KR102232087B1 - Extraction purification of zinc and manganese through physical treatment and wet process from used battery - Google Patents

Abstract

Disclosed is a method of producing zinc sulfate monohydrate for feed additives through recycling of waste batteries. The present invention is a method for producing zinc sulfate monohydrate for feed additives by separating and extracting and purifying zinc and manganese from waste dry batteries through physical treatment and wet processes.(a) Comprising zinc and manganese by pulverizing and sorting waste dry cells. Obtaining a raw material powder; (b) obtaining a zinc sulfate solution including reacting sulfuric acid with the raw material powder; (c) removing heavy metal components contained in the zinc sulfate solution; And (d) concentrating, dehydrating and drying the zinc sulfate solution to obtain zinc sulfate monohydrate.

Description

[EXTRACTION PURIFICATION OF ZINC AND MANGANESE THROUGH PHYSICAL TREATMENT AND WET PROCESS FROM USED BATTERY}

The present invention relates to a method for recycling waste batteries, and more particularly, to a method for using as a feed additive by separating and purifying zinc and manganese from waste batteries.

In Korea, when raising livestock, it is not a grazing type that directly consumes natural grasslands or grains, but intensively supplies various grains, protein sources, and various minerals and vitamins at high concentrations in livestock farms. It is achieved through dense breeding and rich feed supply method.

Rich feed is prepared into feed through heat and physical processing after collecting each raw material in a feed factory and mixing it according to an appropriate mixing ratio, and in the process, various minerals and vitamins are deficient or destroyed and must be added artificially. Therefore, carbohydrates (including fiber), protein and fat must be secured from a large amount of raw materials, and vitamins and minerals must be supplied in the form of separate additives.

Minerals are large amounts of minerals (Macro Minerals: calcium, magnesium, calcium, phosphorus, etc. supplied in an amount of 2 to 5% by weight of feed) and small amounts of minerals (Trace Minerals: as little as 10 to 2,000 ppm in feed, as much as 0.2 weight by weight. It is classified into iron, copper, zinc, manganese, cobalt, selenium, chromium, etc., which are used in less than %), mainly acts as an enzyme or coenzyme in the major metabolic processes of animals, promoting growth and helping the skeleton, skin composition, and growth vitality. Do it.

Among these minerals, zinc (Zn) exerts functions such as vitality of sexual function, enhancement of fertility, treatment of skin inflammation, prevention of hari (diarrhea of newborn pigs) (use at the level of 2,000 ppm ZnO), and reduction of the number of somatic cells in milk. As a source, zinc sulfate (Zinc Sulfate Monohydrate, ZnSO ₄ H ₂ O, Zn 35% by weight) or zinc oxide (Zinc Oxide, ZnO, Zn 80% by weight) is used.

As such, zinc sulfate monohydrate as a source of zinc, which is an essential additive for the growth of animals, has strict standards for feed additives (Zn 35% by weight or more, heavy metal lead 10ppm or less, arsenic 10ppm or less), and flowability to mix well with feed. This is good, and it is used as a feed with an appropriate particle size (less than 220㎛, passing through 60mesh 98%), so a low price is required.

In this respect, Korea, Japan, and Taiwan have very strict regulations compared to other countries (US, Europe, China, Southeast Asia, etc.), and the standards of China, the supplier of major products, are somewhat less stringent, so Korea, Japan, and Taiwan It expects to produce and supply products conforming to national standards.

Conventional production of zinc sulfate monohydrate is a process of producing zinc sulfate monohydrate through spray drying using a zinc sulfate solution made from the reaction of zinc oxide and sulfuric acid or a semi-finished zinc sulfate solution. There is also a complex problem.

On the other hand, in a situation where mineral resources and metal prices are rising recently, the problem of recycling them from waste batteries in which high-purity metals and metal compounds are used is becoming an important issue in Korea, which relies entirely on imports of metal minerals.

