CN106904664A - Hydroxyl cobaltosic oxide and preparation method thereof - Google Patents
Hydroxyl cobaltosic oxide and preparation method thereof Download PDFInfo
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- CN106904664A CN106904664A CN201510962120.4A CN201510962120A CN106904664A CN 106904664 A CN106904664 A CN 106904664A CN 201510962120 A CN201510962120 A CN 201510962120A CN 106904664 A CN106904664 A CN 106904664A
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Abstract
The invention discloses a kind of hydroxyl cobaltosic oxide and preparation method thereof, synthetically produced hydroxyl cobaltosic oxide is solved, high cost, the problem of unstable product quality stabilization, main method includes：Take selective dissolution, it is liquid to add wash water to size mixing rough cobalt carbonate, extraction removing calcium and magnesium, Suan Rong workshop sections except after iron solution can be directly entered extraction workshop section by plate compression and carry out separation, impurity removal, cobalt chloride solution direct hydrogenation sodium oxide molybdena and hydrogen peroxide, regulation pH value control temperature and rotating speed produce varigrained hydroxyl cobaltosic oxide, with reduction production cost, the generation of fluorination calcium and magnesium hazardous waste is reduced, sustainability is strong, product quality stabilization, small investment, produced without ammonia nitrogen waste water, the advantage of low production cost is adapted to the system of hydroxyl cobaltosic oxide.
Description
Technical field：
Present invention relates particularly to a kind of hydroxyl cobaltosic oxide and preparation method thereof, belong to the rough cobalt carbonate of cobalt industry and use selective dissolution, extraction removing calcium and magnesium, the technical field of cobalt chloride liquid and NaOH Hydrogen Peroxide Production hydroxyl cobaltosic oxide.
Background technology：
Rough cobalt carbonate directly uses sulfuric acid CL, the soluble metal ions such as iron are caused all to dissolve, purification and impurity removal is difficult, it is difficult filtering, cobaltous sulfate liquid is not limpid to cause layering bad to extraction workshop section, using regulation pH value selective dissolution, strainability is well except incidental expense is low, while extract workshop section can normally produce.Extraction deliming substitutes former chemical method removing calcium and magnesium technique, production cost reduction, hazardous waste is not produced to be fluorinated calcium and magnesium, extraction removing calcium and magnesium is former to be stripped calcium and magnesium using sulfuric acid, calcium sulfate precipitation is caused to block extraction tank, the anti-ferrous acid for extracting workshop section's generation simultaneously cannot be processed, anti- copper MnZn calcium sour regurgitation is allocated using the anti-ferrous acids of P204, calcium is calcium chloride, copper, MnZn, copper sponge is produced using iron replacement, calcium oxide powder processes MnZn liquid, extract the cobalt chloride solution hydrogenation sodium oxide molybdena of production, hydrogen peroxide adjusts pH value, control temperature, rotating speed, synthetically produced hydroxyl cobaltosic oxide, dried by centrifuge, calcination produces cobaltosic oxide, the technique productions low cost, raw materials consumption is few, product yield is high, product quality stabilization.
The content of the invention：
The purpose of the present invention is exactly to overcome the above not enough, there is provided a kind of using calcium oxide powder replacement soda ash removal of impurities, reduce production cost, reduce the generation of fluorination calcium and magnesium hazardous waste, sustainability is strong, product quality stabilization, small investment, produced without ammonia nitrogen waste water, hydroxyl cobaltosic oxide of low production cost and preparation method thereof.
