CN1317086C - Method for recycling mixed waste batteries - Google Patents
Method for recycling mixed waste batteries Download PDFInfo
- Publication number
- CN1317086C CN1317086C CNB2005100332313A CN200510033231A CN1317086C CN 1317086 C CN1317086 C CN 1317086C CN B2005100332313 A CNB2005100332313 A CN B2005100332313A CN 200510033231 A CN200510033231 A CN 200510033231A CN 1317086 C CN1317086 C CN 1317086C
- Authority
- CN
- China
- Prior art keywords
- battery
- roasting
- batteries
- less
- zinc
- 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.)
- Expired - Fee Related
Links
Images
Landscapes
- Processing Of Solid Wastes (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Secondary Cells (AREA)
Abstract
The method for recycling and treating the mixed waste battery comprises the following steps: unpacking and discharging the waste batteries; the battery is crushed and the electrolyte in the battery is washed away; washing the crushed materials with water, ball-milling, roasting and separating organic matters, mercury, cadmium and zinc; separating the battery shell, the iron current collector and the copper current collector by a screening method; the undersize product is leached with alkali to remove aluminum and zinc, then is roasted and dissolved in acid, and then rare earth elements, impurities, nickel and cobalt elements in the acid solution are separated by using chemical precipitation and solvent extraction methods. The method has the advantages of economic and reasonable process and good effect, and does not need to classify and sort the mixed waste batteries in advance.
Description
(I) technical field
The invention relates to a method for recycling mixed waste batteries, wherein the waste batteries to be processed are nickel-hydrogen batteries, lithium ion batteries and/or mixtures of common batteries such as lithium batteries, nickel-cadmium batteries, zinc-manganese batteries and the like, and belongs to the technical field of recycling treatment of solid wastes.
(II) background of the invention
Primary and secondary batteries including lead-acid, zinc-manganese (including acidic and alkaline), cadmium-nickel, lithium ion, nickel-hydrogen, zinc-silver, lithium-manganese, etc. have been widely used in many fields of modern society, and battery consumption has become an important component of modern life. At present, the batteries produced in China each year need to consume tens of thousands of tons or even tens of thousands of tons of mercury, cadmium, lead, zinc, manganese, cobalt, nickel, copper, sulfuric acid, potassium hydroxide and other substances. These substances are also present in the battery after the battery is out of service, and thus, improper handling of the substances causes environmental pollution and waste of resources.
Nowadays, many methods for recycling waste batteries have been developed and the principles underlying these methods can largely be subsumed into pyrometallurgical and hydrometallurgical process flows. The waste lead-acid battery is easy to collect independently due to the particularity of the external volume and the use occasion, and is recovered and treated based on a pyrometallurgical method. The zinc-silver battery as a special battery can also be recycled and treated separately. Besides, in view of the existing other waste battery recycling methods, most of the waste batteries are directed at a certain type of battery, that is, in the recycling process, the given methods are actually based on sorting and classifying the batteries. In recent years, nickel-cadmium batteries (mainly applied to electric tools and portable electric appliances), nickel-hydrogen batteries and lithium-ion batteries (the number of the two batteries only applied to mobile phones in China is 3 hundred million), and the use amount of batteries such as lithium batteries is rapidly increased (two-digit increase speed), the problem of the waste batteries mainly comprising acid zinc-manganese batteries in the past is changed into the reality that a plurality of varieties (including rapidly-increased alkaline zinc-manganese batteries, nickel-hydrogen batteries, nickel-cadmium batteries, lithium-ion batteries, lithium batteries and the like) coexist in a large scale. For the recovery treatment of other types of waste batteries except lead-acid batteries, two options are available: one is a battery recycling process combining the development of special waste battery sorting and classifying equipment and developing a single variety, and the other is a hybrid waste battery comprehensive utilization technology without sorting and classifying batteries. The battery sorting process is possible for batteries with a large capacity or marked appearance, but it is difficult to practically operate small-sized batteries that are currently in widespread use. Recently, the recycling processes disclosed in CN1349271a (china), TW399347 (taiwan), etc., all embody the concept of comprehensive recycling, but the types of batteries that can be recycled by these patent technologies are few, and particularly, two rechargeable batteries, i.e., nickel-hydrogen batteries and lithium-ion batteries, which are used in increasingly larger quantities at present, are not involved. CN1438729A provides a process method for recycling waste mobile phone batteries based on the fact that mobile phone batteries have relatively obvious external characteristics.