In Korea, zinc manganese batteries and alkaline batteries are currently being treated as general waste, and since most of the battery components are inexpensive metals, there are no attempts to fully recycle waste batteries. Recycling of waste batteries is the recovery of valuable metals. The situation is being dealt with in terms of solving environmental problems rather than in terms of dimensions.

On the other hand, all existing zinc sulfate monohydrate production has been carried out in China, but in the 2010s, the price of raw materials continues to rise due to environmental regulations of the Chinese government and the ban on imports of various recycled raw materials into China.

Therefore, it is required to develop a new process to overcome the situation of crushing and landfilling of waste batteries collected in accordance with the Recycling Promotion Act in Korea, and in this context, development of the production process of zinc sulfate monohydrate for feed additives through recycling of waste batteries is urgently needed. It needs to be done.

[Prior Patent Literature]

-Korean Patent Registration No. 10-0975317 (2010.08.05.)

-Korean Patent Publication No. 10-2012-0122481 (2012.11.07.)

Accordingly, the present invention has been conceived to solve the above problems, and an object of the present invention is to provide a method of manufacturing zinc sulfate monohydrate for feed additives through recycling of waste batteries.

In order to solve the above problems, the present invention is a method for preparing zinc sulfate monohydrate for feed additives by separating and extracting and purifying zinc and manganese from waste dry batteries through physical treatment and wet processes, (a) pulverizing and sorting waste dry cells. Thereby obtaining a raw material powder containing zinc and manganese; (b) obtaining a zinc sulfate solution including reacting sulfuric acid with the raw material powder; (c) removing heavy metal components contained in the zinc sulfate solution; And (d) concentrating, dehydrating and drying the zinc sulfate solution to obtain zinc sulfate monohydrate.

In addition, it provides a method characterized in that the battery is a zinc manganese battery or an alkaline battery.

In addition, it provides a method characterized in that the reaction weight ratio of the raw material powder and the sulfuric acid is 1:0.5 ~ 1:1.5.

According to the present invention, not only provides a waste recycling method in which the environmental load is significantly reduced by recycling the existing waste dry batteries that are completely buried or disposed of incineration as zinc sulfate monohydrate for feed additives, but also provides a stable supply of feed additive raw materials in the future. There is an effect.

In addition, the manganese and zinc components of the waste dry cell are separated in high purity, and zinc sulfate monohydrate exhibiting excellent flowability and particle size is provided, thereby making it possible to provide a raw material that satisfies the strict standards of feed additives.

1 is a photograph showing the appearance after the second concentration, the third concentration, the fourth concentration and the end of concentration in an embodiment of the present invention.

Hereinafter, a preferred embodiment of the present invention will be described in detail. In describing the present invention, when it is determined that a detailed description of a related known technology may obscure the subject matter of the present invention, a detailed description thereof will be omitted. Throughout the specification, when a part "includes" a certain component, it means that other components may be further included rather than excluding other components unless otherwise stated.

As a result of the inventors paying attention to the recycling problem of waste batteries and repeating intensive research to solve them, zinc and manganese are separated and purified from waste batteries through a specific physical treatment and wet process to show high purity, excellent flowability and particle size. It was discovered that it can be recycled as zinc sulfate monohydrate for feed additives, and the present invention was reached.

Therefore, the present invention is a method for producing zinc sulfate monohydrate for feed additives by separating and extracting and purifying zinc and manganese from waste dry batteries through physical treatment and wet processes, and includes zinc and manganese by pulverizing and sorting waste dry batteries. Obtaining a raw material powder; (b) obtaining a zinc sulfate solution including reacting sulfuric acid with the raw material powder; (c) removing heavy metal components contained in the zinc sulfate solution; And (d) concentrating, dehydrating and drying the zinc sulfate solution to obtain zinc sulfate monohydrate.

Zinc sulfate is mainly used as a raw material for producing feed additives (or fertilizers) and derivatives of zinc compounds. Among them, it is important to provide inexpensive raw materials because feed additives must be inexpensive. In the present invention, it is intended to provide an innovative process for extracting zinc sulfate monohydrate from a waste battery that is currently disposed of.

