KR101780473B1 - Recovering method of valuable metal from used denitration catalyst, manufacturing method of ferroalloy and ferroalloy manufactured thereby - Google Patents

Abstract

One embodiment of the present invention provides a method for separating and recovering valuable metal using a wasted denitrification catalyst and a mill scale, comprising: a step of manufacturing a mixture containing the mill scale, the wasted denitrification catalyst, an aluminum containing substance, a sodium chlorate (Na_CI_O_3), and a calcium compound; and a step of reduced-melting the manufactured mixture and separating the generated slag and an alloy. The present invention adds values to a resource from an industrial waste.

Description

TECHNICAL FIELD The present invention relates to a method for recovering and recovering a valuable metal from a waste denitration catalyst using a mill scale, a method for producing an iron alloy, and an iron alloy produced from the waste denitration catalyst using the mill scale. BACKGROUND ART [0002]

The present invention is a, more particularly, mill scale and contain the waste removal catalyst aluminum material and sodium chlorate (NaClO ₃₎ relates to a method for recovering separate the valuable metals, such as titanium, tungsten, vanadium from the mill scale, and waste removal catalyst And a method of concentrating and recovering iron by utilizing iron as a trapping metal of a valuable metal such as titanium, tungsten, and vanadium, and an iron alloy produced thereby.

The mill scale, an industrial waste produced in the hot rolling process of the steelmaking process, contains iron oxide (including FeO, Fe ₃ O ₄ and Fe ₂ O ₃ ) containing approximately 70-73 wt% of iron. On the other hand, the waste denitration catalyst, which is an industrial waste discharged after being used to remove nitrogen oxides from the exhaust gas from a power plant, contains a large amount of valuable metals and is a subject to be recovered. The content of the waste denitration catalyst varies depending on the year of production but is approximately 65 to 70 wt% of titanium oxide (TiO ₂ ), 5-10 wt% of tungsten oxide (WO ₃ ), 1 to 10 wt% of vanadium oxide (V ₂ O ₅ ) It is known that it contains 5 wt%.

Titanium, tungsten, vanadium and the like contained in the waste denitration catalyst may be used as raw materials for ferro-titanium, ferro-tungsten, ferrovanadium and the like, which are used as an alloy raw material for special steel. Particularly, tungsten is a tool steel Since it can be used as a cemented carbide raw material, it is a very bad resource to be treated as industrial waste. Therefore, in order to maximize resource utilization, reuse as an industrial raw material may be required for the national economy, and recycling the industrial raw materials with high added value may be very useful in terms of effective use of resources.

Currently, methods for recovering titanium, tungsten, and vanadium from a petal-based catalyst include a leaching method using strong acid and a wet processing after salt roasting. Among them, the leaching method using strong acid is disadvantageous in that tungsten and titanium can not be recovered by pulverizing the waste denitration catalyst, leaching vanadium from strong acid, recovering only vanadium, and separating the remainder as residue to use as an aggregate. When the salt roasting temperature is low in the salt roasting process after the salt roasting process, there is a disadvantage in that the leaching rate of the tungsten and vanadium is lowered in the wet process process due to the low conversion ratio of the waste denitration catalyst in the salt roasting process, Although the leaching rate of the denitration catalyst is improved and the leaching rate of tungsten and vanadium is improved in the wet treatment process, there is a disadvantage in that the process efficiency is lowered and the process cost is increased due to the rok wall erosion due to the higher salt roasting temperature.

With regard to related prior arts, a method of separating and recovering vanadium, tungsten, and titanium components from a waste denitration catalyst of Korean Patent Registration No. 10-0573004 and a method of recovering vanadium and tungsten from a leaching solution of denitrification catalyst of Korean Patent No. 10-1452179 There is a recovery method.

Korean Patent Registration No. 10-0573004 Korean Patent Registration No. 10-1452179

SUMMARY OF THE INVENTION The object of the present invention is to solve the above-described problems of the prior art, and an object of the present invention is to provide a method for producing a waste denitration catalyst, which comprises mixing a wheat scale and a waste denitration catalyst with an aluminum-containing substance, sodium chlorate (NaClO ₃ ) titanium dioxide (TiO _2), tungsten (WO _3), and vanadium (V ₂ O ₅₎ components and the reduction of the iron oxide _{(FeO, Fe 3 O 4,} Fe 2 O 3) component contained in the mill scale melting and concentrated recovery oxide To be collected in an iron alloy so that different industrial wastes can be treated at the same time, thereby enabling high value-added resources.