Therefore, the exploration of a better process for recycling mixed waste batteries (including zinc-manganese batteries, cadmium-nickel batteries, lithium ions, nickel-hydrogen batteries, lithium batteries and the like) has a good development prospect undoubtedly.
Disclosure of the invention
The invention aims to develop a comprehensive recycling technology without classifying and sorting the mixture of common waste batteries (except lead-acid batteries, zinc-silver batteries and other special batteries) in advance, and provides a process method for recycling the mixture of the common waste batteries such as nickel-hydrogen batteries, lithium ion batteries and/or lithium batteries, nickel-cadmium batteries, zinc-manganese batteries and the like. The method can recover the precious metal elements such as zinc, manganese, nickel, cobalt, copper, rare earth, lithium and the like in the battery, solves the pollution problem of the waste battery, realizes the economical recycling of resources, and is reasonable, economical and practical.
Specifically, the method comprises the following steps:
1. unpacking and complete discharge treatment of the waste batteries: removing the outer package of the waste battery by using a shearing machine and a crushing machine to obtain a single battery, recovering a connecting part in the process, and then sending the obtained single battery to a pretreatment pool filled with purified water and a conductive agent for stirring treatment to enable the battery to generate short circuit and completely discharge residual electric quantity;
2. battery crushing: taking out the completely discharged battery, breaking the outer shell of the battery by using a breaking machine, and putting the battery into a washing treatment pool filled with purified water to wash away electrolyte in the battery;
3. roasting and washing the crushed materials: adding carbon powder into the washed crushed material, putting the mixture into a ball mill together for ball milling, and then putting the mixture into a roasting furnace for separating organic matters, mercury, cadmium and zinc in the mixture by a roasting method;
4. screening and roasting residues: separating the battery shell, the iron electrode current collecting net, the metal nickel and the metal copper in the roasted product by a screening method;
5. alkali treatment of undersize: treating the undersize product obtained in the fourth step with an alkali solution to dissolve and separate aluminum and zinc in the undersize product;
6. alkali treatment of the residue with sulfuric acid solution: oxidizing a large amount of manganese elements in the alkali treatment residue to high-valence manganese oxide by roasting-heating oxidation in the presence of air, and dissolving soluble substances in the high-valence manganese oxide by using sulfuric acid, so that manganese is separated in the form of high-valence manganese oxide which is insoluble in sulfuric acid;
7. separation and purification of acid dissolved substances: separating most of rare earth elements by a method of adjusting the pH value, extracting copper and trace manganese, iron, zinc, aluminum, cadmium and rare earth elements in the solution by using P507, and extracting and separating cobalt and nickel by using Cyanex 272;
8. and (3) treating waste liquid: mixing the waste liquid produced in the treatment process, adjusting the solution to be neutral by adopting an acid-base reagent, concentrating, filtering, and finally discharging the waste liquid after the detection is qualified.
In the first step of the method, when the battery without the shell is completely discharged, the complete discharge treatment of the single battery is carried out in a steel pretreatment container, the conductive agent adopts iron powder, and the time for stirring the single battery in the pretreatment container is not less than 30min;
in the second step, the water washing treatment tank is made of acid and alkali resistant glass fiber reinforced plastic, and a protective cover is added to prevent reaction substances from splashing out.
In the third step, the adding amount of carbon powder is not less than 15% of the mass of the crushed material after water washing, the ball milling time is not less than 30min, and then roasting separation is carried out in a roasting furnace (the structure and the connection relation of the roasting furnace are described in detail in the attached drawing): one is to adopt the way of temperature programming to separate, namely roast and remove moisture among them under 200-300 duC, reclaim and process trace mercury, battery diaphragm and outer plastic film in the battery under 470-570 duC condition, reclaim cadmium under 765-870 duC roasting temperature condition, reclaim zinc under 1100-1300 duC roasting temperature condition, the roasting time under every temperature condition is not less than 1h; the other method is to directly control the roasting temperature to be 1100-1300 ℃ to obtain the mixture of the recycled materials, and the roasting time is not less than 1h.
