CN104117686B - A kind of preparation method of cobalt powder - Google Patents
A kind of preparation method of cobalt powder Download PDFInfo
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- CN104117686B CN104117686B CN201410378434.5A CN201410378434A CN104117686B CN 104117686 B CN104117686 B CN 104117686B CN 201410378434 A CN201410378434 A CN 201410378434A CN 104117686 B CN104117686 B CN 104117686B
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- 229910052803 cobalt Inorganic materials 0.000 title claims abstract description 104
- 239000010941 cobalt Substances 0.000 title claims abstract description 104
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 239000000843 powder Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 40
- -1 lithium cobalt Chemical compound 0.000 claims abstract description 39
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 32
- 235000012501 ammonium carbonate Nutrition 0.000 claims abstract description 30
- 235000011149 sulphuric acid Nutrition 0.000 claims abstract description 30
- UFMZWBIQTDUYBN-UHFFFAOYSA-N Cobalt(II) nitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 29
- 239000001117 sulphuric acid Substances 0.000 claims abstract description 29
- PRKQVKDSMLBJBJ-UHFFFAOYSA-N Ammonium carbonate Chemical compound N.N.OC(O)=O PRKQVKDSMLBJBJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 20
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims abstract description 20
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims abstract description 19
- 239000012535 impurity Substances 0.000 claims abstract description 11
- 238000003825 pressing Methods 0.000 claims abstract description 7
- 238000000746 purification Methods 0.000 claims abstract description 7
- KTVIXTQDYHMGHF-UHFFFAOYSA-L Cobalt(II) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 57
- 229940044175 cobalt sulfate Drugs 0.000 claims description 55
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 55
- 238000000605 extraction Methods 0.000 claims description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 229910052756 noble gas Inorganic materials 0.000 claims description 9
- 238000007792 addition Methods 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 3
- 241000790917 Dioxys <bee> Species 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims 1
- 229910052744 lithium Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 21
- 239000007788 liquid Substances 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 8
- 238000001816 cooling Methods 0.000 abstract description 7
- 235000011121 sodium hydroxide Nutrition 0.000 abstract description 7
- 239000003638 reducing agent Substances 0.000 abstract description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-N Carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000956 alloy Substances 0.000 abstract description 3
- 229910045601 alloy Inorganic materials 0.000 abstract description 3
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical class [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 3
- 239000003317 industrial substance Substances 0.000 abstract description 2
- 239000000654 additive Substances 0.000 abstract 1
- 230000000996 additive Effects 0.000 abstract 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 27
- 229910052802 copper Inorganic materials 0.000 description 27
- 239000010949 copper Substances 0.000 description 27
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 238000007127 saponification reaction Methods 0.000 description 8
- 238000005352 clarification Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 235000017550 sodium carbonate Nutrition 0.000 description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- NMCUIPGRVMDVDB-UHFFFAOYSA-L Iron(II) chloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- VAYOSLLFUXYJDT-RDTXWAMCSA-N LSD Chemical compound C1=CC(C=2[C@H](N(C)C[C@@H](C=2)C(=O)N(CC)CC)C2)=C3C2=CNC3=C1 VAYOSLLFUXYJDT-RDTXWAMCSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000001105 regulatory Effects 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 231100000614 Poison Toxicity 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N Potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- ZJRWDIJRKKXMNW-UHFFFAOYSA-N carbonic acid;cobalt Chemical compound [Co].OC(O)=O ZJRWDIJRKKXMNW-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- KTPIHRZQGZDLSN-UHFFFAOYSA-N cobalt;nitric acid Chemical compound [Co].O[N+]([O-])=O KTPIHRZQGZDLSN-UHFFFAOYSA-N 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 235000021190 leftovers Nutrition 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
Abstract
The present invention relates to industrial chemicals production field, particularly to the preparation method of a kind of cobalt powder, comprise the following steps: in lithium cobalt paper, add sulphuric acid carry out acidolysis；Regulation pH value, to after 13, removes cupra matter；Adding hydrogen peroxide, then regulation pH value is to 25, and the removal of impurity is gone in filter pressing；Purification, and react prepared cobalt nitrate solution；To react with ammonium carbonate, obtain cobalt carbonate；Cobalt carbonate is dried, roasting, cooling, obtain cobalt powder.This preparation method, it is not necessary to liquid caustic soda processes lithium cobalt paper, also without adding reducing agent sulfur dioxide in acidization, replaces soda with ammonium carbonate in heavy cobalt；Use lithium cobalt paper production to prepare cobalt powder, greatly reduce production cost, and will not be to environment；And the cobalt powder prepared, has the highest hardness, high comprcssive strength, acts not only as the catalyst of secondary cell, and may apply to hard alloy additive, have, than cobalt protoxide, the scope that is more widely applied.