In general, waste zinc-manganese batteries are mixtures containing zinc and manganese at a level of 30 to 35% by weight, respectively, as shown in Table 1 below, and a physical method for separating them has not been developed until now, and theoretically separates them at low cost. It is known to be very difficult to do. The method used in conventional smelting plants was the only method of refining by applying high heat, but the cost exceeds the cost of raw materials, so it is not economical, and as a chemical treatment method, a mixture of zinc and manganese in the form of a mixture of zinc and manganese sulfate (ZnSO ₄₎ ·MnSO ₄ ·xH ₂ O) can be made temporarily, but a single product (zinc sulfate monohydrate, manganese sulfate monohydrate) must be obtained in accordance with the standard for veterinary drugs as feed additives.

Ingredient name zinc manganese iron content carbon rod Plastic, paper Electrolyte Content (% by weight) 30~35 30~35 10-15 5-10 1~3 8-15 state ZnO MnO, MnO ₂ Iron Stick powder skin Penetrate into the powder Treatment method Sulfuric acid reaction Sulfuric acid reaction precipitation separation Scrap metal processing Heat source Heat source React with powder

On the other hand, zinc sulfate monohydrate used as a feed additive is defined in accordance with the standards for veterinary medicine, and its contents are shown in Table 2 below.

Zinc content Lead content Arsenic content Remark 35% by weight or more 20ppm or less 10ppm or less Veterinary drug standard use

Therefore, when the waste dry cell is recycled and used as zinc sulfate monohydrate for feed additives, it is necessary to remove manganese mixed in the waste dry cell and extract only zinc with high purity.

The step (a) is a step of obtaining a raw material powder containing zinc and manganese from a waste dry battery, obtained by crushing and pulverizing primary batteries such as zinc manganese batteries and alkaline batteries among the waste dry batteries, and then selecting the raw material powder. do.

Waste batteries used for pulverizing raw materials are sorted according to the type of battery, for example, zinc manganese batteries or alkaline batteries that require zinc manganese batteries, alkaline batteries, Ni-Cd batteries, lithium ion batteries, etc. using a trommel separator. Can only be secured. The crushing or crushing of the secured waste batteries may be performed using, for example, an unta-type shredder. After crushing or pulverization, the iron component can be removed using a magnetic separator, and other carbon bars, plastics, paper, etc. can be removed using a particle size separator, a specific gravity separator, and a non-ferrous separator, and then only raw material powder can be obtained. Silver may include zinc oxide, manganese oxide and manganese dioxide as main components.

The step (b) is a step of substantially separating and purifying zinc and manganese components from the obtained raw material powder, and is obtained in the form of a zinc sulfate solution including the step of reacting sulfuric acid with the raw material powder. The process of obtaining the zinc sulfate solution includes, for example, (b1) filtering and removing _{manganese dioxide (MnO 2) precipitated by reacting the raw material powder with sulfuric acid;} (b2) filtering and removing _{the precipitated manganese hydroxide (Mn(OH) 2} ) by back-leaching the filtrate of step (b1) with caustic soda; (b3) precipitating and separating _{zinc hydroxide (Zn(OH) 2} ) by adjusting the pH of the filtrate of step (b2); And (b4) reacting the separated zinc hydroxide with sulfuric acid to obtain a purified zinc sulfate solution.

In the present invention, for the separation and purification of zinc and manganese components from the raw material powder, a manufacturing process of zincate (Zincate, Na ₂ [Zn(OH) ₄ ]) used in the manufacturing process of nano-zincization may be used. That is, zinc and manganese in the raw material powder are ZnO 30 to 40% by weight (Zn 25 to 33% by weight), MnO 5 to 18% by weight (Mn 4 to 14% by weight) and MnO ₂ 20 to 30% by weight (Mn 15 to 20% by weight) level, and when this is reacted with an excess of sulfuric acid, a zinc sulfate solution and a manganese sulfate solution are generated as shown in Scheme 1 below, and manganese dioxide (MnO ₂ ) is precipitated, and the precipitated manganese dioxide can be removed by filtration. (Step (b1)).