The present invention is achieved in that described hydroxyl cobaltosic oxide and preparation method thereof is it is characterized in that including following preparation method by the following technical programs：
The dissolving method of pure rough cobalt carbonate
1. selective dissolution is taken after rough cobalt carbonate process modification, it is liquid to add wash water to size mixing rough cobalt carbonate, return and be warming up in tank diameter 50 DEG C, start to be slowly added into sulfuric acid, control pH value is no more than 3.5, observation foam appearance has a small amount of white foam, pH value control 3.0 or so, it is minimum to be not less than PH2.8, survey current potential 400MV or so, acid adding speed must be slow, every tank mixing time 3-4 hours, pH value not acid adding when reaching 3.0 or so, pH value keeps constant, may filter that, filter residue carries out second dissolving, intensification adds a small amount of sodium pyrosulfite when reaching 50 DEG C, plus sodium pyrosulfite speed must be slow, often plus one bag will check pH value, when adding sodium pyrosulfite pH value constant, sampling analysis Co discord Fe2+, Cu not, current potential, Co≤0.1%Fe2+≤ 3g/I current potentials≤350MV, Cu not≤0.3%, it is up to standard after be warming up to more than 85 DEG C plus sodium chlorate, sodium chlorate presses Fe2+0.25 times addition, stir 1 hour sampling analysis Fe2+Equal to zero, then add calcium oxide powder regulation pH value, when pH value reaches 3.3, you can directly upper extraction workshop section carries out separation, impurity removal for press filtration.
2. extraction removing calcium and magnesium,Suan Rong workshop sections except after iron solution can be directly entered extraction workshop section by plate compression and carry out separation, impurity removal,Sulfuric acid is taken during removing calcium with solvent extraction magnesium process modification to carry out being stripped calcium slag,Cause calcium sulfate,It is calcium sulfate to use plate compression filter residue,Pour into Ordinary solid waste slag,The muscle power of manpower consumption at that time is big,Extraction cell body is easily blocked,The anti-molysite acid that extraction section is produced simultaneously need to return to Suan Rong workshop sections and be used,Company is by modified technique,The anti-molysite acid of P507 cobalts nickel defiber first,Cobalt section 0.5N hydrochloric acid is washed for P204,The anti-molysite acid of P204,Original 4N sulfuric acid is instead of for anti-copper MnZn 4N hydrochloric acid,Anti- copper MnZn calcium and magnesium cell body is changed into hydrochloric acid system,Without precipitation without blocking,Generation calcium chloride copper MnZn liquid,Liquid adds iron powder reducing to produce copper sponge,After plate-frame filtering liquid add calcium oxide carry out precipitation generation hydroxide MnZn.
3. cobalt chloride solution direct hydrogenation sodium oxide molybdena and hydrogen peroxide regulation pH value control temperature and rotating speed produce varigrained hydroxyl cobaltosic oxide.Wet oxidation cobalt produces basic technology,
Wet oxidation cobalt brief description of the process
1 prepares certain density cobalt chloride (or cobaltous sulfate) solution, alkali lye, compounding agent solution；Under the conditions of uniform temperature, high-speed stirred, by three kinds of solution cocurrents addition containers, the pH value of reactant, cobalt oxide is obtained by way of continuous overflow is aged in control liquid feeding speed regulation container.Cobalt oxide is obtained cobaltosic oxide by being calcined under separation of solid and liquid, uniform temperature.Flow chart see it is attached 1)
Cobalt hydroxide prepares cobalt oxide brief description of the process
2. certain density cobalt chloride (or cobaltous sulfate) solution, ammoniacal liquor (or ammonium chloride is directly added into cobalt chloride), alkali lye are prepared；Under the conditions of uniform temperature, strong stirring, by three kinds of (or two kinds) solution cocurrents addition containers, control liquid feeding speed adjusts the pH value of reactant in container,By way of continuous overflowCobalt hydroxide is obtained.