Description
Technical field
The present invention relates to industrial chemicals production field, in particular to the preparation method of a kind of cobalt powder.
Background technology
At present, owing to metallic cobalt price is high, so that producing ni-mh, nickel chromium triangle secondary battery catalyst-cobalt protoxide one-tenth
This is prohibitively expensive, and uses lithium cobalt paper (being mainly derived from scrapping material and leftover pieces and tearing material open of man of Battery Plant generation) to do former
Material, it is the most cheap that cobalt protoxide is prepared in production, moreover it is possible to reducing the pollution to environment of the lithium cobalt paper, therefore, it is by market
Heat is held in both hands.Prior art produces concretely comprising the following steps of cobalt protoxide with lithium cobalt paper: first by molten for raw material alkali, then acidolysis, then carry out
Purify, extract, precipitate and roasting, obtain cobalt protoxide.But, during alkali in this process for producing is molten, because having
Liquid caustic soda remains in cobalt slag, causes in acid is molten, and sulfuric acid dosage increases, and production cost increases；Further, in acid is molten, because of difficult
Molten cobalt exists, in addition it is also necessary to add reducing agent, and in general production process, reducing agent is sulfur dioxide, and sulfur dioxide is poisonous
Gas, brings atmospheric pollution, and the physical condition of workman is also brought along impact.
Summary of the invention
It is an object of the invention to provide the preparation method of a kind of cobalt powder, to solve above-mentioned problem.
Provide the preparation method of a kind of cobalt powder in an embodiment of the present invention, comprise the following steps:
(a), in lithium cobalt paper add sulphuric acid carry out acidolysis, obtain cobalt sulfate solution；
(b), by described cobalt sulfate solution regulation pH value to 1-3, then remove cupra matter；
(c), will remove cupra matter cobalt sulfate solution add hydrogen peroxide, then regulation pH value go remove impurity to 2-5, filter pressing
Matter, the cobalt sulfate solution being purified；
(d), the cobalt sulfate solution purification that will purify, and react prepared cobalt nitrate solution；
(e), by described cobalt nitrate solution heated and stirred, and add ammonium carbonate, after reaction, obtain cobalt carbonate precipitation；
(f), by described cobalt carbonate dry after in hydrogen reduction system, carry out roasting, the temperature of described roasting is 400-
600 DEG C, after roasting completes, cool down under the protection of noble gas, obtain cobalt powder.
Preferably, in described step (a), also include the filtering residue obtained after lithium cobalt paper acidolysis is carried out acidolysis again.
Preferably, in described step (a), described lithium cobalt paper is 1:0.5-8 with the mass ratio of described sulphuric acid.
Preferably, in described step (a), described filtering residue is 1:2-3 with the mass ratio of described sulphuric acid.
Preferably, in described step (c), the addition of described hydrogen peroxide is that the cobalt sulfate solution of every cubic metre adds
0.08-0.20kg hydrogen peroxide.
Preferably, in described step (d), cobalt sulfate solution is by preparing cobalt nitrate solution after P204, P507 extraction box.
Preferably, in described step (e), described ammonium carbonate is solution state, and the mass percent of sal volatile is 13-
15%, described cobalt nitrate is 1:0.4-4 with the volume ratio of described ammonium carbonate.
Preferably, in described step (f), the temperature of described drying is 115-125 DEG C.
Preferably, the preparation method of described cobalt powder also includes: under the protection of noble gas, uses vacuum pneumatic pulverizer
Described cobalt powder is crushed, prepares even-grained cobalt powder.
Preferably, any one during described noble gas includes nitrogen, carbon dioxide.
The preparation method of a kind of cobalt powder that the embodiment of the present invention provides, it is not necessary to liquid caustic soda processes lithium cobalt paper, acidified
In journey also without add reducing agent sulfur dioxide, in heavy cobalt, replace soda with ammonium carbonate, make cobalt sulfate solution and carbon
In acid ammonium reaction, obtain rod-like crystal, beneficially the uniform cobalt powder of prepared sizes.The preparation method of the cobalt powder that the present invention provides is adopted
Prepare cobalt powder with lithium cobalt paper production, greatly reduce production cost, and will not be to environment；And the cobalt powder prepared,
There is the highest hardness, high comprcssive strength, act not only as the catalyst of secondary cell, and may apply to hard
Alloy addition, has, than cobalt protoxide, the scope that is more widely applied.
