TWM650076U - Recycling equipment for valuable metal in lithium-ion battery - Google Patents

Abstract

This creation provides equipment for recycling valuable metals in lithium-ion batteries, including: alkali leaching equipment, acid leaching equipment, copper removal equipment, iron removal equipment, nickel-manganese recovery equipment, cobalt recovery equipment and lithium recovery equipment. The method for recycling valuable metals in lithium-ion batteries of this invention can remove impurity metals such as aluminum, copper and iron from the carbon ink powder of the cathode material in discarded lithium-ion batteries, and recover valuable metals such as nickel, manganese, cobalt and lithium. metal.

Description

Recycling equipment for valuable metals in lithium-ion batteries

This creation is about the methods and equipment for recycling valuable metals in lithium-ion batteries, especially the removal of impurity metals such as aluminum, copper and iron from discarded lithium-ion batteries and the recovery of valuable metals such as nickel, manganese, cobalt and lithium from lithium-ion batteries. Metal recycling methods and equipment.

After lithium-ion batteries were successfully introduced into the market, due to their relatively light weight, small size and long life, they are commonly used in various 3C products, energy storage equipment and even electric vehicles around the world. However, lithium-ion batteries contain valuable metals such as lithium, cobalt, nickel, and manganese. If they are discarded arbitrarily after use, they can easily pollute the environment with heavy metals and even change the environment and ecology. Due to the rise in environmental awareness and the widespread attention given to environmental issues, industry or academia are also developing resource recycling technologies. There are several methods currently known for recycling valuable metals as follows.

Taiwan invention patent I286850 (hereinafter referred to as Document 1) discloses that the positive electrode part where lithium and cobalt are located is immersed in hydrochloric acid for two hours, and then the pH value of the immersion solution is adjusted to 8 with sodium hydroxide. At this time, it can be Filter to separate the gels containing cobalt, aluminum and nickel, and finally add saturated sodium carbonate solution to the impregnation solution to obtain lithium carbonate powder; in addition, filter the gels containing cobalt, aluminum and nickel, first After pickling with sulfuric acid and adjusting the pH value to 2 to dissolve the contained metal, add ammonia water to adjust the pH value to 8 to filter out the gel containing aluminum ions. Finally, use sulfuric acid to adjust the pH value of the filtered pickling solution. After adjusting to 4.3, pour it into the electrolytic tank for electrolysis recovery. Use a constant temperature water bath to keep the electrolyte temperature at 55°C. After passing a fixed current, the cobalt and nickel metal will be deposited on the cathode stainless steel sheet. After drying, the cobalt can be recovered. and nickel metal to achieve the purpose of recycling waste resources. In other words, Document 1 uses electrolysis to obtain cobalt and nickel.

Taiwan Invention Patent No. 501294 (hereinafter referred to as Document 2) discloses that used waste lithium-ion batteries are roasted and decomposed in a high-temperature furnace to remove the organic electrolyte, then crushed and sieved. The materials above the sieve can be processed by magnetic separation and eddy current separation. , separate the broken iron shell, copper foil, aluminum foil, etc.; and the material under the sieve is dissolved with a mixture of sulfuric acid and hydrogen peroxide, the solution obtained by the dissolution is filtered, and the iron in it is removed by adjusting the pH value. And aluminum ions are precipitated, during which metal copper and metal cobalt are electrolyzed respectively through electrolysis. After electrolysis, carbonate is added to the solution rich in lithium ions to form a carbonate precipitation of lithium and effectively recover lithium. In other words, Document 2 also uses electrolysis to obtain cobalt.

Taiwan Invention Patent No. 511306 (hereinafter referred to as Document 3) discloses that waste lithium-ion batteries are roasted in a high-temperature furnace to decompose and remove the organic electrolyte, crushed and screened, and the materials above the screen are separated by magnetic separation and eddy current separation. The broken iron shell, copper foil, aluminum foil, etc. are removed; while the material under the sieve is directly dissolved and filtered, and through the control of pH value and electrolysis conditions, metallic copper and cobalt are electrolyzed by diaphragm electrolysis method. During the electrolysis process The acid generated on the cathode side can be recovered through diffusion dialysis treatment and recycled to the dissolution step, forming a closed process. After electrolysis of the solution rich in lithium ions, after adjusting the pH value to precipitate metal impurities, carbonate can be added to form a high-purity carbonate of lithium and the lithium can be recovered. In other words, Document 3 also uses electrolysis to obtain cobalt.

Taiwan Invention Patent No. I392745 (hereinafter referred to as Document 4) is limited to a slurry composed of a ternary lithium metal salt and a solvent such as carbon, N-methyl-2-pyrrolidone, polyvinyl alcohol, etc. It is a residue produced during the manufacturing process of lithium secondary batteries. The metal composition in the slurry is generally 10~12% by mass Co, 10~12% by mass Ni, 10~12% by mass Mn, and 4~5% by mass Li. That is, in addition to limiting Co, Ni, and Mn Apart from equal amounts, there is no treatment method for impurities such as aluminum, copper, and iron. Document 4 discloses that the lithium battery residue containing the ternary lithium metal salt of lithium acid metal salt (containing approximately equal amounts of cobalt, nickel and manganese) is stirred and leached with a hydrochloric acid solution with a concentration of 250g/l or more, or Use a sulfuric acid solution with a concentration of 200g/l or more, while heating to 65~80℃ while stirring and leaching, or mix a sulfuric acid solution with a concentration of 200g/l or more and a hydrogen peroxide solution with a concentration of 20g/l or more After the solution is stirred and leached, the leaching solution is solvent extracted with a special extractant, such as DE2HPA extractant for manganese and PC-88A extractant for cobalt and nickel, to extract more than 98% of manganese and cobalt. and nickel to generate solutions containing each metal, and then recover valuable metals such as manganese, cobalt, nickel and lithium from these solutions and the remaining liquid containing lithium after extraction. In other words, although Document 4 does not use the electrolysis method of Documents 1 to 3, it cannot deal with the treatment problems of aluminum, copper, iron and other impurity metals that must be faced in the lithium battery recycling process, and must use a special extraction agent for solvent extraction.

