CN109666797A - A kind of leaching liquid and preparation method thereof of cobalt-containing materials - Google Patents
A kind of leaching liquid and preparation method thereof of cobalt-containing materials Download PDFInfo
- Publication number
- CN109666797A CN109666797A CN201811599150.3A CN201811599150A CN109666797A CN 109666797 A CN109666797 A CN 109666797A CN 201811599150 A CN201811599150 A CN 201811599150A CN 109666797 A CN109666797 A CN 109666797A
- Authority
- CN
- China
- Prior art keywords
- cobalt
- modified
- containing materials
- parts
- hydro
- 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.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 99
- 239000010941 cobalt Substances 0.000 title claims abstract description 97
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 97
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 238000002386 leaching Methods 0.000 title claims abstract description 25
- 239000007788 liquid Substances 0.000 title claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000002023 wood Substances 0.000 claims abstract description 50
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical class [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 35
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 35
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims abstract description 35
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 32
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 32
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 32
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims abstract description 28
- 150000001868 cobalt Chemical class 0.000 claims abstract description 27
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002253 acid Substances 0.000 claims abstract description 18
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims abstract description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 16
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 16
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004202 carbamide Substances 0.000 claims abstract description 14
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims abstract description 14
- 235000019341 magnesium sulphate Nutrition 0.000 claims abstract description 14
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 239000006004 Quartz sand Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 124
- 239000000047 product Substances 0.000 claims description 67
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 54
- 238000010438 heat treatment Methods 0.000 claims description 40
- 238000005406 washing Methods 0.000 claims description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 235000019441 ethanol Nutrition 0.000 claims description 14
- 229920000573 polyethylene Polymers 0.000 claims description 14
- 239000004698 Polyethylene Substances 0.000 claims description 13
- 230000004048 modification Effects 0.000 claims description 13
- 238000012986 modification Methods 0.000 claims description 13
- -1 polyethylene Polymers 0.000 claims description 13
- 238000004108 freeze drying Methods 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 238000010792 warming Methods 0.000 claims description 11
- 239000006227 byproduct Substances 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- SUVIGLJNEAMWEG-UHFFFAOYSA-N propane-1-thiol Chemical compound CCCS SUVIGLJNEAMWEG-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 3
- VYMPLPIFKRHAAC-UHFFFAOYSA-N 1,2-ethanedithiol Chemical compound SCCS VYMPLPIFKRHAAC-UHFFFAOYSA-N 0.000 claims 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 description 12
- 238000012423 maintenance Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 8
- 229940068921 polyethylenes Drugs 0.000 description 8
- 239000010453 quartz Substances 0.000 description 8
- 230000004044 response Effects 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 210000002700 urine Anatomy 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 241000255964 Pieridae Species 0.000 description 2
- OTVPWGHMBHYUAX-UHFFFAOYSA-N [Fe].[CH]1C=CC=C1 Chemical compound [Fe].[CH]1C=CC=C1 OTVPWGHMBHYUAX-UHFFFAOYSA-N 0.000 description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical class CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/0423—Halogenated acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—Sulfurated acids or salts thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention is related to a kind of leaching liquid and preparation method thereof of cobalt-containing materials, including following raw material components: modified cobalt-containing materials, modified wood powder, modified polyvinylalcohol, modified ferrocene, dilute sulfuric acid, dilute hydrochloric acid and water, modified cobalt-containing materials are by cobalt-containing materials, quartz sand and nanometer iron powder reaction are made, modified wood powder is by wood powder, water, hydroxy-ethyl acrylate, 2- acrylamide-2-methyl propane sulfonic, acrylic acid, ammonium persulfate, ammonium sulfate and urea reaction are made, modified polyvinylalcohol is by polyvinyl alcohol, mercaptan, alchlor and magnesium sulfate reaction are made, modified ferrocene is by ferrocene, hydrofluoric acid, fluoboric acid and fluororesin reaction are made.Cobalt element in cobalt-containing materials can be leached in leachate by the invention, excellent to the leaching performance of cobalt element.
Description
Technical field
The invention is related to a kind of leaching liquid and preparation method thereof of cobalt-containing materials.
Background technique
Mass content of the cobalt element in the earth's crust is less than 0.001%, and Chinese cobalt deposit content is lower, and cobalt is widely used
In fields such as space flight, medical treatment, chemical industry, pigment.Therefore, the cobalt in recycling low content cobalt-containing materials is particularly important.It is low
Cobalt in content cobalt-containing materials haves the defects that cobalt leaching rate is low in removal process.Therefore, cobalt-containing materials are in cobalt leaching performance
Aspect needs further to be promoted.The invention uses modified cobalt-containing materials, modified wood powder, modified polyvinylalcohol, is modified ferrocene, is dilute
Sulfuric acid and dilute hydrochloric acid are prepared for the leachate of cobalt-containing materials, and the cobalt element of cobalt-containing materials is leached in leachate by this method,
Leach haveing excellent performance for cobalt element.
Summary of the invention
A kind of leaching liquid and preparation method thereof for being designed to provide cobalt-containing materials of the invention, this method pass through modified-reaction object
The material of raw material and special process mode, preparation has the excellent performance that cobalt element in cobalt-containing materials is leached to leachate.
To achieve the goals above, the technical solution of the invention is as follows.