Detailed description of the invention
Below by specific embodiment, the present invention is described in further detail.
Provide the preparation method of a kind of cobalt powder in an embodiment of the present invention, comprise the following steps:
(a), in lithium cobalt paper add sulphuric acid carry out acidolysis, obtain cobalt sulfate solution；
(b), by described cobalt sulfate solution regulation pH value to 1-3, then remove cupra matter；
(c), will remove cupra matter cobalt sulfate solution add hydrogen peroxide, then regulation pH value go remove impurity to 2-5, filter pressing
Matter, the cobalt sulfate solution being purified；
(d), the cobalt sulfate solution purification that will purify, and react prepared cobalt nitrate solution；
(e), by described cobalt nitrate solution heated and stirred, and add ammonium carbonate, after reaction, obtain cobalt carbonate precipitation；
(f), by described cobalt carbonate dry after in hydrogen reduction system, carry out roasting, the temperature of described roasting is 400-
600 DEG C, after roasting completes, cool down under the protection of noble gas, obtain cobalt powder.
The preparation method of a kind of cobalt powder that the embodiment of the present invention provides, it is not necessary to liquid caustic soda processes lithium cobalt paper, acidified
In journey also without add reducing agent sulfur dioxide, in heavy cobalt, replace soda with ammonium carbonate, make cobalt sulfate solution and carbon
In acid ammonium reaction, obtain rod-like crystal, beneficially the uniform cobalt powder of prepared sizes.The preparation method of the cobalt powder that the present invention provides is adopted
Prepare cobalt powder with lithium cobalt paper production, greatly reduce production cost, and will not be to environment；And the cobalt powder prepared,
There is the highest hardness, high comprcssive strength, act not only as the catalyst of secondary cell, and may apply to hard
Alloy addition, has, than cobalt protoxide, the scope that is more widely applied.
The most thorough in order to extracted by the cobalt in lithium cobalt paper, the impurity obtained is less, to reduce the pollution of environment, preferably
Ground, in described step (a), also includes the filtering residue obtained after lithium cobalt paper acidolysis is carried out acidolysis again.
In order to by the more preferable acidolysis of cobalt composition in lithium cobalt paper, it is preferable that in described step (a), described lithium cobalt paper with
The mass ratio of described sulphuric acid is 1:0.5-8.It is highly preferred that the mass ratio of described lithium cobalt paper and described sulphuric acid is 1:2-4.Such as may be used
To select 1:0.5,1:1,1:2,1:3,1:4,1:5,1:6,1:7,1:8 etc..
In order to by the more preferable acidolysis of cobalt composition in filtering residue, it is preferable that in described step (a), described filtering residue is with described
The mass ratio of sulphuric acid is 1:2-3.
Specifically, in described step (b), described removal cupra matter is by copper extraction box by cobalt sulfate solution.Pass through
The multitple extraction of copper extraction box, removes the cupra matter in cobalt sulfate solution.Copper extraction box concretely comprises the following steps: copper extraction box has
13 grades, the 1st, 2 grades of saponification sections, 3rd level feed clarification, the 4th, 5,6 grades of extractions, the 7th grade of spent acid settling section, wash cobalt section for the 8th, 9 grades,
10th grade of copper clarification of water, washes copper section for the 11st, 12 grades, the 13rd grade of organic clarification level.
Concrete principle is: be first high-efficiency copper extractant and liquid caustic soda generation saponification in copper extraction box, then will acidifying
After cobalt sulfate solution in copper absorption on copper extractant；It is adsorbed with the high-efficiency copper extractant of a large amount of copper at 1.0mol/L
Sulphuric acid in wash, during high-efficiency copper is extracted, the cobalt liquid that is mingled with washs；The high-efficiency copper extractant bringing a large amount of copper afterwards exists
The sulphuric acid of 4mol/L washs, substantial amounts of copper ion is washed, form copper-bath.
The component content of the cobalt sulfate solution before and after entrance copper extraction box is as shown in Table 1 and Table 2.
