（2）Obtained solution adds the hydrogen peroxide that mass concentration is 30% under 60-70 DEG C of insulated and stirred, by several times
Reacted, add the follow-up continuous insulation reaction of hydrogen peroxide more than 30 minutes；
(3) the solution filtering that obtains step (3), concentration, crystallisation by cooling, centrifuge dripping obtain Cobalt monosulfate heptahydrate knot
It is brilliant；
Above-mentioned steps（1）The addition of middle formalin is 0.4-0.5 times of nitrate anion quality in crude product cobalt sulfate solution；
Step（2）The addition of middle hydrogen peroxide is step（1）1.4-1.5 times of formalin addition；Step（3）Striking point be
Hot solution proportion d=1.45-1.48.
In order to ensure that reaction is more smoothed out, above-mentioned steps（2）The pH value of timing monitoring solution is answered in course of reaction, and
It is appropriate to supplement dilute sulfuric acid to keep pH≤2.5 of course of reaction solution.
To avoid formaldehyde volatilization too big, while making reaction gently carry out and fully react, the gradation of above-mentioned formalin adds
It is the formalin for adding about half amount first to enter mode, divides remaining formalin 3-4 times every 15 minutes after 30 minutes
Add.
In order to avoid reaction is too fierce, while make reaction gently carry out and fully react, above-mentioned dioxygen moisture adds for 3-5 time
Enter, every minor tick more than 15 minutes.
In order to reduce the particulate contaminant in solution, the purity of product, above-mentioned steps are more preferably improved（3）First add before filtration
Plus proper amount of active carbon is adsorbed.
For the ease of the calculating of raw material addition, above-mentioned steps（1）Nitric acid in crude product cobalt sulfate solution is first determined before feeding intake
The content of root.
In order to reduce the introducing of impurity, above-mentioned steps (1), step（2）In used dilute sulfuric acid, formalin, hydrogen peroxide
It is chemical pure level.
The NO produced in order to avoid formaldehyde and nitrate anion reaction2Influence environment, above-mentioned steps（1）Reaction be to be connected with
Carried out in the reaction vessel of exhaust gas absorption device, waste gas is absorbed using alkaline solution.
The method of nitrate anion impurity, is removed in cobaltous sulfate using formaldehyde in the efficient removing cobalt sulfate solution of the present invention
Nitrate anion, because the product that formaldehyde and nitrate anion react is gas and water, without other impurities generation, gas escapes in the reaction
Go out, water is stayed in solution, and excessive formaldehyde is removed using hydrogen peroxide, also do not produce impurity influential on product, this
The technological parameter that invention passes through strictly control inventory and course of reaction so that nitrate anion can have in the case where concentration is relatively low
Effect is removed, and nitrate anion impurity content can reach less than 0.02% in the cobaltous sulfate obtained by this method, is adapted to electronic information, electricity
The industries such as pond, catalysis, analysis test are used.The method of the present invention, easy to operate, production procedure is short, and process conditions are gentle and easy
In control, impurity-eliminating effect substantially, is particularly suitable for large-scale industrial production.
Embodiment
Technical scheme is further described with reference to specific embodiment, but these embodiments are not used
To limit the scope of the invention, on the premise of theory of the present invention is not departed from, the change originated to crude product cobalt sulfate solution,
Protection scope of the present invention all should be belonged to.
Embodiment 1
（1）The crude product cobaltous sulfate that wet-leaching extraction is prepared is taken, it is nitre in 1.26, solution to measure its gravity
Acid group content is 0.5%；
（2）Take the above-mentioned solution of 300kg to be placed in 300L enamel reaction stills, add CP grades of dilute sulfuric acid regulation pH value of solution≤2.5,
Open steam to heat and maintain the temperature at 75-80 DEG C, connect and open exhaust gas absorption device, stirring is lower first to be added in thread mode
CP grades of mass concentrations of 350g are reacted for 40% formalin, molten every the 15 minutes addition above-mentioned formaldehyde of 100g after 30 minutes
Liquid, is added 4 times altogether, is added formaldehyde and is observed after no gas effusion, continues insulation reaction 60 minutes, course of reaction gap adds
Enter dilute sulfuric acid to keep pH value of solution≤2.5, course of reaction adds the formalin 750g of CP levels 40% altogether, and waste gas uses sodium hydroxide
Solution absorbs；
（3）Above-mentioned solution is continually maintained at 60-70 DEG C and is incubated and stirs, with 4 addition 1100g matter of thread mode point
The hydrogen peroxide that concentration is 30% is measured, every minor tick 15 minutes adds the follow-up continuous insulation reaction of hydrogen peroxide 30 minutes；
（4）Add after activated carbon about 100g and filter in above-mentioned solution, filtrate is heated in 300L enamel pans and is concentrated into heat
Gravity d=1.46, cooks and puts natural cooling crystallization in container, is cooled to after the abundant crystallization of room temperature, take crystallize in it is encapsulated from
Centrifuge dripping in scheming, obtains Cobalt monosulfate heptahydrate finished product 58kg, it is 0.01% that nitrate radical content is surveyed in sampling.