A kind of leaching liquid and preparation method thereof of cobalt-containing materials, specifically includes the following steps:
It (1), is 10:6~9:7~13:4~8 according to mass parts ratio by ferrocene, hydrofluoric acid, fluoboric acid and fluororesin
It is added in hydrothermal reaction kettle, maintaining hydrothermal temperature is 0.5~3h of hydro-thermal reaction under the conditions of 108~130 DEG C, and product passes through
Filter, 500mL water washing 3 times 500mL ethanol washing 3 times, are dried in vacuo 6min in 40 DEG C, -0.08MPa, obtain modified two cyclopentadienyl
Iron；
It (2), is 30:27~41:1~3:3 according to mass parts ratio by polyvinyl alcohol, mercaptan, alchlor and magnesium sulfate
~9 are added in hydrothermal reaction kettle, and maintaining hydrothermal temperature is 0.5~2h of hydro-thermal reaction under the conditions of 115~132 DEG C, by water
1~5h of hydro-thermal reaction under the conditions of thermal response kettle temperature degree is warming up to 145~180 DEG C, product through 500mL water supersound washing 3 times,
500mL EtOH Sonicate washs 3 times, is dried in vacuo 12min in 47 DEG C, -0.09MPa, obtains modified polyvinylalcohol；
(3), by wood powder, water, hydroxy-ethyl acrylate, 2- acrylamide-2-methyl propane sulfonic, acrylic acid, ammonium sulfate and urine
Element is that 70:88~100:19~30:14~22:5~11:18~26:17~29 are added to hydro-thermal reaction according to mass parts ratio
In kettle, maintaining hydrothermal temperature is 28~40min of hydro-thermal reaction under the conditions of 75~90 DEG C, is 0.4~1 by mass parts ratio
Ammonium persulfate is added in hydrothermal reaction kettle, and maintaining hydrothermal temperature is 0.5~3h of hydro-thermal reaction under the conditions of 78~93 DEG C, is produced
- 80 DEG C of 2~9h of freeze-drying of object warp, product is through crushing, under nitrogen protection, in 200 DEG C of heat treatment 0.5h, 300 DEG C of heat treatments
1h, 400 DEG C of heat treatment 2h to get arrive modified wood powder；
It (4), is that 100:13~17:6~13 are added to according to mass parts ratio by cobalt-containing materials, quartz sand and nanometer iron powder
In vibromill, revolving speed is that 3000~6000r/min reacts 0.5~5h to get modified cobalt-containing materials are arrived；
(5), it is according to mass parts ratio by modified cobalt-containing materials, modified wood powder, the pure and mild modified ferrocene of modified poly ethylene
85:66~80:13~21:2~6 are added in vibromill, and revolving speed is that 6000~8000r/min reacts 15~40min, product warp
Product and mass parts ratio are 69~83:23~31:21~34 dilute sulfuric acid by 400~1000 DEG C of 0.1~3h of heat treatment, dilute
Hydrochloric acid and water are added in hydrothermal reaction kettle, and maintaining hydrothermal temperature is 0.2~5h of hydro-thermal reaction under the conditions of 86~132 DEG C,
Product is filtered to arrive cobalt-containing materials leachate.
The leaching liquid and preparation method thereof of cobalt-containing materials described in the invention, including the following steps:
It (1), is 10:6~9:7~13:4~8 according to mass parts ratio by ferrocene, hydrofluoric acid, fluoboric acid and fluororesin
It is added in hydrothermal reaction kettle, maintaining hydrothermal temperature is 0.5~3h of hydro-thermal reaction under the conditions of 108~130 DEG C, and product passes through
Filter, 500mL water washing 3 times 500mL ethanol washing 3 times, are dried in vacuo 6min in 40 DEG C, -0.08MPa, obtain modified two cyclopentadienyl
Iron；The purpose of the hydrofluoric acid, fluoboric acid and fluororesin is in order to improve the content of ferrocene surface fluorine element.
It (2), is 30:27~41:1~3:3 according to mass parts ratio by polyvinyl alcohol, mercaptan, alchlor and magnesium sulfate
~9 are added in hydrothermal reaction kettle, and maintaining hydrothermal temperature is 0.5~2h of hydro-thermal reaction under the conditions of 115~132 DEG C, by water
1~5h of hydro-thermal reaction under the conditions of thermal response kettle temperature degree is warming up to 145~180 DEG C, product through 500mL water supersound washing 3 times,
500mL EtOH Sonicate washs 3 times, is dried in vacuo 12min in 47 DEG C, -0.09MPa, obtains modified polyvinylalcohol；The mercaptan
Purpose in order to prevent trivalent cobalt element occur.
(3), by wood powder, water, hydroxy-ethyl acrylate, 2- acrylamide-2-methyl propane sulfonic, acrylic acid, ammonium sulfate and urine
Element is that 70:88~100:19~30:14~22:5~11:18~26:17~29 are added to hydro-thermal reaction according to mass parts ratio
In kettle, maintaining hydrothermal temperature is 28~40min of hydro-thermal reaction under the conditions of 75~90 DEG C, is 0.4~1 by mass parts ratio
Ammonium persulfate is added in hydrothermal reaction kettle, and maintaining hydrothermal temperature is 0.5~3h of hydro-thermal reaction under the conditions of 78~93 DEG C, is produced
- 80 DEG C of 2~9h of freeze-drying of object warp, product is through crushing, under nitrogen protection, in 200 DEG C of heat treatment 0.5h, 300 DEG C of heat treatments
1h, 400 DEG C of heat treatment 2h to get arrive modified wood powder；The hydroxy-ethyl acrylate, 2- acrylamide-2-methyl propane sulfonic, sulphur
The purpose of sour ammonium and urea is in order to improve the porosity of wood powder.
It (4), is that 100:13~17:6~13 are added to according to mass parts ratio by cobalt-containing materials, quartz sand and nanometer iron powder
In vibromill, revolving speed is that 3000~6000r/min reacts 0.5~5h to get modified cobalt-containing materials are arrived；It the quartz sand and receives
The purpose of rice iron powder is in order to improve the lattice structures of cobalt-containing materials.
(5), it is according to mass parts ratio by modified cobalt-containing materials, modified wood powder, the pure and mild modified ferrocene of modified poly ethylene
85:66~80:13~21:2~6 are added in vibromill, and revolving speed is that 6000~8000r/min reacts 15~40min, product warp
Product and mass parts ratio are 69~83:23~31:21~34 dilute sulfuric acid by 400~1000 DEG C of 0.1~3h of heat treatment, dilute
Hydrochloric acid and water are added in hydrothermal reaction kettle, and maintaining hydrothermal temperature is 0.2~5h of hydro-thermal reaction under the conditions of 86~132 DEG C,
Product is filtered to arrive cobalt-containing materials leachate.