[Scheme 1]

ZnO + MnO ₂ + MnO + 2H ₂ SO ₄ → ZnSO ₄ (solution) + MnSO ₄ (solution) + MnO ₂ (precipitation) + 2H ₂ O

Thereafter, the manganese dioxide is removed and _{the step of separating and removing manganese hydroxide (Mn(OH) 2} ) from the remaining filtrate is performed, and manganese hydroxide is precipitated by reverse leaching with caustic soda in the filtrate as shown in Reaction Formula 2 below. , The precipitated manganese hydroxide can be removed by filtration (step (b2)).

[Scheme 2]

ZnSO ₄ + MnSO ₄ + H ₂ SO ₄ + 8NaOH → Na ₂ [Zn(OH) ₄ ](solution) + 3Na ₂ SO ₄ (solution) + Mn(OH) ₂ (precipitation) + 2H ₂ O

_{Thereafter, the step of separating and removing zinc hydroxide (Zn(OH) 2} ) from the remaining filtrate after the manganese hydroxide is removed is performed.Zinc hydroxide is adjusted to an appropriate pH by using caustic soda for the filtrate as shown in Scheme 3 below. Precipitated through the formation, the precipitated zinc hydroxide can be separated by filtration (step (b3)).

[Scheme 3]

Na ₂ [Zn(OH) ₄ ] + Na ₂ SO ₄ + 2H ₂ SO ₄ + 2NaOH → 3Na ₂ SO ₄ (solution) + Zn(OH) ₂ (precipitation) + 4H ₂ O

Thereafter, the separated zinc hydroxide may be reacted with sulfuric acid again as shown in Scheme 4 below to obtain a pure zinc sulfate solution (step (b4)).

[Scheme 4]

Zn(OH) ₂ + H ₂ SO ₄ → ZnSO ₄ (solution) + 2H ₂ O

The step (c) is a step of removing the heavy metal component contained in the obtained zinc sulfate solution, and in general, the heavy metal contained in the waste dry cell of a zinc manganese battery or an alkaline battery is 500 to 2,500 ppm in the case of lead (Pb), In the case of cadmium (Cd), it is 1,500 to 5,000 ppm, and in the case of mercury (Hg) and arsenic (As), it is hardly present.

The content of lead and cadmium in the waste batteries itself has been regulated in each country, so they have decreased a lot recently, but batteries with a high content of 0.25-0.5% by weight (2,500-5,000ppm) are also collected for recycling. During the collection process, lead and cadmium are contained in the pulverized powder from actual waste batteries due to contamination of lead acid batteries and Ni-Cd batteries. Therefore, after obtaining the zinc sulfate solution, it is necessary to remove the heavy metals mixed through appropriate physical and chemical reactions and processes.

As a method for removing heavy metal components contained in the obtained zinc sulfate solution in the present invention, for example, the following methods may be used alone or in combination, and at this time, an appropriate temperature of the solution, concentration of the solution, pH of the solution, presence or absence of agitation, heating method, An optimized heavy metal removal process can be selected in consideration of various variables such as stirring speed, setting time and period, selection of filtration material, etc. during standing.

-Fe ₂ (SO ₄ ) ₃ treatment

-ZnO or Zn Dust treatment

-Zn(OH) ₂ treatment

-Al(OH) ₂ treatment

-BaS treatment

-BaCO ₃ treatment

-SrCO ₃ treatment

-Zn powder treatment

-CaCO ₃ (nano) treatment

-PbO·SiO ₂ treatment

-B-Naphthol treatment

-CuSO ₄ 5H2O treatment

-Fe(OH) ₃ treatment

-H ₃ SO ₃ treatment

-Nitroso ß-Naphtthol treatment

-Na ₂ Cr ₂ O ₇ treatment

-CaSx(x=2~5) treatment

-H ₂ S treatment

-Na ₂ CO ₃ treatment

-Reduction precipitation using metal or reducing gas (H ₂ , SO ₂ , CO, etc.)