In order to achieve the above object, one aspect of the present invention is a process for producing a mixture comprising a mill scale, a waste denitration catalyst, an aluminum containing material, sodium chlorate (NaClO3) and a calcium compound (step 1); And a step (2) of reducing slag and alloy produced by reducing and melting the mixture, and separating and recovering valuable metals using the dense scale and the waste denitration catalyst.

In one embodiment, the valuable metal may include at least one selected from the group consisting of tungsten, vanadium, and titanium.

In one embodiment, the dense scale or waste denitration catalyst of step 1 may be one that has been pulverized and then dried to a particle size of 1 mm or less.

In one embodiment, the drying of the mill scale of step 1 may be carried out at a temperature of 200 ° C to 300 ° C for 20 minutes to 40 minutes.

In one embodiment, the drying treatment of the waste denitration catalyst of step 1 may be carried out at a temperature of 500 ° C to 800 ° C for 30 minutes to 60 minutes.

In one embodiment, the mixing of the step 1 is carried out by mixing 43.7 parts by weight to 71.9 parts by weight of a mill scale with respect to 100 parts by weight of the waste denitration catalyst; 61.8 parts by weight to 73.4 parts by weight of an aluminum-containing material; Sodium chlorate (NaClO ₃₎ 12.1 parts to 20.2 parts by weight; And 46.1 parts by weight to 56.1 parts by weight of a calcium compound.

In one embodiment, the reducing and melting treatment in step 2 may be performed by charging 0.5 to 2.5 parts by weight of a complexing agent to 100 parts by weight of the mixture.

In one embodiment, the complexing agent in step 2 comprises 90 parts by weight to 110 parts by weight of an aluminum-containing material relative to 100 parts by weight of iron oxide (Fe ₂ O ₃ ); And 90 parts by weight to 110 parts by weight of sodium chlorate (NaClO ₃ ).

In one embodiment, the reduction melting treatment of step 2 may be performed at a temperature of 1800 ° C to 2300 ° C for 2 to 10 minutes.

In order to achieve the above object, another aspect of the present invention provides a method for manufacturing an iron alloy including a valuable metal, which comprises the steps 1 and 2 described above.

In order to achieve the above object, another embodiment of the present invention is produced by the above manufacturing method, and comprises 33.0 wt% to 40.4 wt% of titanium; From 30.6 wt% to 49.4 wt% of iron; 6.2 wt% to 7.6 wt% tungsten; 0.6 wt% to 0.9 wt% of vanadium; Aluminum balance; And an unavoidable impurity, wherein 70 wt% to 85 wt% of titanium is recovered relative to titanium in the waste denitration catalyst of step 1, wherein the titanium is recovered.

In one embodiment, the iron alloy containing the valuable metal may be one in which 95.0 wt% to 99.5 wt% of tungsten or vanadium is recovered relative to tungsten or vanadium in the waste denitration catalyst of step 1, Iron may be recovered in an amount of 95.0 wt% to 99.5 wt% based on the iron of the scale.

In order to accomplish the above object, another aspect of the present invention is a fuel cell system comprising 43.7 parts by weight to 71.9 parts by weight of a dense scale relative to 100 parts by weight of a waste denitration catalyst; 61.8 parts by weight to 73.4 parts by weight of an aluminum-containing material; 12.1 parts by weight to 20.2 parts by weight of sodium chlorate (NaClO3); And 46.1 parts by weight to 56.1 parts by weight of a calcium compound, and a composition for separating and recovering a valuable metal through reduction melting from a mill scale.

According to an aspect of the present invention, there is provided a waste denitration catalyst, which is an industrial waste discharged after being used to remove nitrogen oxides (NO _x ) from exhaust gas from a power plant, and a waste denitration catalyst that is an industrial waste discharged from a hot- It is possible to concentrate and recover the iron, iron, and the like by collecting titanium, tungsten, vanadium, and the like contained in the waste denitration catalyst through iron in the mill scale.

