KR101966063B1 - Manufacturing method of multi-mineral comprising Zinc sulfate, Iron sulfate, Copper sulfate and manganese sulphate from electric arc furnace dust, copper waste and Manganese waste - Google Patents

Abstract

The present invention relates to a method for producing composite minerals from industrial waste and, more specifically, to a method for producing composite minerals including zinc sulfate, iron sulfate, copper sulfate, and manganese sulfate from industrial waste including steelmaking dust, manganese waste, and copper waste. According to the present invention, the method of producing composite minerals from industrial waste includes: a first reaction step (S100) of obtaining a copper organic phase and a manganese organic phase by performing solvent extraction of copper waste and manganese waste, and obtaining copper sulfate solution and manganese sulfate solution by back extracting using sulfate acid solution; a first pulverization step (S200) of pulverizing the copper sulfate solution and the manganese sulfate solution and obtaining copper sulfate powder and manganese sulfate powder; a second reaction step (S300) of obtaining leachate including zinc sulfate and iron sulfate by reacting steelmaking dust with sulfate acid solution; a heavy metal removing step (S400) of removing heavy metal included in the leachate; and a second pulverization step (S500) of pulverizing the leachate, from which heavy metal is removed, and obtaining zinc sulfate powder and manganese sulfate powder. The present invention can provide composite minerals with high industrial usefulness.

Description

Technical Field The present invention relates to a method for producing a complex mineral containing zinc sulfate, iron sulfate, copper sulfate and manganese sulfate from steelmaking dust, manganese waste and copper waste. furnace dust, copper waste and Manganese waste}

The present invention relates to a method for producing a composite mineral from industrial wastes, and more particularly, to a method for producing a composite mineral from industrial wastes including steelmaking dust, manganese waste and copper waste, comprising zinc sulfate, iron sulfate, copper sulfate, And a method for manufacturing the same.

In recent years, as semiconductor devices have become more compact, semiconductor wiring materials have been replaced by copper, which has better electrical properties than aluminum. As a result, the amount of copper wastewater and copper waste generated in the wiring process is also increasing. The copper wastewater and copper waste contain a large amount of copper, and attempts have been made to recycle it.

As a technique for recycling copper waste, Korean Patent No. 10-0798450 discloses a regeneration process for producing copper sulfate from copper wastewater by using an ion exchange resin. However, since an ion exchange resin is used, expensive treatment There is a cost and a difficulty in mass processing.

On the other hand, with the proliferation of electronic devices, portable computers, mobile phones, and the like, there is a growing demand for secondary batteries. The secondary battery includes a cathode, an anode, an electrolyte, and a separator. Manganese oxide or manganese hydroxide is widely used for the production of the anode. Due to the surge in demand for secondary batteries, the demand for materials for manufacturing such secondary batteries is rapidly increasing, and the amount of manganese waste generated is also increasing.

The electric furnace steel dust generated in the steel industry is an industrial by-product containing various metal elements such as zinc, iron, manganese, copper and the like. In addition to the above metal elements, harmful heavy metals such as lead and cadmium are also included. have. In general, steelmaking dust is known to produce about 1 ~ 1.5% of iron production, and about 400,000 tons of iron is produced in 2013. In Korea, reclamation is gradually increasing due to increased concern about soil and groundwater pollution, and land reclamation rate is 30.1%, recycled 65.3%, other 1.9% and storage 2.7% as of 2013. These dusts contain many valuable metals, such as zinc, iron, and copper, which, when properly treated, create value as waste resources.

As a technique for recycling industrial wastes such as manganese waste and steel dust, Korean Patent No. 10-0889475 discloses a method of recycling industrial waste such as manganese waste and steel dust, in which 10 weight% of zinc ore is contained in a weight ratio of 50 weight% of purity and 100 weight% of sulfuric acid aqueous solution, 8 weight% of ferromanganese, 8 weight% of zinc oxide of plating plant, 4 weight% of scrap iron, 4 weight% of manganese dioxide, 2 weight% of manganese carbonate ore and 2 weight% of ferro-manganese alloy iron electro dust The solution was heated at 95 ° C for 5 hours and then filtered. The filtrate was concentrated to dryness by removing heavy metals by adding 1 to 3% by weight of zinc sulfate to the filtrate. The obtained solution was mixed with zinc sulfate, manganese sulfate and ferrous sulfate. .

The above patent document describes a method for producing complex minerals in high purity and high yield by causing an unbalance in yield due to the simultaneous reaction with the sulfuric acid aqueous solution without considering the ionization tendency and reactivity of the valuable metals (zinc, iron and manganese) It has limitations that are difficult to obtain.

The present invention relates to the production of sulfuric acid complex minerals including zinc sulfate, iron sulfate, copper sulfate and manganese sulfate which can be applied as animal nutritional supplements and plant nutritional supplements from industrial wastes including copper wastes, manganese wastes and steel dusts As a part of the research, the reaction imbalance resulting from the difference in reactivity of the elements to be obtained contained in industrial wastes is minimized while impurities and heavy metals are minimized, and zinc sulfate, iron sulfate, copper sulfate and manganese sulfate are obtained in high purity and high yield, Thereby obtaining a composite mineral powder having a uniform shape and particle size, leading to the present invention.

Korean Patent No. 10-0798450 (regeneration process for producing high-concentration copper sulfate from copper wastewater) Korean Patent No. 10-0889475 (Process for producing minerals mixed with zinc sulfate, manganese sulfate and ferrous sulfate)

In order to solve the above problems, it is an object of the present invention to provide a process for producing sulfur oxide complex minerals containing zinc sulfate, iron sulfate, copper sulfate and manganese sulfate from industrial wastes including copper waste, manganese waste, And zinc sulfate, iron sulfate, copper sulfate and manganese sulfate at a high purity and a high yield to obtain a uniform shape and particle size through spray drying, while minimizing heavy metals and minimizing heavy metals and eliminating the reaction imbalance resulting from the difference in reactivity of elements to be obtained contained in industrial wastes. And a method for producing the composite mineral powder having the above-mentioned properties.

In order to solve the above problems, the present invention provides a method for producing a composite mineral from industrial wastes, comprising the steps of extracting copper waste and manganese waste by solvent extraction to obtain a copper organic phase and a manganese organic phase, and back extracting using an aqueous solution of sulfuric acid, (S200) for obtaining a copper sulfate powder and a manganese sulfate powder by pulverizing the aqueous solution of copper sulfate and an aqueous solution of manganese sulfate (S200); and a step (S200) of adding sulfuric acid solution to the sulfuric acid solution (S400) for removing the heavy metal contained in the leach solution (S400), and a second reaction step (S300) for obtaining a leach solution containing zinc sulfate and iron sulfate, And a second pulverizing step (S500) of obtaining a powder and a manganese sulfate powder.

The first reaction step (S100) comprises a raw material pre-treatment step (S110) of de-ironing copper waste and manganese waste, a step of forming a copper waste aqueous solution by mixing the pretreated copper waste and water, (S120) of obtaining an aqueous solution of copper sulfate to form an aqueous solution of copper sulfate by back-extracting the copper organic phase with an aqueous solution of sulfuric acid, mixing the pretreated manganese waste with water to prepare a manganese waste aqueous solution A step of obtaining an aqueous solution of manganese sulfate to form an aqueous solution of manganese sulfate by reverse extraction using the aqueous solution of sulfuric acid to form a manganese organic phase; ).

The raw material preprocessing step (S110) may be performed by pulverizing copper waste and manganese waste to 5 to 50 mu m, adding an alkaline agent to a mixture of the pulverized raw material and water at a ratio of 1: 1 to 2: To form an iron precipitate, and removing the iron precipitate by solid-liquid separation.

In the second reaction step (S300), a sulfuric acid solution is injected into the steelmaking dust to form a zinc leaching reaction in which zinc is leached, and the zinc leaching reaction is filtered to obtain a zinc sulfate leaching solution (S310 And a step (S320) of obtaining an iron sulfate leach solution obtained by adding a sulfuric acid solution to the precipitate to obtain an iron sulfate leaching solution in which iron is leached.