Embodiment 2
（1）The crude product cobaltous sulfate that wet-leaching extraction is prepared is taken, nitric acid in its gravity 1.28, solution is measured
Radical content is 0.8%；
（2）Take the above-mentioned solution of 300kg to be placed in 300L enamel reaction stills, add CP grades of dilute sulfuric acid regulation pH value of solution≤2.5,
Open steam to heat and maintain the temperature at 80-85 DEG C, connect and open exhaust gas absorption device, stirring is lower first to be added in thread mode
CP grades of mass concentrations of 550g are reacted for 40% formalin, molten every the 15 minutes addition above-mentioned formaldehyde of 150g after 30 minutes
Liquid, is added 3 times altogether, is added formalin and is observed after no gas effusion, continues insulation reaction 70 minutes, between course of reaction
Gap adds dilute sulfuric acid to keep pH≤2.5 of solution, and course of reaction adds the formalin 1000g of CP levels 40% altogether, and waste gas uses hydrogen
Sodium hydroxide solution absorbs；
（3）Above-mentioned solution is continually maintained at 60-70 DEG C and is incubated and stirs, with 5 addition 1500g of thread mode point
Mass concentration is 30% hydrogen peroxide, every minor tick 15 minutes, adds the follow-up continuous insulation reaction of hydrogen peroxide 30 minutes；
（4）Add after activated carbon about 100g and filter in above-mentioned solution, filtrate is heated in 300L enamel pans and is concentrated into heat
Gravity d=1.48, cooks and puts natural cooling crystallization in container, is cooled to after the abundant crystallization of room temperature, takes and crystallize in encapsulated
Centrifuge dripping on centrifuge, obtains Cobalt monosulfate heptahydrate finished product 63kg, it is 0.02% that nitrate radical content is surveyed in sampling.
As can be seen from the above-described embodiment, the Cobalt monosulfate heptahydrate that impurity-removing method of the present invention is obtained, nitrate radical content≤
0.02%, comply fully with the use requirement of the industries such as electronic information, battery, catalysis, analysis test.
Claims (4)
1. a kind of efficient method for removing nitrate anion impurity in cobalt sulfate solution, in turn includes the following steps：
(1) content of nitrate anion in crude product cobalt sulfate solution is first determined, then takes a certain amount of crude product cobalt sulfate solution, is added dilute
Sulfuric acid adjusts its pH value≤2.5, heats and solution temperature is maintained at 75-85 DEG C, under conditions of stirring, and quality is added by several times
Concentration is reacted for 40% formalin, and course of reaction solution has faint yellow gas to produce, when formalin is added and is observed
To when being produced there is no gas, continue insulation reaction at 75-85 DEG C more than 60 minutes；
(2) step（1）Obtained solution adds mass concentration under 60-70 DEG C of insulated and stirred, by several times and carried out for 30% hydrogen peroxide
Reaction, adds the follow-up continuous insulation reaction of hydrogen peroxide more than 30 minutes；
(3) the solution filtering that obtains step (2), concentration, crystallisation by cooling, centrifuge dripping obtain Cobalt monosulfate heptahydrate crystallization；
Above-mentioned steps（1）The addition of middle formalin is 0.4-0.5 times of nitrate anion quality in crude product cobalt sulfate solution, formaldehyde
The gradation feed postition of solution is the formalin for adding about half amount first, every 15 minutes by remaining formaldehyde after 30 minutes
3-4 addition of solution point；Step（2）The addition of middle hydrogen peroxide is step（1）1.4-1.5 times of formalin addition, it is double
The 3-5 addition of oxygen moisture, every minor tick more than 15 minutes；Step（3）Striking point be hot solution proportion d=1.45-1.48.