The roasting furnace used in the third step is formed by connecting an air blower, a roasting furnace body, a cooler and a flue gas filter in sequence, wherein the upper end of the roasting furnace body is provided with a feeding hole, the lower end of the roasting furnace body is provided with a discharging hole, and the roasting furnace body, the cooler and the flue gas filter are connected through a flue gas pipeline. During roasting, the crushed washed battery is added into a roasting furnace body from a feeding hole, the roasting furnace body is controlled at a proper temperature, air is introduced through an air blower in the roasting process, flue gas generated in the roasting process enters a cooler through a flue gas pipeline, roasting residues are taken out through a discharging hole, mercury, cadmium and zinc to be recovered are cooled in the cooler and finally recovered, and carbon dioxide flue gas containing trace substances reaches a flue gas filter through a flue gas pipeline and is discharged to the air after being filtered.
In the fourth step, a sample separating sieve with the sieve pore size of 0.5-5mm is adopted in the screening process.
In the fifth step, the used alkali solution is potassium hydroxide or sodium hydroxide with the mass percentage concentration of not less than 10%, the temperature is not less than 50 ℃, the treatment time is not less than 30min, and the solid-liquid separation is carried out by adopting a filtering method after the treatment is finished.
The roasting temperature in the sixth step is not less than 500 ℃, the time is not less than 1h, the atmosphere is air, and the roasting is carried out in a common roasting furnace; the concentration of sulfuric acid used for dissolving the alkali treatment residues is not less than 1mol/L, the temperature is not less than 50 ℃, the reaction time is not less than 1h, and a filtering method is adopted for solid-liquid separation after the reaction is finished.
In the seventh step, the pH value of the solution is increased by 1mol/L sodium hydroxide or potassium hydroxide, rare earth elements are separated by generating rare earth sulfate double salt precipitation when the pH value is adjusted to 1.5-2.5, and then the P507 with the mass percent concentration of 10-30% is used for extracting copper, manganese, iron, zinc, aluminum and cadmium in the solution under the condition that the pH value is 2.1-2.8; then, in the range of pH value of 5-5.5 and 6-6.5, cyanex272 with concentration of 1-3mol/L is used for extracting cobalt and nickel in turn, and sulfuric acid solution with concentration of 2mol/L is used as stripping agent. Wherein, P507 and Cyanex272 are common extracting agents.
In the eighth step, the waste liquid must be detected by a general waste liquid discharge detection method before being discharged until the waste liquid is qualified.
The invention has the following advantages or effects:
1. the process flow can treat all waste batteries including nickel-hydrogen batteries, nickel-cadmium batteries, lithium ion batteries, zinc-manganese batteries and lithium batteries, does not need to classify and sort the batteries in advance before recovery treatment, and the recovered batteries meet the actual condition of collecting the waste batteries, so that the treatment method has good practical performance. In addition, the invention can be used for recycling one battery or a mixture of several batteries after omitting certain steps and carrying out proper adjustment.
2. The process flow organically utilizes the advantages of pyrometallurgy and hydrometallurgy, has good separation effect on various substances and high recovery rate of valuable elements, and greatly improves the economic benefit of the process flow.
(IV) description of the drawings
FIG. 1 is a process flow diagram of the process of the present invention
FIG. 2 is a schematic view of the structure of a roasting furnace used in step three of the present invention
(V) specific embodiments
Example 1
A recycling example of the present invention will be described in detail with reference to the accompanying fig. 1, in which the mixed spent batteries treated are composed of: 20% of zinc-manganese dry battery, 15% of alkaline zinc-manganese battery, 20% of nickel-hydrogen battery, 20% of nickel-cadmium battery, 20% of lithium ion battery and 5% of lithium battery.
1. The outer package and the connection lines on the collected waste batteries are removed by means of a cutter and a crusher to obtain the unit batteries, and the connection parts therein are recovered in the process.
Meanwhile, because the waste batteries generally have certain residual electric quantity, in order to avoid the danger caused by the short-circuit discharge of the positive and negative plates when the battery shell is opened, the single batteries are put into a steel pretreatment container added with water and iron powder, and the positive and negative electrodes of the single batteries are forced to be short-circuited under the mechanical stirring, so that the complete discharge of the batteries is realized. At this time, the water in the container may play a role of cooling heat discharged when the battery is short-circuited. The battery can be completely discharged after stirring for 30min.