-Pressurized high temperature treatment method (AutoClave)

In the present invention, in terms of removing lead and cadmium, preferably (i) an excess of sulfuric acid is reacted with a zinc sulfate solution, (ii) a zinc sulfate solution is treated with zincation (ZnO) or zinc dust, or (iii) ) The zinc sulfate solution _{may be co-precipitated with carbonate (-CO 3} ), or (iv) the zinc sulfate solution may be co-precipitated with hydroxide (-OH) to remove heavy metals.

In the case of the (i) excessive reaction of sulfuric acid, it can _{be removed as PbSO 4} and CdSO ₄ precipitates to a level of 100 ppm or less, and (ii) 50 ppm in the case of a method of treating zincation (ZnO) or zinc dust. It can be removed at the level below, (iii) _{less than 30ppm in the case of coprecipitation with carbonate (-CO 3} ), and (iv) less than 20ppm of lead in the case of coprecipitation with hydroxide (-OH) , Cadmium can be removed at the level of 10ppm or less.

In addition, in terms of arsenic (A) removal, preferably, as shown in Formula 5 below, BaS may be treated to _{remove As 2} S ₃ precipitate.

[Scheme 5]

As ₂ (SO ₄ ) ₃ + 3BaS -> As ₂ S ₃ (precipitation) + 3BaSO ₄

Step (d) is a step of obtaining zinc sulfate monohydrate used for feed additives from a zinc sulfate solution from which heavy metals have been removed.In the present invention, in the process of concentrating the zinc sulfate solution from which heavy metals have been removed, as before It proposes a process to make it exist in the concentrate as monohydrate powder crystals directly without going through crystals.

In the conventional manufacture of zinc sulfate monohydrate, a zinc sulfate solution (Zn 12% by weight) is directly spray-dried and dried, or the zinc sulfate solution is concentrated to induce zinc sulfate heptahydrate crystals, cooled, filtered, and separated, followed by a dryer (Dry Kiln, Fluidized bed dryer, etc.) to prepare feed additive grade zinc sulfate monohydrate.

However, in the case of the spray drying method, the process is simpler than that of the method for inducing a heptahydrate crystal, but product uniformity is difficult, a large mechanical device is required, and it is difficult to maintain the device, and the method for inducing the heptahydrate crystal In the case of concentration, cooling crystals, filtration separation, zinc sulfate heptahydrate, dehydration, drying, pulverization, and a series of complex processes, the manufacturing efficiency is low and additional facilities are required in terms of environmental treatment.

On the other hand, in the present invention, as a method of inducing zinc sulfate monohydrate powder crystals through a simple process, the steps of: (d1) concentrating the purified zinc sulfate solution and crystallizing powder into zinc sulfate monohydrate; And (d2) separating and drying the powder by dehydration immediately after crystallization of the powder.

That is, in the present invention, concentration is performed so that it exists in the concentrate as monohydrate powder crystals without going through heptahydrate crystals, which is carried out by repeating stirring heating and additional addition of zinc sulfate solution, but the solution temperature is 2 at 100 to 115°C. It can be induced into monohydrate powder crystals by stopping when it decreases to 80 to 95° C. within minutes, and specific embodiments are shown below.

-Zinc concentration in purified zinc sulfate solution: about 12% by weight of Zn, specific gravity 1.3

-Heating method during concentration: Indirect jacket or coil heating

-Stirring speed: 7~35rpm, rotation speed needs to be changed depending on the degree of concentration

-1st concentration step: Concentrate to about 24% by weight of Zn and about 1.45 specific gravity, perform vacuum concentration to increase concentration efficiency (e.g., 3 ton zinc sulfate solution is concentrated so that the remaining concentrate becomes 2 tons)

-Second concentration step: After concentration to about 29~30% by weight of Zn, zinc sulfate solution (temperature about 50℃) is added, and the amount added is 1/2 of the first concentration (for example, 1.5 tons of zinc sulfate solution is added)