In order to use iron in the mill scale to collect titanium, tungsten, vanadium and the like from the waste denitration catalyst to be used as a raw material of ferro-titanium used as an alloy raw material for special steel, titanium is contained in an amount of 33.0 wt% to 40.4 wt% There is an advantage that one ferro-titanium can be produced.

Furthermore, there is an advantage that the mill scale and the expensive titanium-containing waste denitration catalyst can be quickly melted at a high temperature, thereby remarkably reducing the processing cost in the production of ferro-titanium.

Therefore, the present invention provides an energy saving and recycling technique for maximizing resource utilization of industrial byproducts and industrial raw materials with high added value, and also provides a technology for simultaneously converting abandoned different industrial byproducts into a single process.

It should be understood that the effects of the present invention are not limited to the above effects and include all effects that can be deduced from the detailed description of the present invention or the configuration of the invention described in the claims.

1 to 3 are schematic views illustrating an example of a method for separating and recovering valuable metals using a dense scale and a waste denitration catalyst according to an embodiment of the present invention.
4 is a graph showing the results of X-ray diffraction analysis of the iron alloy of Example 1 performed in Experimental Example 2 of the present invention.
Figs. 5 and 6 are low magnification (140x) and high magnification (1000x) photographs of the iron alloy of Example 1 performed in Experimental Example 2 of the present invention through a scanning electron microscope.
7 and 8 are graphs and photographs showing X-ray mapping results of the iron alloy of Example 1 performed in Experimental Example 3 of the present invention.
9 and 10 are graphs and photographs showing X-ray mapping results of the iron alloy of Example 2 performed in Experimental Example 3 of the present invention.
11 and 12 are graphs and photographs showing X-ray mapping results of the iron alloy of Example 3 performed in Experimental Example 3 of the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS The advantages and features of the present invention and the manner of achieving it will become apparent with reference to the embodiments described in detail below with reference to the accompanying drawings.

It should be understood, however, that the present invention is not limited to the disclosed embodiments, but may be embodied in many different forms and should not be construed as limited to the exemplary embodiments set forth herein. To fully inform the inventor of the category of invention. Further, the present invention is only defined by the scope of the claims.

Further, in the following description of the present invention, if it is determined that related arts or the like may obscure the gist of the present invention, detailed description thereof will be omitted.

According to an aspect of the present invention,

(Step 1) (S10) of preparing a mixture comprising a dense scale, a denitration catalyst, an aluminum-containing material, sodium chlorate (NaClO3) and a calcium compound; And

And a step (S20) of reducing slag and alloy produced (step 2) by subjecting the prepared mixture to a reduction melt treatment, and a method of separating and recovering valuable metals using the dense scale and the waste denitration catalyst.

Hereinafter, the method for separating and recovering valuable metals using the mill scale and the waste denitration catalyst according to an embodiment of the present invention will be described in detail for each step.

In the method for separating and recovering valuable metals using a mill scale and a waste denitration catalyst according to an embodiment of the present invention, the step 1 (S10) is a method of separating and recovering valuable metals using a mill scale, a waste denitration catalyst, an aluminum containing material, sodium chlorate (NaClO ₃ ) A mixture comprising a calcium compound is prepared.

The valuable metal may include at least one selected from the group consisting of tungsten, vanadium, and titanium.

The mill scale of step 1 may be discharged in the hot rolling process of the steel making process.

The mill scale of step 1 may contain 70 wt% to 73 wt% of iron and may include iron oxide (FeO, Fe ₃ O ₄ , Fe ₂ O ₃ ).

The mill scale of step 1 may be pulverized and dried to a particle size of 1 mm or less. If the grain size of the mill scale is more than 1 mm, there may occur a problem that the reduction rate of the iron is lowered in the subsequent step.

The drying process of the mill scale of step 1 is preferably performed at a temperature of 200 ° C to 300 ° C in the air atmosphere for 20 minutes to 40 minutes. If the drying temperature is less than 200 ° C, the mill scale may not be completely dried to trap the valuable metal at the subsequent stage. If the temperature is higher than 300 ° C during the drying process, Although drying time is short, its effect on energy is not great. If the drying time is less than 20 minutes, the drying may be incomplete and a large amount of moisture may remain. If the drying time is longer than 40 minutes, drying may be sufficiently performed. However, Energy loss and waste are increased.