From the aforementioned documents 1 to 4, it can be found that documents 1 to 3 all use electrolysis, which consumes a lot of electricity and leads to higher costs, while document 4 uses a special extraction agent for solvent extraction, which will cause environmental problems, and document 4 cannot Dealing with the treatment of impurity metals such as aluminum, copper, iron, etc.

In view of the above-mentioned known problems, the creator of this creation thought about and designed a method and device for recovering valuable metals from the carbon ink powder of the cathode material of discarded lithium-ion batteries, in order to improve the deficiencies of the conventional technology and thereby promote Industrial implementation and utilization.

Based on the above purpose, this invention provides a method for recovering valuable metals in lithium-ion batteries, which sequentially includes a material detection step, an alkali leaching step, an acid leaching step, a metal replacement step, an iron removal step, a nickel and manganese recovery step, a cobalt recovery step, and Lithium recovery step.

The material testing step is to analyze the metal content of carbon ink powder, which is one of the positive electrode materials in discarded lithium-ion batteries, to obtain lithium, nickel, cobalt, manganese, aluminum, copper and iron. The content value of the carbon ink powder also contains carbon.

The alkali leaching step involves mixing an alkaline aqueous solution with the carbon ink powder to precipitate lithium, nickel, cobalt, manganese, copper, iron and carbon in the carbon ink powder into a first filter residue, in which aluminum is dissolved in the carbon ink powder. The alkaline aqueous solution becomes a first aqueous solution, and the first aqueous solution is removed while retaining the first filter residue.

The acid leaching step is to mix an acidic aqueous solution with the first filter residue, so that the lithium, nickel, cobalt, manganese, copper and iron in the first filter residue are dissolved in the acidic aqueous solution to form a second aqueous solution. The carbon in the filter residue precipitates as a second filter residue, and the second filter residue is removed while retaining the second aqueous solution.

The metal replacement step is to mix the second aqueous solution with an additional iron-containing substance, and the equivalent number of iron in the additional iron-containing substance is greater than the equivalent number of copper in the second aqueous solution or the equivalent number of copper in the carbon ink powder, The copper in the copper sulfate in the second aqueous solution is replaced with iron to become iron sulfate and copper metal is precipitated, so that the second aqueous solution is turned into a third aqueous solution, and the precipitated copper metal is precipitated into a third filter residue. , remove the third filter residue and retain the third aqueous solution.

The iron removal step is to adjust the third aqueous solution with a first alkaline substance to make the pH value between 4 and 5, and then allow the iron of ferric sulfate in the third aqueous solution to form with the first alkaline substance. A first alkaline compound is precipitated and the third aqueous solution is converted into a fourth aqueous solution. The precipitated first alkaline compound is an iron compound and precipitates into a fourth filter residue, which is removed The fourth filter residue retains the fourth aqueous solution;

The step of recovering nickel and manganese: the fourth aqueous solution is adjusted with a second alkaline substance to make the pH value between 6 and 8 and a carbonate is added, so that the nickel and nickel of the nickel sulfate in the fourth aqueous solution are The manganese of manganese sulfate and the carbonate form nickel carbonate and manganese carbonate, and the nickel carbonate and the manganese carbonate are precipitated, so that the fourth aqueous solution is converted into a fifth aqueous solution, and the precipitated nickel carbonate and manganese carbonate are precipitated. As a fifth filter residue, separate the fifth filter residue and retain the fifth aqueous solution;

The step of recovering cobalt is to adjust the fifth aqueous solution with a third alkaline substance so that the pH value is between 11 and 13, so that the cobalt of cobalt sulfate in the fifth aqueous solution and the third alkaline substance form a The third basic compound precipitates out and turns the fifth aqueous solution into a sixth aqueous solution. The precipitated third basic compound is a cobalt compound and precipitates into the sixth filter residue, and the third basic compound is separated into a sixth filter residue. Sixth filter residue and retain the sixth aqueous solution;

The step of recovering lithium is to mix the sixth aqueous solution with phosphate. The equivalent number of phosphate ions in the phosphate is greater than the equivalent number of lithium in the sixth aqueous solution or the equivalent number of lithium in the carbon ink powder. The phosphate and The lithium sulfate in the sixth aqueous solution undergoes a metathesis reaction, so that the lithium in the lithium sulfate in the sixth aqueous solution is exchanged for the metal in the phosphate due to the metathesis reaction to become a water-soluble sulfate and precipitate phosphoric acid The sixth aqueous solution is converted into a seventh aqueous solution by adding lithium, and the precipitated lithium phosphate is precipitated into a seventh filter residue. The seventh aqueous solution is removed and the seventh filter residue is retained.

This invention also provides an equipment for recycling valuable metals in lithium-ion batteries, which is used to perform the aforementioned method of recycling valuable metals in lithium-ion batteries. The equipment for recycling valuable metals in lithium-ion batteries includes: an alkali leaching device, an acid leaching device, Copper removal device, iron removal device, nickel manganese recovery device, cobalt recovery device and lithium recovery device.

In this way, this invention first removes impurity metals such as aluminum, copper, and iron and carbon from the carbon ink powder, and then collects nickel carbonate and manganese carbonate, cobalt hydroxide or cobalt oxide, and lithium phosphate to separate and recover valuable metals. It can accurately separate valuable metals from the carbon ink powder of lithium-ion batteries without using electrolysis or special extraction agents during the separation process.

In order to facilitate understanding of the technical features, content and advantages of this creation and the effects it can achieve, the expression form of this creation together with the accompanying drawings is described in detail below. The purpose of the drawings used therein is only to illustrate and assist the instructions. The purpose is not necessarily the true proportion and precise configuration of this creation after its implementation. Therefore, the proportion and configuration relationship of the attached drawings should not be interpreted to limit the scope of rights in the actual implementation of this creation, which is stated in advance.