-3rd concentration step: When the Zn reaches about 30~32% by weight and the specific gravity of about 1.55, add 1/2 amount of zinc sulfate solution (temperature about 50℃) during the first concentration (e.g., 1.5 tons of zinc sulfate solution). adding)

-4th concentration step: Concentration when stirring is minimized without decompressing to the level of about 3 tons (Zn about 36% by weight, specific gravity about 1.65~1.7) of the final concentrate

-End of concentration: A lot of bubbles occur during concentration and then the bubbles disappear suddenly, and the temperature of the solution is suddenly at 100 to 115°C, preferably 105 to 110°C (within about 2 minutes, preferably within 1 minute) 80 to 95°C , Preferably, the concentration is stopped when it is reduced to 90 to 95°C and maintained for 1 to 2 minutes.

If the process is stopped or the temperature decreases after the powder crystallization into zinc sulfate monohydrate through the above concentration process, it is precipitated in the concentrator and is problematic for facility maintenance, so the powder must be separated through a continuous dehydration separator immediately after crystallization of the powder. As the continuous dehydration separator, equipment such as a bottom-type centrifuge, a horizontal rotary filler, a Contabex-type continuous sieve, a pusher-type continuous sieve, and a decanter-type continuous separator may be used.

Zinc sulfate monohydrate that has passed through the continuous dehydration separator has a moisture content of about 6% by weight, and is mostly present in the form of attached moisture. Therefore, the attached moisture is rapidly evaporated so that it does not enter the monohydrate, and is immediately put into a dryer to dry.

In general, it is desirable to select a dryer that allows drying by direct hot air, mixing powders to dry uniformly, and drying equipment that rotates in a certain direction so that the particle size of the powder is uniform and has a standard curve even on the particle distribution chart. Do. Zinc sulfate monohydrate is not used alone as a feed additive, but must be added to the feed and must be evenly dispersed in a very small amount, so it has excellent properties in terms of particle thickness and uniformity, moisture content (less than 0.5% by weight), and degree of mixing with other particles. It is necessary to dry it in the form of a particle powder.

Hereinafter, a specific example according to the present invention will be described.

Example

After crushing the waste zinc-manganese batteries having the composition of Table 1 with an unta-type shredder, use a magnetic separator, particle size separator, specific gravity separator, and non-ferrous separator to remove iron, carbon rods, plastics, paper, etc., and then raw material powder (ZnO 35-40). Wt% (Zn 28 to 33 wt%), MnO 5 to 10 wt% (Mn 4 to 8 wt%) and MnO ₂ 25 to 30 wt% (Mn 15 to 20 wt%) containing) were prepared.

Excess sulfuric acid (98% by weight, specific gravity 1.836) was reacted with the raw material powder to remove the precipitated manganese dioxide by filtration, and the remaining filtrate was back-leached with caustic soda to remove the precipitated manganese hydroxide by filtration. Zinc hydroxide precipitated through pH adjustment was filtered and separated, and sulfuric acid was reacted with the separated zinc hydroxide to obtain a pure zinc sulfate solution.

Thereafter, the zinc sulfate solution _{was co-precipitated with Zn(OH) 2} to remove lead and cadmium to obtain a zinc sulfate solution (Zn concentration of about 12% by weight, specific gravity of about 1.3) from which heavy metals were removed.

Thereafter, for the purified zinc sulfate solution from which heavy metals have been removed, the first concentration (Zn about 24% by weight, specific gravity to about 1.45), the second concentration (Zn about 29~) at a stirring speed of 10 to 30 rpm in an indirect jacket heating method. Concentration to 30% by weight), then add zinc sulfate solution (temperature about 50℃) in 1/2 amount of the first concentration, and then 3rd concentration (concentrate to about 30~32% by weight of Zn, specific gravity of about 1.55) and sulfuric acid Zinc solution (temperature about 50℃) was added in an amount of 1/2 of the first concentration, and the fourth concentration (Zn about 36% by weight, specific gravity about 1.65~1.7 without decompression and concentration by minimizing stirring) was performed. , During the final concentration, a lot of bubbles occur and then the bubbles disappear suddenly and the temperature of the solution suddenly decreases from 105 to 110°C (within about 1 minute) to 90 to 95°C and is maintained for 1 to 2 minutes. Powder crystallization as a hydrate. The appearance after the second concentration, the third concentration, the fourth concentration, and the end of the concentration are shown in FIGS. 1(a) to 1(d).

