Method of recycling spent chemical cells

FIELD: chemistry.

SUBSTANCE: method involves crushing chemical cells, leaching, magnetic separation and electrolysis. The cells are crushed and leached with water in an atmosphere of carbon dioxide gas without access to oxygen. Light fractions are then removed from the scrap by floatation. Filtration is then carried out. The filtrate is treated with sorbents. After filtration, the scrap is washed with water, dried and fragments of ferrous and nonferrous metals are removed by electromagnetic separation, and then leached with sulphuric acid solution. Sulphuric acid pulp is filtered through a filter with an inert material, a filter with a coal medium and a filter with a cation-exchange medium. Ions of row d and row p metals sorbed by a cation-exchange resin are selectively desorbed with sulphuric acid solutions. Solutions containing ions of row d metals are subjected to electrolysis, and solutions containing ions of row p metals are neutralised to pH 3-4 and treated with clay mineral sorbents. The precipitate after sulphuric acid leaching is leached with nitric acid solution; the undissolved manganese dioxide precipitate is removed and the filtrate is neutralised and acidified to pH 3. The precipitate is filtered off. The filtrate containing mercury ions is subjected to cathode reduction and the precipitate containing lead and silver chlorides is dissolved in nitric acid and subjected to cathode reduction in an electrolysis cell with separate deposition of metals on electrodes.

EFFECT: environmental safety of recycling any type of spent chemical cells.

1 dwg

 

The invention relates to environmentally safe disposal of waste chemical current sources. The problem of their disposal is quite relevant. The amount of practical work aimed at a comprehensive solution to the problem of disposal of waste chemical current sources (CCS), is relatively small. The reason is hidden in the natural complexity of its solution, because modern chemical current sources are very diverse in their chemical composition. Part of HIT includes more than thirty-two chemical elements of Mendeleev's table, of which twenty - two metals, in elemental and ionic form. The total number of reactive compounds included in the composition of the HIT, over sixty, and they cover all classes of compounds: metals, metalloids, oxides, bases, acids, salts, and organic compounds. Difficulties for disposal and are modern, the most energy-intensive power sources, which include fire and explosion alkaline and alkaline-earth metals (lithium, sodium, calcium).

Known methods of utilization of chemical current sources are limited to only certain types of HIT.

Thus, the described method of processing waste margantsevokislyj HIT, developed by a Japanese firm Fuji of Denki KAGAKU" (JP 61-261443, 19.11.1986.). The elements HIT crushed and calcined the oven at 400-1000°C for 3 to 20 hours in the presence of air. When this combustible materials (paper, carbon rods, graphite, carbon black, plastic, starch, coal tar) burn. The calcined mass is first crushed in a mill and then passed through a magnetic separator and separating the iron scrap. The crushed material is screened through a sieve to extract Korolkov zinc. Fine powder treated with 20%hydrochloric acid. An aqueous solution containing salts of manganese, zinc, iron, copper, Nickel, cadmium, clear of iron neutralization of ammonia water at pH 5, defend, filtered and removed hydroxides together with other, not dissolved in hydrochloric acid, and impurities. The clarified solution is neutralized by ammonia water to pH 9 and add manganese dioxide, stirred for 24 hours and the precipitated manganese oxide (III). A solution containing salts of zinc, iron, copper, Nickel, manganese, cadmium, and ammonium chloride, is supplied to the operation of extraction of zinc hydrometallurgical method.

The disadvantages of the method:

- narrow range of types of recyclable chemical current sources;

- large energy consumption for calcining materials at high temperatures;

- increased consumption of hydrochloric acid in the almost complete dissolution of crushed fine powder;

- increased consumption of aqueous ammonia and other chemicals in the processing solutions;

- pollution the environment and the working zone of the combustion products, as well as hydrogen chloride and ammonia.

The closest set of features adopted for the prototype, is the method of disposal of waste margantsevokislyj HIT hydrometallurgical method (Patent RU No. 2164955, CL SW 7/00, SW 19/00, SW 47/00, 2001).