Please refer to Figure 1. The method for recovering valuable metals in lithium-ion batteries of this invention sequentially includes a material detection step S00, an alkali leaching step S10, an acid leaching step S20, a metal replacement step S30, an iron removal step S40, and a nickel and manganese recovery step. S50, cobalt recovery step S60 and lithium recovery step S70. Among them, the material detection step S00, the alkali leaching step S10, the acid leaching step S20, the metal replacement step S30 and the iron removal step S40 are collectively referred to as the impurity metal removal step, the nickel and manganese recovery step S50, the cobalt recovery step S60 and the lithium recovery step S70. It is collectively called the step of separating valuable metals.

Material testing step S00: Analyze the metal content in the carbon ink powder taken from the cathode material of the discarded lithium-ion battery to obtain the content of lithium, nickel, cobalt, manganese, aluminum, copper and iron. Numerical value, carbon ink powder also contains carbon. The lithium-ion battery disassembly process can be referred to the aforementioned documents 1 to 4, so it will not be described in detail here. This invention is to sequentially separate impurity metals and valuable metals from the carbon ink powder of the cathode material in the discarded lithium-ion battery. In this invention, the material detection step means that after obtaining the carbon ink powder, atomic absorption spectroscopy (AAS) analysis is first performed. For example, in one embodiment, lithium, nickel, cobalt and lithium in the carbon ink powder are measured. The contents of manganese (weight percentage) are 2.92%, 4.04%, 15.97% and 5.12% respectively; the remaining contents include aluminum, copper, iron, lead, zinc, chromium, calcium, sodium and magnesium, which are 30320 ppm and 15710 ppm respectively. , 23940 ppm, 436 ppm, 3504 ppm, 804 ppm, 622 ppm, 2641 ppm and 496 ppm. Therefore, in this work, valuable metals refer to lithium, nickel, cobalt and manganese; impurity metals refer to aluminum, copper and iron; other metals such as lead, zinc, chromium, calcium, sodium and magnesium are ignored due to their small content. . In other words, the material testing step means that after obtaining the carbon ink powder, the metal content in the carbon ink powder will be analyzed to obtain the content values of lithium, nickel, cobalt, manganese, aluminum, copper and iron. Of course, carbon ink powder also contains carbon.

Alkali leaching step S10: Also known as the aluminum removal step, an alkaline aqueous solution (such as sodium hydroxide aqueous solution) and carbon ink powder are mixed and then stirred at a first predetermined temperature for a first predetermined time to remove lithium from the carbon ink powder. , nickel, cobalt, manganese, copper, iron and carbon precipitate as the first filter residue, aluminum dissolves in the alkaline aqueous solution and becomes the first aqueous solution, the first aqueous solution is removed and the first filter residue is retained. In this invention, the alkali leaching step refers to using alkaline substances to adjust the pH value of the solution to greater than 12; preferably, the pH value is 13. The alkaline substance includes sodium hydroxide and ammonia, preferably sodium hydroxide. More preferably, the concentration used is 5%, 10%, 15%, 20%, 25%, or 30% sodium hydroxide aqueous solution by weight. The conditions of the alkali leaching step, including the alkaline substance used, pH value, heating temperature, heating time, and solid-to-liquid ratio, can be adjusted according to the content of the carbon ink powder and/or each metal in it, and are not bound by theory. The equation of the alkali leaching step can be Al ₂ O ₃ + 2NaOH → 2NaAlO ₂ + H ₂ O. For example, the carbon ink powder mainly contains lithium, nickel, cobalt, manganese, aluminum, copper, iron and carbon and the other substances are ignored. Basically In order to complete the reaction, the equivalent number of the base of the alkaline aqueous solution (for example, the molar number of hydroxide ions) is greater than the equivalent number of aluminum. In one embodiment, the alkali leaching step is to use a sodium hydroxide aqueous solution whose weight is 10 times that of the carbon ink powder and whose concentration is 10%, and the carbon ink powder is mixed with the carbon ink powder and then stirred at a predetermined temperature for a predetermined time, then the Al in the carbon ink powder ₂ O ₃ will form NaAlO ₂ and dissolve in the sodium hydroxide aqueous solution to become the first aqueous solution. The rest containing lithium, nickel, cobalt, manganese, copper, iron and carbon will be insoluble in the sodium hydroxide aqueous solution and precipitate into the first filter residue. . In other words, the alkali leaching step causes the aluminum in the carbon ink powder to form aluminum salts and dissolve in water, while lithium, nickel, cobalt, manganese, copper, iron and carbon form metal-containing carbon powder and precipitate as the first filter residue. And, the first aqueous solution is removed and the first filter residue is retained.

Acid leaching step S20: also known as the carbon removal step, the acidic aqueous solution (such as sulfuric acid aqueous solution) is mixed with the first filter residue and then stirred at a second predetermined temperature for a second predetermined time to remove lithium, nickel, Cobalt, manganese, copper and iron are dissolved in the acidic aqueous solution to form a second aqueous solution, and the carbon in the first filter residue is precipitated to become a second filter residue. The second filter residue is removed and the second aqueous solution is retained. In this invention, the acid leaching step refers to using acidic substances to adjust the pH value of the solution to less than 4, preferably, the pH value is 0.5. The acidic substance includes sulfuric acid, nitric acid or hydrochloric acid, preferably sulfuric acid, more preferably 5%, 10%, 15%, 20%, 25% or 30% sulfuric acid. The conditions of the acid leaching step, including the acidic substance used, pH value, heating temperature, heating time, and solid-to-liquid ratio, can be adjusted according to the content of the carbon ink powder and/or the metals in it, and are not bound by theory. The equation for the acid leaching step can be Co/Ni/Mn/Li/Fe/Cu/C + H ₂ SO ₄ → CoSO ₄ /NiSO ₄ /MnSO ₄ /Li ₂ SO ₄ /Fe ₂ (SO ₄ ) ₃ /CuSO ₄ + C, for example, the first filter residue produced in the aforementioned alkali leaching step contains lithium, nickel, cobalt, manganese, copper, iron and carbon. Basically, for the sake of complete reaction, the equivalent number of sulfate in the acidic aqueous solution is greater than that of lithium, nickel, The sum of the equivalents of cobalt, manganese, copper and iron. In one embodiment, the acid leaching step involves mixing a sulfuric acid aqueous solution with a weight 10 times that of the carbon ink powder and a concentration of 20% with the first filter residue and then stirring at a second predetermined temperature for a second predetermined time. In particular, for the convenience of measurement and to avoid measurement errors caused by the water content of the first filter residue, the acid leaching step is to use a sulfuric acid aqueous solution that is 10 times the weight of the carbon ink powder and has a concentration of 20%, instead of using A sulfuric acid aqueous solution whose weight is 10 times that of the first filter residue and whose concentration is 20%. It can be known from the equation of the above alkali leaching step that the lithium, nickel, cobalt, manganese, copper and iron originally in the first filter residue form lithium sulfate, nickel sulfate, cobalt sulfate, manganese sulfate, copper sulfate and iron sulfate respectively. It dissolves in the acidic aqueous solution and becomes the second aqueous solution. The carbon originally in the first filter residue will not react with sulfuric acid to form sulfate, so it precipitates into the second filter residue that does not contain lithium, nickel, cobalt, manganese, copper and iron. It is also called carbon slag and graphite slag. And, the second filter residue is removed and the second aqueous solution is retained.