2. After the completely discharged battery was taken out of the discharge pretreatment vessel, the battery case was opened by a crusher. The crushing battery can adopt a cutter or a special battery crusher, and can be obtained by purchase. Since the batteries contain corrosive or volatile electrolyte, and the presence of the electrolyte is not beneficial to the separation and extraction of other substances in the subsequent steps, the crushed objects of the batteries are immediately transferred into a treatment tank filled with purified water to wash away the electrolyte. The acid-base property of electrolyte of different batteries is different, and acid-base reaction can occur after the electrolyte is put into a treatment pool, and simultaneously, residual metal lithium in the lithium battery is dissolved by reacting with water, so the material of the water washing treatment pool is acid-base resistant glass fiber reinforced plastic, and a protective cover is added to prevent the reaction and splashing of lithium and water.
3. Washing the crushed material with water to remove the electrolyte, ball milling the crushed material and carbon powder in a ball mill, and roasting in a roasting furnace to separate organic matters, mercury, cadmium and zinc. The organic matter mainly comprises a diaphragm of the battery, a binder and an outer packaging film of the battery, the mercury mainly comes from a zinc-manganese battery, the cadmium mainly comes from a negative active material of a nickel-cadmium battery, and the zinc mainly comes from a zinc shell and the negative active material of the zinc-manganese battery.
The added carbon powder is mainly used as a reducing agent in the roasting process, and the ball milling is to ensure that substances to be separated in the broken objects of the battery are granular and fully contacted with the carbon powder. The adding amount of the carbon powder is determined according to the amount of cadmium and zinc compounds in the crushed materials of the battery, so that the reducing reaction environment can be formed in the roasting process, the two materials are reduced, volatilized and separated, the carbon powder with the waste amount of 15 percent is added, and the ball milling time is 30min.
The selection of the roasting conditions is one of the key links of the recovery process. The water-washed crushed material is roasted in a closed roasting furnace. According to the performance characteristics of all substances contained in the substance to be roasted, mercury, cadmium, zinc and trace other substances can be sequentially recovered by adopting a temperature programming mode in the process, and the other substances cannot volatilize and are separated from the substances. Wherein, the water is removed by roasting at 200-300 ℃; the trace mercury, the battery diaphragm, the outer packaging plastic film and the like can be recovered at the temperature of 470-570 ℃; continuously raising the temperature to 765-870 ℃, reducing and volatilizing cadmium (with the boiling point of 765 ℃) and recovering the cadmium; zinc (boiling point 907 ℃ C.) will also be separated by volatilization at calcination temperatures of 1100-1300 ℃. Experiments show that in the roasting process, fresh air is continuously introduced into the lower layer of a roasted substance to generate a carbon monoxide reducing atmosphere, meanwhile, a filtering device is arranged at the tail part of the receiver, the time of controlling each roasting temperature point is not less than 1h, the separation rate of the substances can reach more than 95%, and the generated gas can be safely discharged after passing through the filtering device.
4. Because the reducing atmosphere is always kept around the roasted material in the roasting process, the iron battery shell and current collecting body, and the conductive nickel and copper metal sheets can be kept in the original state, so that the battery shell and the iron electrode current collecting net, and a small amount of metal nickel and copper in the roasted material can be easily separated by using a sample separating sieve with the sieve pore size of 0.5-5 mm. The powdered undersize is mainly active substance in each battery and powdered current collector, and the related substances are mainly oxides of nickel, cobalt, hydrogen storage alloy, manganese, aluminum and copper or metal monomers of the oxides.
5. By utilizing the property that aluminum and zinc can be dissolved in an alkali solution, sodium hydroxide solution with the mass percent concentration of 20 percent is added into the undersize material, the undersize material is treated for 2 hours at the temperature of 50 ℃, more than 98 percent of aluminum and zinc in the undersize material can be dissolved, and then the solid-liquid separation is carried out by a filtering method.
6. Oxidizing a large amount of manganese elements existing in the alkali treatment residue into high-valence manganese oxides by a heating oxidation method in the presence of air, and dissolving soluble substances in the high-valence manganese oxides by sulfuric acid, wherein insoluble substances are mainly the high-valence manganese oxides, so that manganese is separated.