The method includes grinding of raw materials, magnetic separation chopped margantsevokislyj HIT with the extraction of iron scrap, oxidative roasting the crushed material at 650°C for 2 hours, the classification of the calcined material with separation of metallic zinc, washed cinder is subjected to flotation and acid leaching at a pH of not more than 3, a temperature of 30-60°C, with separation of the solid precipitate of oxides of manganese, and the remaining solution containing sulfates of manganese and zinc, is electrolyzed, with the deposition of metallic zinc on the cathode and manganese dioxide on the anode.

The disadvantages of the prototype:

- narrow range of types of recyclable chemical current sources; in particular, the method eliminates the disposal of the most common and energy-intensive chemical current sources; containing alkaline and alkaline-earth metals such as lithium, sodium, calcium;

- significant energy costs for heat treatment of raw materials;

- environmental pollution and the working zone of the combustion products.

The technical result and the finding is to develop a method is environmentally safe disposal of waste chemical current sources, both mass and limited edition, such as saline, alkaline, lithium, nickelhexahydrite (NiOOH), Nickel-metal hydride (Ni-MH) and other chemical current sources: based on metallic sodium, calcium, cadmium, magnesium, silver, lead and other chemical elements.

This object is achieved in that in the method of disposal of waste chemical current sources, including the grinding of chemical current sources, leaching, magnetic separation, the electrolysis products of leaching metals deposition on the electrodes according to the invention and grinding of chemical current sources, and the subsequent leaching of the resulting scrap water held in the atmosphere of carbon dioxide, without oxygen; shredded scrap leached with water in the reactor to complete oxidation of the alkali metal ions of these metals; released during the reaction hydrogen is cleaned from the associated gas gas cleaning device; after the complete dissolution of alkali metals in water scrap, together with the water baselaceltli, move from the reactor in the flotation machine and flotation removed from the scrap light fractions; further, the scrap is separated from the aqueous solution by filtration; the filtrate is treated with sorbents of organic compounds and clay mineral sorbents for removal of organic substances and ions of the Vatan metals, respectively; after filtering scrap washed with water, dried and removed from electromagnetic separators fragments of ferrous and nonferrous metals; next scrap leached with a solution of sulfuric acid; sulfuric acid slurry sequentially filtered through a filter with an inert material, a filter with a carbon loading of the filter with a cation exchange resin, to remove insoluble particles from a solution of organic compounds and cations of non-ferrous metals respectively; sorbed cation exchange resin ions number of d - and p-metals selectively desorbed by sulphuric acid solutions of specified concentrations, the solutions of the desorbed ions are collected separately; sulfuric acid solutions containing ions of a number of d-metals, separately subjected to electrolysis in the electrolytic deposition of metals on the electrodes and sulfuric acid solutions containing ions of the number of R-metals, neutralize to pH 3-4 and treated clay mineral sorbents; insoluble residue after acid leaching washed with water and subjected to leaching with a solution of nitric acid; nitric acid solution is removed by filtration of the insoluble precipitate of manganese dioxide, and the filtrate is neutralized to pH 7 and acidified with hydrochloric acid to pH 3; the precipitation is filtered off; the filtrate containing ions of mercury, exposing Caton the th restoration in the electrolyzer, and the residue, containing the chlorides of lead and silver dissolved in nitric acid and subjected to cathodic recovery in the cell with the separate deposition of metals on the electrodes.

The use of the proposed technical solution will allow to obtain the following technical result:

- dispose of any type of chemical power sources, including a HIT on the basis of metal lithium, sodium and calcium, which improved explosive and flammable when depressurization;

to return to the production of non-ferrous and precious metals;

to reduce human impact on the environment when disposing of waste HIT.