Invention has the beneficial effects that:
1, the fluorine ion discharged in hydrofluoric acid, fluoboric acid and fluororesin has stronger corrosivity, and ferrocene passes through to fluorine
Ion carries out absorption complexing, improves the fluorine content and corrosion penetration on ferrocene surface；The modification ferrocene of preparation is because of its surface
The leaching rate of cobalt element in cobalt-containing materials can be improved containing strong infiltrative fluorine ion；
2, there is mercaptan stronger reducing property can not only be significantly improved by the way that mercaptan is grafted to polyvinyl alcohol surface
The sulfhydryl content on polyvinyl alcohol surface, moreover it is possible to keep the stability of sulfydryl in use and reduce smell and the pollution of mercaptan
Property；Reproducibility of the modified polyvinylalcohol of preparation because maintaining sulfydryl can prevent the appearance of trivalent cobalt element, improve cobalt-containing materials
The leaching rate of middle cobalt element；
3, the polymer of hydroxy-ethyl acrylate and 2- acrylamide-2-methyl propane sulfonic has stronger rigidity, ammonium sulfate
There is excellent pore-creating performance with urea, pass through hydroxy-ethyl acrylate, 2- acrylamide-2-methyl propane sulfonic, ammonium sulfate and urine
The synergistic effect of element, can improve the porosity of wood powder；After high-temperature process, the porosity and specific surface of wood powder can be further improved
Product；The modified wood powder of preparation can improve the leaching rate of cobalt element in cobalt-containing materials because of its high porosity and high-specific surface area；
4, quartz sand and nanometer iron powder can generate change to cobalt-containing materials lattice surface by high speed machine friction treatment,
Assign the high chemical activity in cobalt-containing materials surface；The modification cobalt-containing materials of preparation can improve in cobalt-containing materials because of its high chemical activity
The leaching rate of cobalt element；
5, under modified cobalt-containing materials, modified wood powder, the pure and mild modified ferrocene synergistic effect of modified poly ethylene, cobalt material will be contained
Cobalt is leached in leachate in material with high leaching rate.
Specific embodiment
It is described below with reference to specific embodiment of the embodiment to the invention, to better understand the invention.
Embodiment 1
A kind of cobalt-containing materials leachate, preparation method includes the following steps:
(1), 10 parts of ferrocene, 7.3 parts of hydrofluoric acid, 8.3 parts of fluoboric acid and 4.3 parts of fluororesin are weighed and are added to hydro-thermal reaction
In kettle, maintaining hydrothermal temperature is hydro-thermal reaction 1h under the conditions of 120 DEG C, and product is through filtering, 500mL water washing 3 times, 500mL
Ethanol washing 3 times, it is dried in vacuo 6min in 40 DEG C, -0.08MPa, obtains modified ferrocene；
(2), 30 parts of polyvinyl alcohol, 32 parts of propanethiols, 1.4 parts of alchlors and 4.5 parts of magnesium sulfate are weighed and are added to hydro-thermal
In reaction kettle, maintaining hydrothermal temperature is hydro-thermal reaction 1h under the conditions of 123 DEG C, and hydrothermal reaction kettle temperature is warming up to 165 DEG C
Under the conditions of hydro-thermal reaction 2.5h, through 500mL water supersound washing 3 times, 500mL EtOH Sonicate washs 3 times product, in 47 DEG C ,-
0.09MPa is dried in vacuo 12min, obtains modified polyvinylalcohol；
(3), weigh 70 parts of wood powders, 90 parts of water, 23 parts of hydroxy-ethyl acrylates, 17 parts of 2- acrylamide-2-methyl propane sulfonics,
7 parts of acrylic acid, 22 parts of ammonium sulfate and 23 parts of urea are added in hydrothermal reaction kettle, under the conditions of maintenance hydrothermal temperature is 77 DEG C
0.5 part of ammonium persulfate is added in hydrothermal reaction kettle by hydro-thermal reaction 30min, under the conditions of maintenance hydrothermal temperature is 86 DEG C
Hydro-thermal reaction 2h, -80 DEG C of freeze-drying 4h of product warp, product is through crushing, under nitrogen protection, in 200 DEG C of heat treatment 0.5h,
300 DEG C of heat treatments 1h, 400 DEG C of heat treatment 2h to get arrive modified wood powder；
(4), 100 part of 1.4% (wt.%) cobalt-containing materials, 15 parts of quartz sands and 9.5 parts of nanometer iron powders are weighed and are added to vibration
In mill, revolving speed is that 5000r/min reacts 2h to get modified cobalt-containing materials are arrived；
(5), pure and mild 2.3 parts of modifications, two cyclopentadienyl of 85 parts of modified cobalt-containing materials, 72 parts of modified wood powders, 16 parts of modified poly ethylenes is weighed
Iron is added in vibromill, and revolving speed is that 7000r/min reacts 20min, and product is through 800 DEG C of heat treatment 0.5h, by product and 73 parts
45% (wt.%) dilute sulfuric acid, 28 part of 15% (wt.%) dilute hydrochloric acid and 26 parts of water are added in hydrothermal reaction kettle, maintain hydro-thermal anti-
Answering temperature is hydro-thermal reaction 0.5h under the conditions of 108 DEG C, and product is filtered to arrive cobalt-containing materials leachate.
Embodiment 2
A kind of cobalt-containing materials leachate, preparation method includes the following steps:
(1), 10 parts of ferrocene, 6 parts of hydrofluoric acid, 7 parts of fluoboric acid and 4 parts of fluororesin are weighed to be added in hydrothermal reaction kettle,
Maintaining hydrothermal temperature is hydro-thermal reaction 3h under the conditions of 108 DEG C, and product through filtering, 500mL water washing 3 times, wash by 500mL ethyl alcohol
It washs 3 times, is dried in vacuo 6min in 40 DEG C, -0.08MPa, obtains modified ferrocene；
(2), weighing 30 parts of polyvinyl alcohol, 27 parts of dithioglycols, 1 part of alchlor and 3 parts of magnesium sulfate, to be added to hydro-thermal anti-
It answers in kettle, maintaining hydrothermal temperature is hydro-thermal reaction 2h under the conditions of 115 DEG C, and hydrothermal reaction kettle temperature is warming up to 145 DEG C of items
Hydro-thermal reaction 5h under part, product is through 500mL water supersound washing 3 times, and 500mL EtOH Sonicate washs 3 times, in 47 DEG C, -0.09MPa
It is dried in vacuo 12min, obtains modified polyvinylalcohol；
(3), weigh 70 parts of wood powders, 88 parts of water, 19 parts of hydroxy-ethyl acrylates, 14 parts of 2- acrylamide-2-methyl propane sulfonics,
5 parts of acrylic acid, 18 parts of ammonium sulfate and 17 parts of urea are added in hydrothermal reaction kettle, under the conditions of maintenance hydrothermal temperature is 75 DEG C
0.4 part of ammonium persulfate is added in hydrothermal reaction kettle by hydro-thermal reaction 40min, under the conditions of maintenance hydrothermal temperature is 78 DEG C
Hydro-thermal reaction 3h, -80 DEG C of freeze-drying 2h of product warp, product is through crushing, under nitrogen protection, in 200 DEG C of heat treatment 0.5h,
300 DEG C of heat treatments 1h, 400 DEG C of heat treatment 2h to get arrive modified wood powder；
(4), 100 part of 0.02% (wt.%) cobalt-containing materials, 13 parts of quartz sands and 6 parts of nanometer iron powders are weighed and are added to vibration
In mill, revolving speed is that 3000r/min reacts 5h to get modified cobalt-containing materials are arrived；
(5), 85 parts of modified cobalt-containing materials, 66 parts of modified wood powders, pure and mild 2 parts of 13 parts of modified poly ethylenes modified ferrocene are weighed
It is added in vibromill, revolving speed is that 6000r/min reacts 40min, and product is through 400 DEG C of heat treatment 3h, by product and 69 part 12%
(wt.%) dilute sulfuric acid, 23 part of 10% (wt.%) dilute hydrochloric acid and 21 parts of water are added in hydrothermal reaction kettle, maintain hydro-thermal reaction temperature
Degree is hydro-thermal reaction 5h under the conditions of 86 DEG C, and product is filtered to arrive cobalt-containing materials leachate.
