CN109536724A - A method of the cobalt nickel purification based on old and useless battery metals recovery processes - Google Patents
A method of the cobalt nickel purification based on old and useless battery metals recovery processes Download PDFInfo
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- CN109536724A CN109536724A CN201811635321.3A CN201811635321A CN109536724A CN 109536724 A CN109536724 A CN 109536724A CN 201811635321 A CN201811635321 A CN 201811635321A CN 109536724 A CN109536724 A CN 109536724A
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0006—Controlling or regulating processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
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- 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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/005—Preliminary treatment of scrap
-
- 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
-
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
- C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
- C22B3/3846—Phosphoric acid, e.g. (O)P(OH)3
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00177—Controlling or regulating processes controlling the pH
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00184—Controlling or regulating processes controlling the weight of reactants in the reactor vessel
-
- 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
Abstract
The method for the cobalt nickel purification based on old and useless battery metals recovery processes that the invention discloses a kind of, belong to old and useless battery recycling field, a method of the cobalt nickel purification based on old and useless battery metals recovery processes, include the steps that ternary battery waste residue recycles, it passes through the improvement to original old and useless battery metals recovery processes, on the one hand compared to the prior art in the impurity removal process of iron ion, the impurities removing efficiency of iron ion can be increased, the dust removal rate to iron ion can be increased simultaneously, improve the recycling purity to cobalt and nickel, the process of integrated artistic is accelerated simultaneously, improve recovery efficiency, on the other hand compared to the prior art in, invention increases to the detection except the GOLD FROM PLATING SOLUTION category impurity after miscellaneous operation, the reacting phenomenon generated in solution plays the role of feedback, make removal of impurities can more thoroughly, further improve metallic cobalt and nickel The purity of recycling.
Description
Technical field
The present invention relates to old and useless battery recycling fields, are based on old and useless battery metal recovery work more specifically to one kind
The method of the cobalt nickel purification of skill.
Background technique
The technology path of ternary battery material recycling and reusing are as follows: 1, inorganic acid acidleach；2, copper ferro-aluminum cleans；3, it extracts back
Receive nickel cobalt；4, nickel cobalt product is obtained.It is mainly studied in above-mentioned metals recovery processes: the 1. type, concentration and acidleach of inorganic acid
Time；2. being suitable for the technique of the impurity such as the removing copper ferro-aluminum of this system；3. recycling the extraction process of nickel cobalt.
In existing old and useless battery metals recovery processes, when cleaning to metal impurities, wherein cleaning to iron
When, generally use yellow modumite method --- in the solution containing trivalent iron ion, pH value is adjusted to 1.6-1.8 or so, and will
When solution is heated to 85-95 DEG C, sodium sulphate is added, just has lurid sodium jarosite crystal and is precipitated, the crystal grain is coarse,
Settling velocity is fast, is easy filtering, but is removing the iron in solution, while producing acid during the reaction can be such that solution pH value drops
Low, solution pH value reduces, and the reaction that will affect iron ion is precipitated, and remove the iron ion for reacting the later period can not completely, influences cobalt
With the purity of the extraction of nickel.
Summary of the invention
1. technical problems to be solved
Aiming at the problems existing in the prior art, the purpose of the present invention is to provide one kind to be based on old and useless battery metal recovery
The method of the cobalt nickel purification of technique, it is by the improvement to original old and useless battery metals recovery processes, on the one hand compared to existing
To the impurity removal process of iron ion in technology, the impurities removing efficiency of iron ion can be increased, while the removal of impurities effect to iron ion can be increased
Rate improves the recycling purity to cobalt and nickel, while accelerating the process of integrated artistic, improves recovery efficiency, on the other hand
In compared to the prior art, invention increases to the detection except the GOLD FROM PLATING SOLUTION category impurity after miscellaneous operation, generated in solution
Reacting phenomenon plays the role of feedback, and removal of impurities is made more thoroughly further can to improve the purity of metallic cobalt and nickel recycling.
2. technical solution
To solve the above problems, the present invention adopts the following technical scheme that.