The method is environmentally waste chemical current sources, including the grinding of chemical current sources, leaching, magnetic separation, the electrolysis products of leaching metals deposition on the electrodes, different from the known, taken as a prototype, so that the grinding of chemical current sources, and the subsequent leaching of the resulting scrap water held in the atmosphere of carbon dioxide, without oxygen; shredded scrap leached with water in the reactor to complete oxidation of the alkali metal ions of these metals; released during the reaction hydrogen is cleaned from the associated gas gas cleaning device; after the complete dissolution of the alkaline what's metals in water scrap, together with the water baselaceltli, move out of the reactor in the flotation machine and flotation removed from the scrap light fractions; further, the scrap is separated from the aqueous solution by filtration; the filtrate is treated with sorbents of organic compounds and clay mineral sorbents for removal of organic substances and non-ferrous metals ions, respectively; after filtering scrap washed with water, dried and removed from electromagnetic separators fragments of ferrous and nonferrous metals; next scrap leached with a solution of sulfuric acid; sulfuric acid slurry sequentially filtered through a filter with an inert material, a filter with a carbon loading of the filter with a cation exchange resin, to remove insoluble particles from the solution, organic compounds and cations of non-ferrous metals respectively; sorbed cation exchange resin ions number of d - and p-metals selectively desorbed by sulphuric acid solutions of specified concentrations, the solutions of the desorbed ions are collected separately; sulfuric acid solutions containing ions of a number of d-metals, separately subjected to electrolysis in the electrolytic deposition of metals on the electrodes and sulfuric acid solutions containing ions of the number of R-metals, neutralize to pH 3-4 and treated clay mineral sorbents; insoluble precipitate the donkey sulfuric acid leaching washed with water and subjected to leaching with a solution of nitric acid; from the nitric acid solution is removed by filtration of the insoluble precipitate of manganese dioxide, and the filtrate is neutralized to pH 7 and acidified with hydrochloric acid to pH 3; the precipitation is filtered off; the filtrate containing ions of mercury, is subjected to cathodic recovery in the electrolyzer, and the residue, containing the chlorides of lead and silver dissolved in nitric acid and subjected to cathodic recovery in the cell with the separate deposition of metals on the electrodes.

Comparable analysis of the proposed solutions with the known leads to the conclusion that the proposed solution meets the criteria of the invention of "novelty."

From the patent and scientific literature is not known, the method of disposal of waste chemical current sources, including the grinding of chemical current sources, leaching, magnetic separation, the electrolysis products of leaching metals deposition on the electrodes, characterized in that the grinding of chemical current sources and the subsequent leaching of the resulting scrap water is carried out in carbon dioxide atmosphere without oxygen; shredded scrap leached with water in the reactor to complete oxidation of the alkali metal ions of these metals; released during the reaction hydrogen is cleaned from the associated gas gas cleaning device; after complete dissolution of Molochny the metals in the water scrap, together with the water baselaceltli, move out of the reactor in the flotation machine and flotation removed from the scrap light fractions; further, the scrap is separated from the aqueous solution by filtration; the filtrate is treated with sorbents of organic compounds and clay mineral sorbents for removal of organic substances and non-ferrous metals ions, respectively; after filtering scrap washed with water, dried and removed from electromagnetic separators fragments of ferrous and nonferrous metals; next scrap leached with a solution of sulfuric acid; sulfuric acid slurry sequentially filtered through a filter with an inert material, a filter with a carbon loading of the filter with a cation exchange resin, to remove insoluble particles from the solution, organic compounds and cations of non-ferrous metals respectively; sorbed cation exchange resin ions number of d - and p-metals selectively desorbed by sulphuric acid solutions of specified concentrations, the solutions of the desorbed ions are collected separately; sulfuric acid solutions containing ions of a number of d-metals, separately subjected to electrolysis in the electrolytic deposition of metals on the electrodes and sulfuric acid solutions containing ions of the number of R-metals, neutralize to pH 3-4 and treated clay mineral sorbents; insoluble precipitate the donkey sulfuric acid leaching washed with water and subjected to leaching with a solution of nitric acid; from the nitric acid solution is removed by filtration of the insoluble precipitate of manganese dioxide, and the filtrate is neutralized to pH 7 and acidified with hydrochloric acid to pH 3; the precipitation is filtered off; the filtrate containing ions of mercury, is subjected to cathodic recovery in the electrolyzer, and the residue, containing the chlorides of lead and silver dissolved in nitric acid and subjected to cathodic recovery in the cell with the separate deposition of metals on the electrodes to achieve the described effect. Thus, the proposed technical solution meets the criterion of "inventive step".

The proposed solution can be used for industrial, environmentally safe disposal of all types of waste chemical current sources.

Thus, the proposed technical solution meets the criterion of "industrial applicability".