The aforementioned solid-liquid ratio refers to the weight ratio of solid to liquid. The solid-liquid ratio can be 5, 10, 15, and 20, which means that the weight of the liquid is 5 times, 10 times, 15 times, and 20 times the weight of the solid respectively; the aforementioned The heating temperature or predetermined temperature mentioned later can be room temperature 25°C (unheated), 60°C, 70°C, 80°C or 90°C; the heating time or predetermined time mentioned later can be 2 hours, 4 hours, 6 hours, 8 hours. hours or 10 hours.

Regarding the aforementioned metal replacement step, in this invention, the metal replacement step refers to adding excess other metals so that the excess other metals replace the metal to be obtained or removed. The excess ratio means that the number of other metal equivalents is 1.05 times, 1.1 times, 1.15 times, 1.2 times, 1.25 times or 1.3 times the number of metal equivalents to be obtained or removed. The condition for the metal replacement reaction to occur is the active order of the metal. The equation of the metal replacement step in this creation can be 3CuSO ₄ + 2Fe → Fe ₂ (SO ₄ ) ₃ + 3Cu.

Metal replacement step S30: also known as the copper removal step, the second aqueous solution is mixed with an additional iron-containing substance (such as iron powder) and then stirred at a third predetermined temperature for a third predetermined time. The additional iron-containing substance (iron powder) The equivalent number of iron in the second aqueous solution or the carbon ink powder is greater than the equivalent number of copper in the second aqueous solution or the equivalent number of copper in the carbon ink powder, so that the copper in the copper sulfate in the second aqueous solution is replaced with iron to become iron sulfate and copper metal is precipitated. The second aqueous solution turns into the third aqueous solution, and the precipitated copper metal precipitates into the third filter residue. The third filter residue is removed and the third aqueous solution is retained. In this invention, the metal replacement step refers to making the pH value of the second aqueous solution less than 4 (for example, adding an acidic substance such as sulfuric acid) and mixing the second aqueous solution with an additional iron-containing substance (for example, iron powder). The equation of the metal replacement step can be 3CuSO ₄ + 2Fe → Fe ₂ (SO ₄ ) ₃ + 3Cu. In one embodiment, the metal replacement step is to mix the second aqueous solution and iron powder, where the equivalent number of iron in the iron powder is The equivalent number of copper in the second aqueous solution or the equivalent number of copper in the carbon ink powder is 1.2 times. It can be known from the equation of the above metal replacement step that under the condition that the pH value is less than 4, the copper in the copper sulfate originally in the second aqueous solution is replaced with iron to become iron sulfate and copper metal precipitates to become the third aqueous solution, so The precipitated copper metal precipitates as the third filter residue. Then the third filter residue is removed and the third aqueous solution is retained. Therefore, the third aqueous solution contains lithium sulfate, nickel sulfate, cobalt sulfate, manganese sulfate and iron sulfate, and the copper of copper sulfate originally in the second aqueous solution is precipitated as the third aqueous solution. Filter residue.

Regarding the aforementioned iron removal step, nickel and manganese recovery step, and cobalt recovery step, in this creation, it refers to the precipitation of metals in environments with different pH values after adjusting the pH value. This creation includes an iron removal step, a nickel and manganese recovery step, and a cobalt recovery step. The equations of the iron removal step, the nickel and manganese recovery step, and the cobalt recovery step can respectively be Fe ₂ (SO ₄ ) ₃ + 6NaOH → 2Fe(OH) ₃ + 3Na ₂ SO ₄ , NiSO ₄ + Na ₂ CO ₃ → NiCO ₃ + Na ₂ SO ₄ , MnSO ₄ + Na ₂ CO ₃ → MnCO ₃ + Na ₂ SO ₄ and CoSO _{4 +} NaOH → Co(OH) ₂ + Na ₂ SO ₄ .

Iron removal step S40: The third aqueous solution is adjusted with a first alkaline substance (such as sodium hydroxide) so that the pH value is between 4 and 5 (preferably, the pH value is 4.5), and then a fourth predetermined step is performed. Stirring for a fourth predetermined time at high temperature, so that the iron of ferric sulfate in the third aqueous solution and the first alkaline substance form a first alkaline compound (such as iron hydroxide) and precipitate the first alkaline compound (such as iron hydroxide) The third aqueous solution is turned into the fourth aqueous solution, and the precipitated first basic compound is an iron compound (such as ferric hydroxide), which precipitates into the fourth filter residue. The fourth filter residue is removed and the fourth aqueous solution is retained. The equation for the iron removal step may be Fe ₂ (SO ₄ ) ₃ + 6NaOH → 2Fe(OH) ₃ + 3Na ₂ SO ₄ . It can be known from the equation of the above iron removal step that under the condition that the pH value is between 4 and 5, in one embodiment, the first alkaline substance is sodium hydroxide, and the original sulfuric acid in the third aqueous solution The iron and hydroxide ions of the iron form iron hydroxide and precipitate the iron hydroxide precipitate (the fourth filter residue), so that the third aqueous solution turns into the fourth aqueous solution, the fourth filter residue is removed and the fourth aqueous solution is retained, so the fourth aqueous solution is The aqueous solution contains lithium sulfate, nickel sulfate, cobalt sulfate and manganese sulfate, and the iron of ferric sulfate originally in the third aqueous solution is precipitated as iron hydroxide precipitate (the fourth filter residue).