The heavy metal removal step (S400) is characterized in that the heavy metal is removed using an agate of 5 to 50 mu m.

As described above, the method for producing a complex mineral from industrial wastes according to the present invention is a method for producing complex minerals from industrial wastes including copper wastes, manganese wastes, steel dusts, and the like by using sulfuric acid composite including zinc sulfate, iron sulfate, In order to obtain the minerals, zinc sulfate, iron sulfate, copper sulfate and manganese sulfate are obtained in high purity and high yield and the spray drying is carried out by minimizing impurities and heavy metals while minimizing impurities and heavy metals, It is possible to provide a composite mineral having a high industrial use value by having a uniform shape and particle size.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a flow chart showing a method for producing a composite mineral from industrial wastes of the present invention.

Specific features and advantages of the present invention will be described in detail below with reference to the accompanying drawings. The detailed description of the functions and configurations of the present invention will be omitted if it is determined that the gist of the present invention may be unnecessarily blurred.

The term 'manganese waste' of the present invention may include industrial wastes and industrial by-products generated in industrial fields such as steel making, steel making, dry batteries, non-ferrous metal alloys, colorants of the glass industry, welding, and the like. Specific examples thereof include waste manganese batteries, Manganese electric furnace dust, and the like, but the present invention is not limited thereto. In addition, it may include manganese nodules such as pyrolusite, psilomelane, and manganite obtained in nature, not limited to industrial wastes and industrial by-products. I never do that. More preferably, the manganese waste and the manganese content used in the present invention may contain at least 5 to 55% manganese, and more preferably, the spent manganese battery, ferromanganese electric furnace dust, The spent manganese battery and the ferromanganese electric furnace dust have manganese as a main component and also zinc metal and iron as well as zinc sulfate and iron sulfate can be obtained.

The term 'copper waste' of the present invention is not limited to industrial wastes including copper and industrial by-products, but specific examples thereof include copper wastewater generated in electrolytic copper foil manufacturing and PCB manufacturing processes, industrial copper-based plating stripping solution, Low grade copper oxide and copper concentrate. Copper slag generated in a dry smelting process can also be included. More preferably, the copper waste used in the present invention may contain at least 15% of copper.

The present invention relates to a method for producing a composite mineral from industrial wastes, and more particularly, to a method for producing a composite mineral from industrial wastes including steelmaking dust, manganese waste and copper waste, comprising zinc sulfate, iron sulfate, copper sulfate, And a method for manufacturing the same.

In the present invention, in leaching an object element (zinc, iron, copper and manganese) obtained from industrial wastes including copper waste, manganese waste and steel dust, etc., In order to solve the reaction imbalance and consequently to obtain zinc sulfate, iron sulfate, copper sulfate and manganese sulfate in a high purity and a high yield, industrial wastes are mixed and are not reacted with the sulfuric acid solution at once, but steelmaking dust, copper waste and manganese waste are separated The sulfuric acid solution was reacted to obtain sulfur oxides. Further, copper and manganese are selectively obtained from copper wastes and manganese wastes by solvent extraction, thereby improving the purity of copper sulfate and manganese sulfate.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a flow chart showing a method for producing a complex mineral from industrial wastes of the present invention.

A method for producing a composite mineral from industrial wastes according to the present invention comprises the steps of: subjecting a copper waste and a manganese waste to a solvent extraction to obtain a copper organic phase and a manganese organic phase; subjecting the copper organic phase and the manganese organic phase to back extraction using an aqueous sulfuric acid solution to obtain an aqueous solution of copper sulfate and an aqueous solution of manganese sulfate A first pulverization step (S200) of obtaining a copper sulfate powder and a manganese sulfate powder by pulverizing the aqueous solution of copper sulfate and the aqueous solution of manganese sulfate into a reaction step (S100); and a step of reacting the sulfuric acid solution with the sulfuric acid solution to obtain zinc sulfate and iron sulfate (S400) for removing the heavy metal contained in the leach liquor (S400), and a second reaction step (S300) for obtaining the leach liquor from which the heavy metal is removed. And a pulverizing step (S500).

The first reaction step (S100) comprises a raw material pre-treatment step (S110) for de-ironing copper waste and manganese waste, a pre-treated copper waste and water to form a copper waste aqueous solution, and an oxime-based solvent extractant is added to the copper waste And reacting the copper organic phase with a copper organic phase to obtain a copper organic phase. The copper organic phase is back-extracted with an aqueous solution of sulfuric acid to obtain an aqueous solution of copper sulfate to form an aqueous solution of copper sulfate to form an aqueous manganese waste solution by mixing the pretreated manganese waste with water, And a step (S130) of obtaining an aqueous manganese sulfate solution by forming a manganese organic phase by adding a phosphoric acid solvent extractant to the manganese waste and reacting the manganese organic phase and back extracting the manganese organic phase with an aqueous sulfuric acid solution to form a manganese sulfate aqueous solution.

The raw material preprocessing step (S110) is a step of washing, crushing and degassing copper waste and manganese waste.

Copper and manganese wastes contain impurities such as Fe, Cl, Na, K, and Ca in addition to copper and manganese. In particular, Fe has a higher ionization tendency than copper and manganese. It is preferable to perform de-ironing prior to reacting copper waste and manganese waste with sulfuric acid to inhibit the leaching of copper and manganese from manganese waste so as to make it difficult to produce copper sulfate and manganese sulfate. At this time, the impurities such as Cl, Na, K, and Ca can be removed through one to five washings.

The decarburization step is not limited as long as it is for removing iron, but a method of precipitating iron and adjusting solid-liquid separation by adjusting the pH can be used as a specific example.

More specifically, the copper waste and the manganese waste are pulverized to 5 to 50 탆, and then the mixture is mixed with the pulverized raw material and water at a weight ratio of 1: 1 to 2, and the pH is adjusted to 3 to 5, For 150 minutes to form an iron precipitate, and the iron precipitate can be removed by solid-liquid separation. At this time, the separated iron precipitate may be added to the raw material together with the steel making dust in the subsequent second reaction step (S300) to form iron sulfate.

The kind of the alkali agent is not limited, but specific examples include sodium hydroxide, calcium hydroxide, calcium hydroxide, ammonia and the like, preferably sodium hydroxide of 1 to 2N concentration.

At this time, the pH is controlled to 3 to 5. When the pH is less than 3, iron is not precipitated and remains in the form of ions. When the pH is more than 5, since the precipitation amount of iron due to the increase in pH is insignificant, It is preferable not to deviate.

The step (S120) of obtaining an aqueous copper sulfate solution is a step of solvent extraction of the pre-treated copper waste to obtain a copper organic phase, and back extracting the copper organic phase with an aqueous sulfuric acid solution to obtain an aqueous copper sulfate solution, To 3 parts by weight to form a copper waste aqueous solution, and 150 to 300 parts by weight of a solvent extractant is added to 100 parts by weight of the copper waste aqueous solution to obtain a copper organic phase. The copper organic phase and the aqueous sulfuric acid solution are mixed at a ratio of 1: 2 by weight and then back-extracted to obtain an aqueous copper sulfate solution.

At this time, it is preferable that the copper waste aqueous solution is controlled to a pH of 2 to 5 by adding an alkali agent such as NaOH to increase the extraction efficiency before the solvent extractant is added.

Then, 150 to 300 parts by weight of the solvent extractant is added to 100 parts by weight of the prepared copper waste aqueous solution, stirred at 25 to 60 ° C and 150 to 300 rpm for 30 minutes to 2 hours, and then allowed to stand for 30 minutes to 1 hour to obtain a copper organic phase . At this time, an alkaline agent may be injected to adjust the pH to 2 to 5 in order to prevent deterioration of reactivity due to pH drop caused during extraction.

When the solvent extractant is added in an amount of less than 150 parts by weight, it is difficult to obtain copper. When the solvent extractant is added in an amount exceeding 300 parts by weight, It is preferable that the addition range is not out of the range because the increase is insignificant and the remaining solvent extractant can act as an impurity in the subsequent step.

The solvent extractant may include any one of a phosphoric acid-based solvent, an oxime-based solvent, a trialkylphosphine-based solvent and a combination thereof, and oxime-based solvents may be preferably used.