Table 1 enters the component content of the cobalt sulfate solution before copper extraction box
Table 2 enters the component content of the cobalt sulfate solution after copper extraction box
As can be seen from Table 1 and Table 2, the copper content in cobalt sulfate solution is after copper extraction box processes, and its content is the lowest.
Preferably, in described step (c), the addition of described hydrogen peroxide is that the cobalt sulfate solution of every cubic metre adds
0.08-0.20kg hydrogen peroxide.Such as hydrogen peroxide can select 0.08kg, 0.10kg, 0.12kg, 0.15kg, 0.18kg, 0.20kg
Deng.Hydrogen peroxide is to be ferric ion by the oxidation of divalent iron ion in cobalt sulfate solution, and then the going of follow-up iron ion
Remove.
Preferably, in described step (d), cobalt sulfate solution is by preparing cobalt nitrate solution after P204, P507 extraction box.
Wherein, P204 extraction box has 34 grades, and dominant response flow process is: 2 grades of saponification, 3 grades of feed clarifications, 9 grades of extractions, and 7
Level washing, 1 grade of spent acid clarification, wash copper, manganese, 1 grade of spent acid clarification, 4 grades of washed metals, 3 grades of extractant clarifications for 4 grades.Concrete principle is:
P204 extractant and liquid caustic soda generation saponification, saponification rate about 70%, the copper in the extraction section of 9 grades, P204 and solution, manganese
Big quantitative response；The cobalt being mingled with the salt acid elution of 1mol/L in 7 grades of washing sections, washes copper for 4 grades, and the sulphuric acid of manganese section 2.5mol/L is washed
Copper and manganese, at 4 grades with the hydrochloric acid washed metal washed metal of 6mol/L.The purpose of purification of sulphuric acids cobalt liquor is reached with this.
As shown in table 3 by component content each in cobalt sulfate solution after P204 extraction box.
Table 3 enters the component content of the cobalt sulfate solution after P204 extraction box
| Element | Cobalt | Nickel | Copper | Ferrum | Manganese | Calcium | Magnesium |
| Concentration (g/L) | 15.7 | 0.68 | 0.0004 | 0.001 | 0.0006 | 0.002 | 0.002 |
P507 extraction box has 32 grades, and dominant response flow process is: 2 grades of saponification, 3 grades of feed clarifications, 7 grades of extractions, washes for 5 grades
Wash, 1 grade of finished product clarification, 4 grades of washings, 1 grade of spent acid clarification, 4 grades of washed metals, 3 grades of extractant clarifications.Concrete principle is: P507 extracts
Agent and liquid caustic soda generation saponification, saponification rate about 65%；7 grades of extraction sections, the big quantitative response of nickel in P507 and feed liquid, 5 grades
Washing section, washs the cobalt being mingled with the nitric acid of 1.2mol/L；At 4 grades of washing sections, wash cobalt with the nitric acid of 3mol/L, form nitric acid
Cobalt；4 grades of washed metal sections, with the hydrochloric acid washed metal of 6mol/L.
As shown in table 4 by component content each in cobalt nitrate solution after P507 extraction box.
Table 4 enters the component content of the cobalt nitrate solution after P507 extraction box
| Element | Cobalt | Nickel | Copper | Ferrum | Manganese | Calcium | Magnesium |
| Concentration (g/L) | 73.5 | 0.001 | 0.001 | 0.001 | 0.001 | 0.006 | 0.003 |
Cobalt sulfate solution is by after P204, P507 extraction box, and its composition obtains purification and purification, and cobaltous sulfate generates nitre
Acid cobalt.Using P204, P507 extraction box, cobalt sulfate solution directly carries out multitple extraction, method is easy, in the cobalt nitrate obtained
Cobalt composition is the purest.
In order to preferably be reacted with ammonium carbonate by cobalt nitrate, it is preferable that in described step (e), described ammonium carbonate is molten
Liquid, the mass percent of sal volatile is 13-15%, and described cobalt nitrate is 1:0.4-4 with the volume ratio of described ammonium carbonate,
Prepare solid carbonic acid cobalt.Wherein, cobalt nitrate can select 1:0.4,1:1,1:2,1:3,1:4 etc. with the volume ratio of ammonium carbonate.
In the step that cobalt nitrate and ammonium carbonate react, both are 65-75 DEG C at the temperature of reaction, keep stirring in course of reaction
Mixing, the speed of stirring is 25-35r/min.