Recovering nickel and manganese step S50: adjust the fourth aqueous solution with a second alkaline substance (such as sodium hydroxide) to make the pH value between 6 and 8 (preferably, the pH value is 7) and add carbonate (such as sodium carbonate) and then stirred at a fifth predetermined temperature for a fifth predetermined time, so that the nickel of nickel sulfate and the manganese of manganese sulfate in the fourth aqueous solution form nickel carbonate and manganese carbonate, and nickel carbonate and manganese carbonate are precipitated. Manganese carbonate turns the fourth aqueous solution into the fifth aqueous solution, and the precipitated nickel carbonate and manganese carbonate precipitate into the fifth filter residue. The fifth filter residue is separated and the fifth aqueous solution is retained. The equations of the nickel and manganese recovery steps can be NiSO ₄ + Na ₂ CO ₃ → NiCO ₃ + Na ₂ SO ₄ , MnSO ₄ + Na ₂ CO ₃ → MnCO ₃ + Na ₂ SO ₄ . It can be known from the equation of the above step of recovering nickel and manganese that under the condition that the pH value is between 6 and 8, in one embodiment, the carbonate is sodium carbonate, and the original nickel sulfate in the fourth aqueous solution is The manganese and carbonate of nickel and manganese sulfate form nickel carbonate and manganese carbonate, and nickel carbonate and manganese carbonate are precipitated, turning the fourth aqueous solution into the fifth aqueous solution, and the precipitated nickel carbonate and manganese carbonate are precipitated into the fifth filter residue. The fifth filter residue is separated and the fifth aqueous solution is retained, so the fifth aqueous solution contains lithium sulfate and cobalt sulfate.

Cobalt recovery step S60: The fifth aqueous solution is adjusted with an alkaline substance (such as sodium hydroxide) so that the pH value is between 11 and 13 (preferably, the pH value is 12) and then heated at a sixth predetermined temperature. Stir for a sixth predetermined time, so that the cobalt of cobalt sulfate in the fifth aqueous solution and the alkaline substance form an alkaline compound (such as cobalt hydroxide) and precipitate the alkaline compound (such as cobalt hydroxide), so that the fifth aqueous solution is turned It becomes the sixth aqueous solution, and the precipitated basic compound is a cobalt compound (such as cobalt hydroxide) and precipitates into the sixth filter residue. The sixth filter residue is separated and the sixth aqueous solution is retained. The equation for the cobalt recovery step can be CoSO _{4 +} NaOH → Co(OH) ₂ + Na ₂ SO ₄ . It can be known from the equation of the above cobalt recovery step that under the condition that the pH value is between 11 and 13, in one embodiment, the alkaline substance is sodium hydroxide, and the original cobalt sulfate in the fifth aqueous solution is Cobalt and hydroxide ions form cobalt hydroxide and precipitate cobalt hydroxide precipitate (sixth filter residue), turning the fifth aqueous solution into the sixth aqueous solution, separating the sixth filter residue and retaining the sixth aqueous solution, so the sixth aqueous solution The content contains lithium sulfate, and the cobalt sulfate originally in the fifth aqueous solution is precipitated as cobalt hydroxide precipitate (sixth filter residue). Of course, the cobalt hydroxide precipitate (sixth filter residue) can also be heated and dried to transform into cobalt oxide.

Lithium recovery step S70: The sixth aqueous solution is mixed with a phosphate (such as sodium phosphate) and then stirred at a seventh predetermined temperature for a seventh predetermined time. The equivalent number of phosphate ions in the phosphate (such as sodium phosphate) is greater than The equivalent number of lithium in the sixth aqueous solution or the equivalent number of lithium in the carbon ink powder, the phosphate carries out a metathesis reaction with the lithium sulfate in the sixth aqueous solution, so that the lithium of the lithium sulfate in the sixth aqueous solution is decomposed due to the metathesis reaction. Exchange the metal (such as sodium) in the phosphate (such as sodium phosphate) to become a water-soluble sulfate (such as sodium sulfate) and precipitate lithium phosphate, turning the sixth aqueous solution into the seventh aqueous solution, and the precipitated phosphoric acid Lithium is precipitated as the seventh filter residue, and the seventh aqueous solution is removed while the seventh filter residue is retained. In this invention, the step of recovering lithium refers to mixing the sixth aqueous solution with phosphate (such as sodium phosphate). The equation of the lithium recovery step can be 3Li ₂ SO ₄ + 2Na ₃ PO ₄ → 2Li ₃ PO ₄ + 3Na ₂ SO ₄ . In one embodiment, the lithium recovery step is to mix the sixth aqueous solution with sodium phosphate, wherein sodium phosphate is The equivalent number of phosphate ions is 1.2 times the equivalent number of lithium in the sixth aqueous solution or the equivalent number of lithium in the carbon ink powder. It can be known from the above equation of the lithium recovery step that the lithium of the lithium sulfate in the sixth aqueous solution is exchanged for the sodium in the sodium phosphate to become water-soluble sodium sulfate and lithium phosphate is precipitated, causing the sixth aqueous solution to become In the seventh aqueous solution, the precipitated lithium phosphate is precipitated as the seventh filter residue. The seventh aqueous solution is removed and the seventh filter residue is retained.

Therefore, this invention first removes aluminum, copper, iron and other impurity metals and carbon in the carbon ink powder, and then collects the nickel carbonate and manganese carbonate of the fifth filter residue, the cobalt hydroxide or cobalt oxide of the sixth filter residue, and the seventh filter residue. Lithium phosphate in the filter residue is used to separate and recover valuable metals lithium, nickel, cobalt and manganese.