The manganese element is mainly from a zinc-manganese battery, and a small amount of manganese element is from a hydrogen storage alloy in a negative active material of a nickel-hydrogen battery. The valence states of the battery at the time of battery breakage are tetravalent, trivalent and divalent, wherein tetravalent manganese is mainly manganese dioxide without discharge. During the above calcination process, most of the manganese oxide is reduced to divalent manganese oxide which can be dissolved in sulfuric acid. Since sulfuric acid is used to dissolve the alkali-treated material and recover nickel, cobalt and copper with high recovery value, if manganese with high content is dissolved into the solution together, the separation difficulty of these high-valence elements will be increased. The process comprises the step of roasting for 1h at 850 ℃ under the condition of introducing air, so that bivalent manganese oxide in the material can be oxidized into manganese dioxide insoluble in sulfuric acid.
The roasted product was dissolved in 1mol/l sulfuric acid at 85 ℃ for 1 hour. And filtering and washing after the reaction is finished, wherein filter residues are mainly manganese dioxide, main elements in the filtrate are copper, nickel, cobalt and rare earth elements, and trace manganese, iron, zinc, aluminum and cadmium which can be completely separated are not contained in the step.
7. The method for separating and purifying various substances in the acid dissolving solution comprises the following steps: firstly, the pH value of the solution is adjusted to enable rare earth elements and sulfate ions in the solution to generate rare earth sulfate double salt to be precipitated and separated, then P507 is used for extracting copper and trace manganese, iron, zinc, aluminum and cadmium in the solution, and Cyanex272 is used for extracting and separating cobalt and nickel respectively.
Wherein, sodium hydroxide or potassium hydroxide with the concentration of 1mol/L is used for adjusting the pH value of the solution to 1.5-2.5, more than 94 percent of rare earth elements in the solution can be precipitated and separated by a filtering method. And then under the condition that the pH value is 2.1-2.8, P507 with the mass percent concentration of 10-30% is used as an extracting agent to extract copper, manganese, iron, zinc, aluminum, cadmium and rare earth elements in the filtrate. Then using Cyanex272 with the concentration of 1-3mol/L as an extracting agent to extract cobalt and nickel from the raffinate filtrate in turn when the pH value of the solution is 5-5.5 and 6-6.5 respectively. When the substances in the extract phase obtained above were stripped, the stripping agents used were all sulfuric acid solutions having a concentration of 2 mol/L. After the operations, the comprehensive recovery rate of the valuable metal elements of nickel, cobalt, copper and rare earth can reach more than 94%.
8. Waste liquid is generated in the processes of washing broken objects of the battery, dissolving by alkali and finally treating, and the process adopts a waste liquid treatment method as follows: mixing all the process waste liquids together, adjusting the solution to be neutral, and then concentrating. And (4) detecting the waste liquid by adopting a universal waste liquid detection method before the waste liquid is discharged until the waste liquid is qualified.
Example 2
The other contents and operations were the same as in example 1, except that the composition of the treated battery was: 20% of zinc-manganese dry batteries, 15% of alkaline zinc-manganese batteries, 20% of nickel-hydrogen batteries, 20% of nickel-cadmium batteries and 25% of lithium ion batteries. The stirring time when the discharge is completed in the first step is 60min; in the third step, the amount of the added carbon powder is 25% during ball milling, the ball milling time is 30min, and the roasting modes are respectively that roasting is carried out at 200 ℃ to remove water in the carbon powder, micro mercury in the battery, the battery diaphragm and an outer packaging plastic film are recovered and treated at 470 ℃, cadmium is recovered at 750 ℃, zinc is recovered at 1100 ℃, and the roasting time at each temperature is 4h; step five, treating for 30min at the reaction temperature of 85 ℃ by using 10% potassium hydroxide; in the sixth step, the roasting temperature is 500 ℃, the roasting time is 5 hours, the concentration of sulfuric acid used for dissolving the battery waste is 4mol/L, the temperature is 50 ℃, and the reaction time is 2 hours; the concentration of the P507 extractant used in the seventh step is 10 percent, and the concentration of the Cyanex272 extractant is 3mol/L.
With these conditions, the same effect of the recovery treatment as in example 1 can be also achieved.
Example 3
The other contents and operations are the same as example 1, except that in the third step, the temperature is directly controlled between 1100-1300 ℃ to bake for not less than 1h, and the volatile matter is collected to obtain the mixture of zinc, cadmium and mercury. The same effect of the recovery treatment as in example 1 can be achieved.
The closed roasting furnace used in step three of the present invention will be described in detail with reference to fig. 2. In fig. 2, 1 is a blower, 2 is a roasting furnace body, 3 is a feed inlet, 4 is a discharge outlet, 5 is a pharyngeal conduit, 6 is a cooler, and 7 is a flue gas filter. The connection relationship is as follows: the air blower 1, the roasting furnace body 2, the cooler 6 and the flue gas filter 7 are sequentially connected, a feeding hole 3 is installed at the upper end of the roasting furnace body 2, a discharging hole 4 is installed at the lower end of the roasting furnace body 2, and the roasting furnace body 2, the cooler 6 and the flue gas filter 7 are connected through a flue gas pipeline 5. During roasting, crushed materials of the water-washed battery are added into a roasting furnace body 2 through a feeding hole 3, the roasting furnace body 2 is controlled at a proper temperature, air is introduced through an air blower 1 in the roasting process, flue gas generated in the roasting process enters a cooler 6 through a flue gas pipeline 5, roasting residues are taken out through a discharging hole 4, materials to be recovered, namely mercury, cadmium and zinc, are cooled in the cooler 6 and finally recovered, carbon dioxide flue gas containing trace substances reaches a flue gas filter 7 through the flue gas pipeline 5, and the flue gas is discharged after being filtered. The equipment has no special requirements on all components, and can be assembled by adopting models commonly used in the field.
Claims (9)
1. A method for recycling and treating mixed waste batteries is characterized by comprising the following steps:
1. unpacking and complete discharge treatment of the waste batteries: removing the outer package of the waste battery by using a shearing machine and a crushing machine to obtain a single battery, recovering a connecting part in the process, and then sending the obtained single battery to a pretreatment pool filled with purified water and a conductive agent for stirring treatment to enable the battery to generate short circuit and completely discharge residual electric quantity;
2. battery crushing: taking out the completely discharged battery, breaking the outer shell of the battery by using a breaking machine, and putting the battery into a washing treatment pool filled with purified water to wash away electrolyte in the battery;
3. roasting and washing the crushed materials: adding carbon powder into the washed and crushed material, putting the washed and crushed material into a ball mill together for ball milling, and then putting the material into a roasting furnace for separating organic matters, mercury, cadmium and zinc in the material by a roasting method;
4. screening and roasting residues: separating the battery shell, the iron electrode current collecting net, the metal nickel and the metal copper in the roasted product by a screening method;
5. alkali treatment of undersize: treating the undersize product obtained in the fourth step with an alkali solution to dissolve and separate aluminum and zinc in the undersize product;
6. alkali treatment of the residue with sulfuric acid solution: oxidizing most of manganese in the alkali-treated residue to high-valence manganese oxide by roasting in the presence of air, and dissolving the soluble substances in the alkali-treated residue by using sulfuric acid, so that manganese is separated in the form of high-valence manganese oxide which is insoluble in sulfuric acid;
7. separation and purification of acid dissolved substances: separating most of rare earth elements by a method of adjusting the pH value, extracting copper, manganese, iron, zinc, aluminum, cadmium and rare earth elements in the solution by using P507, and respectively extracting and separating cobalt and nickel by using cyane 272;
8. and (3) treating waste liquid: mixing the waste liquid produced in the treatment process, adjusting the solution to be neutral by adopting an acid-base reagent, concentrating, filtering, and finally discharging the waste liquid after the detection is qualified.
2. The method of claim 1, wherein: in the first step, the complete discharge treatment of the single batteries is carried out in a steel pretreatment container, the conductive agent adopts iron powder, and the time for stirring the single batteries in the pretreatment container is not less than 30min.
3. The method of claim 1, wherein: in the second step, the water washing treatment tank is made of acid and alkali resistant glass fiber reinforced plastic and is provided with a protective cover.
4. The method of claim 1, wherein: in the third step, the adding amount of the carbon powder is not less than 15 percent of the mass of the crushed material after water washing, and the ball milling time is not less than 30min; there are two methods of firing in a firing furnace: one is to adopt a temperature programming mode to separate, namely roasting to remove water in the battery at 200-300 ℃, recovering and treating trace mercury in the battery, a battery diaphragm and an outer packaging plastic film at 470-570 ℃, recovering cadmium at 765-870 ℃, recovering zinc at 1100-1300 ℃, and roasting for not less than 1h at each temperature; the other method is to directly control the roasting temperature to be 1100-1300 ℃ to obtain the mixture of the recovered substances, and the roasting time is not less than 1h.
5. The method of claim 1, wherein: the roasting furnace used in the third step is formed by sequentially connecting an air blower (1), a roasting furnace body (2), a cooler (6) and a flue gas filter (7), a feeding hole (3) is installed at the upper end of the roasting furnace body (2), a discharging hole (4) is installed at the lower end of the roasting furnace body, and the roasting furnace body (2), the cooler (6) and the flue gas filter (7) are connected through a flue gas pipeline (5).
6. The method of claim 1, wherein: in the fourth step, a sample separating sieve with the sieve pore size of 0.5-5mm is adopted in the screening process.
7. The method of claim 1, wherein: in the fifth step, the used alkali solution is potassium hydroxide or sodium hydroxide with the mass percentage concentration of not less than 10%, the temperature is not less than 50 ℃, the treatment time is not less than 30min, and a filtering method is adopted for solid-liquid separation after the treatment is finished.
8. The method of claim 1, wherein: the roasting temperature in the sixth step is not less than 500 ℃, and the time is not less than 1h; the concentration of sulfuric acid used for dissolving the alkali treatment residues is not less than 1mol/L, the temperature is not less than 50 ℃, the reaction time is not less than 1h, and a filtering method is adopted for solid-liquid separation after the reaction is finished.
9. The method of any one of claims 1-8, wherein: in the seventh step, the pH value of the solution is increased by 1mol/L sodium hydroxide or potassium hydroxide, rare earth elements are separated by generating rare earth sulfate double salt precipitation when the pH value is adjusted to 1.5-2.5, and then the P507 with the mass percentage concentration of 10-30% is used for extracting copper and trace manganese, iron, zinc, aluminum and cadmium in the solution under the condition that the pH value is 2.1-2.8; then, in the range of pH value of 5-5.5 and 6-6.5, cyanex272 with concentration of 1-3mol/L is used for sequentially extracting cobalt and nickel, and sulfuric acid solution with concentration of 2mol/L is used as stripping agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100332313A CN1317086C (en) | 2005-02-21 | 2005-02-21 | Method for recycling mixed waste batteries |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100332313A CN1317086C (en) | 2005-02-21 | 2005-02-21 | Method for recycling mixed waste batteries |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1692997A CN1692997A (en) | 2005-11-09 |
| CN1317086C true CN1317086C (en) | 2007-05-23 |
Family
ID=35352231
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100332313A Expired - Fee Related CN1317086C (en) | 2005-02-21 | 2005-02-21 | Method for recycling mixed waste batteries |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1317086C (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100392899C (en) * | 2006-06-15 | 2008-06-04 | 深圳市格林美高新技术股份有限公司 | Waste battery sorting and disassembling process and system |
| CN102136583A (en) * | 2011-02-14 | 2011-07-27 | 华南师范大学 | Regeneration method of zinc powder as negative electrode material of waste alkaline zinc-manganese dioxide battery |
| CN102780014A (en) * | 2012-08-09 | 2012-11-14 | 遵义师范学院 | Method for regenerating manganese sulfate from waste alkaline zinc-manganese battery |
| RU2538863C2 (en) * | 2013-03-05 | 2015-01-10 | Открытое акционерное общество "Объединенная химическая компания "УРАЛХИМ" | Re-extraction method of rare-earth metals from organic solutions and obtainment of concentrate from rare-earth metals |
| CN107293819B (en) * | 2017-06-08 | 2019-06-14 | 深圳市恒创睿能环保科技有限公司 | A kind of waste lithium ion dry method discharge processes |
| CN108579896B (en) * | 2018-05-31 | 2019-01-22 | 鉴奕霖 | A kind of old and useless battery treatment device |