A method of the cobalt nickel purification based on old and useless battery metals recovery processes, comprising the following steps:
Step 1: ternary battery waste residue is dissolved in sulfuric acid solution, obtain sulfur acid nickel, cobaltous sulfate and a small amount of copper, iron,
The solution of the impurity such as manganese, zinc；
Step 2: sodium sulphate is added in above-mentioned solution, when reaction carries out, the PH being connected with chemical reaction case is observed in real time
Value tester detects the pH value in solution, and weakly alkaline solution is added into reaction solution according to the variation of pH value and is neutralized,
It reacts ferric ion and sodium sulphate in solution and generates lurid sodium jarosite crystal precipitation；
Step 3: for example with alkyl phosphoric acid: two -2- ethylhexyl phosphoric acids (D-2-EHPA) or other alkyl phosphoric acid esters extraction
The metal impurities such as remaining copper, iron, manganese, zinc in agent extraction solution are taken, and obtain cobaltous sulfate, the nickel sulfate solution that extraction obtains；
Step 4: cobaltous sulfate, nickel sulfate solution that extraction obtains, are added excessive sodium hydroxide solution thereto, observe
Whether there is Precipitation, when finding to there is precipitating in solution, repeat step 3 after the reaction solution of this step is filtered again,
Next step operation is carried out again until precipitating does not occur in discovery；
Step 5: ammonium oxalate is added into above-mentioned filtrate, cobalt and nickel are respectively formed precipitating, when being purified to cobalt, led to
It can often be precipitated and be made with ammonium oxalate solution in cobalt chloride solution or cobalt sulfate solution, key reaction is as follows: (NH4) 2C2O4+
CoCl2==CoC2O4 ↓+2NH4Cl, then precipitating is filtered, evaporation drying；
Step 6: the high temperature carried out under different temperatures is forged by cobalt oxalate obtained by above-mentioned steps, nickel oxalate precipitation mixture
It burns, respectively obtains cobalt oxide, nickel oxide powder；
Step 7 is reduced into metallic cobalt and metallic nickel according to recycling needs, then by cobalt oxide and nickel oxide, due to cobalt respectively
It is unstable with two kinds of metal simple-substance properties of nickel, it is easily oxidized to cobalt oxide and nickel oxide in air, is needing to cobalt and nickel
It is more convenient by the way of being transported in the form of its metal oxide when metal transports.
Further, the solution ph in the step 2 is between 1.6-1.8, and solution temperature is 85-95 DEG C, is being changed
Under reaction condition, iron ion fast reaction can be generated crystal and be precipitated, achieve the purpose that clean to iron ion.
Further, the chemical reaction case upper end has snapped connection sealed platform cover, and the sealed platform cover outer end, which is dug, to be had
Feed opening, the chemical reaction case is interior to be equipped with auxiliary fixing plate, slidably connects conduit, the sliding slot in the auxiliary fixing plate
One end inner wall is fixedly connected with compressed spring, and the compressed spring is moved block with limit and is fixedly connected, and the limiting block is anti-far from chemistry
Answering one end of case to dig has multiple inlet openings, and the inlet opening and chemical reaction case are interconnected.
Further, the chemical reaction case lower end wall is dug fluted, and rotary shaft, institute are rotatably connected in the groove
It states rotary shaft to be fixedly connected with auxiliary fixing plate, the conduit left and right ends are fixedly connected to multiple stirring rod, staff
Auxiliary fixing plate can be made to rotate along rotary shaft, when reacting progress in chemically reacting case, pass through the rotation of auxiliary fixing plate, band
Dynamic stirring rod is rotated along rotary shaft, is played the role of stirring reaction solution, is increased the reaction rate in solution.
Further, telescopic rod is equipped in the conduit, the telescopic rod upper end is fixedly connected with electric telescopic rod, described
Telescopic rod lower end is fixedly connected with sealing piston, and the sealing piston is slidably connected with conduit, passes through telescopic rod and electric expansion
Cooperation between bar is able to drive sealing piston and moves up and down vertically along conduit, by the neutralizer in conduit, can pass through liquid liquid
Exchange hole flows into chemical reaction case.