This invention also provides a device for recycling valuable metals in lithium-ion batteries, which is used to perform the aforementioned method of recycling valuable metals in lithium-ion batteries.

Please refer to Figure 2 together, the valuable metal recovery equipment 100 in lithium-ion batteries includes: alkali leaching device 1, acid leaching device 2, copper removal device 3, iron removal device 4, nickel manganese recovery device 5, cobalt recovery device 6 and lithium recovery device 7.

The alkali leaching device 1 includes an alkali leaching tank 11, a first stirring device 12 disposed in the alkali leaching tank 11, a first filtering device 13 connected to the bottom of the alkali leaching tank 11 by a pipeline system P, and a first filtering device 13 connected to the bottom of the alkali leaching tank 11 by a pipeline system P. An aluminum salt tank 14 with a filtering device 13 . The alkali leaching device 1 is used to implement the alkali leaching step S10. After mixing the sodium hydroxide aqueous solution with a weight of 10 times that of the carbon ink powder and a concentration of 10% with the carbon ink powder in the alkali leaching tank 11, the first predetermined temperature is The first stirring device 12 is used to stir at 80° C. for a first predetermined time of 4 hours to form the first aqueous solution and the first filter residue. After the reaction is completed, the pipeline system P at the bottom of the alkali leaching tank 11 is opened and the first aqueous solution in the alkali leaching tank 11 is An aqueous solution and the first filter residue are transported to the first filtering device 13 . The first filtering device 13 separates the first aqueous solution and the first filter residue, and stores the first aqueous solution in the aluminum salt tank 14 . Among them, the carbon ink powder is weighed to be 1000Kg (kg), and converted according to the atomic absorption spectrometry analysis results in the aforementioned material testing step S00 to obtain the carbon ink powder, in which lithium is 29.2Kg, nickel is 40.4Kg, cobalt is 159.7Kg and manganese is 51.2Kg.

The acid leaching device 2 includes an acid leaching tank 21 connected to the first filtering device 13 by a pipeline system P to receive the first filter residue, a second stirring device 22 disposed in the acid leaching tank 21, and an acid leaching tank 22 connected to the first filtering device 13 by the pipeline system P. The second filter device 23 at the bottom of the tank 21. The acid leaching device 2 is used to implement the acid leaching step S20. After using a sulfuric acid aqueous solution that is 10 times the weight of the carbon ink powder and has a concentration of 20% and the first filter residue in the acid leaching tank 21, the second predetermined temperature is 80°C. Next, the second stirring device 22 is used to stir for a second predetermined time of 8 hours to form the second aqueous solution and the second filter residue. After the reaction is completed, the pipeline system P at the bottom of the acid leaching tank 21 is opened and the second aqueous solution in the acid leaching tank 21 is and the second filter residue is transported to the second filtering device 23, and the second filter device 23 separates the second aqueous solution and the second filter residue.

The copper removal device 3 includes a copper removal tank 31 connected to the second filtration device 23 via a piping system P to receive the second aqueous solution, a third stirring device 32 disposed in the copper removal tank 31, and a copper removal tank 32 connected to the piping system P. The third filter device 33 at the bottom of the tank 31. The copper removal device 3 is used to implement the metal replacement step S30, making the pH value of the second aqueous solution less than 4 in the copper removal tank 31 and mixing it with iron powder, where the equivalent number of iron in the iron powder is the equivalent number of copper in the second aqueous solution Or 1.2 times the equivalent number of copper in the carbon ink powder, the third predetermined temperature is room temperature and the third predetermined time is 4 hours for stirring with the third stirring device 32 to form the third aqueous solution and the third filter residue. After the reaction is completed, open The pipeline system P at the bottom of the copper removal tank 31 transports the third aqueous solution and the third filter residue in the copper removal tank 31 to the third filtering device 33, and the third filtering device 33 separates the third aqueous solution and the third filter residue.

The iron removal device 4 includes an iron removal tank 41 connected to the third filtering device 33 via a pipeline system P to receive the third aqueous solution, a fourth stirring device 42 disposed in the iron removal tank 41, and a pipeline system P connected to the iron removal tank 41. The fourth filter device 43 at the bottom of the tank 41. The iron removal device 4 is used to implement the iron removal step S40. Sodium hydroxide is used in the iron removal tank 41 to make the pH value of the third aqueous solution 4.5. The fourth predetermined temperature is room temperature and the fourth stirring device 42 is used to stir the fourth step. The predetermined time is 4 hours to form the fourth aqueous solution and the fourth filter residue. After the reaction is completed, the pipeline system P at the bottom of the iron removal tank 41 is opened to transport the fourth aqueous solution and the fourth filter residue in the iron removal tank 41 to the fourth filtering device 43 , the fourth filtering device 43 separates the fourth aqueous solution and the fourth filter residue.

The nickel-manganese recovery device 5 includes a nickel-manganese recovery tank 51 connected to the fourth filtering device 43 with a piping system P to receive the fourth aqueous solution, a fifth stirring device 52 disposed in the nickel-manganese recovery tank 51, and a nickel-manganese recovery tank 52 with a piping system P. It is connected to the fifth filtering device 53 at the bottom of the nickel-manganese recovery tank 51 . The nickel-manganese recovery device 5 is used to implement the step S50 of recovering nickel and manganese. Sodium hydroxide is used in the nickel-manganese recovery tank 51 to make the pH value of the fourth aqueous solution 7, and the fifth predetermined temperature is 80°C with the fifth stirring device 52 Stir for a fifth predetermined time of 4 hours to form a fifth aqueous solution and a fifth filter residue. After the reaction, open the pipeline system P at the bottom of the nickel-manganese recovery tank 51 to transport the fifth aqueous solution and the fifth filter residue in the nickel-manganese recovery tank 51 to the fifth filtering device 53, which separates the fifth aqueous solution and the fifth filter residue. The fifth filter residue is nickel carbonate and manganese carbonate. The weight of the filter residue is 180.3Kg. After calculation by atomic absorption spectrometry analysis, the nickel is 38.58Kg and the manganese is 48.9Kg. Then divided by the nickel and manganese content of the carbon ink powder (nickel (40.4Kg and 51.2Kg for manganese), and the recovery rate of nickel and manganese was 96%.