In order to reduce the hardness of the cobalt carbonate obtained, empirical tests, the sal volatile of interpolation is preheated to 75-85 DEG C, then
Mixing with the cobalt nitrate being heated to 70-80 DEG C, control temperature, to 65-75 DEG C, is kept stirring in course of reaction, stirring
Speed is 25-35r/min, is 7.8-8.2 to pH, and reaction completes, and the cobalt carbonate hardness obtained is suitable.
In order to be evaporated faster by the moisture in cobalt carbonate, prevent the cobalt in cobalt carbonate oxidized again, it is preferable that
In described step (f), the temperature of described drying is 115-125 DEG C.
Cobalt carbonate is 400-600 DEG C in temperature and carries out roasting, and cobalt carbonate can be decomposed under the reduction of hydrogen, by
Step decomposition obtains metallic cobalt, empirical tests, it is preferable that the hydrogen flowing quantity being passed through in hydrogen reduction system is 4-6L/h, it is possible to very well
Meet its reduction.But metallic cobalt is prone to oxidation in atmosphere, therefore, uses lazy after roasting completes during cooling
Property gas is protected.Wherein, sintering temperature can select 400 DEG C, 450 DEG C, 500 DEG C, 520 DEG C, 550 DEG C, 580 DEG C, 600 DEG C
Etc..
In order to prevent the cobalt powder granularity that temperature is the highest and prepared too big, it is unfavorable for follow-up crushing.Preferably, described roasting
Temperature be 470-540 DEG C.Further, described roasting uses the mode being gradually lowered temperature to carry out roasting.As roasting uses
Metal powder reduction stove is carried out, 470-540 DEG C is arranged to 530-540 DEG C, 515-525 DEG C, 495-505 DEG C, 475-485 DEG C,
465-470 DEG C, 465-470 DEG C of temperature section, respectively at each temperature section roasting 40-80min, i.e. can get granule size suitable
Cobalt powder.Roasting enters cooling zone cooling after completing, cool down 2.5-3.5h, obtain the cobalt powder that temperature is 32-38 DEG C.
Cobalt powder granularity owing to obtaining in step (f) is uneven, in order to obtain uniform cobalt powder, needs to enter it
Crushing of one step.In order to prevent cobalt powder in shattering process oxidized, it is preferable that the preparation method of described cobalt powder also includes: lazy
Property gas protection under, use vacuum pneumatic pulverizer described cobalt powder is crushed, prepare even-grained cobalt powder.
Empirical tests, when noble gas is any one in nitrogen, carbon dioxide, its protected effect is good, and nitrogen and dioxy
Changing carbon gas is common gas, low cost.Preferably, any one during described noble gas includes nitrogen, carbon dioxide.
Being below the preparation method specific embodiment of cobalt powder, wherein, the amount containing cobalt in the lithium cobalt paper that embodiment uses is at 35-
45%.
Embodiment 1
The preparation method of cobalt powder, comprises the following steps:
(a), in lithium cobalt paper, add sulphuric acid, the mass ratio of lithium cobalt paper and sulphuric acid is 1:0.5, and it is molten that acidolysis obtains cobaltous sulfate
Liquid；Cobalt sulfate solution being crossed pressure filter, again adds sulphuric acid in filtering residue, filtering residue is 1:2 with the ratio of sulphuric acid；
(b), add mass percent be the soda ash solution of 6% as nertralizer, cobalt sulfate solution is regulated pH value to 1,
Then by cobalt sulfate solution by copper extraction box, cupra matter is removed；
(c), will remove cupra matter cobalt sulfate solution add hydrogen peroxide, the addition of hydrogen peroxide is the sulphuric acid of every cubic metre
Cobalt liquor adds 0.08kg hydrogen peroxide, is subsequently adding the soda ash solution that mass percent is 6%, and regulation pH value is to 2, and filter pressing is removed
Impurity, the cobalt sulfate solution being purified；
(d), by the cobalt sulfate solution purified by preparing cobalt nitrate solution after P204, P507 extraction box；
(e), cobalt nitrate solution is put into heated and stirred in reactor, and add sal volatile, the matter of sal volatile
Amount percent is 13%, and cobalt nitrate is 1:4 with the volume ratio of ammonium carbonate, obtains cobalt carbonate precipitation after reaction；
(f), cobalt carbonate is dried at 115 DEG C, be then placed in metal powder reduction stove, carry out in hydrogen reduction system
Roasting, carries out roasting through temperature below section: 530 DEG C, 515 DEG C, 495 DEG C, 475 DEG C, 465 DEG C, 465 DEG C, each temperature section successively
Roasting 80min, roasting enters cooling zone after completing and cools down under the protection of nitrogen, cools down 2.5h, obtain the cobalt that temperature is 38 DEG C
Powder；
Under the protection of nitrogen, using vacuum pneumatic pulverizer to be crushed by cobalt powder, preparing even-grained, granularity is
Cobalt powder about 1.2 μm.