As a specific example of the solvent extracting agent, the oxime-based extracting agent includes aldooxime as a main component. Concretely, there may be mentioned, but not limited to, a mixture of 2-hydroxy-5-nonyl acetophenone oxime (trade name: LIX84), 5-dodecylsilyl aldoxime (trade name: LIX860), LIX84 and LIX860 ), Lix 973 (5-dodecyl-salicylad oxime), and 5-nonyl salicylaldoxime (trade name: ACORGA M5640).

The phosphoric acid solvent may be di (2-ethylhexyl) phosphate acid (D2EHPA) manufactured by SYTEK, USA, and Cyanex 923 (Trialkylphosphine oxide) manufactured by SYTEK, USA.

In addition, when the solvent extractant is added to the aqueous solution of copper waste, it may be diluted with a hydrocarbon-based organic solvent. Examples of the organic solvent include aromatic solvents, paraffin solvents, and naphthenic solvents. The organic solvent may be diluted to 10 to 25 parts by weight with respect to 100 parts by weight of the copper waste aqueous solution in consideration of viscosity, phase separation property, extraction speed, and the like.

The copper contained in the copper waste is adsorbed to the organic phase (organic solvent) by the reaction between the copper waste aqueous solution and the solvent extractant, and residues and impurities other than copper contained in the copper waste are present in the water phase.

The organic phase and the water phase can be separated and obtained by difference in specific gravity using a settler, and a scrubbing process can be performed to remove valuable metals and heavy metals other than copper contained in the organic phase by an additional process.

The scrubbing step may be performed using an aqueous acid solution, and the acid may be selected from sulfuric acid, hydrochloric acid, nitric acid, acetic acid, and a combination thereof. Preferably, a sulfuric acid aqueous solution having a concentration of 1N to 2N Can be used.

Further, when a copper waste additionally containing a valuable metal such as zinc is used as a raw material, the water separated in the solvent extraction step contains zinc and a trace amount of copper that is not adsorbed on the oil phase. In step S300, zinc sulfate and copper sulfate may be formed as raw materials together with steelmaking dust.

The copper organic phase obtained after the solvent extraction and scrubbing process is then mixed with an aqueous solution of sulfuric acid to back-extract the copper adsorbed on the copper organic phase with water.

At this time, the aqueous sulfuric acid solution having a concentration of 1.5 to 3N is used, and the copper organic phase and the aqueous sulfuric acid solution are mixed at a ratio of 1: 1 to 2 and back-extracted, whereby the copper adsorbed on the copper organic phase is back- And the oil phase are separated using a settler to obtain an aqueous phase (an aqueous solution of copper sulfate).

In the step (S130) of obtaining the manganese sulfate aqueous solution, the manganese organic phase is recovered by solvent extraction, and the manganese organic phase is back extracted using an aqueous solution of sulfuric acid to obtain an aqueous manganese sulfate solution. : 2 to 3 parts by weight to form a manganese waste aqueous solution, 150 to 300 parts by weight of a solvent extractant is added to 100 parts by weight of the manganese waste aqueous solution to obtain a manganese organic phase, 1 to 2 by weight and then back-extracted to obtain a manganese sulfate aqueous solution.

At this time, the manganese waste aqueous solution is preferably adjusted to a pH of 2 to 5 by adding an alkali agent such as NaOH to increase the extraction efficiency before the solvent extractant is added.

Thereafter, 150 to 300 parts by weight of a solvent extractant is added to 100 parts by weight of the prepared manganese waste aqueous solution, stirred at 25 to 60 ° C and 150 to 300 rpm for 30 minutes to 2 hours, and then allowed to stand for 30 minutes to 1 hour to obtain a manganese organic phase . At this time, an alkaline agent may be injected to adjust the pH to 2 to 5 in order to prevent deterioration of reactivity due to pH drop caused during extraction.

When the solvent extractant is added in an amount of less than 150 parts by weight, it is difficult to obtain manganese. When the solvent extractant is added in an amount exceeding 300 parts by weight, the extraction ratio of manganese It is preferable that the addition range is not out of the range because the increase is insignificant and the remaining solvent extractant can act as an impurity in the subsequent step.

The solvent extractant may include any one of a phosphoric acid-based solvent, an oxime-based solvent, a trialkylphosphine-based solvent, and a combination thereof, preferably a phosphoric acid-based solvent.

As a specific example of the phosphoric acid type solvent, D2EHPA (di (2-ethylhexyl) phosphate acid of SYTEK, USA) may be used.

In addition, when the solvent extractant is added to the manganese waste aqueous solution, it may be diluted with a hydrocarbon-based organic solvent. Examples of the organic solvent include aromatic solvents, paraffin solvents, and naphthenic solvents. The organic solvent may be diluted to 10 to 25 parts by weight with respect to 100 parts by weight of the manganese waste aqueous solution in consideration of viscosity, phase separation property, extraction speed, and the like.

The manganese contained in the manganese waste is adsorbed to the organic phase (organic solvent) by the reaction between the manganese waste aqueous solution and the solvent extractant. Residues and impurities other than manganese contained in the manganese waste are present in the water phase.

The organic phase and the water phase can be separated and obtained by difference in specific gravity using a settler, and a scrubbing process can be performed to remove valuable metals and heavy metals other than manganese contained in the organic phase by an additional process.

The scrubbing step may be performed using an aqueous acid solution, and the acid may be selected from sulfuric acid, hydrochloric acid, nitric acid, acetic acid, and a combination thereof. Preferably, a sulfuric acid aqueous solution having a concentration of 1N to 2N Can be used.

In addition, when manganese waste further including a valuable metal such as zinc is used as a raw material, the water separated in the solvent extraction process contains manganese and a trace amount of copper that is not adsorbed on the oil phase. As a result, In step S300, zinc sulfate and manganese sulfate may be formed as raw materials together with steelmaking dust.

The manganese organic phase obtained after the solvent extraction and scrubbing process is then mixed with the aqueous sulfuric acid solution to back-extract manganese adsorbed on the manganese organic phase with water.

The manganese organic phase and the aqueous sulfuric acid solution are mixed at a ratio of 1: 1 to 2 by volume and back-extracted, and the manganese adsorbed on the manganese organic phase is back-extracted with the aqueous phase. And the oil phase were separated using a settler to obtain an aqueous phase (aqueous solution of manganese sulfate).

In the first pulverization step (S200), an aqueous solution of copper sulfate and an aqueous solution of manganese sulfate are dried to obtain a copper sulfate powder and a manganese sulfate powder. At this time, it is also possible to prepare powders by separately preparing an aqueous solution of copper sulfate and a solution of manganese sulfate, or to mix powders of an aqueous solution of copper sulfate and an aqueous solution of manganese sulfate to prepare powders at one time. Preferably, It is preferable to obtain a powder.

The pulverization method may include high temperature drying or spray drying. Preferably, the aqueous copper sulfate solution and the aqueous manganese sulfate solution are concentrated by evaporation at 100 to 150 ° C for 30 minutes to 12 hours before high temperature drying or spray drying, 1.6. ≪ / RTI >

By evaporating and concentrating, it is possible to remove remaining organic substances and improve drying efficiency at high temperature drying or spray drying. In particular, when using spray drying, it is possible to facilitate control of shape and particle size of powder of copper sulfate and manganese sulfate by having appropriate moisture content and viscosity through evaporation and concentration.

Wherein the spray drying apparatus is set to have an inlet temperature of 150 to 170 DEG C, an outlet temperature of 90 to 105 DEG C, a spray pressure of 5 to 10 kPa, and a hot air flow rate of 0.30 to 0.50 m < ³ & Spherical copper sulfate sulphate and manganese sulfate powder having an average particle diameter of 1 to 100 mu m can be obtained under a spray pressure and an air amount.

In addition, in the first pulverization step (S200) according to another embodiment, a slurry for spray drying is prepared using an evaporation concentrate, and spray drying is performed to obtain a zinc sulfate powder having a more uniform shape and particle size. More particularly, the present invention relates to a spray drying slurry preparation step (S210) in which an evaporation concentrate and an additive are mixed and controlled to have a viscosity of 200 to 700 cps to produce a spray-drying slurry, and a spray drying step (S220 ).