The cobalt recovery device 6 includes a cobalt recovery tank 61 connected to the fifth filtering device 53 via a pipeline system P to receive the fifth aqueous solution, a sixth stirring device 62 disposed in the cobalt recovery tank 61, and a cobalt recovery tank 62 connected to the fifth filtering device 53 via a pipeline system P. The sixth filter device 63 at the bottom of the tank 61. The cobalt recovery device 6 is used to implement the cobalt recovery step S60, using sodium hydroxide in the cobalt recovery tank 61 to make the pH value of the fifth aqueous solution 12, and stirring the sixth predetermined temperature with the sixth stirring device 62 at 80°C. The predetermined time is 8 hours to form the sixth aqueous solution and the sixth filter residue. After the reaction is completed, the pipeline system P at the bottom of the cobalt recovery tank 61 is opened to transport the sixth aqueous solution and the sixth filter residue in the cobalt recovery tank 61 to the sixth filtering device 63 , the sixth filtering device 63 separates the sixth aqueous solution and the sixth filter residue. The sixth filter residue is cobalt hydroxide. The weight of the filter residue is 240.55Kg. According to atomic absorption spectrometry analysis, the cobalt is 152.5Kg. Then divided by the cobalt content of the carbon ink powder, 159.7Kg, the recovery rate of cobalt is 95%.

The lithium recovery device 7 includes a lithium recovery tank 71 connected to the sixth filtering device 63 by a pipeline system P to receive the sixth aqueous solution, a seventh stirring device 72 disposed in the lithium recovery tank 71, and a lithium recovery tank 72 connected to the sixth filtering device 63 by the pipeline system P. The seventh filter device 73 at the bottom of the tank 71 . The lithium recovery device 7 is used to implement the lithium recovery step S70. After the sixth aqueous solution and sodium phosphate are mixed in the lithium recovery tank 71, the equivalent number of phosphate ions in the sodium phosphate is the equivalent number of lithium or carbon in the sixth aqueous solution. 1.2 times the equivalent number of lithium in the ink powder. The seventh predetermined temperature is 70°C and the seventh stirring device 72 is used to stir the seventh predetermined time for 4 hours to form the seventh aqueous solution and the seventh filter residue. After the reaction is completed, the lithium removal is opened. The pipeline system P at the bottom of the recovery tank 71 transports the seventh aqueous solution and the seventh filter residue in the lithium recovery tank 71 to the seventh filtering device 73, and the seventh filtering device 73 separates the seventh aqueous solution and the seventh filter residue. The seventh filter residue is lithium phosphate. The weight of the filter residue is 155.1Kg. The lithium content is calculated by atomic absorption spectrometry analysis to be 27.9Kg. Then divided by the lithium content of the carbon ink powder of 29.2Kg, the recovery rate of lithium is 96%.

Specifically, the first filtering device 13, the second filtering device 23, the third filtering device 33, the fourth filtering device 43, the fifth filtering device 53, the sixth filtering device 63 and the seventh filtering device 73 of the present invention can be It is a plate and frame filter press, also known as a plate press. The first stirring device 12 , the second stirring device 22 , the third stirring device 32 , the fourth stirring device 42 , the fifth stirring device 52 , the sixth stirring device 62 and the seventh stirring device 72 may be blade mixers.

The method and equipment for recycling valuable metals in lithium-ion batteries of this invention can effectively separate valuable metals without using electrolysis reaction and without using special extractants. Furthermore, this invention first removes aluminum, copper, iron and other impurity metals and carbon in the carbon ink powder, and then collects the nickel carbonate and manganese carbonate of the fifth filter residue, the cobalt hydroxide or cobalt oxide of the sixth filter residue, and the Seven filter residues of lithium phosphate to achieve the purpose of separating and recovering valuable metals lithium, nickel, cobalt and manganese. In addition, this creation first removes aluminum, copper, iron and other impurity metals and carbon from the carbon ink powder, so the recovery rate of valuable metals obtained from subsequent recycling can be as high as more than 95%.

The above-mentioned embodiments are only for illustrating the technical ideas and characteristics of this invention. Their purpose is to enable those familiar with this art to understand the content of this invention and implement it accordingly. They should not be used to limit the patent scope of this invention. That is to say, all equivalent changes or modifications made in accordance with the spirit revealed by this creation should still be covered by the patent scope of this creation.

P:Pipeline system

S00: Material testing steps

S10: Alkali leaching step

S20: Acid leaching step

S30: Metal replacement step

S40: Iron removal step

S50: Steps to recover nickel and manganese

S60: Cobalt recovery step

S70: Lithium recovery step

100: Recovery equipment for valuable metals in lithium-ion batteries

1:Alkali leaching device

11:Alkali soaking tank

12: The first stirring device

13: First filtering device

14:Aluminum salt tank

2: Acid leaching device

21:Acid soaking tank

22: Second stirring device

23:Second filtering device

3: Copper removal device

31: Copper removal tank

32: The third stirring device

33:Third filtering device

4: Iron removal device

41: Iron removal tank

42: The fourth stirring device

43: The fourth filtering device

5: Nickel manganese recovery device

51: Nickel manganese recovery tank

52: The fifth stirring device

53:Fifth filter device

6: Cobalt recovery device

61:Cobalt recovery tank

62:Sixth stirring device

63:Sixth filter device

7: Lithium recovery device

71:Lithium recovery tank

72:Seventh stirring device

73:Seventh filtering device

Figure 1 is a flow chart of the recycling method of valuable metals in lithium-ion batteries of this invention. Figure 2 is a schematic diagram of the recycling equipment for valuable metals in lithium-ion batteries of this invention.