Further, the conduit left and right ends, which are dug, liquid liquid exchange hole, and the liquid liquid exchange hole left and right ends are equal
Cutting has sliding slot, is equipped with limiting block in the liquid liquid exchange hole, the limiting block left and right ends are fixedly connected with limited shifting block, institute
Limit shifting block is stated to be slidably connected with sliding slot.
Further, the limiting block is fixedly connected with hush panel close to one end of chemical reaction case, the hush panel with
Liquid liquid exchange hole is mutually matched, can be to the reaction solution in neutralizer in conduit and chemical reaction case under the action of hush panel
Separation, convenient for staff's control to the addition rate of neutralizer in conduit, while under the detection of pH value tester, to molten
PH value in liquid is fed back, and controls staff to the addition rate of neutralizer.
Further, the alkyl phosphoric acid in the step 3 is two -2- ethylhexyl phosphoric acids (D-2-EHPA) or other alkane
Base phosphoric acid ester extractant.
Further, the calcination temperature in the step 6 reaches 380 DEG C and obtains nickel oxide, and calcination temperature reaches 450 DEG C
Cobalt oxide is obtained, according to the nuance of cobalt oxalate and nickel oxalate property, cobalt and nickel are separated.
3. beneficial effect
Compared with the prior art, the present invention has the advantages that
(1) this programme can be by the improvement to original old and useless battery metals recovery processes, on the one hand compared to existing skill
To the impurity removal process of iron ion in art, the impurities removing efficiency of iron ion can be increased, while the dust removal rate to iron ion can be increased,
The recycling purity to cobalt and nickel is improved, while accelerating the process of integrated artistic, recovery efficiency is improved, on the other hand compares
In in the prior art, invention increases the reactions to the detection except the GOLD FROM PLATING SOLUTION category impurity after miscellaneous operation, generated in solution
Phenomenon plays the role of feedback, and removal of impurities is made more thoroughly further can to improve the purity of metallic cobalt and nickel recycling.
(2) solution ph in step 2 is between 1.6-1.8, and solution temperature is 85-95 DEG C, is changing reaction condition
Under, iron ion fast reaction can be generated crystal and be precipitated, achieve the purpose that clean to iron ion.
(3) chemical reaction case upper end has snapped connection sealed platform cover, and sealed platform cover outer end, which is dug, feed opening, chemically reacts
It is equipped with auxiliary fixing plate in case, slidably connects conduit in auxiliary fixing plate, sliding slot one end inner wall is fixedly connected with compressed spring,
Compressed spring is moved block with limit and is fixedly connected, and limiting block is dug far from one end of chemical reaction case multiple inlet openings, inlet opening with
Case is chemically reacted to be interconnected.
(4) chemical reaction case lower end wall is dug fluted, is rotatably connected to rotary shaft in groove, rotary shaft be auxiliarily fixed
Plate is fixedly connected, and conduit left and right ends are fixedly connected to multiple stirring rod, and staff can make auxiliary fixing plate along rotation
Axis rotation when reacting progress in chemically reacting case, by the rotation of auxiliary fixing plate, drives stirring rod to rotate along rotary shaft,
Play the role of stirring reaction solution, increases the reaction rate in solution.
(5) telescopic rod is equipped in conduit, telescopic rod upper end is fixedly connected with electric telescopic rod, and telescopic rod lower end is fixedly connected
There is sealing piston, sealing piston is slidably connected with conduit, by the cooperation between telescopic rod and electric telescopic rod, is able to drive close
Envelope piston moves up and down vertically along conduit, and the neutralizer in conduit can be flowed into chemical reaction case by liquid liquid exchange hole.
(6) conduit left and right ends, which are dug, liquid liquid exchange hole, and liquid liquid exchange hole left and right ends, which are dug, sliding slot, liquid liquid
Limiting block is equipped in exchange hole, limiting block left and right ends are fixedly connected with limited shifting block, and limit moves block and is slidably connected with sliding slot.
(7) limiting block is fixedly connected with hush panel close to one end of chemical reaction case, and hush panel and liquid liquid exchange hole are mutual
Matching can be convenient for work to the separation of the reaction solution in neutralizer in conduit and chemical reaction case under the action of hush panel
Personnel control carries out the pH value in solution to the addition rate of neutralizer in conduit, while under the detection of pH value tester
Feedback, controls staff to the addition rate of neutralizer.