In the spray drying slurry preparation step (S210), a spray drying slurry having a viscosity of 200 to 700 cps is prepared by mixing any one of additives of a dispersant, a binder, a plasticizer, an antifoaming agent and a combination thereof in an evaporated concentrate.

The dispersing agent prevents the aggregation between the components during the preparation of the spray-drying slurry and during the spray-drying, thereby making it possible to obtain a powder having a uniform shape and a uniform particle size. The kind of the dispersant is not limited as long as it is for preventing agglomeration, but it is preferable to use a surfactant such as a polycarboxylic acid type, naphthalenesulfonic acid, a phosphate, a polyhydric alcohol ester, a polyester, an amine, a sulfonic acid, May be used. When the dispersant is added in an amount of less than 0.1 parts by weight, it is difficult to expect an anti-aggregation effect. When the dispersant is added in an amount of more than 0.5 parts by weight, It is preferable that it does not deviate from the above range because it forms a thick granular surface layer while moving to the surface of the droplet upon drying.

The binder improves the bonding property between the particles to improve the viscosity, and the binder is not limited as long as it is for improving the viscosity, but specific examples include PVA, PVP, PEO, and combinations thereof . The binder is added in an amount of 1 to 5 parts by weight based on 100 parts by weight of the evaporated concentrate. When the binder is added in an amount of less than 1 part by weight, viscosity improvement effect is hardly expected. When added in an amount exceeding 5 parts by weight, , The binder is separated into the surface layer of the granules to form a hard surface layer and the granules are disintegrated according to the pressure difference between the inside and outside of the granule surface. As a result, it becomes difficult to obtain uniformly shaped particles, desirable.

The plasticizer prevents the viscosity of the slurry for spray drying from becoming too high and lowers the glass transition temperature so that breakage of the interface of the granules is easily caused during spray drying, thereby increasing sinterability. The plasticizer may be any one of glycol, glycerin, and phthalate, but is not limited thereto. Preferred examples include PEG, TEG, and combinations thereof. The plasticizer is added in an amount of 0.1 to 0.5 parts by weight based on 100 parts by weight of the evaporated concentrate. When the plasticizer is added in an amount of less than 0.1 part by weight, viscosity control effect is hardly expected. When the plasticizer is added in an amount exceeding 0.5 parts by weight, It is preferable that the particle size of the particles is not deviated from the range of addition because the particle size of the particles is small and cohesion between particles may occur.

The defoaming agent prevents bubbles generated in the slurry for spray drying by the reaction and stirring of an organic material such as a plasticizer and a binder to prevent shape distortion of particles due to bubbles. The defoaming agent is a low-alcohol, mineral oil Based, polymer-based, polymer-based, silicone-based, non-silicone-based polymer antifoaming agents and combinations thereof. The defoaming agent may be added in an amount of 0.01 to 0.3 parts by weight based on 100 parts by weight of the evaporated concentrate.

In the spray drying step S220, the spray drying slurry is spray-dried and pulverized using a spray drying apparatus. The spray drying apparatus has an inlet temperature of 150 to 170 DEG C, an outlet temperature of 90 to 105 DEG C, 10 kPa, and the amount of hot air is set to 0.30 to 0.50 m ³ / min. Spherical copper sulfate and manganese sulfate powder having an average particle diameter of 1 to 50 μm can be obtained at the inlet temperature, outlet temperature, spray pressure and air volume .

If the inlet temperature of the spray drying apparatus is less than 150 ° C and the outlet temperature is less than 90 ° C, the granules are not properly formed and the granules do not sufficiently dry to cause agglomerates to form agglomerates, The granules adhere to the chamber wall of the spray dryer.

If the inlet temperature of the spray dryer exceeds 170 ° C and the outlet temperature exceeds 105 ° C, the granules may have a non-uniform shape or non-spherical granules.

The spray pressure for spraying the slurry is preferably from 5 to 10 kPa. If the spray pressure is less than 5 kPa, the slurry is not sufficiently sprayed or exists in a bulk phase, so that it is difficult to form granules and drying property is lowered. It is preferable that the shape of the granules does not deviate from the above range because it can have an irregular shape or a non-uniform shape.

Hot-air-air quantity is 0.30 to 0.50m ³ / min is preferred, with 0.30m ³ / min different from the non-dried granules present is less than generate the other drying the granules and agglomeration or pressing, and can be attached to the inner wall of the spray device, 0.50m ³ / Minute, the physical properties of the granules deteriorate or have a non-uniform shape.

The second reaction step (S300) is a step of reacting the steelmaking dust and the sulfuric acid solution to leach out the zinc and iron contained in the steelmaking dust to obtain an extrudate containing zinc sulfate and iron sulfate.

In this case, the second reaction step (S300) may include zinc precipitation as the raw material, or iron precipitation obtained through the de-ironing process in the first raw material pretreatment step (S100), or zinc, copper and manganese obtained in the solvent extraction (Hereinafter, the raw material to be added to the second reaction step is described as the second raw material).

The second reaction step (S300) may include a second raw material pretreatment step of washing and pulverizing the second raw material before the reaction with the sulfuric acid solution.

More specifically, the second raw material pretreatment step includes washing the second raw material 1 to 5 times, and pulverizing the second raw material that has been washed with water to an average particle size of 10 to 50 μm using a wet ball mill do.

Iron and zinc are contained in the steelmaking dust in a large amount and impurities such as Cl, Na, K, and Ca are included. Among them, Cl prevents dioxin in the acid leaching process, And alkali metals such as Na and K are not easily removed from the solution phase due to high solubility, and Ca, which is an alkaline earth metal, increases the consumption of acid. Since the impurities interfere with the reaction with the sulfuric acid aqueous solution and the filtration, the efficiency of obtaining zinc sulfate, iron sulfate and manganese sulfate can be improved through removal of impurities and washing with water.

In the washing step, the second raw material may be subjected to simple washing with water 1 to 5 times. However, sodium hydroxide at a concentration of 1 to 2N is added to a mixture of the second raw material and water at a weight ratio of 1: 1 to 2, And the mixture is stirred for 30 to 90 minutes and filtered to obtain a second raw material from which impurities have been removed.

In the second reaction step (S300) according to the first embodiment, a sulfuric acid solution is added to the second raw material, zinc and iron are leached out in a single step, and an extract solution containing zinc sulfate and iron sulfate in a mixed form can be obtained have.

At this time, the sulfuric acid solution having a concentration of 1 to 3N is used, and the second raw material and the sulfuric acid solution are mixed at a weight ratio of 1: 1 to 3, and reacted at 40 to 60 ° C for 60 to 180 minutes to leach zinc and iron.

In the second reaction step S300 according to the second embodiment, a sulfuric acid solution is added to the second raw material to form a zinc leaching reaction in which zinc is leached, and the zinc leaching reaction is filtered to remove sulfuric acid from the precipitate and the zinc sulfate leaching solution (S310) of obtaining a zinc leaching solution and a step (S320) of obtaining an iron sulfate leach solution obtained by adding a sulfuric acid solution to the precipitate to obtain an iron sulfate leaching solution in which iron is leached.

The iron present in the steelmaking dust has a lower ionization degree than zinc, and the reaction with sulfuric acid is started relatively late due to the presence of zinc in the reaction with sulfuric acid. When excess sulfuric acid is injected at once, It is difficult to be converted into iron, and there is a limit in that the reaction time for obtaining iron sulfate is prolonged.

In other words, it was difficult to produce sulfuric acid in a balanced manner by adding sulfuric acid to the steelmaking dust, and in order to increase the amount of sulfuric acid simply to produce iron sulfate, impurities and reduction of reaction efficiency were limited there was.

In the second reaction step (S300) according to the second embodiment, irregularities in the production rate and the production amount due to the difference in ionization tendency are solved during the reaction with the sulfuric acid solution, and the generation of impurities is prevented to ultimately lead to high purity zinc sulfate and sulfuric acid To obtain iron, a zinc sulfate leach solution is obtained first, and a sulfuric acid solution is added to the remaining precipitate to obtain an iron sulfate leach solution.