With in lithium cobalt paper containing cobalt gauge, the yield of cobalt powder is 92%.
Prepared cobalt powder atomic absorption spectrophotometer is calculated the various impurity contents in cobalt powder；With carbon, sulfur
Analyser, analyzes carbon therein, sulfur content；The purity calculating cobalt powder with minusing is 99.95%.
Embodiment 2
The preparation method of cobalt powder, comprises the following steps:
(a), in lithium cobalt paper, add sulphuric acid, the mass ratio of lithium cobalt paper and sulphuric acid is 1:4, and acidolysis obtains cobalt sulfate solution；
Cobalt sulfate solution being crossed pressure filter, again adds sulphuric acid in filtering residue, filtering residue is 1:2.5 with the ratio of sulphuric acid；
(b), add mass percent be the soda ash solution of 7% as nertralizer, cobalt sulfate solution is regulated pH value to 2,
Then by cobalt sulfate solution by copper extraction box, cupra matter is removed；
(c), will remove cupra matter cobalt sulfate solution add hydrogen peroxide, the addition of hydrogen peroxide is the sulphuric acid of every cubic metre
Cobalt liquor adds 0.15kg hydrogen peroxide, is subsequently adding the soda ash solution that mass percent is 7%, and regulation pH value is to 3.5, and filter pressing is gone
The removal of impurity, the cobalt sulfate solution being purified；
(d), by the cobalt sulfate solution purified by preparing cobalt nitrate solution after P204, P507 extraction box；
(e), cobalt nitrate solution is put into heated and stirred in reactor, and add sal volatile, the matter of sal volatile
Amount percent is 14%, and cobalt nitrate is 1:0.4-4 with the volume ratio of ammonium carbonate, obtains cobalt carbonate precipitation after reaction；
(f), cobalt carbonate is dried at 120 DEG C, be then placed in metal powder reduction stove, carry out in hydrogen reduction system
Roasting, carries out roasting through temperature below district: 540 DEG C, 525 DEG C, 500 DEG C, 480 DEG C, 470 DEG C, 470 DEG C, each temperature section successively
Roasting 60min, roasting enters cooling zone after completing and cools down under the protection of carbon dioxide, cools down 3h, and obtaining temperature is 35 DEG C
Cobalt powder；
Under the protection of carbon dioxide, use vacuum pneumatic pulverizer to be crushed by cobalt powder, prepare even-grained, grain
Degree is the cobalt powder about 1.2 μm.
With in lithium cobalt paper containing cobalt gauge, the yield of cobalt powder is 95%.
Prepared cobalt powder atomic absorption spectrophotometer is calculated the various impurity contents in cobalt powder；With carbon, sulfur
Analyser, analyzes carbon therein, sulfur content；The purity calculating cobalt powder with minusing is 99.98%.
Embodiment 3
The preparation method of cobalt powder, comprises the following steps:
(a), in lithium cobalt paper, add sulphuric acid, the mass ratio of lithium cobalt paper and sulphuric acid is 1:8, and acidolysis obtains cobalt sulfate solution；
Cobalt sulfate solution being crossed pressure filter, again adds sulphuric acid in filtering residue, filtering residue is 1:3 with the ratio of sulphuric acid；
(b), add mass percent be the soda ash solution of 7% as nertralizer, cobalt sulfate solution is regulated pH value to 3,
Then by cobalt sulfate solution by copper extraction box, cupra matter is removed；
(c), will remove cupra matter cobalt sulfate solution add hydrogen peroxide, the addition of hydrogen peroxide is the sulphuric acid of every cubic metre
Cobalt liquor adds 0.20kg hydrogen peroxide, is subsequently adding the soda ash solution that mass percent is 7%, and regulation pH value is to 5, and filter pressing is removed
Impurity, the cobalt sulfate solution being purified；
(d), by the cobalt sulfate solution purified by preparing cobalt nitrate solution after P204, P507 extraction box；
(e), cobalt nitrate solution is put into heated and stirred in reactor, and add sal volatile, the matter of sal volatile
Amount percent is 15%, and cobalt nitrate is 1:0.4-4 with the volume ratio of ammonium carbonate, obtains cobalt carbonate precipitation after reaction；
(f), cobalt carbonate is dried at 125 DEG C, be then placed in metal powder reduction stove, carry out in hydrogen reduction system
Roasting, carries out roasting through temperature below district: 540 DEG C, 525 DEG C, 505 DEG C, 485 DEG C, 470 DEG C, 470 DEG C, each temperature section successively
Roasting 40min, roasting enters cooling zone after completing and cools down under the protection of nitrogen, cools down 3.5h, obtain the cobalt that temperature is 32 DEG C
Powder；
Under the protection of nitrogen, using vacuum pneumatic pulverizer to be crushed by cobalt powder, preparing even-grained, granularity is
Cobalt powder about 1.2 μm.