The waste denitration catalyst of step 1 may include titanium oxide (TiO ₂ ), tungsten oxide (WO ₃ ) and vanadium oxide (V ₂ O ₅ ), and specifically includes 65 wt% to 70 wt %; From 5 wt% to 10 wt% tungsten oxide (WO3); And 1 wt% to 5 wt% vanadium oxide (V2O5).

The waste denitration catalyst of step 1 may also be one that has been pulverized and then dried to a particle size of 1 mm or less. If the pulverization is carried out so that the particle size of the waste denitration catalyst exceeds 1 mm, the rate of reduction and melting of the metal is lowered in the subsequent step, so that titanium oxide (TiO ₂ ), tungsten oxide (WO ₃ ) and vanadium oxide ₂ O ₅ ) is lowered and the loss of the slag of the valuable metal becomes large.

The waste denitration catalyst of step 1 may be dried at a temperature of 500 ° C to 800 ° C in an air atmosphere for 30 minutes to 60 minutes. When the drying temperature is less than 500 ° C., there is a disadvantage in that the drying time of the pulverized waste denitration catalyst is increased. When the drying temperature is higher than 800 ° C., the drying time of the pulverized waste denitration catalyst is shortened, not.

If the time of drying the waste denitration catalyst in step 1 is less than 30 minutes, there may occur a problem that a large amount of moisture remains in the dried powder due to incomplete drying. If the drying time is longer than 60 minutes, However, there is a disadvantage in that energy loss and waste are increased as the holding time becomes longer.

The aluminum-containing material of step 1 may be aluminum, a 1000-series aluminum alloy, an Al-Si alloy, a Ti-Al alloy, an Al-Cu alloy, an Al-Mg alloy or an Al- .

The calcium compound of step 1 may be calcium oxide (CaO) and calcium hydroxide (Ca (OH) ₂ ).

The mixing of the step 1 is performed in a ratio of 100 parts by weight of the waste denitration catalyst

43.7 parts by weight to 71.9 parts by weight of a mill scale;

61.8 parts by weight to 73.4 parts by weight of an aluminum-containing material;

12.1 parts by weight to 20.2 parts by weight of sodium chlorate (NaClO3); And

46.1 parts by weight to 56.1 parts by weight of a calcium compound.

If the mill scale of the step 1 is added in an amount of less than 43.7 parts by weight, the amount of iron serving as a trapping metal of tungsten, vanadium and titanium is small in the subsequent step, and the trapping rate of the valuable metal to the iron alloy is decreased If the mill scale is added in an amount exceeding 71.9 parts by weight, the precious metal in the waste denitration catalyst can be recovered. However, as the mill scale content is increased, the addition amount of the aluminum-containing substance and the calcium compound Thereby causing a problem that the process cost is increased.

If the aluminum-containing material is added in an amount of less than 61.8 parts by weight in the mixing of the step 1, there may be a problem that the amount of aluminum is insufficient in the subsequent step and the mill scale can not be sufficiently reduced and melted, Containing material is added in an amount of more than 73.4 parts by weight, the recovery of the valuable metal to the iron alloy can be performed in the subsequent step, but at the same time, the content of aluminum in the iron alloy is increased and the quality of the titanium in the iron alloy is lowered May occur.

If sodium chloride (NaClO ₃ ) is added in an amount of less than 12.1 parts by weight during the mixing of the step 1, a problem may arise that the waste denitration catalyst and the mill scale can not be sufficiently reduced and melted in the subsequent step, and sodium chloride If it is added in an amount exceeding 20.2 parts by weight, it is possible to sufficiently reduce the waste denitration catalyst and the mill scale in the subsequent step, but at the same time, the reaction heat is excessively generated and the molten material is ejected to the slag of the reduced titanium, tungsten, vanadium and iron The problem may arise.