(8) alkyl phosphoric acid in step 3 is two -2- ethylhexyl phosphoric acids (D-2-EHPA) or other alkyl phosphoric acid esters
Extractant.
(9) calcination temperature in step 6 reaches 380 DEG C and obtains nickel oxide, and calcination temperature reaches 450 DEG C and obtains cobalt oxide,
According to the nuance of cobalt oxalate and nickel oxalate property, cobalt and nickel are separated.
Detailed description of the invention
Fig. 1 is the improved broad flow diagram of the present invention；
Fig. 2 is metal recovery broad flow diagram in the prior art；
Fig. 3 is the structural schematic diagram of present invention chemical reaction box part；
Fig. 4 faces the schematic diagram of the section structure for present invention chemical reaction box part；
Fig. 5 is the side elevational cross-section structural schematic diagram of present invention chemical reaction box part；
Fig. 6 is the top view cross section structural schematic diagram of present invention chemical reaction box part；
Fig. 7 is structural schematic diagram when present invention chemical reaction box part is not used at the A of Fig. 6；
Fig. 8 is structural schematic diagram when present invention chemical reaction box part uses at the A of Fig. 6.
Figure label explanation:
1 chemical reaction case, 2 sealed platform covers, 3 feed openings, 4 grooves, 5 rotary shafts, 6 auxiliary fixing plates, 7 conduits, 8 sealings are lived
Plug, 9 telescopic rods, 10 stirring rod, 11 electric telescopic rods, 12 sliding slots, 13 compressed springs, 14 limits move block, 15 limiting blocks, 16 water inlets
Hole, 17 hush panels.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description；Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments, is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
In the description of the present invention, it should be noted that the instruction such as term " on ", "lower", "inner", "outside", " top/bottom end "
Orientation or positional relationship be based on the orientation or positional relationship shown in the drawings, be merely for convenience of description the present invention and simplification retouch
It states, rather than the device or element of indication or suggestion meaning must have a particular orientation, be constructed and operated in a specific orientation,
Therefore it is not considered as limiting the invention.In addition, term " first ", " second " are used for description purposes only, and cannot understand
For indication or suggestion relative importance.
In the description of the present invention, it should be noted that unless otherwise clearly defined and limited, term " installation " " is set
Be equipped with ", " be arranged/connect ", " connection " etc., shall be understood in a broad sense, such as " connection ", may be a fixed connection, be also possible to removable
Connection is unloaded, or is integrally connected, can be mechanical connection, is also possible to be electrically connected, can be directly connected, it can also be in
Between medium be indirectly connected, can be the connection inside two elements, for the ordinary skill in the art, can be specific
Situation understands the concrete meaning of above-mentioned term in the present invention.
Embodiment 1:
A method of the cobalt nickel purification based on old and useless battery metals recovery processes, comprising the following steps:
Step 1: ternary battery waste residue is dissolved in sulfuric acid solution, obtain sulfur acid nickel, cobaltous sulfate and a small amount of copper, iron,
The solution of the impurity such as manganese, zinc.
Step 2: sodium sulphate is added in above-mentioned solution, when reaction carries out, observation in real time is connected with chemical reaction case 1
PH value tester detects the pH value in solution, is added according to the variation of pH value into reaction solution in weakly alkaline solution progress
With react ferric ion and sodium sulphate in solution and generate lurid sodium jarosite crystal and be precipitated.
Step 3: for example with alkyl phosphoric acid: two -2- ethylhexyl phosphoric acids (D-2-EHPA) or other alkyl phosphoric acid esters extraction
Agent is taken, the metal impurities such as remaining copper, iron, manganese, zinc in extraction solution, and obtain cobaltous sulfate, the nickel sulfate solution that extraction obtains.
Step 4: cobaltous sulfate, nickel sulfate solution that extraction obtains, are added excessive sodium hydroxide solution thereto, observe
Whether there is Precipitation, when finding to there is precipitating in solution, repeat step 3 after the reaction solution of this step is filtered again,
Next step operation is carried out again until precipitating does not occur in discovery.