With in lithium cobalt paper containing cobalt gauge, the yield of cobalt powder is 92%.
Prepared cobalt powder atomic absorption spectrophotometer is calculated the various impurity contents in cobalt powder；With carbon, sulfur
Analyser, analyzes carbon therein, sulfur content；The purity calculating cobalt powder with minusing is 99.96%.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for the skill of this area
For art personnel, the present invention can have various modifications and variations.All within the spirit and principles in the present invention, that is made any repaiies
Change, equivalent, improvement etc., should be included within the scope of the present invention.
Claims (7)
1. the preparation method of a cobalt powder, it is characterised in that comprise the following steps:
(a), in lithium cobalt paper add sulphuric acid carry out acidolysis, obtain cobalt sulfate solution；
(b), by described cobalt sulfate solution regulation pH value to 1-3, then remove cupra matter；
(c), will remove cupra matter cobalt sulfate solution add hydrogen peroxide, then regulation pH value go the removal of impurity to 2-5, filter pressing,
To the cobalt sulfate solution purified；
(d), the cobalt sulfate solution purification that will purify, and react prepared cobalt nitrate solution；
(e), by described cobalt nitrate solution heated and stirred, and add ammonium carbonate, the ammonium carbonate of interpolation is preheated to 75-85 DEG C, reaction
Temperature is 65-75 DEG C, and the speed of stirring is 25-35r/min, is 7.8-8.2 to pH, and reaction completes, and obtains cobalt carbonate after reaction
Precipitation；
(f), by described cobalt carbonate dry after in hydrogen reduction system, carry out roasting, the temperature of described roasting is 400-600 DEG C,
After roasting completes, cool down under the protection of noble gas, obtain cobalt powder；
Under the protection of noble gas, use vacuum pneumatic pulverizer to be crushed by described cobalt powder, prepare even-grained cobalt
Powder；
In described step (c), the addition of described hydrogen peroxide is that the cobalt sulfate solution of every cubic metre adds 0.08-0.20kg pair
Oxygen water；
In described step (e), described ammonium carbonate is solution state, and the mass percent of sal volatile is 13%-15%, described
Cobalt nitrate is 1:0.4-4 with the volume ratio of described ammonium carbonate.
The preparation method of cobalt powder the most according to claim 1, it is characterised in that in described step (a), also includes lithium
The filtering residue obtained after cobalt paper acidolysis carries out acidolysis again.
The preparation method of cobalt powder the most according to claim 2, it is characterised in that in described step (a), described lithium cobalt paper
It is 1:0.5-8 with the mass ratio of described sulphuric acid.
The preparation method of cobalt powder the most according to claim 3, it is characterised in that in described step (a), described filtering residue with
The mass ratio of described sulphuric acid is 1:2-3.
The preparation method of cobalt powder the most according to claim 2, it is characterised in that in described step (d), cobalt sulfate solution
By preparing cobalt nitrate solution after P204, P507 extraction box.
The preparation method of cobalt powder the most according to claim 2, it is characterised in that in described step (f), described drying
Temperature is 115-125 DEG C.
The preparation method of cobalt powder the most according to claim 1, it is characterised in that described noble gas includes nitrogen, dioxy
Change any one in carbon.
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| CN201410378434.5A CN104117686B (en) | 2014-08-01 | A kind of preparation method of cobalt powder |
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| CN201410378434.5A CN104117686B (en) | 2014-08-01 | A kind of preparation method of cobalt powder |
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| CN104117686B true CN104117686B (en) | 2017-01-04 |
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