Immediately after crystallization of the powder, the powder was separated using a bottom-type centrifuge and immediately dried to a moisture content of 0.5% by weight or less in a hot air dryer to prepare a final zinc sulfate monohydrate powder.

Test example

The prepared zinc sulfate monohydrate powder was measured or analyzed for heavy metal content, flowability, and particle characteristics by the following method, and the results are shown in Table 3 below.

[Measurement method of heavy metal content]

Lead, cadmium, and arsenic contents were measured using an AAS (Atomic Absorption Spectrometer, SHIMADZU) instrument.

[Flow analysis method]

The angle of response was measured with an angle of repose measuring device (BT-200 Tester with Funnel 5㎜) to evaluate the flowability of the powder. The angle of repose refers to the maximum angle of inclination that can be deposited without flowing down when unsolidified powder is deposited on a slope. In general, a small angle of repose is evaluated as having good flowability of the powder.

[Particle characteristics analysis method]

The shape of the powder particles was observed with an electron microscope (SEM: Scanning Electron Microscope), and the particle size of the powder particles suspended in hexane was measured with a laser particle analyzer (Mastersizer X, Malvern Instruments) by a light transmission method. The cumulative distribution of the size was obtained, from which the average particle diameter and particle size distribution index of the particles were obtained by the following method.

-Average particle diameter (D ₅₀ ): The size of particles corresponding to 50% of the cumulative weight

-Particle size distribution index (P): P = (D ₉₀ -D ¹⁰ )/D ₅₀

division Measures
Heavy metal content Pb 10ppm CD 5ppm As Not detected Flow Angle of repose 28±0.5°
Particle properties Particle shape Mostly old Average particle diameter 85㎛ Particle size distribution index 0.76

Referring to Table 3, the zinc sulfate monohydrate powder produced according to the present invention utilizes waste batteries that have been disposed of in the past, while the content of heavy metals is 10 ppm lead, 5 ppm cadmium, and does not contain arsenic. It satisfies the strict standard, has very good flowability when considering a small angle of repose, and has a uniform shape in terms of particle characteristics, and from a narrow particle size distribution index, it can be seen that mixing with other raw materials as a feed additive is very good.

The preferred embodiments of the present invention have been described in detail above. The description of the present invention is for illustrative purposes only, and those of ordinary skill in the art to which the present invention pertains will be able to understand that other specific forms can be easily modified without changing the technical spirit or essential features of the present invention.

Therefore, the scope of the present invention is indicated by the claims to be described later rather than the detailed description, and all changes or modified forms derived from the meaning, scope and equivalent concepts of the claims are included in the scope of the present invention. It must be interpreted.

Claims (2)

A method of producing zinc sulfate monohydrate for feed additives by separating and extracting and purifying zinc and manganese from waste dry batteries through physical treatment and wet processes,
(a) pulverizing and screening the waste batteries to obtain a raw material powder containing zinc and manganese;
(b) obtaining a zinc sulfate solution including reacting sulfuric acid with the raw material powder;
(c) removing heavy metal components contained in the zinc sulfate solution; And
(d) concentrating, dehydrating and drying the zinc sulfate solution to obtain zinc sulfate monohydrate;
Including,
The step (d) may include: (d1) concentrating the zinc sulfate solution and crystallizing powder into zinc sulfate monohydrate; And (d2) separating and drying the powder by dehydration immediately after crystallization of the powder; wherein the concentration is performed by repeating stirring heating and additional addition of a zinc sulfate solution, but the solution temperature is 100 to 115° C. for 2 minutes A method, characterized in that it stops when it decreases to 80~95℃ within. The method of claim 1,
The method, characterized in that the battery is a zinc manganese battery or an alkaline battery.

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