3. cobalt hydroxide is obtained cobaltosic oxide by being calcined under separation of solid and liquid, uniform temperature.(flow chart is shown in attached 2)
4. cobalt chloride spray pyrolysis prepare cobalt oxide brief description of the process
Prepare certain density cobalt chloride solution；Under the conditions of uniform temperature hot blast, oxygen-enriched atmosphere, by cobalt chloride solution adverse current addition high temperature pyrolysis stove, spray gun size, spray rate, hot blast temperature are controlled,By continuous spray pyrolysis modeCobaltosic oxide is obtained by being calcined under uniform temperature.(flow chart is shown in attached 3)
5. cobalt carbonate prepares cobalt oxide brief description of the process
Prepare certain density cobalt chloride solution, ammonium bicarbonate solution；Under agitation, two kinds of solution are reacted in container, controls liquid feeding speed, whole process control temperature to pass throughBatch (-type)Cobalt carbonate is obtained.Cobalt carbonate is obtained cobaltosic oxide by separation of solid and liquid, drying, high temperature sintering
The present invention has the advantage that compared with prior art：Soda ash removal of impurities is substituted using calcium oxide powder, production cost is reduced, the generation of fluorination calcium and magnesium hazardous waste is reduced, sustainability is strong, product quality stabilization, small investment is produced, low production cost advantage without ammonia nitrogen waste water.
Brief description of the drawings：
The wet oxidation cobalt wastewater treatment process figure of accompanying drawing 1
The cobalt hydroxide wastewater treatment process figure of accompanying drawing 2
The spray pyrolysis exhaust-gas treatment flow figure of accompanying drawing 3
The cobalt carbonate wastewater treatment process figure of accompanying drawing 4
Specific embodiment：
With reference to embodiment, the present invention is described in further detail, and described hydroxyl cobaltosic oxide and preparation method thereof is mainly included the following steps that：
1. takes selective dissolution, it is liquid to add wash water to size mixing rough cobalt carbonate, return and be warming up in tank diameter 50 DEG C, start to be slowly added into sulfuric acid, control pH value is no more than 3.5, observation foam appearance has a small amount of white foam, pH value control 3.0 or so, it is minimum to be not less than PH2.8, survey current potential 400MV or so, acid adding speed must be slow, every tank mixing time 3-4 hours, pH value not acid adding when reaching 3.0 or so, pH value keeps constant, may filter that, filter residue carries out second dissolving, intensification adds a small amount of sodium pyrosulfite when reaching 50 DEG C, plus sodium pyrosulfite speed must be slow, often plus one bag will check pH value, when adding sodium pyrosulfite pH value constant, sampling analysis Co discord Fe2+, Cu not, current potential, Co≤0.1%Fe2+≤ 3g/I current potentials≤350MV, Cu not≤0.3%, it is up to standard after be warming up to more than 85 DEG C plus sodium chlorate, sodium chlorate presses Fe2+0.25 times addition, stir 1 hour sampling analysis Fe2+Equal to zero, then add calcium oxide powder regulation pH value, when pH value reaches 3.3, you can directly upper extraction workshop section carries out separation, impurity removal for press filtration.
2. extractions removing calcium and magnesium, Suan Rong workshop sections except after iron solution can be directly entered extraction workshop section by plate compression and carry out separation, impurity removal, the anti-molysite acid of P507 cobalts nickel defiber first, cobalt section 0.5N hydrochloric acid is washed for P204, the anti-molysite acid of P204 instead of original 4N sulfuric acid for anti-copper MnZn 4N hydrochloric acid, anti- copper MnZn calcium and magnesium cell body is changed into hydrochloric acid system, generation calcium chloride copper MnZn liquid, liquid add iron powder reducing produce copper sponge, after plate-frame filtering liquid add calcium oxide carry out precipitation generation hydroxide MnZn.