Step 5: ammonium oxalate is added into above-mentioned filtrate, cobalt and nickel are respectively formed precipitating, when being purified to cobalt, led to
It can often be precipitated and be made with ammonium oxalate solution in cobalt chloride solution or cobalt sulfate solution, key reaction is as follows: (NH4) 2C2O4+
CoCl2==CoC2O4 ↓+2NH4Cl, then precipitating is filtered, evaporation drying.
Step 6: the high temperature carried out under different temperatures is forged by cobalt oxalate obtained by above-mentioned steps, nickel oxalate precipitation mixture
It burns, respectively obtains cobalt oxide, nickel oxide powder.
Step 7 is reduced into metallic cobalt and metallic nickel according to recycling needs, then by cobalt oxide and nickel oxide, due to cobalt respectively
It is unstable with two kinds of metal simple-substance properties of nickel, it is easily oxidized to cobalt oxide and nickel oxide in air, is needing to cobalt and nickel
It is more convenient by the way of being transported in the form of its metal oxide when metal transports.
Referring to Fig. 4, chemical reaction 1 upper end of case has snapped connection sealed platform cover 2,2 outer end of sealed platform cover, which is dug, charging
Mouth 3, is added neutralizer into conduit 7 convenient for staff, and the pH value for chemically reacting solution in case 1 is made to maintain 1.6- always
Between 1.8, reacting between iron ion and sodium sulphate is made to be able to maintain that higher reaction rate always, chemically reacts 1 lower end of case
Wall digs fluted 4, is rotatably connected to rotary shaft 5 in groove 4,5 upper end of rotary shaft is fixedly connected with auxiliary fixing plate 6, passes through
The effect of rotary shaft 5, staff can be such that auxiliary fixing plate 6 rotates along rotary shaft 5, react and carry out in chemical reaction case 1
When, by the rotation of auxiliary fixing plate 6, stirring rod 10 is driven to rotate along rotary shaft 5, plays the role of stirring reaction solution,
Increase the reaction rate in solution.
Conduit 7 is slidably connected in auxiliary fixing plate 6, is equipped with telescopic rod 9 in conduit 7,9 lower end of telescopic rod is fixedly connected with
Sealing piston 8, sealing piston 8 are slidably connected with conduit 7, and 9 upper end of telescopic rod is fixedly connected with electric telescopic rod 11, by flexible
Cooperation between bar 9 and electric telescopic rod 11 is able to drive sealing piston 8 and moves up and down vertically along conduit 7, will be in conduit 7
Neutralizer can be flowed into chemical reaction case 1 by liquid liquid exchange hole, please refer to Fig. 6 and Fig. 7,7 left and right ends of conduit are dug
There is liquid liquid exchange hole.
Liquid liquid exchange hole left and right ends, which are dug, sliding slot 12, and limiting block 15 is equipped in liquid liquid exchange hole, and limiting block 15 is left
Right both ends are fixedly connected with limited shifting block 14, and limit moves block 14 and is slidably connected with sliding slot 12, and 12 one end inner wall of sliding slot is fixedly connected with
Compressed spring 13, compressed spring 13 are moved block 14 with limit and are fixedly connected, and limiting block 15 has more far from one end cutting of chemical reaction case 1
A inlet opening 16, inlet opening 16 and chemical reaction case 1 are interconnected, and one end of the close chemical reaction case 1 of limiting block 15 is fixed to be connected
It is connected to hush panel 17, hush panel 17 is mutually matched with liquid liquid exchange hole, can be in conduit 7 under the action of hush panel 17
With the separation of the reaction solution in liquid and chemical reaction case 1, the addition rate to neutralizer in conduit 7 is controlled convenient for staff,
Simultaneously under the detection of pH value tester, the pH value in solution is fed back, further adds staff to neutralizer
Enter rate to be controlled.
Experiment reaction step of the invention be according in the prior art the step of improved, the present invention used in chemistry
Structure in reaction chamber 1 is the improvement according to improved step to existing reaction chamber again, is enabled and improved step
It is rapid to form preferably cooperation, the efficiency and quality of old and useless battery recycling are promoted, compared to the prior art, the present invention has certain
, there is the effect used for reference to existing Retrieving Technology of Waste and Used Battery in progress meaning.