Embodiment 3
A kind of cobalt-containing materials leachate, preparation method includes the following steps:
(1), 10 parts of ferrocene, 9 parts of hydrofluoric acid, 13 parts of fluoboric acid and 8 parts of fluororesin are weighed to be added in hydrothermal reaction kettle,
Maintaining hydrothermal temperature is hydro-thermal reaction 0.5h under the conditions of 130 DEG C, and product is through filtering, 500mL water washing 3 times, 500mL ethyl alcohol
Washing 3 times is dried in vacuo 6min in 40 DEG C, -0.08MPa, obtains modified ferrocene；
(2), 30 parts of polyvinyl alcohol, 41 parts of ethyl mercaptans, 3 parts of alchlors and 9 parts of magnesium sulfate are weighed and are added to hydro-thermal reaction
In kettle, maintaining hydrothermal temperature is hydro-thermal reaction 0.5h under the conditions of 132 DEG C, and hydrothermal reaction kettle temperature is warming up to 180 DEG C of items
Hydro-thermal reaction 1h under part, product is through 500mL water supersound washing 3 times, and 500mL EtOH Sonicate washs 3 times, in 47 DEG C, -0.09MPa
It is dried in vacuo 12min, obtains modified polyvinylalcohol；
(3), 70 parts of wood powders, 100 parts of water, 30 parts of hydroxy-ethyl acrylates, 22 parts of 2- acrylamide -2- methyl-prop sulphurs are weighed
Acid, 11 parts of acrylic acid, 26 parts of ammonium sulfate and 29 parts of urea are added in hydrothermal reaction kettle, and maintenance hydrothermal temperature is 90 DEG C of items
1 part of ammonium persulfate is added in hydrothermal reaction kettle by hydro-thermal reaction 28min under part, and maintenance hydrothermal temperature is 93 DEG C of conditions
Lower hydro-thermal reaction 0.5h, -80 DEG C of freeze-drying 9h of product warp, product is through crushing, and under nitrogen protection, is heat-treated in 200 DEG C
0.5h, 300 DEG C of heat treatments 1h, 400 DEG C of heat treatment 2h to get arrive modified wood powder；
(4), 100 part of 56% (wt.%) cobalt-containing materials, 17 parts of quartz sands and 13 parts of nanometer iron powders are weighed and are added to vibromill
In, revolving speed is that 6000r/min reacts 0.5h to get modified cobalt-containing materials are arrived；
(5), 85 parts of modified cobalt-containing materials, 80 parts of modified wood powders, pure and mild 6 parts of 21 parts of modified poly ethylenes modified ferrocene are weighed
It is added in vibromill, revolving speed is that 8000r/min reacts 15min, and product is through 1000 DEG C of heat treatment 0.1h, by product and 83 parts
52% (wt.%) dilute sulfuric acid, 31 part of 18% (wt.%) dilute hydrochloric acid and 34 parts of water are added in hydrothermal reaction kettle, maintain hydro-thermal anti-
Answering temperature is hydro-thermal reaction 0.2h under the conditions of 132 DEG C, and product is filtered to arrive cobalt-containing materials leachate.
Embodiment 4
A kind of cobalt-containing materials leachate, preparation method includes the following steps:
(1), 10 parts of ferrocene, 6.2 parts of hydrofluoric acid, 7.3 parts of fluoboric acid and 4.1 parts of fluororesin are weighed and are added to hydro-thermal reaction
In kettle, maintain hydrothermal temperature be 109 DEG C under the conditions of hydro-thermal reaction 0.6h, product through filtering, 500mL water washing 3 times,
500mL ethanol washing 3 times, it is dried in vacuo 6min in 40 DEG C, -0.08MPa, obtains modified ferrocene；
(2), 30 parts of polyvinyl alcohol, 28 parts of propanethiols, 1.2 parts of alchlors and 3.2 parts of magnesium sulfate are weighed and are added to hydro-thermal
In reaction kettle, maintaining hydrothermal temperature is hydro-thermal reaction 0.7h under the conditions of 117 DEG C, and hydrothermal reaction kettle temperature is warming up to 146
Hydro-thermal reaction 1.3h under the conditions of DEG C, through 500mL water supersound washing 3 times, 500mL EtOH Sonicate washs 3 times product, in 47 DEG C ,-
0.09MPa is dried in vacuo 12min, obtains modified polyvinylalcohol；
(3), weigh 70 parts of wood powders, 89 parts of water, 20 parts of hydroxy-ethyl acrylates, 16 parts of 2- acrylamide-2-methyl propane sulfonics,
5.5 parts of acrylic acid, 18.6 parts of ammonium sulfate and 17.8 parts of urea are added in hydrothermal reaction kettle, and maintaining hydrothermal temperature is 77 DEG C
Under the conditions of hydro-thermal reaction 29min, 0.5 part of ammonium persulfate is added in hydrothermal reaction kettle, maintain hydrothermal temperature be 79 DEG C
Under the conditions of hydro-thermal reaction 0.7h, -80 DEG C of freeze-drying 2.5h of product warp, product is through crushing, under nitrogen protection, in 200 DEG C of heat
0.5h is handled, 300 DEG C of heat treatments 1h, 400 DEG C of heat treatment 2h are to get to modified wood powder；
(4), 100 part of 8% (wt.%) cobalt-containing materials, 14.6 parts of quartz sands and 6.5 parts of nanometer iron powders are weighed and are added to vibration
In mill, revolving speed is that 3500r/min reacts 0.7h to get modified cobalt-containing materials are arrived；
(5), pure and mild 2.6 parts of modifications, two cyclopentadienyl of 85 parts of modified cobalt-containing materials, 68 parts of modified wood powders, 15 parts of modified poly ethylenes is weighed
Iron is added in vibromill, and revolving speed is that 6500r/min reacts 16min, and product is through 450 DEG C of heat treatment 0.3h, by product and 69.4
19% (wt.%) dilute sulfuric acid of part, 23.8 part of 12% (wt.%) dilute hydrochloric acid and 22 parts of water are added in hydrothermal reaction kettle, maintain water
Thermal response temperature is hydro-thermal reaction 0.4h under the conditions of 87 DEG C, and product is filtered to arrive cobalt-containing materials leachate.