P:Pipeline system

100: Recovery equipment for valuable metals in lithium-ion batteries

1:Alkali leaching device

11:Alkali soaking tank

12: The first stirring device

13: First filtering device

14:Aluminum salt tank

2: Acid leaching device

21:Acid soaking tank

22: Second stirring device

23:Second filtering device

3: Copper removal device

31: Copper removal tank

32: The third stirring device

33:Third filtering device

4: Iron removal device

41: Iron removal tank

42: The fourth stirring device

43: The fourth filtering device

5: Nickel manganese recovery device

51: Nickel manganese recovery tank

52: The fifth stirring device

53:Fifth filter device

6: Cobalt recovery device

61:Cobalt recovery tank

62:Sixth stirring device

63:Sixth filter device

7: Lithium recovery device

71:Lithium recovery tank

72:Seventh stirring device

73:Seventh filtering device

Claims (1)

A recycling equipment for valuable metals in lithium-ion batteries, including at least: An alkali immersion device (1), which includes an alkali immersion tank (11) that mixes a sodium hydroxide aqueous solution and a carbon ink powder with a pH value greater than 12, and a first alkali immersion tank (11) disposed in the alkali immersion tank (11). The stirring device (12) is connected to a first filtering device (13) at the bottom of the alkali soaking tank (11) with a pipeline system (P), and the first filtering device (13) is connected with the pipeline system (P). An aluminum salt tank (14), the pipeline system (P) at the bottom of the alkali leaching tank (11) transports a first aqueous solution and a first filter residue in the alkali leaching tank (11) to the first filter Device (13), the first filtering device (13) separates the first aqueous solution and the first filter residue, and stores the first aqueous solution in the aluminum salt tank (14), wherein the carbon ink powder contains lithium, nickel , cobalt, manganese, aluminum, copper, iron and carbon, the first aqueous solution is aluminum salt, the first filter residue contains lithium, nickel, cobalt, manganese, copper, iron and carbon; An acid leaching device (2), which includes an acid leaching tank (2) connected to the first filtering device (13) with the pipeline system (P) to receive the first filter residue and mix it with an acidic aqueous solution to make the pH value less than 4. 21), a second stirring device (22) provided in the acid leaching tank (21) and a second filtering device (23) connected to the bottom of the acid leaching tank (21) with the piping system (P), The pipeline system (P) at the bottom of the acid leaching tank (21) transports a second aqueous solution and a second filter residue in the acid leaching tank (21) to the second filtering device (23). The device (23) separates the second aqueous solution and the second filter residue, and the second filter residue is carbon residue; A copper removal device (3), which includes a copper removal tank (31) connected to the second filtering device (23) with the piping system (P) to receive the second aqueous solution and mix iron powder with a pH value less than 4 , a third stirring device (32) installed in the copper removal tank (31) and a third filtering device (33) connected to the bottom of the copper removal tank (31) with the piping system (P). The pipeline system (P) at the bottom of the copper tank (31) transports a third aqueous solution and a third filter residue in the copper removal tank (31) to the third filtering device (33), and the third filtering device (33) 33) Separate the third aqueous solution and the third filter residue, and the third filter residue is copper; An iron removal device (4), which includes connecting the third filtering device (33) with the pipeline system (P) to receive the third aqueous solution and mix sodium hydroxide to make the pH value between 4 and 5. An iron removal tank (41), a fourth stirring device (42) provided in the iron removal tank (41), and a fourth filter connected to the bottom of the iron removal tank (41) with the pipeline system (P) Device (43), the pipeline system (P) at the bottom of the iron removal tank (41) transports a fourth aqueous solution and a fourth filter residue in the iron removal tank (41) to the fourth filtering device (43) , the fourth filtering device (43) separates the fourth aqueous solution and the fourth filter residue, and the fourth filter residue is ferric hydroxide; A nickel-manganese recovery device (5), which includes connecting the fourth filtering device (43) with the pipeline system (P) to receive the fourth aqueous solution and mixing sodium carbonate and sodium hydroxide to make the pH value between 6 and A nickel-manganese recovery tank (51) between 8, a fifth stirring device (52) provided in the nickel-manganese recovery tank (51), and the pipeline system (P) connected to the nickel-manganese recovery tank (51) ), a fifth filtering device (53) at the bottom of the nickel-manganese recovery tank (51), and the pipeline system (P) at the bottom of the nickel-manganese recovery tank (51) transports a fifth aqueous solution and a fifth filter residue in the nickel-manganese recovery tank (51) To the fifth filtering device (53), the fifth filtering device (53) separates the fifth aqueous solution and the fifth filter residue, and the fifth filter residue is nickel carbonate and manganese carbonate; A cobalt recovery device (6), which includes connecting the fifth filtration device (53) with the pipeline system (P) to receive the fifth aqueous solution and mix sodium hydroxide to make the pH value between 11 and 13 A cobalt recovery tank (61), a sixth stirring device (62) provided in the cobalt recovery tank (61), and a sixth filter connected to the bottom of the cobalt recovery tank (61) with the pipeline system (P) Device (63), the pipeline system (P) at the bottom of the cobalt recovery tank (61) transports a sixth aqueous solution and a sixth filter residue in the cobalt recovery tank (61) to the sixth filtering device (63) , the sixth filtering device (63) separates the sixth aqueous solution and the sixth filter residue, the sixth filter residue is cobalt hydroxide; and, A lithium recovery device (7), including a lithium recovery tank (71) connected to the sixth filtering device (63) with the pipeline system (P) to receive the sixth aqueous solution and mix sodium phosphate, and is provided in the lithium recovery device A seventh stirring device (72) in the tank (71) and a seventh filtering device (73) connected to the bottom of the lithium recovery tank (71) by the pipeline system (P), and the bottom of the lithium recovery tank (71) The pipeline system (P) transports a seventh aqueous solution and a seventh filter residue in the lithium recovery tank (71) to the seventh filtering device (73), and the seventh filtering device (73) The aqueous solution and the seventh filter residue are separated, and the seventh filter residue is lithium phosphate.

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