3. cobalt chloride solutions direct hydrogenation sodium oxide molybdena and hydrogen peroxide, adjust pH value control temperature and rotating speed produce varigrained hydroxyl cobaltosic oxide, and wet oxidation cobalt produces basic technology,
Wet oxidation cobalt brief description of the process
1 prepares certain density cobalt chloride (or cobaltous sulfate) solution, alkali lye, compounding agent solution；Under the conditions of uniform temperature, high-speed stirred, by three kinds of solution cocurrents addition containers, the pH value of reactant, cobalt oxide is obtained by way of continuous overflow is aged in control liquid feeding speed regulation container.Cobalt oxide is obtained cobaltosic oxide by being calcined under separation of solid and liquid, uniform temperature.Flow chart see it is attached 1)
Cobalt hydroxide prepares cobalt oxide brief description of the process
2. certain density cobalt chloride (or cobaltous sulfate) solution, ammoniacal liquor (or ammonium chloride is directly added into cobalt chloride), alkali lye are prepared；Under the conditions of uniform temperature, strong stirring, by three kinds of (or two kinds) solution cocurrents addition containers, control liquid feeding speed adjusts the pH value of reactant in container,By way of continuous overflowCobalt hydroxide is obtained.
3. cobalt hydroxide is obtained cobaltosic oxide by being calcined under separation of solid and liquid, uniform temperature.(flow chart is shown in attached 2)
4. cobalt chloride spray pyrolysis prepare cobalt oxide brief description of the process
Prepare certain density cobalt chloride solution；Under the conditions of uniform temperature hot blast, oxygen-enriched atmosphere, by cobalt chloride solution adverse current addition high temperature pyrolysis stove, spray gun size, spray rate, hot blast temperature are controlled,By continuous spray pyrolysis modeCobaltosic oxide is obtained by being calcined under uniform temperature.(flow chart is shown in attached 3)
5. cobalt carbonate prepares cobalt oxide brief description of the process
Prepare certain density cobalt chloride solution, ammonium bicarbonate solution；Under agitation, two kinds of solution are reacted in container, controls liquid feeding speed, whole process control temperature to pass throughBatch (-type)Cobalt carbonate is obtained.Cobalt carbonate is obtained cobaltosic oxide by separation of solid and liquid, drying, high temperature sintering.
Claims (1)
1. hydroxyl cobaltosic oxide and preparation method thereof is mainly included the following steps that：
1. takes selective dissolution, and it is liquid to add wash water to size mixing rough cobalt carbonate,
Return and be warming up in tank diameter 50 DEG C, start to be slowly added into sulfuric acid, control pH value
No more than 3.5, observation foam appearance has a small amount of white foam, pH value control 3.0
Left and right, it is minimum to be not less than PH2.8, survey current potential 400MV or so, acid adding speed one
It is calmly slow, every tank mixing time 3-4 hours, pH value is not added with when reaching 3.0 or so
Acid, pH value keeps constant, you can filtering, filter residue carries out second dissolving, heats up
Add a small amount of sodium pyrosulfite when reaching 50 DEG C, plus sodium pyrosulfite speed must
Slowly, often adding one bag will check pH value, when adding sodium pyrosulfite pH value constant,
Sampling analysis Co discord Fe2+, Cu not, current potential, Co≤0.1%Fe2+≤3g/I
Current potential≤350MV, Cu not≤0.3%, it is up to standard after be warming up to more than 85 DEG C plus
Sodium chlorate, sodium chlorate presses Fe2+0.25 times addition, stir 1 hour sampling point
Analysis Fe2+Equal to zero, calcium oxide powder regulation pH value, pH value is then added to reach 3.3
When, you can directly upper extraction workshop section carries out separation, impurity removal for press filtration；
2. extractions removing calcium and magnesium, Suan Rong workshop sections can by plate compression except solution after iron
Separation, impurity removal, first P507 cobalts nickel defiber are carried out to be directly entered extraction workshop section