The inventive method is carried out using the process line, the concept of which is shown in figure 1.

The method is as follows.

Waste chemical current sources are served with the auger in the hopper and through a rotary feeder metered load to the crusher 1 and pulverized to a particle size of minus 3-5 mm. Shredded scrap through the second rotary feeder metered served in reactivating leaching 2, filled with 0.5 volume of water. The reactor 2 is a tank type tank with lid and doors, equipped with a stirrer, jacketed for cooling and regulating the temperature of the reaction environment. Leaching of scrap water is carried out at a temperature of 30-40°C, until complete oxidation of water to alkali metal ions of these metals, with the formation of the hydroxides of lithium, sodium, calcium.

Crushing HIT and leaching of scrap water is in the atmosphere of carbon dioxide, without oxygen. To create a carbon dioxide atmosphere misletoe space, in which the crusher 1, and the free space of the reactor 2 is filled with carbon dioxide under low pressure. Released during the reaction the hydrogen away from the reactor through the exhaust system and clear of associated gas gas cleaning device 3. In an environment of carbon dioxide combustion of hydrogen is excluded for lack of oxygen.

After complete dissolution of alkali metals in water scrap, together with the water baselaceltli, is pumped from the reactor in the flotation cell 4 and flotation removed from the scrap light "waterfowl" faction: charcoal, graphite, coke, organic sorbents, polymers, paper, flocculent suspended hydroxides of aluminum and iron (III). Further, the scrap is separated from the water pixelates filtering filter 5 and washed with water.

The filtrate,depending on the types of recyclable HIT likely to contain organic compounds - geleobrazovanie, solvents, and these ions are water-soluble inorganic compounds: cations of lithium, potassium, sodium, calcium, magnesium, barium, copper, zinc, Nickel, bismuth, titanium, hydrogen, ammonia, anions of fluorine, chlorine, bromine, iodine, hydroxyl anions, bichromate-anions, hypochlorous anion, perchloric, sulfuric, tin, armenistis acids.

For purification of the filtrate from the above compounds and ions it is served in a sorption apparatus 6 and under stirring consistently treated sorbent (e.g., "Paralist-F) removal from aqueous solution of organic substances and after filtering, the filter 7 is treated in the apparatus 6 clay mineral sorbents (for example, "Irlit-1" or "Irlit-7") to remove ions from a solution of non-ferrous metals. Recommended loading of the sorbent is not more than 5 g/l (see patent RU No. 2263718, CL SU 3/24, 2005.11.10). Water is filtered from the sorbents non-ferrous metals on the filter 7 and return into circulation. Clay mineral sorbents after leaching with acids and alkalis disposed of in landfills.

After washing scrap water it is dried in the device 8 and served in the device 9, where electromagnetic separators, ferrous and non-ferrous metals are removed from the scrap ferrous and non-ferrous metals: iron, zinc, cadmium, magnesium, about the ovo, antimony, lanthanum, lead, silver, and alloys of metals: lithium/aluminum, lithium/cobalt, cobalt/manganese, lanthanum/Nickel, bismuth/indium.

After removal of metal scrap containing oxides (copper, zinc, manganese, bismuth, lead, mercury, silver), hydroxides (Nickel, lead, tin, barium) and insoluble salts of silver, loaded into the reactor 10 and his leached with a solution of 3 N. sulfuric acid for 0.5 hour. Pulp sulfuric acid leaching contains cations (Nickel, zinc, copper, bismuth), insoluble in sulfuric acid oxides (manganese dioxide, mercuric oxide, silver oxide), insoluble salts (sulphate of lead, silver sulphate, silver chloride, barium sulfate) and ions (zinc, Nickel, copper).

The pulp of the sulfuric acid leaching sequentially filtered through a filter 11 with an inert material, resistant to acids, through the filter 12 with coal load (for example, AG-3, AG-S) and the filter 13 with a cation exchange resin (for example, KU-23Na) removal of the sulfuric acid solution to remove insoluble particles, organic compounds and cations of non-ferrous metals, respectively.