Embodiment 5
A kind of cobalt-containing materials leachate, preparation method includes the following steps:
(1), 10 parts of ferrocene, 7.2 parts of hydrofluoric acid, 8.3 parts of fluoboric acid and 5.1 parts of fluororesin are weighed and are added to hydro-thermal reaction
In kettle, maintain hydrothermal temperature be 112 DEG C under the conditions of hydro-thermal reaction 0.9h, product through filtering, 500mL water washing 3 times,
500mL ethanol washing 3 times, it is dried in vacuo 6min in 40 DEG C, -0.08MPa, obtains modified ferrocene；
(2), 30 parts of polyvinyl alcohol, 31 parts of lauryl mercaptans, 1.8 parts of alchlors and 4.5 parts of magnesium sulfate are weighed and are added to water
In thermal response kettle, maintaining hydrothermal temperature is hydro-thermal reaction 0.9h under the conditions of 119 DEG C, and hydrothermal reaction kettle temperature is warming up to
Hydro-thermal reaction 2.5h under the conditions of 157 DEG C, product is through 500mL water supersound washing 3 times, and 500mL EtOH Sonicate washs 3 times, in 47
DEG C, -0.09MPa be dried in vacuo 12min, obtain modified polyvinylalcohol；
(3), 70 parts of wood powders, 92 parts of water, 22 parts of hydroxy-ethyl acrylates, 16.9 parts of 2- acrylamide -2- methyl-prop sulphurs are weighed
Acid, 8.2 parts of acrylic acid, 21 parts of ammonium sulfate and 19 parts of urea are added in hydrothermal reaction kettle, and maintaining hydrothermal temperature is 81 DEG C
Under the conditions of hydro-thermal reaction 32min, 0.6 part of ammonium persulfate is added in hydrothermal reaction kettle, maintain hydrothermal temperature be 86 DEG C
Under the conditions of hydro-thermal reaction 0.7h, -80 DEG C of freeze-drying 4h of product warp, product is through crushing, under nitrogen protection, in 200 DEG C heat at
0.5h is managed, 300 DEG C of heat treatments 1h, 400 DEG C of heat treatment 2h are to get to modified wood powder；
(4), 100 part of 16% (wt.%) cobalt-containing materials, 14.5 parts of quartz sands and 7.8 parts of nanometer iron powders are weighed and are added to vibration
In dynamic mill, revolving speed is that 3600r/min reacts 2h to get modified cobalt-containing materials are arrived；
(5), pure and mild 3.3 parts of modifications, two cyclopentadienyl of 85 parts of modified cobalt-containing materials, 71 parts of modified wood powders, 14 parts of modified poly ethylenes is weighed
Iron is added in vibromill, and revolving speed is that 6300r/min reacts 18min, and product is through 600 DEG C of heat treatment 0.8h, by product and 73 parts
35% (wt.%) dilute sulfuric acid, 26 part of 14% (wt.%) dilute hydrochloric acid and 23 parts of water are added in hydrothermal reaction kettle, maintain hydro-thermal anti-
Answering temperature is hydro-thermal reaction 1.5h under the conditions of 97 DEG C, and product is filtered to arrive cobalt-containing materials leachate.
Embodiment 6
A kind of cobalt-containing materials leachate, preparation method includes the following steps:
(1), 10 parts of ferrocene, 7 parts of hydrofluoric acid, 10 parts of fluoboric acid and 5 parts of fluororesin are weighed to be added in hydrothermal reaction kettle,
Maintaining hydrothermal temperature is hydro-thermal reaction 2h under the conditions of 120 DEG C, and product through filtering, 500mL water washing 3 times, wash by 500mL ethyl alcohol
It washs 3 times, is dried in vacuo 6min in 40 DEG C, -0.08MPa, obtains modified ferrocene；
(2), weighing 30 parts of polyvinyl alcohol, 40 parts of dithioglycols, 2 parts of alchlors and 4 parts of magnesium sulfate, to be added to hydro-thermal anti-
It answers in kettle, maintaining hydrothermal temperature is hydro-thermal reaction 1h under the conditions of 125 DEG C, and hydrothermal reaction kettle temperature is warming up to 160 DEG C of items
Hydro-thermal reaction 3h under part, product is through 500mL water supersound washing 3 times, and 500mL EtOH Sonicate washs 3 times, in 47 DEG C, -0.09MPa
It is dried in vacuo 12min, obtains modified polyvinylalcohol；
(3), weigh 70 parts of wood powders, 95 parts of water, 26 parts of hydroxy-ethyl acrylates, 18 parts of 2- acrylamide-2-methyl propane sulfonics,
7 parts of acrylic acid, 22 parts of ammonium sulfate and 25 parts of urea are added in hydrothermal reaction kettle, under the conditions of maintenance hydrothermal temperature is 83 DEG C
0.5 part of ammonium persulfate is added in hydrothermal reaction kettle by hydro-thermal reaction 34min, under the conditions of maintenance hydrothermal temperature is 81 DEG C
Hydro-thermal reaction 1.5h, -80 DEG C of freeze-drying 5h of product warp, product is through crushing, under nitrogen protection, in 200 DEG C of heat treatment 0.5h,
300 DEG C of heat treatments 1h, 400 DEG C of heat treatment 2h to get arrive modified wood powder；
(4), 100 part of 23% (wt.%) cobalt-containing materials, 15 parts of quartz sands and 8 parts of nanometer iron powders are weighed and are added to vibromill
In, revolving speed is that 4100r/min reacts 3h to get modified cobalt-containing materials are arrived；
(5), 85 parts of modified cobalt-containing materials, 73 parts of modified wood powders, pure and mild 4 parts of 18 parts of modified poly ethylenes modified ferrocene are weighed
It is added in vibromill, revolving speed is that 6800r/min reacts 32min, and product is through 900 DEG C of heat treatment 1.5h, by product and 76 parts
41% (wt.%) dilute sulfuric acid, 30 part of 15% (wt.%) dilute hydrochloric acid and 28 parts of water are added in hydrothermal reaction kettle, maintain hydro-thermal anti-
Answering temperature is hydro-thermal reaction 3.5h under the conditions of 118 DEG C, and product is filtered to arrive cobalt-containing materials leachate.