The foregoing is intended to be a preferred embodiment of the present invention；But scope of protection of the present invention is not limited thereto.
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
It improves design and is subject to equivalent substitution or change, should be covered by the scope of protection of the present invention.
Claims (10)
1. a kind of method of the cobalt nickel purification based on old and useless battery metals recovery processes, it is characterised in that: the following steps are included:
Step 1: ternary battery waste residue is dissolved in sulfuric acid solution；
Step 2: sodium sulphate is added in above-mentioned solution, when reaction carries out, the PH being connected with chemical reaction case (1) is observed in real time
Value tester detects the pH value in solution, and weakly alkaline solution is added into reaction solution according to the variation of pH value and is neutralized；
Step 3: with metal impurities such as copper remaining in alkyl phosphoric acid extraction solution, iron, manganese, zinc, and obtain the sulphur that extraction obtains
Sour cobalt, nickel sulfate solution；
Step 4: cobaltous sulfate, nickel sulfate solution that extraction obtains, excessive sodium hydroxide solution is added thereto, sees whether
There is Precipitation, when finding to there is precipitating in solution, repeats step 3 after the reaction solution of this step is filtered again, until
Next step operation is carried out again it was found that not occurring precipitating；
Step 5: ammonium oxalate is added into above-mentioned filtrate, cobalt and nickel are respectively formed precipitating, then be filtered to precipitating, evaporation is dried
It is dry；
Step 6: cobalt oxalate obtained by above-mentioned steps, nickel oxalate precipitation mixture are subjected to the high-temperature calcination under different temperatures,
Respectively obtain cobalt oxide, nickel oxide powder；
Step 7 is reduced into metallic cobalt and metallic nickel according to recycling needs, then by cobalt oxide and nickel oxide respectively.
2. a kind of method of cobalt nickel purification based on old and useless battery metals recovery processes according to claim 1, feature
Be: the solution ph in the step 2 is between 1.6-1.8, and solution temperature is 85-95 DEG C.
3. a kind of method of cobalt nickel purification based on old and useless battery metals recovery processes according to claim 1, feature
Be: chemical reaction case (1) upper end has snapped connection sealed platform cover (2), and sealed platform cover (2) outer end, which is dug, charging
Mouth (3), the chemical reaction case (1) is interior to be equipped with auxiliary fixing plate (6), slidably connects conduit in the auxiliary fixing plate (6)
(7), described sliding slot (12) one end inner wall is fixedly connected with compressed spring (13), and the compressed spring (13) and limit move block (14) admittedly
Fixed connection, the limiting block (15) is dug far from one end of chemical reaction case (1) multiple inlet openings (16), the inlet opening
(16) it is interconnected with chemical reaction case (1).
4. a kind of method of cobalt nickel purification based on old and useless battery metals recovery processes according to claim 3, feature
Be: chemical reaction case (1) lower end wall digs fluted (4), is rotatably connected to rotary shaft (5), institute in the groove (4)
Rotary shaft (5) is stated to be fixedly connected with auxiliary fixing plate (6).
5. a kind of method of cobalt nickel purification based on old and useless battery metals recovery processes according to claim 3, feature
Be: conduit (7) left and right ends are fixedly connected to multiple stirring rod (10).
6. a kind of method of cobalt nickel purification based on old and useless battery metals recovery processes according to claim 3, feature
It is: is equipped with telescopic rod (9) in the conduit (7), telescopic rod (9) upper end is fixedly connected with electric telescopic rod (11), institute
It states telescopic rod (9) lower end to be fixedly connected with sealing piston (8), the sealing piston (8) is slidably connected with conduit (7).
7. a kind of method of the cobalt nickel purification based on old and useless battery metals recovery processes, special according to claim 3 or 6
Sign is: conduit (7) left and right ends, which are dug, liquid liquid exchange hole, and the liquid liquid exchange hole left and right ends, which are dug, cunning
Slot (12), the liquid liquid exchange hole is interior to be equipped with limiting block (15), and limiting block (15) left and right ends are fixedly connected with limited shifting
Block (14), the limit move block (14) and are slidably connected with sliding slot (12).