Sorbed cation exchange resin ions number of d - and p-metals selectively desorbed by sulphuric acid solutions, respectively: zinc - 0.2 N. the solution; Nickel - 2 N. solution; copper - 5 N. solution of bismuth - 3 BC (see http://referat.dirx.ru/?i=4134091 Cleaning chromiferous stock the x water galvanoplastics). Solutions of desorbed ions are collected separately. Sulfuric acid solutions containing ions of a number of d-metals (zinc, copper, Nickel), separately subjected to electrolysis in the electrolytic cells 14 with the deposition of metals on the electrodes, and a solution containing ions of a series R-metals, such as bismuth ions, neutralized to pH 3-4 and treated clay mineral sorbents in the device 6.

The insoluble residue after acid leaching washed with water and subjected to leaching with a solution of 2 N. nitric acid in the apparatus 15 for 0.5 hours. Salts of mercury, barium, lead and silver dissolved in nitric acid. Insoluble manganese dioxide is filtered by the filter 16 and washed with water. The filtrate is neutralized to pH 7 and acidified with 1 N. hydrochloric acid to pH 3 in the device 17. The precipitation is filtered by the filter 18, and the filtrate containing ions of mercury and barium, is subjected to cathodic recovery in the electrolyzer 19, with deposition of elemental mercury. The precipitate containing the chlorides of lead and silver dissolved in nitric acid in the apparatus 20 and is subjected to cathodic recovery in the electrolyzer 21, with separate deposition of metals on the electrodes.

The method of disposal of waste chemical current sources, including the grinding of chemical current sources, leaching, flotation, magnetic separation, e is Stralis of leaching solutions with metals deposition on the electrodes, characterized in that the grinding of chemical current sources and the subsequent leaching of the resulting milled scrap water held in the atmosphere of carbon dioxide without access of oxygen to complete the oxidation of the alkali metal ions of these metals, and released during the reaction of dissolved hydrogen purged from associated gas gas cleaning device, after the complete dissolution of alkali metals in water scrap together with the water baselaceltli move from the reactor in the flotation machine and flotation removed from the scrap light fractions, then the scrap is separated from the aqueous solution by filtration, the filtrate is treated with sorbents of organic compounds and clay mineral sorbents for removal of organic substances and ions of non-ferrous metals, accordingly, after filtering scrap washed with water, dried and removed from electromagnetic separators fragments of ferrous and non-ferrous metals, then scrap leached with a solution of sulfuric acid, sulfuric acid slurry sequentially filtered through a filter with an inert material, a filter with a carbon loading of the filter with a cation exchange resin, thus guarantee the removal of insoluble particles from a solution of organic compounds and cations of non-ferrous metals, respectively, adsorbed cation exchange resin ions number of d - and p-metals selective behaviour is about desorbed by sulphuric acid solutions of specified concentrations, moreover, the solutions of the desorbed ions are collected separately, sulfuric acid solutions containing ions of a number of d-metals, separately subjected to electrolysis in the electrolytic deposition of metals on the electrodes and sulfuric acid solutions containing ions of the number of R-metals, neutralize to pH 3-4 and treated clay mineral sorbents, insoluble residue after acid leaching washed with water and subjected to leaching with a solution of nitric acid from the nitric acid solution is removed by filtration of the insoluble precipitate of manganese dioxide, and the filtrate is neutralized to pH 7 and acidified with hydrochloric acid to pH 3, the precipitation is filtered off, the filtrate containing ions of mercury, is subjected to cathode recovery in the electrolyzer, and the residue, containing the chlorides of lead and silver dissolved in nitric acid and subjected to cathodic recovery in the cell with the separate deposition of metals on the electrodes.



 

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1 dwg, 1 tbl, 1 ex

FIELD: metallurgy.

SUBSTANCE: procedure consists in separation of coal electrode and zinc cylinder, in flushing and dissolving in sulphuric acid. Also, flushing from ammonia chloride and zinc hydroxide is carried out with 0.2 M solution of sulphuric acid (H2SO4). Upon flushing residue of manganese oxide (IV) (MnO2), oxy-hydroxide of manganese (MnOOH) and coal mass (C) is crumbled in ball mills. Crumbled residue is dissolved in sulphuric solutions of concentration 0.05 mole/l containing 0.05-0.1 mole/l of oxalic acid at ratio of concentrations of ions of manganese and oxalic acid 1:5 at pH=1-2.2 and temperature of solution 80°C. Upon dissolving solution is filtered for removal of coal mass. Residues of zinc ions are removed from solution with isoamyl alcohol of 200 ml volume at presence of 2 M solution of ammonia thiocyanate and 0.5 M HCl, and there is performed neutralisation with 0.5 M solution of caustic soda (NaOH). Further, produced solution is evaporated at temperature 100°C to obtaining mass of crystalline compounds of composition sodium trioxalomanganate (IV) Na4[Mn(C2O42-)3] and salt of sodium oxalate (Na2C2O4). Produced mass is baked in atmosphere containing oxygen at temperature 400-500°C with production of MnO2 as a final product.

EFFECT: raised efficiency and ecological safety of procedure.

4 dwg, 3 tbl, 2 ex

FIELD: metallurgy.

SUBSTANCE: procedure consists in sorption of cobalt on complex forming ionite from manganese containing solution and of desorption of cobalt from ionite. Desorption of cobalt is performed with solution with pH value=4.5÷5.5 containing ions of copper and(or) nickel possessing higher affinity to functional groups of ionite, than cobalt.

EFFECT: reduced amount of solution processing stages, reduced consumption of reagents and process equipment, increased efficiency and reduction of process cost.

1 dwg, 1 ex

FIELD: metallurgy.

SUBSTANCE: procedure for separation of scandium from manganese consists in contacting solution containing scandium and manganese with extractant in interval of pH 2.9-3.3 during 30 minutes. Contacting is carried out with extraction of manganese. As extractant there is used 0.25 M solution of N-(hydroxi-5-nonobensyl-β-hydroxi-ethyl-methyl-amine (NBEA-2) in thinner.

EFFECT: raised coefficient of metals separation.

5 ex

FIELD: metallurgy.

SUBSTANCE: invention refers to metallurgy, particularly to procedure for purification of manganese concentrates from phosphorus. The procedure consists in agglomeration of concentrate with sodium salts at 950-1000°C and weight ratio 1:0.4, and in successive water leaching with transfer of phosphorus into solution. Further concentrate is filtered and dried. Also leaching is carried out under effect of ultrasonic oscillations of 18·103-22·103 Hz per second frequency during 15-30 minutes. Finished concentrate is filtered and dried in ultrasonic fields of 18·103-22·103 Hz per second frequency.

EFFECT: upgraded quality of manganese concentrate by means of reducing concentration of phosphorus in it.

2 tbl, 1 ex

FIELD: metallurgy.

SUBSTANCE: thermal reduction by heating charge containing reducer and manganese compound is performed at temperature 700-750°C in inert atmosphere. As manganese compound there is used manganese oxide (III) or manganese oxide (IV), or manganese chloride, while as reducer there is used hydride of lithium taken in excess at amount of 25-50 wt %. Also lithium chloride is additionally introduced into charge at ratio of lithium to lithium hydride taken in excess in moles equal to 2:1. Heated charge is conditioned during 30-90 min. Further manganese is extracted out of reaction mixture by means of cooling, flushing with water and filtering.

EFFECT: production of manganese in form of fine crystal powder and reduced expenditures.

7 cl, 4 ex

FIELD: metallurgy.

SUBSTANCE: proposed method comprises multistep leaching of red slag by the mix of sodium carbonate and bicarbonate on forcing annealing furnace flue gases containing carbon dioxide there through to obtained solution. Then, three-step holding of said solution at increased temperatures is performed along with selective separation of precipitates after every said step. At first step, said solution is heated to temperature not exceeding 80°C for, at least, 1 hour. Thereafter, it is settled for, at least, two hours at natural cooling. At second step, said solution is boiled and mixed for, at least, two hours. At third step, said solution is evaporated to 50% of initial volume to add 46%-solution of sodium hydroxide to concentration of Na2Ocaustic of 1.5-2.0 kg/m3. Now, it is boiled for, at least, 2 hours and precipitate containing scandium oxide is settled for 10-16 hours at natural cooling.

EFFECT: simplified process, higher yield of scandium oxide.

1 ex

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