If the calcium compound is added in an amount of less than 46.1 parts by weight during the mixing of the step 1, the melting temperature of the slag generated in the subsequent step is increased so that the reduced iron, tungsten, vanadium and titanium are not trapped in the iron alloy phase, And the loss of titanium, tungsten, vanadium and iron in the slag phase may increase. When the calcium compound is added in an amount of more than 56.1 parts by weight, the melting temperature of the slag is excessively increased in the subsequent step, so that the reduced iron, tungsten, vanadium and titanium are not trapped in the iron alloy phase, Tungsten, vanadium, and iron. In order to prevent such a problem, aluminum oxide (Al ₂ O ₃ ) must be added to increase the process cost.

In the method for separating and recovering valuable metals using a mill scale and a waste denitration catalyst according to an embodiment of the present invention, the step 2 (S20) comprises reducing and melting the mixture thus prepared, and separating the generated slag and the alloy .

The reduction melting treatment in step 2 may be performed by further injecting the complexing agent at a predetermined weight ratio. The complexing agent in the step 2 comprises 90 parts by weight to 110 parts by weight of an aluminum-containing material to 100 parts by weight of iron oxide (Fe ₂ O ₃ ); And 90 parts by weight to 110 parts by weight of sodium chlorate (NaClO ₃ ). In the above weight ratio range, the prepared mixture can be stably ignited.

The reduction melting treatment in step 2 may be performed by adding 0.5 to 2.5 parts by weight of a complexing agent to 100 parts by weight of the mixture. If the amount of the complexing agent added is less than 0.5 part by weight, the complexation of the mixture is unstable, so that the complexing reaction of the mixture is not sufficiently carried out so that iron oxide (FeO, Fe ₃ O ₄ , Fe ₂ O ₃₎ and the waste removal catalyst titanium dioxide (TiO ₂ in), tungsten oxide (WO ₃₎ and vanadium oxide (V ₂ O ₅₎ of a metal reduction reaction, to the phenomenon of degradation of iron, tungsten, vanadium, and the slag of titanium There is a problem that the loss increases. If the amount of the complexing agent added during the reduction and melting treatment is more than 2.5 parts by weight, the reduction-melting reaction of the waste denitration catalyst and the mill scale can proceed normally, but the process cost may increase.

The reduction melting treatment in the step 2 may be performed through an induction heating furnace.

The reduction melting treatment of step 2 may be performed at a temperature of 1800 캜 to 2300 캜 for 2 minutes to 10 minutes. If the reduction melting temperature of step 2 is less than 1800 ° C, there is a fear that the produced mixture can not be completely melted and melted. If the reduction melting temperature of step 2 is higher than 2300 ° C, There is a possibility that the energy loss may increase sharply as the temperature rises remarkably.

If the time during the reduction melting treatment in step 2 is less than 2 minutes, the reduction metal melting of the valuable metal oxide contained in the prepared mixture may become unstable, resulting in the loss of valuable metal in the slag phase, If the treatment time is more than 10 minutes, the metal oxide contained in the prepared mixture can be sufficiently reduced and melted, but energy loss and waste are increased as the holding time becomes longer.

The separation of the slag and the alloy in the step 2 may be performed by releasing and discharging the slag after completion of the reduction and melting and immediately cooling in the reactor.

In another aspect of the present invention,

There is provided a method for producing an iron alloy including a valuable metal, which comprises the steps 1 and 2 described above.

The specific constitution and effect of the iron alloy manufacturing method may be as described in the method for separating and recovering valuable metals using the mill scale and the waste denitration catalyst.

According to another aspect of the present invention,

Which is prepared according to the above production method,

33.0 wt% to 40.4 wt% of titanium;

From 30.6 wt% to 49.4 wt% of iron;

6.2 wt% to 7.6 wt% tungsten;

0.6 wt% to 0.9 wt% of vanadium;

Aluminum balance; And

Other unavoidable impurities,

The present invention provides an iron alloy including a valuable metal in which 70 wt% to 85 wt% of titanium is recovered relative to titanium in the waste denitration catalyst of step 1 above.

The iron alloy may be ferro-titanium.

The iron alloy may be one in which 95.0 wt% to 99.5 wt% of tungsten or vanadium is recovered relative to tungsten or vanadium in the waste denitration catalyst of step 1 above.

The iron alloy may be recovered from 95.0 wt% to 99.5 wt% of iron based on the iron of the scale scale of the step 1.