In the step of obtaining zinc sulfate leach solution (S310), 90 to 98% of concentrated sulfuric acid and the second raw material are mixed at a weight ratio of 1: 1 to 2 and reacted for 10 to 60 minutes to form a zinc leached reaction product in which zinc is leached. The reaction product is filtered to separate the zinc sulfate leaching solution and the precipitate.

The precipitate contains an iron component that has not reacted with the unreacted sulfuric acid. The precipitate is added to the iron sulfate leach solution obtaining step (S320) to form an iron sulfate leach solution, and the zinc sulfate leaching solution is subjected to a heavy metal removal step (S400) The heavy metal is removed.

In the step (S320) of obtaining an iron sulfate leached solution, a sulfuric acid solution is injected into the precipitate to obtain an iron sulfate leached with iron leaching. More specifically, 30 to 50 parts by weight of precipitate is added to 100 parts by weight of 2 to 3N sulfuric acid aqueous solution And the mixture is reacted for 30 minutes to 90 minutes to form an iron leached reaction product in which iron is leached, and the iron leaching reaction product is filtered to obtain an iron sulfate leach solution.

At this time, the step (S320) of obtaining the iron sulfate leached solution may further include a step of removing calcium sulfate contained in the precipitate and a step of selectively separating iron before the sulfuric acid solution is added to the precipitate.

The precipitate contains heavy metals such as calcium sulfate, lead, cadmium, chromium, nickel, and impurities in addition to iron. In order to obtain a higher purity iron sulfate extract, calcium sulfate contained in the precipitate is removed, And a step of separating.

In the process of treating steelmaking dust with sulfuric acid solution, a trace amount of calcium contained in the steelmaking dust reacts with sulfuric acid to generate calcium sulfate precipitate, which remains in the precipitate. Calcium sulfate should be removed as it not only makes it difficult to leach iron and react with sulfuric acid, but also acts as an impurity to make it difficult to form a mixed powder having a uniform shape and particle size. However, calcium sulfate is not easy to remove because of its water solubility, and can be removed by converting it into a water soluble form.

More specifically, calcium sulfate and soda ash (sodium carbonate) are reacted to produce calcium carbonate and sodium sulfate. At this time, the calcium carbonate is present in the form of a precipitate, the sodium sulfate is removed by filtration, and the calcium carbonate is reacted with the acid solution to change it into calcium carbonate which is soluble in water.

For this purpose, 0.5 to 5 parts by weight of soda ash is added to 100 parts by weight of a suspension in which the precipitate and water are mixed at a weight ratio of 1: 1 to 2, and the mixture is reacted at 45 to 85 ° C for 30 minutes to 6 hours.

At this time, if the soda ash is added in an amount of less than 0.5 part by weight based on 100 parts by weight of the suspension, the substitution reaction does not occur smoothly and it is difficult to change calcium sulfate into calcium carbonate. When more than 5 parts by weight of soda ash is added to 100 parts by weight of the suspension The soda ash can be added to the soda ash, and the remaining soda ash can act as an impurity. In the post-process heavy metal removal step and the pulverization step, zinc sulfate is reacted with zinc sulfate when mixed with the zinc sulfate leaching solution and the iron sulfate leaching solution, And the yield of zinc sulfate can be lowered, so that it is preferable not to deviate from the above range.

If the reaction temperature is lower than the above-mentioned reaction temperature, the reactivity and the reaction rate are slow, and when the reaction temperature is higher than the above reaction temperature, the effect of increasing reactivity with respect to the reaction temperature increase is insignificant and unnecessary energy consumption occurs. .

If the reaction time is longer than the reaction time, the effect of increasing soda ash and the reactivity is insignificant. In addition to the calcium contained in the sulfuric acid solution, It is preferable that the reaction time is not exceeded because impurities are formed.

The precipitate containing calcium carbonate is reacted with an acid solution to convert it to water-soluble calcium hydrogencarbonate, wherein the acid solution comprises nitric acid, hydrochloric acid, and acetic acid except sulfuric acid. When sulfuric acid is added, the calcium sulfate is regenerated It is preferable not to add sulfuric acid as an acid solution.

At this time, the pH of the acid solution is controlled to 3 to 6, and it is preferable not to deviate from the above-mentioned pH range because calcium carbonate is changed easily from calcium carbonate to calcium carbonate within the above pH range and unnecessary acid reaction is not generated.

When the reaction time is less than 3 hours, the unreacted calcium carbonate remains and acts as an impurity. When the reaction time exceeds 12 hours, the reaction time is increased It is preferable that the reaction time range is not deviated in consideration of the process efficiency because the amount of produced calcium hydrogen carbonate is small.

Calcium hydrogencarbonate is present in a state of being dissolved in water, and the reaction product is filtered to remove the filtrate. As a result, calcium sulfate is removed from the precipitate to leave only the iron component, and the precipitate and the sulfuric acid The reaction efficiency can be improved during the reaction.

In addition, the step (S320) of obtaining the ferrous sulfate leached solution may further include a step of selectively separating the iron contained in the precipitate before the sulfuric acid solution is added to the precipitate.

As a method for separating iron, an alkaline agent is added to a suspension in which water and the precipitate are mixed with 1: 1 to 2 parts by weight of the suspension, and the reaction is carried out for 30 minutes to 120 minutes while controlling the pH to 3 to 5 to form iron To obtain a solution.

At this time, the kind of the alkaline agent is not limited, but specific examples include sodium hydroxide, calcium hydroxide, calcium hydroxide, ammonia and the like, preferably sodium hydroxide of 1 to 2N concentration.

 Iron has a higher reactivity than heavy metals and impurities such as lead, cadmium, chromium, and nickel, and is easily precipitated in the form of hydroxide. Thus, iron can be selectively separated and obtained only by pH control using an alkali agent.

In the heavy metal removal step (S400), a trace amount of heavy metal contained in the leach solution (zinc sulfate leaching solution and iron sulfate leaching solution) is removed.

The zinc sulfate leaching solution and the iron sulfate leaching solution can remove heavy metals by separate processes or remove heavy metals. For example, when the leaching solution is obtained by mixing zinc sulfate and iron sulfate by the second reaction step (S300) according to the first embodiment, the heavy metal is removed at one time, and the second reaction step (S300), when the zinc sulfate leaching solution and the iron sulfate leaching solution are respectively obtained by an independent process, the heavy metal can be removed by a separate process. Of course, even if the zinc sulfate leaching solution and the iron sulfate leaching solution are obtained by independent processes by the second reaction step S300 according to the second embodiment, it is also possible to remove heavy metals by mixing them in the heavy metal removal step.

The heavy metal removal step (S400) according to the first embodiment uses an end-of-life end, and 0.5 to 5 parts by weight of an alumina seed having an average particle diameter of 5 to 50 占 퐉 is added to 100 parts by weight of the leach solution, The mixture is stirred for 90 minutes to precipitate the remaining heavy metals such as lead and cadmium by a cementation reaction, and the heavy metals can be removed by filtration.

When the average particle diameter of the zinc powder is less than 5 탆, the cohesion is generated and the reactivity is lowered. When the average particle diameter of the zinc powder is more than 50 탆, It is preferable to use zinc powder within a particle diameter range.

In addition, 0.5 to 5 parts by weight of zinc sulfate is added to 100 parts by weight of the second leach solution. If zinc sulfate is added in an amount of less than 0.5 part by weight, heavy metals which have not reacted with cementation may remain. If zinc sulfate is added in an amount exceeding 5 parts by weight , The increase in the removal rate of heavy metal with respect to the end-of-the-year end-use amount is insignificant, and the residual zinc salt may cause the purity of the zinc sulfate powder and the iron sulfate powder to be lowered.

The precipitated heavy metal is removed through filtration, and the method of filtering the heavy metal is not limited, but a filter press can be used more preferably.

A filter press is a pressure filtration device in which a substance to be filtered is placed between filter cloths and pressure is applied to perform solid-liquid separation. The operation method thereof is well known and its detailed description is omitted.