Embodiment 7
A kind of cobalt-containing materials leachate, preparation method includes the following steps:
(1), weighing 10 parts of ferrocene, 8.7 parts of hydrofluoric acid, 12.3 parts of fluoboric acid and 7.6 parts of fluororesin, to be added to hydro-thermal anti-
Answer in kettle, maintain hydrothermal temperature be 127 DEG C under the conditions of hydro-thermal reaction 2.9h, product through filtering, 500mL water washing 3 times,
500mL ethanol washing 3 times, it is dried in vacuo 6min in 40 DEG C, -0.08MPa, obtains modified ferrocene；
(2), 30 parts of polyvinyl alcohol, 40.3 parts of ethyl mercaptans, 2.6 parts of alchlors and 8.2 parts of magnesium sulfate are weighed and are added to water
In thermal response kettle, maintaining hydrothermal temperature is hydro-thermal reaction 1.8h under the conditions of 131 DEG C, and hydrothermal reaction kettle temperature is warming up to
Hydro-thermal reaction 4.5h under the conditions of 177 DEG C, product is through 500mL water supersound washing 3 times, and 500mL EtOH Sonicate washs 3 times, in 47
DEG C, -0.09MPa be dried in vacuo 12min, obtain modified polyvinylalcohol；
(3), 70 parts of wood powders, 97 parts of water, 28.9 parts of hydroxy-ethyl acrylates, 21.7 parts of 2- acrylamide -2- methyl-props are weighed
Sulfonic acid, 10.6 parts of acrylic acid, 25.6 parts of ammonium sulfate and 28.1 parts of urea are added in hydrothermal reaction kettle, maintain hydrothermal temperature
Hydro-thermal reaction 38min under the conditions of being 88 DEG C, 0.6 part of ammonium persulfate is added in hydrothermal reaction kettle, maintains hydrothermal temperature
Hydro-thermal reaction 2.6h under the conditions of being 91 DEG C, -80 DEG C of freeze-drying 7.5h of product warp, product is through crushing, under nitrogen protection, in
200 DEG C of heat treatments 0.5h, 300 DEG C of heat treatments 1h, 400 DEG C of heat treatment 2h to get arrive modified wood powder；
(4), 100 part of 37% (wt.%) cobalt-containing materials, 16.2 parts of quartz sands and 12.8 parts of nanometer iron powders are weighed and are added to vibration
In dynamic mill, revolving speed is that 5500r/min reacts 4.5h to get modified cobalt-containing materials are arrived；
(5), the pure and mild 5.8 parts of modifications two of 85 parts of modified cobalt-containing materials, 79 parts of modified wood powders, 20.7 parts of modified poly ethylenes are weighed
Luxuriant iron is added in vibromill, and revolving speed is that 7600r/min reacts 38min, and product is through 900 DEG C of heat treatment 2.2h, by product and 81
46% (wt.%) dilute sulfuric acid of part, 28 part of 17% (wt.%) dilute hydrochloric acid and 32 parts of water are added in hydrothermal reaction kettle, maintain hydro-thermal
Reaction temperature is hydro-thermal reaction 4h under the conditions of 127 DEG C, and product is filtered to arrive cobalt-containing materials leachate.
Embodiment 8
A kind of cobalt-containing materials leachate, preparation method includes the following steps:
(1), 10 parts of ferrocene, 7 parts of hydrofluoric acid, 11 parts of fluoboric acid and 6.5 parts of fluororesin are weighed and are added to hydrothermal reaction kettle
In, maintaining hydrothermal temperature is hydro-thermal reaction 2.2h under the conditions of 121 DEG C, and product is through filtering, 500mL water washing 3 times, 500mL
Ethanol washing 3 times, it is dried in vacuo 6min in 40 DEG C, -0.08MPa, obtains modified ferrocene；
(2), 30 parts of polyvinyl alcohol, 34 parts of lauryl mercaptans, 2.3 parts of alchlors and 6 parts of magnesium sulfate are weighed and are added to hydro-thermal
In reaction kettle, maintaining hydrothermal temperature is hydro-thermal reaction 1.3h under the conditions of 128 DEG C, and hydrothermal reaction kettle temperature is warming up to 167
Hydro-thermal reaction 3.5h under the conditions of DEG C, through 500mL water supersound washing 3 times, 500mL EtOH Sonicate washs 3 times product, in 47 DEG C ,-
0.09MPa is dried in vacuo 12min, obtains modified polyvinylalcohol；
(3), weigh 70 parts of wood powders, 91 parts of water, 26 parts of hydroxy-ethyl acrylates, 18 parts of 2- acrylamide-2-methyl propane sulfonics,
8.8 parts of acrylic acid, 21 parts of ammonium sulfate and 22 parts of urea are added in hydrothermal reaction kettle, and maintenance hydrothermal temperature is 85 DEG C of conditions
0.6 part of ammonium persulfate is added in hydrothermal reaction kettle by lower hydro-thermal reaction 37min, and maintenance hydrothermal temperature is 85 DEG C of conditions
Lower hydro-thermal reaction 2.1h, -80 DEG C of freeze-drying 6h of product warp, product is through crushing, and under nitrogen protection, is heat-treated in 200 DEG C
0.5h, 300 DEG C of heat treatments 1h, 400 DEG C of heat treatment 2h to get arrive modified wood powder；
(4), 100 part of 44% (wt.%) cobalt-containing materials, 15 parts of quartz sands and 10 parts of nanometer iron powders are weighed and are added to vibromill
In, revolving speed is that 5500r/min reacts 3h to get modified cobalt-containing materials are arrived；
(5), 85 parts of modified cobalt-containing materials, 76 parts of modified wood powders, pure and mild 4 parts of 17 parts of modified poly ethylenes modified ferrocene are weighed
It is added in vibromill, revolving speed is that 7700r/min reacts 26min, and product is through 600 DEG C of heat treatment 2.6h, by product and 76 parts
33% (wt.%) dilute sulfuric acid, 28 part of 16% (wt.%) dilute hydrochloric acid and 27 parts of water are added in hydrothermal reaction kettle, maintain hydro-thermal anti-
Answering temperature is hydro-thermal reaction 3h under the conditions of 122 DEG C, and product is filtered to arrive cobalt-containing materials leachate.