According to another aspect of the present invention,

100 parts by weight of waste denitration catalyst

43.7 parts by weight to 71.9 parts by weight of a mill scale;

61.8 parts by weight to 73.4 parts by weight of an aluminum-containing material;

Sodium chlorate (NaClO ₃₎ 12.1 parts to 20.2 parts by weight; And

46.1 parts by weight to 56.1 parts by weight of a calcium compound, and a composition for separating and recovering a valuable metal through reduction melting from a mill scale.

The valuable metal may be the same as the valuable metal described in the above method.

Problems that arise when the weight ratios of the respective components in the composition are exceeded may be as described in the above method.

The composition can be subjected to reduction melting under the conditions of the reduction melting treatment described in the above method, and an iron alloy phase in which a valuable metal is readily captured can be produced.

The composition may further include 0.5 to 2.5 parts by weight of a complexing agent in 100 parts by weight of the composition.

The complexing agent may have a composition as described in the above method.

Hereinafter, the present invention will be described in more detail with reference to Examples and Experimental Examples. However, the following examples and experimental examples are for illustrative purposes only and are not intended to limit the scope of the present invention.

< Example  1 > Ferro-titanium  Manufacturing 1

Step 1: A waste denitration catalyst containing 71.8 wt% of titanium oxide (TiO ₂ ), 7.7 wt% of tungsten oxide (WO ₃ ) and 1.2 wt% of vanadium oxide (V ₂ O ₅ ) After grinding, it was dried in the air at a temperature of 800 DEG C for 30 minutes. Then, the mill scale containing 70 wt% of iron was pulverized to have a particle size of 1 mm or less, and then dried in the air at 300 캜 for 20 minutes. Next, based on 100 parts by weight (1659.8 g) of the desiccated waste denitration catalyst, 71.9 parts by weight (1193.4 g) of the dry-treated mill scale; 73.4 parts by weight (1218.0 g) of aluminum powder; 16.2 parts (268.1 g) of sodium chlorate (NaClO ₃ ) and 56.1 parts (931.6 g) of calcium oxide (CaO) were mixed to prepare a uniformly stirred mixture through a stirrer (Sungil Machinery Co., Korea).

Step 2: A complexing agent prepared by charging the prepared mixture into an induction heating furnace and further mixing iron oxide (Fe ₂ O ₃ ) powder, aluminum powder and sodium chlorate (NaClO ₃ ) at a weight ratio of 1: 1: Was added in an amount of 0.5 part by weight based on 100 parts by weight of the mixture and subjected to reduction melting treatment at a temperature of 1900 캜 for 3 minutes. After the reduction and melting treatment, the steel sheet was naturally cooled, the slag phase was separated and discharged, and an iron alloy having concentrated titanium, tungsten, and vanadium was recovered.

< Example  2 > Ferro-titanium  Manufacturing 2

In step 1 of Example 1, the mill scale was dried at a temperature of 200 DEG C for 40 minutes, the waste denitration catalyst was dried at a temperature of 700 DEG C for 40 minutes, and 100 parts by weight (1659.8 g) Was mixed with 60.0 parts by weight (995.9 g) of wheat scale, 71.4 parts by weight (1185.2 g) of aluminum powder, 20.2 parts by weight (335.1 g) of sodium chlorate (NaClO ₃ ) and 54.3 parts by weight (900.7 g) of calcium oxide However,

The iron alloy was recovered in the same manner as in Example 1 except that 1.0 part by weight of the same complexing agent was added to 100 parts by weight of the mixture in the step 2 of Example 1.

< Example  3 > Ferro-titanium  Manufacturing 3

In Step 1 of Example 1, the mill scale was dried at a temperature of 250 DEG C for 30 minutes, the waste denitration catalyst was dried at a temperature of 500 DEG C for 60 minutes, and 100 parts by weight (1659.8 g) (725.3 g) of Mill scale, 61.8 parts (1025.8 g) of aluminum powder, 12.1 parts (201.1 g) of sodium chlorate (NaClO ₃ ) and 46.4 parts (770.6 g) of calcium oxide (CaO) However,

The iron alloy was recovered in the same manner as in Example 1 except that 2.5 parts by weight of the same complexing agent was added to 100 parts by weight of the mixture in the step 2 of Example 1.