Anti- molysite acid, cobalt section 0.5N hydrochloric acid is washed for P204, and the anti-molysite acid of P204 is used
Original 4N sulfuric acid, anti-copper MnZn calcium and magnesium cell body are instead of in anti-copper MnZn 4N hydrochloric acid
It is changed into hydrochloric acid system, generates calcium chloride copper MnZn liquid, liquid adds iron powder reducing to produce
Copper sponge, after plate-frame filtering liquid add calcium oxide carry out precipitation generation manganous hydroxide
Zinc；
3. cobalt chloride solutions direct hydrogenation sodium oxide molybdena and hydrogen peroxide, adjust pH value control
Temperature processed and rotating speed produce varigrained hydroxyl cobaltosic oxide, finite concentration processed
Cobalt chloride (or cobaltous sulfate) solution, alkali lye, compounding agent solution；Uniform temperature,
Under the conditions of high-speed stirred, by three kinds of solution cocurrents addition containers, control liquid feeding is fast
The pH value of reactant, the system by way of continuous overflow is aged in degree regulation container
Obtain cobalt oxide.Cobalt oxide is obtained four oxygen by being calcined under separation of solid and liquid, uniform temperature
Change three cobalts；Prepare certain density cobalt chloride (or cobaltous sulfate) solution, ammoniacal liquor (or
Ammonium chloride is directly added into cobalt chloride), alkali lye；In uniform temperature, strong stirring
Under the conditions of, by three kinds of (or two kinds) solution cocurrents addition containers, control liquid feeding
The pH value of reactant, is obtained by way of continuous overflow in speed regulation container
Cobalt hydroxide；Cobalt hydroxide is obtained four by being calcined under separation of solid and liquid, uniform temperature
Co 3 O；Prepare certain density cobalt chloride solution；Uniform temperature hot blast,
Under the conditions of oxygen-enriched atmosphere, by cobalt chloride solution adverse current addition high temperature pyrolysis stove, control
Spray gun size processed, spray rate, hot blast temperature, by continuous spray pyrolysis mode
Cobaltosic oxide is obtained by being calcined under uniform temperature；Prepare certain density chlorination
Cobalt liquor, ammonium bicarbonate solution；Under agitation, two kinds of solution are reacted in container,
Control liquid feeding speed, whole process control temperature, passes throughBatch (-type)Cobalt carbonate is obtained.
Cobalt carbonate is obtained cobaltosic oxide by separation of solid and liquid, drying, high temperature sintering.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109439900A (en) * | 2018-12-04 | 2019-03-08 | 浙江中金格派锂电产业股份有限公司 | Raffinate liquor treating process and its device in metallurgical industry |
| CN113189088A (en) * | 2021-05-28 | 2021-07-30 | 金川集团股份有限公司 | Method for measuring contents of elemental copper and zinc in cobaltosic oxide |
| CN113233516A (en) * | 2021-05-28 | 2021-08-10 | 金川集团股份有限公司 | Preparation method of single crystal small-granularity cobaltosic oxide |
| CN115417460A (en) * | 2022-09-02 | 2022-12-02 | 格林美（江苏）钴业股份有限公司 | Back-dissolving treatment method for intermediate product of hydroxyl cobalt in cobaltosic oxide production process |
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| CN102534248A (en) * | 2012-01-19 | 2012-07-04 | 江苏润捷新材料有限公司 | Method for leaching cobalt selectively from high-ferrum cobalt material |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109439900A (en) * | 2018-12-04 | 2019-03-08 | 浙江中金格派锂电产业股份有限公司 | Raffinate liquor treating process and its device in metallurgical industry |
| CN113189088A (en) * | 2021-05-28 | 2021-07-30 | 金川集团股份有限公司 | Method for measuring contents of elemental copper and zinc in cobaltosic oxide |
| CN113233516A (en) * | 2021-05-28 | 2021-08-10 | 金川集团股份有限公司 | Preparation method of single crystal small-granularity cobaltosic oxide |
| CN115417460A (en) * | 2022-09-02 | 2022-12-02 | 格林美（江苏）钴业股份有限公司 | Back-dissolving treatment method for intermediate product of hydroxyl cobalt in cobaltosic oxide production process |
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Application publication date: 20170630 |