2. the efficient method for removing nitrate anion impurity in cobalt sulfate solution according to claim 1, it is characterised in that：It is described
Step（2）In the pH value of course of reaction timing monitoring solution, and suitably supplement dilute sulfuric acid with keep the pH of course of reaction solution≤
2.5。
3. the efficient method for removing nitrate anion impurity in cobalt sulfate solution according to claim 1 or 2, it is characterised in that：
The step (1), step（2）In used dilute sulfuric acid, formalin, hydrogen peroxide be chemical pure level.
4. the efficient method for removing nitrate anion impurity in cobalt sulfate solution according to claim 3, it is characterised in that：It is described
Step（1）Reaction be to be carried out in the reaction vessel for be connected with exhaust gas absorption device, waste gas absorbed using alkaline solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610402437.7A CN105905951B (en) | 2016-06-08 | 2016-06-08 | A kind of efficient method for removing nitrate anion impurity in cobalt sulfate solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610402437.7A CN105905951B (en) | 2016-06-08 | 2016-06-08 | A kind of efficient method for removing nitrate anion impurity in cobalt sulfate solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105905951A CN105905951A (en) | 2016-08-31 |
| CN105905951B true CN105905951B (en) | 2017-11-03 |
Family
ID=56750767
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610402437.7A Active CN105905951B (en) | 2016-06-08 | 2016-06-08 | A kind of efficient method for removing nitrate anion impurity in cobalt sulfate solution |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105905951B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109911948A (en) * | 2019-03-20 | 2019-06-21 | 金川集团股份有限公司 | The method of nitrate anion is removed in a kind of ambrose alloy cobalt sulfate liquor |
Family Cites Families (2)
| 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 |
| EP2799400B1 (en) * | 2011-12-26 | 2019-06-26 | Sumitomo Metal Mining Co., Ltd. | Method for producing cobalt sulfate |
-
2016
- 2016-06-08 CN CN201610402437.7A patent/CN105905951B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN105905951A (en) | 2016-08-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2020220559A1 (en) | Recovery method for valuable metals in waste nickel-cobalt-manganese ternary lithium batteries | |
| CN104229898B (en) | Method for preparing high-purity manganese sulfate and zinc sulfate by using waste zinc-manganese batteries as raw materials | |
| CN102603000B (en) | Process for preparing high-purity vanadium pentoxide by adopting ammonium metavanadate as raw material | |
| CN108550939A (en) | A method of selective recovery lithium and preparing lithium carbonate from waste lithium cell | |
| CN109704408A (en) | A kind of production method of LITHIUM BATTERY high purity manganese sulfate | |
| CN105803199B (en) | A kind of method that hydroxide precipitation method prepares low-sulfur rare earth oxide | |
| CN109761250A (en) | A method of lithium ion sieve is prepared using waste and old lithium ion battery | |
| CN102887545B (en) | Method for preparing electronic-grade manganese carbonate from manganese-copper-zinc-cobalt-calcium chloride solution | |
| CN105776254A (en) | Technology for preparing lithium carbonate by means of recycling of slag obtained in purifying process of lepidolite | |
| CN107540025A (en) | A kind of method for preparing hydrate ruthenium trichloride | |
| CN109809440B (en) | Method for preparing high-purity lithium chloride, high-purity lithium formate and high-purity lithium carbonate | |
| WO2020019854A1 (en) | Method for producing zinc oxide by means of double leaching | |
| CN108910958A (en) | A method of manganese sulfate is produced using aniline reduction electrolytic manganese anode mud | |
| CN104129814B (en) | A kind of method that is raw material production ammonium meta-vanadate with oil hydrogenation spent catalyst | |
| CN106367601B (en) | A kind of method of wet-treating fuel oil flying dust extraction valuable metal | |
| CN105948104A (en) | Method for preparing sodium stannate by using tin anode slime oxygen pressure alkaline leaching | |
| CN108622938A (en) | A method of preparing ammonium dimolybdate from containing molybdenum solution | |
| CN105905951B (en) | A kind of efficient method for removing nitrate anion impurity in cobalt sulfate solution | |
| CN111057846B (en) | Method for separating and recovering cobalt, copper and iron in white alloy | |
| CN102633292A (en) | Method for preparing copper sulphate by using copper sponge without roasting and evaporating | |
| CN105645475A (en) | Preparation method of high-purity manganese source applied to lithium battery anode materials | |
| CN106745288A (en) | A kind of production method of high-purity manganese sulphate | |
| CN104610407B (en) | The process for purification of hydrocortisone acetate | |
| CN100408234C (en) | Production of cuprous oxide powder and bronze powder using sulfur dioxide reduction method | |
| CN108796234B (en) | Method for separating antimony and arsenic from antimony-arsenic material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |