[go: up one dir, main page]

WO2012025568A2 - Récupération d'ions métalliques à partir de piles usagées - Google Patents

Récupération d'ions métalliques à partir de piles usagées Download PDF

Info

Publication number
WO2012025568A2
WO2012025568A2 PCT/EP2011/064560 EP2011064560W WO2012025568A2 WO 2012025568 A2 WO2012025568 A2 WO 2012025568A2 EP 2011064560 W EP2011064560 W EP 2011064560W WO 2012025568 A2 WO2012025568 A2 WO 2012025568A2
Authority
WO
WIPO (PCT)
Prior art keywords
acid
leaching
solution
alkaline
hours
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.)
Ceased
Application number
PCT/EP2011/064560
Other languages
English (en)
Other versions
WO2012025568A3 (fr
Inventor
Jarmo Pudas
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
AKKUSER Oy
Original Assignee
AKKUSER Oy
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by AKKUSER Oy filed Critical AKKUSER Oy
Publication of WO2012025568A2 publication Critical patent/WO2012025568A2/fr
Publication of WO2012025568A3 publication Critical patent/WO2012025568A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

Definitions

  • the present application relates to processes for recovery and recycling of metals found in spent alkaline batteries.
  • the processes and methods described herein primarily relates to spent alkaline batteries as opposed to e.g. re-chargeable lithium based batteries.
  • Alkaline batteries make up about 80% of all collected spent batteries. Consequently, there is a need and interest of finding process for recovery of the metals used in alkaline spent batteries.
  • Alkaline batteries are primarily batteries consisting mainly of zinc/zinc oxide and manganese dioxide (Zn/ZnO andMn0 2 ).
  • the anode (negative) is made of zinc powder, which gives more surface area for increased current, and the cathode (positive) is composed of manganese dioxide.
  • the alkaline battery cell nominal voltage of a fresh alkaline cell is 1.5 V
  • there is an alkaline electrolyte of potassium hydroxide whereas zinc-carbon batteries have acidic electrolytes.
  • WO 03021708 relates a process in which used cells are crushed and magnetically separated, or being subjected to a thermal treatment, are treated by alkalic attrition to remove any soluble salts (e.g. chlorides). The remaining solid is then leached by sulphuric acid under ultrasonication in presence of a reducing agent (such as e.g. hydrogen peroxide). From the solution is then removed Hg by addition of a reducing agent (such as e.g. hydrogen peroxide).
  • a reducing agent such as e.g. hydrogen peroxide
  • An alternative route may be according to an article by Ferella et a/. Journal of Power Sources 183 (2008) 805-811 , suggesting a route where zinc is leached from crushed alkaline batteries using H 2 S0 4 and the remaining carbon and manganese is roasted at 900°C to produce manganese oxides and disposing the carbon residual as carbon dioxide.
  • the zinc solution will contain zinc and sulfuric acid.
  • the article suggests an electro winning (or electroextraction) route for zinc.
  • Present invention relates to methods for recovery of metals from recycled spent alkaline batteries.
  • the metals can be e.g. zinc and/or manganese.
  • a sorting process may optionally be employed as a first step.
  • Such a sorting process has the aim of separating alkaline batteries from any other kinds of batteries such as e.g. re-chargeable lithium batteries.
  • a sorting process that may be employed for this purpose is exemplified in PCT/EP2011/053963 by the same applicant.
  • this process can be described as a batch of mixed batteries entering the process.
  • the batches with batteries may also contain non-battery items such as electronic devices containing batteries.
  • Other assorted waste may also be present in these in the batch.
  • the large waste mass to be recycled is sorted manually, to separate batteries from other electronic waste material.
  • batteries are sorted and separated from alkaline batteries. These battery types may be lead-, Li-lon polymer-, Ni-Cd-, mercury-, Ni-Metal Hydride-, larger lithium primary, small Lithium primary batteries.
  • the raw material is subjected to a sieve (shaking) system removing so called button cell batteries.
  • This process removes the small lithium primary batteries, also known as button cell batteries. These are round, approximately a half inch in diameter and an eighth of an inch in width. They are used in many consumer electronic products, such as some cameras.
  • the button cell batteries are removed by passing through a metal "sieve.”
  • This sieve consists of approx. 15 V-shaped metal ridges, which are all connected such that the same piece of metal forms the left side of one ridge and the right side of another ridge.
  • the left and right sides are at an approximately 45 degree angle such that any small object would fall to the middle of each ridge.
  • the side of each ridge is approximately one inch long.
  • the bottom of each ridge, what one could call the bottom of the "V,” is empty. It is an open slot approximately one-quarter of an inch wide. Thus any small button cell battery which was on top of the "V" would slide to the bottom of the ridge, and then through it.
  • the metal bars which form the left side of one "V" and the right side of another are approximately each 10 feet long. These metal bars are placed directly next to the rubber conveyer belt of equal width. The batteries, when they first come into the plant, are placed on this conveyer belt and sorted as described above.
  • the smaller lithium button cell batteries are not dealt with. They remain on the conveyer belt and thus pass from the conveyer belt to the metal "V" shaped ridges.
  • the bars which form the sides of the ridges shake at a moderate pace. This encourages the smaller batteries to fail to the bottom of the ridge and then through the ridge. They then fall into boxes placed below the ridge. Larger items do not fall though the ridges.
  • the batteries are put on a flat, rubber conveyor belt.
  • This conveyer belt is approximately 20 feet long.
  • the batteries fall off the end of the conveyor belt onto another rubber conveyor belt.
  • This second rubber conveyor belt is tilted upward at an approximately 45 degree angle. Every approximately 1.5 feet this conveyor belt has a slap of rubber attached to it.
  • This slab is approximately 2 inches in height, is as long as the conveyor belt is wide, and is attached to the conveyor belt. This rubber slab picks up the batteries as they fall off the flat rubber conveyor belt.
  • the second rubber conveyor belt is approximately 20 feet long. It takes the batteries this distance, where they fall into the first metal crusher.
  • the first crusher crushes the batteries at 100-400 revolutions per minute. These batteries are crushed by a device with teeth or blades of approximately 8 inches long. The blades or teeth go into each battery, breaking the batteries into pieces.
  • a computer monitors and adjusts the speed of the crusher so the result is battery pieces of the right size.
  • This process crushes the batteries so that they are in pieces. Each piece is approximately 0.5 - 1.0 inches long (about 1.25 cm to about 2.5 cm). The temperature inside the chamber where the batteries are crushed reaches only 40-50 degrees Celsius.
  • the released hydrogen and oxygen may be removed from the process. These gases mix with the air current the cyclone and are sucked out, as described below.
  • Oxygen can cause a fire. Removing the oxygen therefore significantly lowers the risk of fire. Moreover the low temperature of this process also reduces the risk of fire.
  • the air surrounding the crushing step is sucked up in a cyclone process expelling the air.
  • the cyclone process pulls out metals still in dust. This consists of a spinning blade at the top of a chamber which is tapered so it gets narrower as the gases moves towards the bottom of the chamber. This creates a tornado-like effect which blows the air containing the gases down, through the chamber, and out of the chamber.
  • the air containing the gases that has passed through the cyclone then goes to a filter.
  • the air also contains may contain also light plastic or cardboard, which may be a battery component. It may be beneficial for the following process to have this material removed.
  • the expelled air, which contains the hydrogen and oxygen then goes into a tube which is connected to the outside atmosphere. A second filter catches any remaining particles, insuring that what is released to the atmosphere is only normal air, plus the hydrogen and oxygen present in the batteries. This mixture of light plastic and cardboard may be added to the process of recycling
  • Nickel Metal Hydride batteries as these small particles of plastic and paper may serve as attachment points of small particles of metals. This light plastic and cardboard may thus be thus be included along with the other parts of the recycled nickel metal hydride batteries, to a nickel smelter. Even very small amounts of other meta!s such as e.g. cobalt (2-4%) in the mixture, can thus be recycled.
  • a screen At the end of the crushing chamber is a screen. This is adjusted so particles of different sizes can pass though, in this way the size of the battery pieces are regulated, making sure that only those that are small enough can pass through.
  • the mix of battery pieces and dust After passing through this first crushing chamber, the mix of battery pieces and dust passes into a tube.
  • This tube is approximately 10 inches in diameter and is air-tight. The pieces and dust mixture will pass through this tube to the second crushing chamber, during which the dust is in this tube it is cooled down to room temperature.
  • the transfer tube brings the dust to a second crusher.
  • This crusher is of the same basic design as the first crusher but is made to operate at higher speed. It turns at 1 ,000-1 ,200 revolutions per minute. This is the stronger crusher of the two crushers, it reduces the battery pieces to up to 6 mm in size.
  • the dust produced in this process is collected in a second cyclone.
  • This second cyclone has two dust filters. Each dust filter is the same as the second filter from the first cyclone, as described above.
  • Magnetic separator pulls the iron from the powder. This iron is in the form of flakes.
  • the magnetic separator is positioned about 25 cm above the shaking conveyor belt.
  • the magnetic separator is approximately a half meter wide and two and a half meters long,
  • the key component of the magnetic separator is a magnet.
  • the iron flakes are attracted to this magnet. As the iron flakes leave the powder and instead attach themselves to the magnet they are removed from the powder.
  • a belt Below the magnet is a belt.
  • the magnet behind the belt attracts and then holds the iron flakes onto the belt.
  • the belt moves approx. 40 centimetres at which point it ends. When the belt ends there are no more magnets. The flakes then fall off the belt and are collected.
  • the starting material for the method according to the invention is Alkaline Black mass (denoted AB), which has been produced through dismantling and magnetic separation of iron metals as described above.
  • the AB powder is a mixture of the cathodic (manganese oxide and graphite) and the anodic (zinc oxides and electrolytic solution) materials.
  • the resulting material may optionally undergo a pre-treatment method in order to remove any no metallic material present in the batteries. These may be e.g. plastic films, paper pieces, electric wires etc from the dismantling operation non-woven cellulose or synthetic polymers. However, the material may also not be pre-treated in any way before use, and hence the material still contained plastic films, paper pieces, electric wires etc from the dismantling operation.
  • the AB is then subjected to different methods to separate metals in the spent alkaline batteries.
  • the AB powder may have initial concentration of e.g. aluminum (in an amount of such as e.g. 1.2%), e.g. Iron (in an amount of e.g.
  • the pH is elevated in steps after the dissolution of the metals.
  • Zinc and manganese will precipitate at different pH values as hydroxides.
  • the zinc will precipitate at a pH of about 7 while most manganese is still in solution. All manganese will have precipitated at pH 10.
  • This route may be used to precipitate zinc as ZnS and manganese as MnC0 3 .By optimization of the parameters with respect to filtering and filter cakes such as e.g.
  • This route aims to precipitate Manganese as Mn0 2 from the metals dissolution step using Caros's acid which is 26 % H 2 S0 5 , 58 % H 2 S0 4 and 2 % H 2 0 2 (according to preparation instructions from the literature). In this way the zinc containing solution could be sold and no waste water is left on the plant.
  • DEHPA di-(2-ethylhexyl)phosphoric acid
  • DEHPA-concentration could be e.g. about 35 % and aromatic free solvents should be used (such as e.g. kerosene).
  • O/A ratio should be 2.5 with a temperature of 55°C.
  • the stripping step will work at lower temperatures such as e.g. about 40-45°C.
  • the pH needs to be adjusted so that the leaving solution has of about e.g. pH 2. In this way zinc will be extracted while manganese stays in the aquatic phase.
  • an aqueous solution with a sulfuric acid concentration of 250 g/l may be used.
  • the product would optimally contain 100 g/l zinc and 100 g/l sulfuric acid. This solution can be used as is.
  • the original solution, now containing the manganese, may then be treated with Na 2 C0 3 to oduce MnC0 3 .
  • present invention relates to a method for separating metals present in alkaline batteries.
  • the method according to the invention comprises the following steps: a) crushing alkaline batteries and collecting the alkaline black mass resulting from the crushing process,
  • Alkaline batteries make up about 80% of the collected batteries. They are primary batteries containing mainly of zinc/zinc oxide and manganese dioxide (Zn/ZnO andMn0 2 ). In the alkaline battery, the anode (negative) is made of zinc powder, which gives more surface area for increased current, and the cathode (positive) is composed of manganese dioxide. In the alkaline battery cell (nominal voltage of a fresh alkaline cell is 1.5 V), there is an alkaline electrolyte of potassium hydroxide whereas zinc-carbon batteries have acidic electrolytes.
  • Spent alkaline batteries are collected and may optionally be sorted prior to further actions in order to have alkaline batteries only as the starting material for preparation of the alkaline black mass.
  • Alkaiine batteries are crushed to alkaline black mass (BM) in a mechanical process.
  • Alkaline BM is produced in the recycling process of alkaline batteries. Iron is separated magnetically from the alkaline BM prior to the leaching process.
  • Alkaline black mass as a raw material Alkaline BM powder is a mixture of cathodic (manganese oxide and graphite) and anodic (zinc oxides and electrolytic solution) materials. In general it contains the following main metals; Al 1.2 %, Fe 0.6 %, Mn 30.0 % and Zn 21.8 % (vol%). However, it is to be clearly understood that any alkaline BM can be used according to the invention and in particular wherein the majority of metal content is Mn and/or Zn.
  • the average particle size of alkaline BM is 250-500 ⁇ . Metals are known to be concentrated on the smaller fractions, however the method presented herein is suitable of use on any particle sizes raging from e.g.
  • any particle sizes up to about 0.6 mm may be used in a process according o the invention.
  • the alkaline biack mass may be used as is, the method may also involve any technique resulting in a smaller particle size, such as e.g. grinding of the alkaline black mass prior to the dissolution step of the metals.
  • any ferrous material is removed magnetically as described above.
  • a method is presented based on an acidic reductive leaching system, based on sulphuric acid (H 2 S0 4 ).
  • Zinc and manganese oxides can be
  • a reducing agent e.g. hydrogen peroxide or S0 2
  • other reducing agents such as e.g. citric acid, oxalic acid or isocitric acid etc.
  • the reduction of manganese dioxide and hydrogen peroxide in acidic solution is given as follows:
  • the leaching process may be performed by the use of an acid in order to dissolve the metals in the alkaline black mass.
  • the acid may be any organic or inorganic acid and may typically be an oxoacid.
  • Examples of oxoacids are, but not limited to, a carboxylic acids, sulphuric acid, persulphuric acid (also known as
  • peroxymonosulfuric acid a sulphonic acid, a sulphinic acid, nitric acid, nitrous acid, phosphoric acid, hypochlorous acid, chlorous acid, chloric acid, perchloric acid, perbromic acid, metaperiodic acid.
  • the acids are used as an aqueous solution in various concentrations, but may also be in solution of mixtures of solvents of both organic and inorganic origin as long as solvent is inert to the reaction conditions.
  • the acid may be attached to a solid resin such as e.g. a poiymer or matrix.
  • the concentration of the solution of the acid used in the leaching process may be in the range of about 0.1 M to about 10 M, such as e.g. about 0.5 M to about 8M, such as e.g. about 1M to about 6M, such as about 2M to about 4M, or the acid solution may be of a concentration of at least 0.5M, such as e.g. at least about 1M, such as e.g. at least about 2M, such as e.g. at least about 3M such as e.g. at least about 4M, such as e.g. at least about 5M, such as e.g. at least about 6M, such as e.g. at least about 7M, such as e.g.
  • the concentration of the acid in solution may be e.g. about 1 M or such as e.g. about 2 , such as e.g. about 3M, such as e.g. about 4M, such as e.g. about 5M, such as e.g. about 6M, such as e.g. about 7M, such as e.g. about 8M, such as e.g. about 9M, such as e.g. about 10M.
  • the leaching process may be performed in a ratio of the alkaline black mass to acid (measured as weight to weight % ratio; w/w %) of e.g. about 1 w/w%, such as e.g. about 5 w/w%, such as e.g. about 10 w/w%, such as e.g. about 15 w/w%, such as e.g. about 20 w/w%, such as e.g. about 25 w/w%, v such as e.g. about 30 w/w%, such as e.g. about 40 w/w%, such as e.g. about 50 w/w%, such as e.g.
  • the temperature of the reaction mixture during the leaching process may be in the range of e.g. about 5°C to about 100°C, such as e.g. about 10°C to about 90°C, such as e.g. about 20°C to about 80°C, such as e.g. about 30°C to about 70°C, such as e.g. about 40°C to about 60°C, or such as e.g. about 40°C to about 50°C, such as e.g. about 30°C to about 60°C, or about 30°C, about 40°C, about 50°C, about 60°C, about 70°C, about 80°C, about 90°C, about 100°C.
  • the reaction time during the leaching process may be in the range of any time to completely or almost completely dissolve the metals of the alkaline black mass.
  • Such time ranges may be in the range of e.g. about 30 minutes to about 24 hours, such as e.g. about 1 hour to about 10 hours, such as e.g. about 2 hours to about 3 hours, such as e.g. about 2 hours to about 9 hours such as e.g. about 3 hours to about 8 hours, such as e.g. about 4 hours to about 7 hours, such as e.g. 5 hours to about 6 hours.
  • the reaction during the leaching step i.e. the dissolution of the metal content of the alkaline black mass may optionally be performed in the presence of a gas such as e.g. oxygen (0 2 ) or sulphurdioxide (S0 2 ).
  • a reducing agent may optionally be present in order to reduce any insoluble metal oxides formed by reaction of the acid (such as e.g. sulphuric acid).
  • the reducing agent may be e.g. hydrogen peroxide (H 2 0 2 ) or S0 2 , or it may be e.g. a carboxylic acid (mon-, di- or tri- carboxylic acid) such as e.g.
  • perbenzoic acids such as metha-ch!oroperbenzoic acid, citric acid, oxalic acid, malonic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azaleic acid, tartaric acid, isocitric acid, aconitic acid, propane-1 ,2,3-tricarboxylic acid or trimesic acid or any combinations thereof.
  • the concentration of the reducing agent may be in the range of about e.g. 0.01 M to about 10 M, such as e.g. about 0.1 M to about 9M, such as e.g. about 0.12 M to about 8.5 , such as e.g.
  • about 0.125 M to about 8.45 M such as e.g. 0.5 M to about 8M, such as e.g. about 1 to about 6M, such as about 2 to about 4M, or may be of a concentration of at least 0.5M, such as e.g. at least about 1 M, such as e.g. at least about 2M, such as e.g. at least about 3M such as e.g. at least about 4 , such as e.g. at least about 5M, such as e.g. at least about 6M, such as e.g. at least about 7M, such as e.g. at least about 8M, such as e.g. at least about 9M, such as e.g. at least about 10M.
  • 0.5 M to about 8M such as e.g. about 1 to about 6M, such as about 2 to about 4M
  • concentration of at least 0.5M such as e.g. at least about 1 M, such as e.g. at least about 2
  • the leaching process may be performed in a ratio of the alkaline black mass to reducing agent (measured as weight to weight % ratio; w/w %) of e.g. about 1 w/w%, such as e.g. such as about 2 w/w %, such as e.g. about 3 w/w%, such as e.g. about 5 w/w%, such as e.g. about 10 w/w%, such as e.g. about 15 w/w%, such as e.g. about 20 w/w%, such as e.g. about 25 w/w%, v such as e.g. about 30 w/w%, such as e.g.
  • about 40 w/w% such as e.g. about 50 w/w%, such as e.g. about 60 w/w%, such as e.g. about 70 w/w%, such as e.g. about 75 w/w%, as long as the molar equivalence of the acids is enough to dissolve the metals.
  • the entire metal content is in solution or at least about 60%, or at least about 70%, or at least about 80%, or at least about 85%, or at least about 90%, or at least about 95%, or at least about 00% of the metal content is in solution, i.e. have been converted to their respective cations in solution.
  • the dissolution percentages between the different metals may vary such that e.g. 85% of one metal may be in solution and 95% of another metal may be in solution after completion of the leaching process.
  • residues may optionally be removed by e.g. filtration.
  • residues may be any insoluble remains such as metals, papers such as e.g. non-woven layers of cellulose or synthetic polymers.
  • the total amount of liquid solution in relation to the alkaline black mass may be e.g. about 1/0.5, such as e.g. about 1/1, such as e.g. about 1/2, such as e.g. about 1/3, such as e.g. about 1/4, such as e.g. about 1/5, such as e.g. about 1/6, such as e.g. about 1/7, such as e.g. about 1/8, such as e.g. about 1/9, such as e.g. about 1/10.
  • a total volume of 100 ml of solution is used.
  • this is performed by raising the pH slowly and under controlled conditions, such as incrementally increasing the pH by portion wise addition of e.g. a base during careful monitoring of the pH of the resulting solution.
  • This process may optionally be performed under stirring. This can be done by any well known techniques in the art such as e.g. automated drop-wise addition of the base while electronically monitoring the pH of the solution under e.g. magnetic stirring.
  • a suitable agent that may be used for raising the pH of the leaching solution may be any base.
  • a base may be, but is not limited to organic or inorganic bases such as amines or inorganic hydroxides such as e.g. sodium hydroxide or potassium hydroxide.
  • the addition of the base is primarily in the form of an aqueous solution of appropriate concentration.
  • the solution may be a mix of water and any other appropriate solvent, such as e.g. an alcohol in from of methanol or ethanol.
  • the base may be attached to a solid support, such as e.g. having an organic base attached to a polymer resin, wherein the immobilized base on solid support is contacted with the leaching solution.
  • the addition of the base to the leaching solution is performed in order to bring about a selective precipitation of the metals present as cations in the leaching solution.
  • the metal cation is converted into its corresponding hydroxide which is depending on its chemical nature soluble or insoluble at varying pH of the leaching solution. Consequently, by monitoring the pH a selective precipitation of separate metal hydroxides can be accomplished, thereby allowing collection of separate hydroxide fraction of metals.
  • the method according to the invention does not require electrolytic separation of the metals present in the leaching solution.
  • the concentration of the base in solution may be in range of at least 0.5 M, such as e.g. at least about 1 M, such as e.g. at least about 2 M, such as e.g. at least about 3 M such as e.g. at least about 4 M, such as e.g. at least about 5 M, such as e.g. at least about 6 M, such as e.g. at least about 7 M, such as e.g. at least about 8 , such as e.g. at least about 9 , such as e.g. at least about 10 M, such as e.g. at least about 11 M, such as e.g. at least about 12 M, such as at least about 13 M, such as at least about 14 M depending on the based used.
  • 0.5 M such as e.g. at least about 1 M, such as e.g. at least about 2 M, such as e.g. at least about 3 M such as e.g. at least about 4 M, such as
  • the metals to be regained form the alkaline black mass are e.g. zinc and manganese it has been found that zinc hydroxide is precipitated in a pH range of about 6.4 to about 6.7. In this pH range the manganese is still in solution and thus pure zinc hydroxide can be collected and separated by filtration form the leaching solution. Raising the pH to about 7,6 initiates precipitation of manganese to manganese hydroxide which continues to precipitate up to a pH of about 1.
  • the pH may enable selective precipitation of different meta!s as their respective salts, wherein the salt may be e.g. the corresponding hydroxide.
  • the collected solid product e.g. the corresponding metal hydroxide
  • the collected solid product may be washed.
  • the aqueous solutions used during the entire process can be recycled, thereby minimizing the amount of waste water produced during the process and thus making the method according to the invention cost efficient and environmentally friendly.
  • reaction temperature in the leaching process e.g. 50 °C
  • reaction time e.g. 3 h
  • concentration of citric acid (reducing agent) e.g. 0.127 M
  • a sulphuric acid concentration e.g. 2 M etc.
  • FIG. 1 Illustrates the recovery process for zinc and manganese from spent alkaline batteries.
  • Figure 2 Illustrates the precipitation of zinc and manganese with NaOH from spent alkaline batteries (after dissolution in H 2 S0 4 ). The figure illustrates the narrow pH interval in which zinc is precipitated.
  • Figure 3 Illustrates the size distribution of particles in the alkaline black mass
  • Figure 4. Illustrates the distribution of manganese (upper curve) and zinc (lower curve) according to the particle size distribution in the alkaline black mass.
  • Example 1 Alkaline BM was not pre-treated before the dissolution, I.e. any residues from the batteries such as e.g. cellulose or plastic polymers was not removed. Dissolution process was carried out in a reactor vessel containing a temperature control (under atmospheric pressure). In the reactor system, reaction temperature was carefully controlled and citric acid was added. Metal concentrations in the residues and liquids were determined by ICP- MS and AAS.
  • Iron is first separated magnetically from the alkaline black mass and as described herein. Iron free alkaline black mass is leached with sulphuric acid (H 2 SC ). Leaching is a critical step because all metals should be in the liquid phase as metal sulphates (see Figure 1).
  • the leaching reaction may be performed in the presence of a gas ⁇ such as e.g. oxygen or S0 2 ) or by using acids as a reducing agent.
  • a gas such as e.g. oxygen or S0 2
  • acids as a reducing agent.
  • the use of acids make it a two-phase reaction in which mass and heat transfer phenomena are more easy to control (compared with a three-phase reactions with gas, i.e. a system wherein a solid, liquid and gas is used).
  • Leaching of alkaline black mass was done by mixing the black mass (10 g or 20 g) with the sulfuric acid (2 M), at pH from 1 to 2, with the ratio 20 w/w% (optimized aikaline BM to acid ratio). Leaching temperature around 40-50°C (exothermic); leaching time 2-3 hours (lab-scale batch operation). Leaching was made in the presence of reducing agent using citric acid as the reducing agent under stirring. The concentration of citric acid was 0.127 M or 2.72 g of citric acid to 20 g of alkaline black mass. The total leaching volume was 100 ml, i.e. in a ratio of 1/5 where 20 g of black alkaline mass was used.
  • Leaching residue (solid) of alkaline BM was around 22.5% of the aikaline black mass (raw material). This residue consists mostly of organic matter. Leaching residue contains e.g. material from the alkaline battery separator which is made of a non-woven layer of cellulose or a synthetic polymer etc, which is removed by filtration.
  • Zinc and manganese are separated from the leaching solution (acidic) by a two or three stage sequential precipitation procedure (see Figure 1).
  • Sodium hydroxide (NaOH) is used as a precipitating agent in a concentration of 6 M and added slowly under controlled conditions and allowing the pH to stabilize between additions of further portions of NaOH. pH must be controlled very carefully as precipitation occurs in a very narrow pH window (see Figure 2).
  • the precipitation is done as a batch process to get the optimized control for pH.
  • In the first stage in the pH range of 6.4-6.7, zinc hydroxide is precipitated well separated from manganese which, at this pH, stays in the solution.
  • manganese is precipitated as Mn(OH) 2 which is easily oxidised to Mn0 2 .
  • pH is this stage is increased starting from 7.6 up to 11.
  • Solid product, Mn(OH) 2 and Mn0 2 may be used as raw material in various applications. Solid products are washed between the precipitations. This water can be recycled and reused in the batch process.
  • the yield of zinc as Zn(OH) 2 quantitative in comparison with the zinc content of the leaching solution, and 97% of the manganese as Mn(OH) 2 in comparison with the leaching solution.
  • the amount of waste material flows is minimized in the process by recirculation. Precipitation reactions are carried out at room temperature which also minimizes the energy need.
  • a typical laboratory work setup is as follows. The desired amount of AB is placed in a beaker. The desired amount of sulphuric acid solution is poured into the beaker. The suspension is stirred by a magnetic stirrer and heated to the desired temperature.
  • Hydrogen peroxide is added into the beaker in small aliquots during the entire reaction time.
  • the solids are removed from the liquor by filtration on a Buhner.
  • the liquor is stored "as such" at room temperature.
  • Zinc and Manganese are precipitated from the solutions by a selection of routes. Typically, 50 - 100 ml of the solution is placed in a beaker and stirred by a heated magnetic stirrer.
  • the desired precipitation agent is added by a peristaltic pump. After completed reaction the solids are separated from the liquor by filtration on a Buhner. All amounts are as described above.
  • the AB powder had the following initial concentrations:
  • the amount of H 2 0 2 , the concentration of H 2 S0 4 and the amount of the Alkaline Black were varied.
  • the alkaline black powder had the following initial concentrations:
  • the leaching conditions were as presented in Table 2 below.
  • the hydrogen peroxide was added with a peristaltic pump at a rate of 0.2 mi in every 90 seconds. Water was added into the liquor after the digestion before the filtration of the solids in two tests.
  • the starting materia! (the Alkaline Black powder) for these digestion tests and the solid residues of the tests 20 g and 35 g of starting material were analyzed by the OMG laboratory (XRF analysis).
  • the concentrations of the elements in the starting material and in the solid residues are presented in the Table 3.
  • the last column presents the concentrations of the elements reported by the supplier of the Alkaline Black powder (Akkuser Oy) and these should match the first column values.