In the present invention, a filter press having a plate size of 700 mm, a chamber volume of 200 to 500 L / cycle and a processing rate of 1.5 Ton / Hr per hour was used, and a filtration process was performed under a filter cloth size of 50 to 1000 mesh and a pressure of 2 to 15 kgf / .

More specifically, when the size of the filter cloth exceeds 1000 mesh, frequent occlusion of the filter cloth occurs and the filtration efficiency decreases. If the filter cloth size is less than 50 mesh, it is difficult to filter heavy metals and remove the filter cloth. Do.

If the pressure of the filter press is less than 2 kgf / cm 2, it is difficult to remove heavy metals. If the pressure exceeds 15 kgf / cm 2, it is difficult to expect an increase in solid-liquid separation efficiency due to an increase in pressure. It is preferable not to deviate from the above-mentioned pressure range.

In the heavy metal removal step (S400) according to the second embodiment, a surfactant is added to the leaching solution to form an aggregate in which a heavy metal is adsorbed by an electrostatic attraction, and the precipitate is filtered after cooling sedimentation to remove the heavy metal .

The surfactant may be an anionic surfactant, a nonionic surfactant, a cationic surfactant, an amphoteric surfactant, or a combination thereof, although the surfactant may have adsorbability to heavy metals such as lead and cadmium. , And more preferably an anionic surfactant capable of adsorbing and aggregating heavy metal lead, cadmium and the like of a cation effectively by an electrostatic attractive force and separating the precipitate can be used.

The anionic surfactant may be selected from a carboxylic acid salt, a sulfonic acid salt, a sulfuric acid ester salt, a phosphoric acid ester salt and a combination thereof. Specific examples thereof include sodium dodecyl sulfate (SDS), ammonium lauryl (ALS), sodium lauryl ethylenesulfate (SLES), linear alkyl benzene sulfonate (LAS), alpha -olefin sulfonate (AOS) alkyl But is not limited to, any one of Alkyl Sulfate (AS), Alkyl Ether Sulfate (AES), Sodium Alkane Sulfonate (SAS), and combinations thereof. More preferably, sodium dodecyl sulfate (SDS) can be used.

If the amount of the surfactant to be added is less than the above range, it is difficult to adsorb and separate heavy metals. When the amount of the surfactant is more than the above range, the amount of the heavy metal The effect of adsorption and separation is insignificant, and therefore it is preferable that the above range does not deviate from the above range.

The surfactant may be performed for 2 to 6 hours from the time of input to separation of the heavy metal adsorbent aggregate. The initial amount of the surfactant (30% of the total reaction time from the start) during the entire reaction time is from 150 to 300 The mixture was stirred at rpm to uniformly disperse the surfactant in the suspension. Stirring was stopped when the total reaction time was more than 30% to 70%, and the mixture was allowed to stand at room temperature (20 to 25 ° C) Has a time for adsorbing stably to form an aggregate, and coagulates are precipitated by cooling at 3 to 5 캜 until the total reaction time exceeds 70% to the end point.

The cooled sedimented aggregates are obtained by solid-liquid separation and filtration using an ion-exchange resin. The aggregates obtained are dissolved in cold water at 30 to 50 DEG C and repeatedly washed with water to separate heavy metal components adsorbed on the aggregates, The heavy metal component can be separated and separated.

In the second pulverization step (S500), the leaching solution (zinc sulfate leaching solution and iron sulfate leaching solution) from which the heavy metal is removed is pulverized to obtain zinc sulfate powder and manganese sulfate powder.

The pulverization process may comprise high temperature drying or spray drying and preferably the evaporation is concentrated by evaporation at 100 to 150 ° C for 30 minutes to 12 hours prior to the high temperature drying or spray drying process so as to have a specific gravity of 1.3 to 1.6 And may further comprise an evaporation concentration step.

Wherein the spray drying apparatus is set to have an inlet temperature of 150 to 170 DEG C, an outlet temperature of 90 to 105 DEG C, a spray pressure of 5 to 10 kPa, and a hot air flow rate of 0.30 to 0.50 m < ³ & Spherical zinc sulfate and iron sulfate powder having an average particle size of 1 to 100 mu m can be obtained under the spraying pressure and the air amount.

In the second pulverization step S500 according to another embodiment, the slurry for spray drying is prepared using an evaporation concentrate, and spray drying is performed to obtain a zinc sulfate powder having a more uniform shape and particle size. More particularly, the present invention relates to a spray drying slurry preparation step (S510) for preparing a spray-drying slurry by mixing the evaporation concentrate and an additive and controlling the slurry to have a viscosity of 200 to 700 cps, and a spray drying step (S520 ).

In the spray drying slurry preparation step (S510), 0.5 to 5 parts by weight of an additive of any one of a dispersant, a binder, a plasticizer, a defoaming agent and a combination thereof is mixed with 100 parts by weight of the evaporated concentrate, Thereby producing a slurry for use.

The content and the kind of the additive are applied in the same manner as described above in the first pulverization step (S200), and a detailed description thereof will be omitted.

In the spray drying step (S520), the spray drying slurry is spray-dried and pulverized using a spray drying apparatus. The spray drying apparatus has an inlet temperature of 150 to 170 DEG C, an outlet temperature of 90 to 105 DEG C, 10 kPa and a hot air volume of 0.30 to 0.50 m ³ / min. Under the inlet temperature, outlet temperature, spray pressure and air volume, spherical zinc sulfate and iron sulfate powder having an average particle diameter of 1 to 50 μm can be obtained have.

1. Preparation of zinc sulfate and iron sulfate powder

1-1. Pretreatment of steelmaking dust

Steelmaking dust (1 kg) was prepared from the steelmaking dust recycling company A and 250 g of iron precipitate (250 g) obtained from the copper waste and manganese waste decarburization process described below were prepared and mixed.

The properties of the raw materials were analyzed using XRF (MXF-2400). As a result of the analysis, the ingredients were measured as shown in Table 1 below.

The raw materials and water were mixed at a weight ratio of 1: 1, and sodium hydroxide was added at a concentration of 1.5 N to maintain the pH at 10, and the mixture was stirred for 30 minutes, and impurities were removed by using a filtration apparatus. ICP-OES (using Varian Vista-MPX) confirmed the change of impurities before and after washing the raw material. The contents of zinc, iron, and heavy metals were almost unchanged. The contents of impurities Cl, Na, K and Ca decreased by 97.3%, 82.1% and 67.5%, respectively, by 35.1%.

The raw material from which the impurities were removed had an average particle size of about 16 mu m and was ground to an average particle size of about 9 mu m using a wet ball mill to improve the reactivity with the aqueous sulfuric acid solution.

1-2. Preparation of zinc sulfate and iron sulfate leachate

The efficiency of leaching of zinc and iron over time was examined by varying the concentrations of sulfuric acid and sulfuric acid. The steelmaking dust and sulfuric acid were injected at a weight ratio of 1: 1, and the leaching reaction was performed for 10 minutes to 90 minutes. The reaction temperature was maintained at 45 ° C.

The leaching efficiency of zinc and iron was confirmed by measuring the zinc content and the content (wt%) in the filtrate after filtration of the leach solution after completion of the reaction (as shown in Table 2).

As a result, it was confirmed that leaching of zinc and iron rapidly proceeded with higher sulfuric acid concentration, and it was confirmed that there was a difference in leaching contents due to the difference in reactivity between zinc and iron and sulfuric acid. In the case of using concentrated sulfuric acid (90 ~ 98%), the leaching rate of zinc was about 96 ~ 98.5% in 10 min of reaction time, whereas the leaching rate of iron was 33 ~ 47% after 90 min of reaction time gave.

Through this process, it is possible to react zinc, which has a higher leaching rate, for a short time than leaching zinc and iron in a single process in case of reaction with steelmaking dust and sulfuric acid solution, to separate unreacted iron after separate zinc sulfate leaching solution, Suggesting that it could be efficient.

The reaction mixture was reacted with 98% sulfuric acid for 60 minutes to separate the zinc sulfate leaching solution and the precipitate.