| CN109022779B (en) * | 2018-07-26 | 2019-08-30 | 华中科技大学 | A method of pH changes during control acidic extractant demanganization |
| CN109900790B (en) * | 2019-03-22 | 2021-04-02 | 东北大学 | Composite material dynamic fatigue test device and method based on reverse resonance |
| CN109839254B (en) * | 2019-03-22 | 2020-07-10 | 东北大学 | Composite material thermal vibration fatigue test device and method based on reverse resonance |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5567223A (en) * | 1993-11-25 | 1996-10-22 | Boliden Mineral Ab | Method for dealing with mercury-containing waste |
| JP2003203680A (en) * | 2002-01-08 | 2003-07-18 | Sumitomo Metal Mining Co Ltd | Method of recovering valuable metal from used nickel- hydrogen secondary cell |
| CN1438729A (en) * | 2003-03-14 | 2003-08-27 | 华南师范大学 | Comprehensive recovering treatment technology for waste and old mobile-telephone cell |
-
2005
- 2005-02-21 CN CNB2005100332313A patent/CN1317086C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5567223A (en) * | 1993-11-25 | 1996-10-22 | Boliden Mineral Ab | Method for dealing with mercury-containing waste |
| JP2003203680A (en) * | 2002-01-08 | 2003-07-18 | Sumitomo Metal Mining Co Ltd | Method of recovering valuable metal from used nickel- hydrogen secondary cell |
| CN1438729A (en) * | 2003-03-14 | 2003-08-27 | 华南师范大学 | Comprehensive recovering treatment technology for waste and old mobile-telephone cell |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1692997A (en) | 2005-11-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101599563B (en) | Method for efficiently recovering active materials of positive poles in waste lithium batteries | |
| Zheng et al. | Leaching procedure and kinetic studies of cobalt in cathode materials from spent lithium ion batteries using organic citric acid as leachant | |
| JP3452769B2 (en) | Battery treatment method | |
| JP4865745B2 (en) | Method for recovering valuable metals from lithium batteries containing Co, Ni, Mn | |
| CN100595970C (en) | Method for selectively removing copper from waste lithium ion battery | |
| KR100930453B1 (en) | How to Recover Metals from Battery Residues | |
| Chandran et al. | Comprehensive review on recycling of spent lithium-ion batteries | |
| CN102751549B (en) | Full-component resource reclamation method for waste positive electrode materials of lithium ion batteries | |
| JP4144820B2 (en) | Method for regenerating positive electrode active material from lithium ion secondary battery | |
| CN107326181A (en) | Waste and old lithium ion battery, which is peeled off, leaches the recovery method that a step is completed | |
| US20160251740A1 (en) | Method for recycling electrode materials of lithium ion batteries | |
| CN108486376A (en) | A method of leaching metal in waste lithium ion cell anode material | |
| WO2017145099A1 (en) | Process for recovery of pure cobalt oxide from spent lithium ion batteries with high manganese content | |
| CN1601805A (en) | Recovery and treatment method for waster lithium ion cell | |
| CN104485493B (en) | The reparative regeneration method of lithium cobaltate cathode active material in used Li ion cell | |
| CN101603126B (en) | Process for efficiently leaching anode active material of waste lithium battery | |
| KR101086769B1 (en) | Recovery Method of valuable Metal from the waste Lithium ion battery and the scrap | |
| Li et al. | Recycling and treatment of waste batteries | |
| CN1317086C (en) | Method for recycling mixed waste batteries | |
| CN104466293A (en) | Regeneration method of lithium ion battery anode material lithium cobalt oxide waste | |
| CN104485494A (en) | Method for regenerating anode active materials in lithium cobalt oxide spent lithium-ion batteries | |
| CN115161483B (en) | Method for fully recycling waste lithium ion batteries and realizing metal separation | |
| KR102038954B1 (en) | Separation of valuable metals from waste secondary batteries by alkaline fritting method | |
| CN103221557A (en) | Method for producing nickel-ontaining acidic solution | |
| CN115275415A (en) | Method for recovering lithium from retired lithium battery and regenerating positive electrode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20051230 Address after: Guangdong Province, Tianhe District City, the Department of scientific research South China Normal University Guangzhou Shipai Street Applicant after: South China Normal University Co-applicant after: Guangzhou Research Institute of Non-ferrous Metals Address before: Guangdong Province, Tianhe District City, the Department of scientific research South China Normal University Guangzhou Shipai Street Applicant before: South China Normal University |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20070523 Termination date: 20110221 |