8. a kind of method of cobalt nickel purification based on old and useless battery metals recovery processes according to claim 7, feature
Be: the limiting block (15) is fixedly connected with hush panel (17) close to one end of chemical reaction case (1), the hush panel (17)
It is mutually matched with liquid liquid exchange hole.
9. a kind of method of cobalt nickel purification based on old and useless battery metals recovery processes according to claim 1, feature
Be: the alkyl phosphoric acid in the step 3 is that two -2- ethylhexyl phosphoric acids (D-2-EHPA) or other alkyl phosphoric acid esters extract
Take agent.
10. a kind of method of cobalt nickel purification based on old and useless battery metals recovery processes according to claim 1, feature
Be: the calcination temperature in the step 6 reaches 380 DEG C and obtains nickel oxide, and calcination temperature reaches 450 DEG C and obtains cobalt oxide.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811635321.3A CN109536724A (en) | 2018-12-29 | 2018-12-29 | A method of the cobalt nickel purification based on old and useless battery metals recovery processes |
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| CN201811635321.3A CN109536724A (en) | 2018-12-29 | 2018-12-29 | A method of the cobalt nickel purification based on old and useless battery metals recovery processes |
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| CN110172579A (en) * | 2019-04-01 | 2019-08-27 | 武汉理工大学 | The recovery method of cobalt in the perovskite cathode material of solid oxide fuel cell |
| CN110273068A (en) * | 2019-07-05 | 2019-09-24 | 武汉理工大学 | The method of recovering copper and cobalt in waste and old solid oxide fuel cell |
| CN110964926A (en) * | 2019-12-26 | 2020-04-07 | 甘肃睿思科新材料有限公司 | Method for removing lithium from nickel cobalt oxalate |
| CN112079395A (en) * | 2020-09-17 | 2020-12-15 | 常宁市华兴冶化实业有限责任公司 | Method for preparing high-purity cobalt sulfate crystal |
| WO2022003198A1 (en) | 2020-07-02 | 2022-01-06 | Basf Se | Process for separating a mixture of oxalates of two or more of ni, co, and mn |
| CN114210305A (en) * | 2021-11-26 | 2022-03-22 | 广东邦普循环科技有限公司 | Magnetic aluminum-based adsorbent and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110172579A (en) * | 2019-04-01 | 2019-08-27 | 武汉理工大学 | The recovery method of cobalt in the perovskite cathode material of solid oxide fuel cell |
| CN110172579B (en) * | 2019-04-01 | 2020-08-04 | 武汉理工大学 | Method for recovering cobalt in perovskite cathode material of solid oxide fuel cell |
| CN110273068A (en) * | 2019-07-05 | 2019-09-24 | 武汉理工大学 | The method of recovering copper and cobalt in waste and old solid oxide fuel cell |
| CN110964926A (en) * | 2019-12-26 | 2020-04-07 | 甘肃睿思科新材料有限公司 | Method for removing lithium from nickel cobalt oxalate |
| WO2022003198A1 (en) | 2020-07-02 | 2022-01-06 | Basf Se | Process for separating a mixture of oxalates of two or more of ni, co, and mn |
| CN112079395A (en) * | 2020-09-17 | 2020-12-15 | 常宁市华兴冶化实业有限责任公司 | Method for preparing high-purity cobalt sulfate crystal |
| CN114210305A (en) * | 2021-11-26 | 2022-03-22 | 广东邦普循环科技有限公司 | Magnetic aluminum-based adsorbent and preparation method thereof |
| WO2023093188A1 (en) * | 2021-11-26 | 2023-06-01 | 广东邦普循环科技有限公司 | Magnetic aluminum-based adsorbent and preparation method therefor |
| CN114210305B (en) * | 2021-11-26 | 2023-11-03 | 广东邦普循环科技有限公司 | Magnetic aluminum-based adsorbent and preparation method thereof |
| GB2622516A (en) * | 2021-11-26 | 2024-03-20 | Guangdong Brunp Recycling Technology Co Ltd | Magnetic aluminum-based adsorbent and preparation method therefor |
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