Prior to selectively obtaining iron contained in the precipitate, the calcium sulfate contained in the precipitate was removed to improve the leaching and reactivity of iron.

In pretreatment of steelmaking dust, Ca of impurities decreased by pH control and washing, but did not show satisfactory removal rate. It can be deduced that Ca can be contained in the reactant, and Ca is present in the precipitate by generating calcium sulfate which is not easily removed in the reaction with sulfuric acid. The calcium sulfate contained in the precipitate was considered to be necessary to remove iron because it made it difficult to leach out and to increase the consumption of acid.

To remove the calcium sulfate contained in the precipitate, the precipitate and water were mixed at a weight ratio of 1: 1 to form a suspension. 15 g of soda ash was added per 100 g of the suspension, and the mixture was reacted at 80 캜 for 3 hours to form calcium sulfate , And the sodium sulfate filtrate was separated. The obtained precipitate containing calcium carbonate and water were mixed and suspended in a weight ratio of 1: 1, and then nitric acid at a concentration of 2N was added thereto to adjust the pH to 4, and the reaction was continued at a temperature of 60 ° C for 30 minutes, And then converted into the form of hydrogen calcium. Thereafter, Ca was reduced to 94.31% through ICP-OES (Varian Vista-MPX).

 Then, in order to selectively obtain iron contained in the precipitate, sodium hydroxide was added to a suspension of 1: 1 mixture of precipitate and water, and iron was precipitated in the form of hydroxide by reacting for 30 minutes while controlling the pH to 4. The precipitated iron was then obtained and reacted with an aqueous sulfuric acid solution to form an iron sulfate leach solution.

In order to confirm the leaching rate of iron according to the concentration of aqueous sulfuric acid solution, the leaching reaction was carried out as shown in Table 3 below, and after the completion of the reaction, the leaching solution was filtered and the content of iron contained in the filtrate was measured and confirmed ).

As a result, the iron content in the iron sludge began to decrease rapidly from the concentration of 2N, and the iron content in the iron sludge continued to decrease with increasing sulfuric acid concentration up to the concentration of 3N. However, It was judged that it would be inefficient to use an aqueous solution of sulfuric acid exceeding the concentration of 3N. Hereafter, the experiment was conducted using an iron sulfate leach solution reacted with a sulfuric acid aqueous solution having a concentration of 2.5N.

1-3. Heavy metal removal

Zinc powder was added to remove heavy metals (Pb, Cd, As) contained in the leach solution (zinc sulfate leaching solution + iron sulfate leaching solution). Zinc powder having an average particle size of 1, 5, 25, 50, 60, and 100 ㎛ in average particle size was put in and ICP-OES (using Varian Vista-MPX) was added to check the heavy metal removal efficiency according to the average particle size of the zinc powder. The heavy metal content (wt%) contained in the leach solution before and after the reaction was confirmed and the heavy metal removal rate (%) was calculated (as shown in Table 4). The zinc powder was added in an amount of 3 g per 100 g of the reaction filtrate, and the reaction time was 60 minutes. The reaction was carried out at 100 rpm for 30 minutes in the initial reaction time. After the reaction, the crystals formed by the cementation reaction were removed using a filter press (Note). The filtration process was carried out under a plate size of 700 mm, a chamber volume of 200 l / cycle, a filtration size of 500 mesh, and a pressure of 10 kgf / cm 2.

As a result, it was confirmed that when the zinc powder having an average particle size of 1 μm, 60 μm and 100 μm was added, the heavy metal removal rate did not become relatively high. When the particle size was too small, It was judged that the reaction area was reduced and the reactivity was lowered. It was judged that it would be preferable to use zinc powder having an average particle diameter of 5 mu m to 50 mu m.

The removal efficiency of heavy metals was about 10 ~ 40% when filter press was used, compared to the solid - liquid separation using vacuum concentration. It was considered that it would be desirable to use a filter press with high measurement.

Surfactants were used as an alternative method to remove heavy metals.

25 g of an anionic surfactant SDS (Sodium Dodecyl Sulfate) was added per 100 g of the leach solution. The mixture was stirred at 150 rpm for 30 minutes and then at 120 rpm for 30 minutes. The aggregates were visually observed, and the formed aggregates were subjected to cold precipitation treatment at 4 캜 for 90 minutes, and the aggregates were removed through a filtration process using MF (Innomedec Co., Ltd., 5 탆), and the removal efficiency of heavy metals was confirmed. The heavy metal content (wt%) contained in the reaction filtrate before and after the reaction was determined using ICP-OES (Varian Vista-MPX) and the removal rate (%) of heavy metal was calculated.

As a result, the removal efficiencies of heavy metals Pb, Cd and As contained in the reaction filtrate were 98.92%, 97.11%, and 99.32%, respectively, showing excellent heavy metal removal efficiency.

1-4. Powdered

The leached liquid from which the heavy metal was removed was dried at 130 캜 for 24 hours to obtain a mixed powder of zinc sulfate and iron sulfate having a moisture content of 10 wt% (Comparative Example 1). The shape and average particle size distribution of the obtained mixed powders were checked. As a result, the powder had uneven shapes such as angular shape and flake shape. The particle size distribution was broadly confirmed from about 50 μm to 650 μm, and the average particle size was 135.1 μm. The spray drying process was performed to obtain mixed powder having more uniform shape and particle size distribution.

The leachate from which the heavy metal was removed was concentrated by evaporation at 130 DEG C for 3 hours to obtain an evaporated concentrate having a specific gravity of 1.35. PVA as a binder, PEG as a plasticizer, and ethanol as an antifoaming agent were prepared as an additive for preparing a spray-drying slurry.

0.3 g of a dispersant, 3 g of a binder, 0.3 g of a plasticizer and 0.01 g of an antifoaming agent were mixed with 100 g of the above-mentioned evaporated concentrate to prepare a spray-drying slurry having a viscosity of 225 cps at 25 ° C (Example 1). The slurry for spray drying was formed by firstly mixing the evaporated concentrate and the dispersant, adding and mixing the binder and the plasticizer in the second place, and then defoaming the mixture by injecting the defoamer in the third order.

In order to confirm the compositional characteristics of the spray-drying slurry and the spray drying characteristics according to the spraying pressure, the formulations and the average particle size were measured as shown in Table 5, spray-dried. At this time, the inlet temperature of the spray drying apparatus was set to 150 ° C, the outlet temperature to 100 ° C, and the hot air amount to 0.50m ³ / min.

(5 points for hollow spherical particles: 5 points, 4 points for hollow spherical particles: ~ 30%, and ~ 50% for hollow spherical particles) Observed: 3 points, when the flake phase and breakdown particles are observed at ~ 10%: 2 points, when the flake phase and breakdown particles are observed at more than 10%: 1 point)

The mixed powders according to Examples 1 and 2 had a spherical shape and their particle size distributions were 2.9 to 25.33 mu m, 1.24 to 35.4 mu m, and average particle diameters were 7.3 mu m and 8.9 mu m, respectively.

It was confirmed that the constituents of the additive, the composition ratio and the spraying pressure are closely related to the shape and the average particle size. In order to obtain iron sulfate powder having uniform shape and particle size, the drying method, the composition characteristics at spray drying, Conditions and the like.

The mixed powders were mixed at a mixing ratio of about 48% of iron sulfate and about 52% of zinc sulfate, and the purity was 99.45%.

2. Obtaining copper sulfate and manganese sulfate from copper waste and manganese waste

2-1. Pretreatment of copper waste and manganese waste

Copper sludge and manganese waste produced from PCB H from copper wire waste were obtained from Company A and from Company B. Ferromanganese Electric Furnace dust obtained from Company B was obtained. 1 by weight.

The analysis of the raw materials was carried out using XRF (MXF-2400). As a result of the analysis, the copper wastes contained 32.4 wt% of copper, 7.3 wt% of iron, other chlorides, heavy metals, It was confirmed that the waste contained 35.6wt% of manganese, 11.3wt% of zinc, and other chloride and heavy metals.