Reference examples 1
In this reference examples, modified ferrocene is not added, and other components and preparation method are same as Example 4.
Reference examples 2
In this reference examples, modified polyvinylalcohol is not added, other components and preparation method are same as Example 4.
Reference examples 3
In this reference examples, modified wood powder is not added, other components and preparation method are same as Example 4.
Reference examples 4
In this reference examples, with the modification ferrocene in common ferrocene alternate embodiment 4, other components and preparation method with
Embodiment 4 is identical.
Reference examples 5
In this reference examples, with the modified polyvinylalcohol in common polythene alcohol alternate embodiment 4, other components and preparation side
Method is same as Example 4.
Reference examples 6
In this reference examples, with the modified wood powder in common wood powder alternate embodiment 4, other components and preparation method and implementation
Example 4 is identical.
Reference examples 7
In this reference examples, with the modification cobalt-containing materials in common cobalt-containing materials alternate embodiment 4, other components and preparation side
Method is same as Example 4.
Effect example
The content of the cobalt element in cobalt-containing materials leachate obtained to embodiment 4 and reference examples 1~7 is according to national standard GB/
T6730.52-2004 is tested, and the leaching rate of cobalt element, calculation formula are then calculated according to formula are as follows:
The leaching rate of cobalt element=(m1 × a%)/(m2 × b%)
M1 is the quality of leachate, and a% is the mass percentage of cobalt element in leachate, and m2 is the matter of cobalt-containing materials
Amount, b% are the mass percentage of cobalt element in cobalt-containing materials.
Test result is shown in Table 1.Data show that the leaching rate of embodiment 4 is 91.6% in table, than the leaching of control rate 1~7
Rate is higher by 20.1%~50.0%, illustrates that the high leaching rate of cobalt element in cobalt-containing materials can be leached to leachate by the present invention
In.
Cobalt element leaching rate in the leachate of cobalt-containing materials made from 1 embodiment 1 of table and reference examples 1~7
The above is the preferred embodiment of the invention, it is noted that for those skilled in the art
For, under the premise of not departing from the inventive principle, several improvements and modifications can also be made, these improvements and modifications are also considered as
The protection scope of the invention.
Claims (4)
1. a kind of leaching liquid and preparation method thereof of cobalt-containing materials, it is characterised in that: including following raw material components: modified cobalt-containing materials,
Modified wood powder, modified polyvinylalcohol, modified ferrocene, dilute sulfuric acid, dilute hydrochloric acid and water, the modification cobalt-containing materials, innovation wood
Powder, modified polyvinylalcohol are modified the mass parts ratio of ferrocene, dilute sulfuric acid, dilute hydrochloric acid and water as 85:66~80:13~21:2
~6:69~83:23~31:21~34, wherein the modification cobalt-containing materials are anti-by cobalt-containing materials, quartz sand and nanometer iron powder
It should be made, the mass parts ratio of the cobalt-containing materials, quartz sand and nanometer iron powder is 100:13~17:6~13, and described changes
Property wood powder by wood powder, water, hydroxy-ethyl acrylate, 2- acrylamide-2-methyl propane sulfonic, acrylic acid, ammonium persulfate, ammonium sulfate and
Urea reaction is made, the wood powder, water, hydroxy-ethyl acrylate, 2- acrylamide-2-methyl propane sulfonic, acrylic acid, persulfuric acid
The mass parts ratio of ammonium, ammonium sulfate and urea is 70:88~100:19~30:14~22:5~11:0.4~1:18~26:17
~29, the modified polyvinylalcohol is reacted by polyvinyl alcohol, mercaptan, alchlor and magnesium sulfate to be made, the polyethylene
Alcohol, mercaptan, alchlor and magnesium sulfate mass parts ratio be 30:27~41:1~3:3~9, the modification ferrocene by
Ferrocene, hydrofluoric acid, fluoboric acid and fluororesin reaction are made, the quality of the ferrocene, hydrofluoric acid, fluoboric acid and fluororesin
Portion rate is 10:6~9:7~13:4~8, and preparation step is as follows:
It (1), is the addition of 10:6~9:7~13:4~8 according to mass parts ratio by ferrocene, hydrofluoric acid, fluoboric acid and fluororesin
Into hydrothermal reaction kettle, maintain hydrothermal temperature be 108~130 DEG C under the conditions of 0.5~3h of hydro-thermal reaction, product through filtering,
500mL water washing 3 times, 500mL ethanol washing 3 times, it is dried in vacuo 6min in 40 DEG C, -0.08MPa, obtains modified ferrocene；
(2), polyvinyl alcohol, mercaptan, alchlor and magnesium sulfate are added according to mass parts ratio for 30:27~41:1~3:3~9
Enter into hydrothermal reaction kettle, maintaining hydrothermal temperature is 0.5~2h of hydro-thermal reaction under the conditions of 115~132 DEG C, by hydro-thermal reaction
1~5h of hydro-thermal reaction under the conditions of kettle temperature degree is warming up to 145~180 DEG C, product is through 500mL water supersound washing 3 times, 500mL ethyl alcohol
Supersound washing 3 times, it is dried in vacuo 12min in 47 DEG C, -0.09MPa, obtains modified polyvinylalcohol；
(3), wood powder, water, hydroxy-ethyl acrylate, 2- acrylamide-2-methyl propane sulfonic, acrylic acid, ammonium sulfate and urea are pressed
It is that 70:88~100:19~30:14~22:5~11:18~26:17~29 are added in hydrothermal reaction kettle according to mass parts ratio,
Maintaining hydrothermal temperature is 28~40min of hydro-thermal reaction under the conditions of 75~90 DEG C, the over cure for being 0.4~1 by mass parts ratio
Sour ammonium is added in hydrothermal reaction kettle, and maintaining hydrothermal temperature is 0.5~3h of hydro-thermal reaction under the conditions of 78~93 DEG C, product
Through -80 DEG C of 2~9h of freeze-drying, product is through crushing, under nitrogen protection, in 200 DEG C of heat treatments 0.5h, 300 DEG C of heat treatment 1h,
400 DEG C of heat treatment 2h to get arrive modified wood powder；
It (4), is that 100:13~17:6~13 are added to vibration according to mass parts ratio by cobalt-containing materials, quartz sand and nanometer iron powder
In mill, revolving speed is that 3000~6000r/min reacts 0.5~5h to get modified cobalt-containing materials are arrived；
(5), will be modified cobalt-containing materials, modified wood powder, the pure and mild modified ferrocene of modified poly ethylene according to mass parts ratio is 85:66
~80:13~21:2~6 are added in vibromill, and revolving speed is that 6000~8000r/min reacts 15~40min, product through 400~
1000 DEG C of 0.1~3h of heat treatment, by product and mass parts ratio be 69~83:23~31:21~34 dilute sulfuric acid, dilute hydrochloric acid and
Water is added in hydrothermal reaction kettle, and maintaining hydrothermal temperature is 0.2~5h of hydro-thermal reaction under the conditions of 86~132 DEG C, product warp
It filters to get the leachate of cobalt-containing materials is arrived.