  • a precipitation test was made in the laboratory of OMG with 2-component solution ⁇ Zn 64 g/l and Mn 40 g/l) to precipitate Zn first as ZnS and then Mn as MnCC>3 from a sulphuric acid solution using H 2 S. 400 ml of solution was heated to 70°C. H 2 S was sparged into the solution at a rate of 22 liters/h for 1 hour at pH 2.5. (The theoretical amount of H 2 S to precipitate Zn is 11 liters/h.) A solution of 220g/l NaOH was used to control the pH. The precipitate was filtered and weighed. The mass of the ZnS precipitate was 4 .7 g. The calculated yield was 09 %.
  • the filtrate had 20 mg/l of Zn left.
  • the concentration of Zn in the precipitate was 61.1 % and the theoretical concentration in ZnS is 67 %.
  • the concentrations of Mn and Na in the precipitate were 0.36 % and 0.15 % respectively.
  • 400 ml of the filtrate from the ZnS precipitation was used to precipitate Mn as MnC0 3 .
  • 321 ml of 140 g/l Na z C0 3 was added into the filtrate at 70 °C.
  • the solution was agitated with a propeller type stirrer and the reaction time was 0.5 h. Approximately 20 g of precipitate was formed.
  • the filtrate had 8 mg/l of Mn left.
  • the concentration of Mn in the precipitate was 43.3 % while the theoretical amount of Mn in MnC0 3 is 47.7 %.
  • the concentrations of Zn and Na in the precipitate were 0.016 % and 1.16 % respectively.
  • Fresh precipitate of MnC0 3 is difficult (slow) to filtrate.
  • a known volume of leaching liquor was measured into a 200 - 500 ml beaker.
  • the liquor wasstirred with a magnetic stirrer and heated with a heating plate if necessary.
  • pH was measured with a SenTix 81 pH electrode.
  • a precipitating reagent was added into the liquor in 0.1 - 0.5 ml portions at a defined rate and pHwas adjusted after each addition in ZnS precipitations. In MnC0 3 precipitations pH was notcontrolled. After the addition of the defined amount of precipitating reagent the solution was cooled and filtered. Zn, Mn, AI and Fe were analyzed from the filter cakes and the filtrates.
  • a 400-ml solution containing 38.5 g/I of Mn was sparged at 70°C with 0 2 /S0 2 mixture (8,2 liters/h of 0 2 and 0.25 liters/h of S0 2 ).
  • the pH was continuously adjusted to 3.5 using 220 g/I NaOH solution.
  • the Mn concentration of the solution was monitored at 1 , 3, and 4.5 hours and the concentration was 33.5 g/l 35 g/l and 33.1 g/l, respectively.
  • Caro's acid was used in an experiment to precipitate Mn0 2 from a leaching liquor of the Alkaline Black.
  • the composition of Caro's acid was 26 % H 2 S0 5 , 58 % H 2 S0 4 and 2 % H 2 0 2 (according to preparation instructions from the literature).
  • 50 % of the stoichiometric amount of Caro's acid was used. 50 mi of liquor (containing 68.0 g/l Mn and 63.6 g/l Zn) was measured into an erienmeyer flask. The pH is adjusted to 2.5 - 3 by H 2 S0 4 solution or 50 % NaOH solution. The solution was agitated by a magnetic stirrer at room temperature. 40.7 g of Caro's acid was added drop wise into the liquor and the pH was kept between 2.5 - 3. The stirring continued 2 hours after the last drops of Caro's acid. Solids were separated by vacuum filtration. The filtrate and the precipitate were analyzed for Zn and Mn.
  • the precipitate was washed with 146 ml of water (+75°C) and twice with 100 ml of 5 M H 2 S0 4 solution. Zn and Mn were analyzed from the washing water and the washing acids. The solids were dried in an oven at +105°C.
  • the Mn0 2 precipitate (8.99 g) contained 304.2 mg/g of Mn and 40.2 mg/g of Zn.
  • the filtrate (0.22 liters) contained 0.25 mg/i Mn and 1645 mg/l Zn. 80 % of Mn and 11 % of Zn were found from the precipitate. 80 % of Zn and 0.002 % of Mn were found from the filtrate.
  • the Zn and Mn contents of the washing water and 5 M H2SO4 solutions were the following:
  • the acid solution was then combined with the wash water to elevate the pH and an additional amount of 90 ml 10 NaOH was added to get to the final pH of 11.5.
  • the precipitate was filtered and analyzed.
  • the Mn precipitate contained 31 % Mn, 21 % Zn, 4.8 % Na and traces of K, Fe and other metals.
  • the acid solution was then combined with the wash water to elevate the pH and an additional amount of 90 ml 10 M NaOH was added to get to the final pH of 11.5.
  • Mn precipitates as Mn(OH) 2 , and Zn stays in solution as zincate ions.
  • the precipitate was filtered and analyzed.
  • the Mn precipitate contained 31 % Mn, 21 % Zn, 4.8 % Na and traces of K, Fe and other metals.
  • Waste water contains 1.8% Na but very little anything else.
  • the alkaline black mass was sieved and the fractions were collected. Every fraction was individually dissolved using microwave oven and aqua regia.
  • the sample solutions were diluted and measures using ICP-MS.
  • the plant trials were conducted as follows. Three different leaching trials were performed with slightly different recipes. On the plant a 4 m3 reactor was charged with the desired amount of sulphuric acid (200 g/l). The temperature of the reactor was ambient ( ⁇ 20°C). The AB powder was charged to the reactor using a vacuum transported. When the reactor was charged the stirring was continued for another hour (1 H). During addition of AB the temperature rose to 55- 60°C. The temperature was kept at 60°C for the remaining of the trial. After completed leaching the content of the reactor was emptied into filtration big bags to separate the bulk of the undissolved mate al. The liquor was finally filtered though a bag filter (5 ⁇ ) and a polishing filter.
  • a bag filter (5 ⁇ ) and a polishing filter.
  • a trial was conducted to precipitate Zn as Zn(OH) 2 by raising the pH of the solution to 7 by addition of Sodium hydroxide. The trial was conducted on 1000 I of the leach solution from the previous step.
  • the pH of the filtered solution from previous step was increased to 10 using sodium carbonate to precipitate Mn as MnC0 3 . A very fine precipitate was formed.
  • a process for the selective recovery of metal ions from alkaline batteries comprising the steps of:
  • step (d) filtering the product of step (c);
  • step (e) from the filtered product of step (d), selectively precipitating the
  • solubilized metal ions with a precipitating agent to form a precipitate
  • step (e) filtering the mixture of step (c);
  • step ( f ) from the filtered mixture of step (d), selectively precipitating the
  • solubilized metal ions with a precipitating agent to form a precipitate
  • step (d) filtering the product of step (c);
  • step (e) from the filtered product of step (d), precipitating the solubilized Zn(ll)

Landscapes

  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Processing Of Solid Wastes (AREA)
  • Secondary Cells (AREA)

Abstract

La présente invention concerne un procédé nouveau et efficace de récupération de métaux présents dans des piles alcalines usagées.
PCT/EP2011/064560 2010-08-24 2011-08-24 Récupération d'ions métalliques à partir de piles usagées Ceased WO2012025568A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US37633710P 2010-08-24 2010-08-24
US61/376,337 2010-08-24

Publications (2)

Publication Number Publication Date
WO2012025568A2 true WO2012025568A2 (fr) 2012-03-01
WO2012025568A3 WO2012025568A3 (fr) 2012-04-26

Family

ID=44645085

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2011/064560 Ceased WO2012025568A2 (fr) 2010-08-24 2011-08-24 Récupération d'ions métalliques à partir de piles usagées

Country Status (1)

Country Link
WO (1) WO2012025568A2 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112820974A (zh) * 2020-11-26 2021-05-18 清华四川能源互联网研究院 一种锂电池报废正极材料回收过程中的除杂和处理方法
CN113151670A (zh) * 2021-04-28 2021-07-23 四川省有色冶金研究院有限公司 一种回收失效锂电池的方法
CN113584308A (zh) * 2020-04-30 2021-11-02 福图姆股份公司 从碱性电池中回收成分的过程
CN113772693A (zh) * 2021-10-27 2021-12-10 江西金辉锂业有限公司 一种从磷酸铁锂废料中选择性浸出提取锂的方法
CN114317984A (zh) * 2022-01-04 2022-04-12 华北理工大学 一种利用旋流分级-离子液体-超声协同选择性浸锌方法
CN114836631A (zh) * 2022-06-15 2022-08-02 蜂巢能源科技股份有限公司 一种电池材料萃取回收产生的铜锰液的再生利用方法
WO2023029573A1 (fr) * 2021-09-06 2023-03-09 广东邦普循环科技有限公司 Procédé d'extraction de lithium à partir d'une batterie au lithium-ion
ES2938647A1 (es) * 2021-10-07 2023-04-13 Envirobat Espana S L Proceso de preparación de una aleación de aluminio
CN119153836A (zh) * 2024-11-20 2024-12-17 北京理工大学深圳汽车研究院(电动车辆国家工程实验室深圳研究院) 废旧镍锌电池负极材料的有机酸浸出再生的方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0620607A1 (fr) 1993-04-16 1994-10-19 Institut National Polytechnique De Grenoble Procédé de traitement de piles usagées par électrolyse
WO2003021708A2 (fr) 2001-07-23 2003-03-13 Recupyl Sa Procede de recyclage des piles electriques usagees par traitement hydrometallurgique
WO2005101564A1 (fr) 2004-04-06 2005-10-27 Recupyl Procede de recyclage en melange des piles et batteries a anode a base de lithium

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE1013311A4 (fr) * 2000-04-17 2001-11-06 Revatech S A Procede de recyclage et de valorisation de piles salines et alcalines