Copper waste and manganese waste were pulverized to 9 탆 and 11 탆 respectively using a wet ball mill, and then pulverized and water were mixed at a weight ratio of 1: 1 to form a mixed solution. Thereafter, 1.5 N sodium hydroxide was added to the mixed solution to adjust the pH to 4 to 4.5, and the reaction was carried out for 60 minutes to precipitate iron contained in the raw material, which was then removed by filtration. As a result of analysis of the components of copper waste and manganese waste after iron removal, iron removal rate was 96.4% and 93.8%, respectively, and most of chloride was removed. Copper and manganese contents were almost not changed.

2-2. Solvent extraction

1,000 g of D2EHPA (SYTEK), an oxime-based solvent extractant, was added to 500 g of an aqueous solution obtained by mixing pretreated manganese waste and water at a weight ratio of 1: 2, stirred at 25 to 30 ° C for 1 hour at a stirring speed of 150 rpm, To give a manganese organic phase. During the extraction of the solvent, the pH was maintained at 2 to 3 by the addition of NaOH.

Subsequently, the impurities contained in the manganese organic phase were transferred to the aqueous phase by using a sulfuric acid solution, and the manganese was back-extracted with the aqueous phase (sulfuric acid aqueous solution) and the reaction was terminated by mixing the scrubbed organic phase and the aqueous 3N sulfuric acid solution in a volume ratio of 1: An aqueous manganese sulfate solution was obtained using a post-settler.

The pre-treated copper waste was subjected to solvent extraction using 5-dodecylsilycidoloxime (trade name: LIX860) of Henkel, a solvent extracting agent. Other solvent extraction conditions were the same as the solvent extraction method of the manganese waste described above to obtain an aqueous solution of copper sulfate.

2-3. Powdered

The aqueous solution of copper sulfate and the aqueous solution of manganese sulfate were dried at 135 DEG C for 48 hours to obtain a mixed powder of manganese sulfate and copper sulfate having a water content of 13 wt%. As a result of checking the shape and average particle size distribution of the obtained mixed powder, it showed uneven shapes such as angular shape and flake shape. The particle size distribution was broadly confirmed from about 60 탆 to 520 탆, and the average particle size was 43.5 탆. The spray drying process was performed to obtain mixed powder having more uniform shape and particle size distribution.

The aqueous solution of copper sulfate and the aqueous solution of manganese sulfate were concentrated by evaporation at 140 占 폚 for 12 hours to obtain an evaporated concentrate having a specific gravity of 1.42 to prepare a slurry for spray drying under the same conditions as those of the spray drying slurry described in Examples 1-4. Respectively.

At this time, a mixed powder of copper sulfate and manganese sulfate was obtained by spray-drying at an inlet temperature of 150 ° C, an outlet temperature of 100 ° C and a hot air amount of 0.50 m ³ / min and spray-drying at a spray pressure of 10 Kpa.

It was confirmed that the particle size distribution was 3.2 to 39.1 탆 and the average particle diameter was 8.8 탆. Hollow spherical particles were not identified in the shape of the powder, and it was confirmed that the powder had a spherical shape, and the purity was 99.11%, indicating high purity.

The yield and purity of complex minerals and the yield and purity of complex minerals produced by the process according to the present invention were compared when a sulfuric acid solution was reacted with industrial waste mixed raw materials (copper waste, manganese waste and steel dust).

The copper waste, manganese waste, and steelmaking dust described in the above-described examples were mixed in a weight ratio of 1: 1: 1, and the components of the mixed raw materials were identified through XRF (MXF-2400).

The mixed raw materials were washed with water and pulverized to an average particle size of about 9 mu m using a wet ball mill. 30 g of 98% concentrated sulfuric acid was added per 100 g of the pretreated raw material and reacted for 90 minutes. After the filtrate was removed, the content (g) of zinc, iron, copper and manganese contained in the precipitate was determined, and zinc sulfate, iron sulfate, .

As a result, the removal rates of zinc, iron, manganese and copper before and after the sulfuric acid reaction were found to be 98.2%, 93.4%, 89.7%, and 15.9%, respectively. As a result, zinc, Iron and manganese sulfate could be converted, but no satisfactory results were obtained with copper.

Further, when heavy metals were removed by the same conditions and methods as those of the above-described example, it was confirmed that the heavy metal removal efficiency also had a half of the heavy metal removal efficiency according to the examples, so that industrial wastes were mixed and reacted with sulfuric acid at once, It is preferable to perform the process in consideration of the reactivity of the main components.

Accordingly, in the present invention, it was attempted to obtain composite minerals in high purity and high yield by performing the reaction of steel-making dust containing a large amount of zinc and iron having relatively high reactivity, copper waste and manganese waste in separate processes.

However, it is considered that it is desirable to perform the reaction by separating the steelmaking dust and manganese waste in consideration of the process efficiency, and improve the leaching characteristics of zinc and iron, which are the main components of steelmaking dust, Copper and manganese were selectively obtained from copper wastes and manganese wastes, so that the yield and purity of copper sulfate and manganese sulfate could be increased. Thus, it was confirmed that it was efficient to produce complex minerals by the production method of the present invention.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is clearly understood that the same is by way of illustration and example only and is not to be taken as limiting the scope of the present invention. The present invention can be variously modified or modified. The scope of the invention should, therefore, be construed in light of the claims set forth to cover many of such variations.

Claims (5)

A method for producing a composite mineral comprising zinc sulfate, iron sulfate, copper sulfate and manganese sulfate from steelmaking dust, manganese waste and copper waste,
A first reaction step (SlOO) in which a copper organic phase and a manganese organic phase are obtained by solvent extraction of copper waste and manganese waste, and a reverse reaction is carried out using an aqueous sulfuric acid solution to obtain an aqueous solution of copper sulfate and an aqueous solution of manganese sulfate;
A first pulverizing step (S200) of obtaining a copper sulfate powder and a manganese sulfate powder by pulverizing the aqueous solution of copper sulfate and the aqueous solution of manganese sulfate;
A second reaction step (S300) of reacting the steel making dust with a sulfuric acid solution to obtain an extract solution containing zinc sulfate and iron sulfate;
A heavy metal removal step (S400) for removing the heavy metal contained in the leach solution;
And a second pulverization step (S500) of pulverizing the leached solution from which the heavy metal is removed to obtain a zinc sulfate powder and a manganese sulfate powder,
The first reaction step (SlOO)
A raw material pre-treatment step (S110) of de-ironing copper waste and manganese waste;
The copper organic phase is back-extracted with an aqueous solution of sulfuric acid to form a copper organic phase. The copper organic phase is recovered by back extraction using an aqueous solution of sulfuric acid, A step (S120) of obtaining an aqueous solution of copper sulfate to form an aqueous solution;
The manganese organic phase is back-extracted with an aqueous solution of sulfuric acid to form a manganese organic phase. The manganese organic phase is extracted with a sulfuric acid aqueous solution to obtain a manganese waste aqueous solution, (S130) of obtaining an aqueous solution of manganese sulfate to form a manganese aqueous solution
A method for producing a composite mineral from industrial wastes.
delete The method according to claim 1,
The raw material preprocessing step (S110)
The copper waste and the manganese waste are pulverized to 5 to 50 탆, and then an alkali agent is added to a mixture of the pulverized raw material and water at a ratio of 1: 1 to 2: 1 to adjust the pH to 3 to 5 to form an iron precipitate, Characterized in that the iron precipitate is removed by solid-liquid separation
A method for producing a composite mineral from industrial wastes.
The method according to claim 1,
The second reaction step (S300)
A step (S310) of obtaining a zinc sulfate leaching solution for separating a precipitate and a zinc sulfate leaching solution by filtering the zinc leaching reaction product by injecting a sulfuric acid solution into the steelmaking dust to form a zinc leaching reaction product leached with zinc;
(S320) of obtaining an iron sulfate leach solution obtained by adding a sulfuric acid solution to the precipitate to obtain an iron sulfate leaching solution in which iron is leached
A method for producing a composite mineral from industrial wastes.
The method according to claim 1,
The heavy metal removal step (S400)
Characterized in that heavy metals are removed by using an agate of 5 to 50 mu m
A method for producing a composite mineral from industrial wastes.

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