2. the leaching liquid and preparation method thereof of a kind of cobalt-containing materials according to claim 1, it is characterised in that: the dilute sulfuric acid matter
Measuring concentration is 12%~52%, and dilute hydrochloric acid mass concentration is 10%~18%.
3. the leaching liquid and preparation method thereof of a kind of cobalt-containing materials according to claim 1, it is characterised in that: the cobalt-containing materials
Cobalt element mass content is 0.02%~56%.
4. the leaching liquid and preparation method thereof of a kind of cobalt-containing materials according to claim 1, it is characterised in that: the mercaptan is second
One of mercaptan, dithioglycol, propanethiol and lauryl mercaptan.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811599150.3A CN109666797A (en) | 2018-12-26 | 2018-12-26 | A kind of leaching liquid and preparation method thereof of cobalt-containing materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811599150.3A CN109666797A (en) | 2018-12-26 | 2018-12-26 | A kind of leaching liquid and preparation method thereof of cobalt-containing materials |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109666797A true CN109666797A (en) | 2019-04-23 |
Family
ID=66146152
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811599150.3A Pending CN109666797A (en) | 2018-12-26 | 2018-12-26 | A kind of leaching liquid and preparation method thereof of cobalt-containing materials |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109666797A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4239529A (en) * | 1979-10-22 | 1980-12-16 | Hazen Research, Inc. | Process for beneficiating sulfide ores |
| CN106279548A (en) * | 2015-06-12 | 2017-01-04 | 中国石油化工集团公司 | A kind of for polyvinyl alcohol hydrogel processing heavy metal ion-containing waste water and preparation method thereof |
| CN108084481A (en) * | 2017-12-11 | 2018-05-29 | 南京工业职业技术学院 | A kind of high water conservation polyacrylamide water-absorbing resin and preparation method thereof |
| CN108728670A (en) * | 2018-06-21 | 2018-11-02 | 柴迪汉 | A kind of cobalt leaching polypropylene-base leachate and preparation method thereof |
-
2018
- 2018-12-26 CN CN201811599150.3A patent/CN109666797A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4239529A (en) * | 1979-10-22 | 1980-12-16 | Hazen Research, Inc. | Process for beneficiating sulfide ores |
| CN106279548A (en) * | 2015-06-12 | 2017-01-04 | 中国石油化工集团公司 | A kind of for polyvinyl alcohol hydrogel processing heavy metal ion-containing waste water and preparation method thereof |
| CN108084481A (en) * | 2017-12-11 | 2018-05-29 | 南京工业职业技术学院 | A kind of high water conservation polyacrylamide water-absorbing resin and preparation method thereof |
| CN108728670A (en) * | 2018-06-21 | 2018-11-02 | 柴迪汉 | A kind of cobalt leaching polypropylene-base leachate and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 马祥志主编.: "《有机化学》", 31 July 2014, 中国医药科技出版社 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102659274B (en) | Recycling harmless treatment method of stainless steel pickling waste water | |
| CN107262049A (en) | A kind of material modified preparation method of sepiolite and application in the treatment of waste water | |
| CN105617981B (en) | The application in the treatment of waste water of the method for modifying of a kind of meerschaum and modified meerschaum | |
| Bai et al. | High efficiency biosorption of Uranium (VI) ions from solution by using hemp fibers functionalized with imidazole-4, 5-dicarboxylic | |
| CN103382044A (en) | Method of preparing compound flocculating agent by utilizing fly ash and killing pickle | |
| CN109304139A (en) | A kind of modified technique improving attapulgite absorption property | |
| CN111530434A (en) | Silica gel adsorbent for adsorbing heavy metal ions and preparation method thereof | |
| CN109232901A (en) | A kind of preparation method and application of bimetallic organic framework material Fe/Mg-MIL-88B | |
| CN109046403A (en) | A kind of regeneration method of useless mercuric chloride catalyst | |
| CN109797290A (en) | A kind of environment-friendly highly efficient soaks the synthetic method of golden agent | |
| CN105949639A (en) | Preparation method of modified bentonite PVC heat stabilizer | |
| CN109666797A (en) | A kind of leaching liquid and preparation method thereof of cobalt-containing materials | |
| Li et al. | Highly effective adsorption, porous and charged CAP@ Ui0-66-NH2@ PPy hybrid fibrous membrane based on MOFs for Cr (VI) removal from wastewater | |
| CN105710106B (en) | The method for the treatment of of wastes produced containing chromium | |
| CN102671644B (en) | Silica gel loaded polymeric amine and 8-hydroxyquinoline dual-function base compound adsorption material and preparation method | |
| CN106669672A (en) | Activated carbon catalyst for sulfur dioxide recovery and preparation method of activated carbon catalyst | |
| CN109052500A (en) | A kind of Industrial waste water treatment agent and preparation method thereof | |
| CN107159101A (en) | A kind of preparation method of modified meerschaum sorbing material and application in the treatment of waste water | |
| CN103275356B (en) | Method for preparing high-performance low-cobalt borate acylated cobalt adhesion promoter | |
| CN108946778A (en) | A kind of polyaluminium chloride and its cleanly production technique | |
| CN102925683B (en) | Indium-iron separation method by using persimmontannin | |
| CN106587314A (en) | Efficient phosphorus removal agent and preparation method thereof | |
| CN105819474A (en) | Method for producing magnesium sulfate from waste acid produced in cation exchange resin production process | |
| CN106241890A (en) | A kind of production method of bodied ferric sulfate | |
| CN103207171B (en) | Digestion method of electroplating chromium mud |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20190423 |