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0620607A1 (fr) 1993-04-16 1994-10-19 Institut National Polytechnique De Grenoble Procédé de traitement de piles usagées par électrolyse
WO2003021708A2 (fr) 2001-07-23 2003-03-13 Recupyl Sa Procede de recyclage des piles electriques usagees par traitement hydrometallurgique
WO2005101564A1 (fr) 2004-04-06 2005-10-27 Recupyl Procede de recyclage en melange des piles et batteries a anode a base de lithium

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
FERELLA, JOURNAL OF POWER SOURCES, vol. 183, 2008, pages 805 - 811

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113584308A (zh) * 2020-04-30 2021-11-02 福图姆股份公司 从碱性电池中回收成分的过程
CN112820974A (zh) * 2020-11-26 2021-05-18 清华四川能源互联网研究院 一种锂电池报废正极材料回收过程中的除杂和处理方法
CN113151670A (zh) * 2021-04-28 2021-07-23 四川省有色冶金研究院有限公司 一种回收失效锂电池的方法
US12062765B2 (en) 2021-09-06 2024-08-13 Guangdong Brunp Recycling Technology Co., Ltd. Method for extracting lithium from waste lithium battery
GB2623222A (en) * 2021-09-06 2024-04-10 Guangdong Brunp Recycling Technology Co Ltd Method for extracting lithium from waste lithium battery
WO2023029573A1 (fr) * 2021-09-06 2023-03-09 广东邦普循环科技有限公司 Procédé d'extraction de lithium à partir d'une batterie au lithium-ion
ES2938647A1 (es) * 2021-10-07 2023-04-13 Envirobat Espana S L Proceso de preparación de una aleación de aluminio
CN113772693A (zh) * 2021-10-27 2021-12-10 江西金辉锂业有限公司 一种从磷酸铁锂废料中选择性浸出提取锂的方法
CN114317984B (zh) * 2022-01-04 2023-04-25 华北理工大学 一种利用旋流分级-离子液体-超声协同选择性浸锌方法
CN114317984A (zh) * 2022-01-04 2022-04-12 华北理工大学 一种利用旋流分级-离子液体-超声协同选择性浸锌方法
CN114836631B (zh) * 2022-06-15 2023-12-01 蜂巢能源科技股份有限公司 一种电池材料萃取回收产生的铜锰液的再生利用方法
CN114836631A (zh) * 2022-06-15 2022-08-02 蜂巢能源科技股份有限公司 一种电池材料萃取回收产生的铜锰液的再生利用方法
CN119153836A (zh) * 2024-11-20 2024-12-17 北京理工大学深圳汽车研究院(电动车辆国家工程实验室深圳研究院) 废旧镍锌电池负极材料的有机酸浸出再生的方法
CN119153836B (zh) * 2024-11-20 2025-08-19 北京理工大学深圳汽车研究院(电动车辆国家工程实验室深圳研究院) 废旧镍锌电池负极材料的有机酸浸出再生的方法

Also Published As

Publication number Publication date
WO2012025568A3 (fr) 2012-04-26

Similar Documents

Publication Publication Date Title
TWI873308B (zh) 有價物的回收方法
WO2012025568A2 (fr) Récupération d'ions métalliques à partir de piles usagées
US12412941B2 (en) Method for recycling lithium batteries
Tanong et al. Recovery of metals from a mixture of various spent batteries by a hydrometallurgical process
WO2013124399A1 (fr) Récupération d'ions métalliques provenant de déchets de batterie en utilisant de l'ammoniac
JP5128272B2 (ja) リチウム基材アノードバッテリーおよびセルの混合リサイクルのための方法
Zheng et al. Leaching procedure and kinetic studies of cobalt in cathode materials from spent lithium ion batteries using organic citric acid as leachant
CN116096929A (zh) 钴及镍的分离方法
AU2019300253A1 (en) Process for the recycling of spent lithium ion cells
US20130312254A1 (en) Method for manufacturing a valuable-metal sulfuric-acid solution from a waste battery, and method for manufacturing a positive electrode active material
WO2019060996A1 (fr) Procédé de recyclage de batteries lithium-ion
KR102737366B1 (ko) 폐건전지로부터의 망간 회수 방법 및 회수 설비
KR102740711B1 (ko) 폐건전지로부터의 망간 회수 방법 및 회수 설비
JP7443483B2 (ja) 有価物の回収方法
Singh et al. Recovery of zinc and cadmium from spent batteries using Cyphos IL 102 via solvent extraction route and synthesis of Zn and Cd oxide nanoparticles
KR20230155496A (ko) 설파이드 침전을 통한 표적 금속 제거 방법
Kursunoglu et al. Recovery of lithium from spent coin-type lithium manganese dioxide CR cells by acidic leaching in the presence of potassium permanganate as oxidant
EP4468450A1 (fr) Procédé de récupération de substance précieuse
WO2024124341A1 (fr) Procédé de traitement de déchets électroniques et de récupération de métaux de valeur et d'éléments de terres rares à partir de ceux-ci
Jung et al. Current commercial hydrometallurgical recycling process
JP2025096184A (ja) 有価物の回収方法
CN118556323A (zh) 有价物的回收方法
Tas et al. An integrated study on pyrolysis, flotation, and leaching for optimized recycling of industrial battery materials
Mishra et al. Cutting-edge recycling solution at pilot-scale for end-of-life LiFePO4 batteries and recovery of graphite using centrifuge filtration
CN118742657A (zh) 废干电池中含有的锰的回收方法和回收设备

Legal Events

Date Code Title Description
NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11755037

Country of ref document: EP

Kind code of ref document: A2