< Comparative Example  1> Ferroalloy manufacturing 1

In Step 1 of Example 1, 30.0 parts by weight (497.9 g) of a mill scale, 59.2 parts by weight (983.0 g) of aluminum powder, 16.2 parts by weight of sodium chlorate (NaClO ₃ ) based on 100 parts by weight (1659.8 g) (268.1 g) and calcium oxide (CaO) in an amount of 40.8 parts by weight (676.8 g) were mixed to recover the iron alloy.

< Comparative Example  2> Ferroalloy manufacturing 2

In Step 1 of Example 1, 80.0 parts by weight (1327.8 g) of wheat scale, 78.2 parts by weight (1297.4 g) of aluminum powder, 20.2 parts by weight of sodium chlorate (NaClO ₃ ) (335.1 g) and calcium oxide (CaO) 60.0 parts by weight (996.3 g) were mixed in the same manner as in Example 1, to thereby recover the iron alloy.

< Experimental Example  1> Evaluation of titanium, tungsten, vanadium and iron recovery of manufactured iron alloys

The recovery rates of titanium, tungsten, vanadium and iron in the above Examples and Comparative Examples were measured by ICP analysis, and the results are shown in Table 1.

division Ti recovery (%) W Recovery (%) V Recovery (%) Fe recovery (%) Each component content (wt%) of the recovered iron-based alloy Ti W V Example 1 75.3 98.6 98.5 99.0 33.0 6.2 0.7 Example 2 73.3 98.4 98.0 99.0 35.3 6.8 0.8 Example 3 72.8 96.6 96.5 98.2 40.4 7.6 0.9 Comparative Example 1 45.6 77.6 79.8 85.4 34.6 8.4 1.0 Comparative Example 2 75.5 98.6 98.7 99.0 31.3 5.8 0.7

Referring to Table 1, it can be seen that in all of the examples, the titanium recovery rate is 70% or more, the tungsten, vanadium, iron recovery rate is 95% or more, the titanium content is 33.0 wt% to 40.4 wt%, the tungsten content is 6.2 wt% %.

In the case of Comparative Example 1, it was confirmed that the recovery rate of titanium was significantly lower than that of Examples, and the recovery rate of tungsten, vanadium and iron was also not more than 90%.

In the case of Comparative Example 2, it was confirmed that the titanium content and the tungsten content of the recovered iron-rich alloy were lower than the intended content.

< Experimental Example  2> X-ray diffraction analysis and shape analysis of the manufactured iron alloy

The iron alloy prepared in Example 1 was analyzed by X-ray diffractometry. The surface shape was photographed at a low magnification and a high magnification through a scanning electron microscope, and the results are shown in FIGS. 4 to 6.

As shown in FIG. 4, it was confirmed that the intermetallic compounds of tungsten, iron, titanium, iron, vanadium and iron were formed in Example 1.

Referring to FIGS. 5 and 6, the iron alloy produced in Example 1 can be confirmed to have a low magnification (140x) and a high magnification (1000x).

< Experimental Example  3> X-ray of the manufactured iron alloy Mapping  Results analysis

The X-ray mapping results of the iron alloys prepared in Examples 1 to 3 were measured by an energy dispersive X-ray spectroscope and are shown in FIGS. 7 to 12.

Referring to FIGS. 7 and 8, it was confirmed that valuable metals such as titanium, tungsten, and vanadium in the iron alloy produced in Example 1 were collected.

Further, as shown in Figs. 9 and 10, it was confirmed that the iron alloy produced in Example 2 also collected valuable metals such as titanium, tungsten, and vanadium.

11 and 12, it was confirmed that the iron alloy produced in Example 3 also collected valuable metals such as titanium, tungsten, and vanadium.

While the present invention has been particularly shown and described with respect to a specific embodiment thereof with reference to a method for recovering and recovering valuable metals from a waste denitration catalyst using a mill scale according to an embodiment of the present invention, It is evident that various modifications can be made without departing from the spirit of the invention.

Therefore, the scope of the present invention should not be construed as limited to the embodiments described, but should be determined by the scope of the appended claims, as well as the claims.

It is to be understood that the foregoing embodiments are illustrative and not restrictive in all respects and that the scope of the present invention is indicated by the appended claims rather than the foregoing description, It is intended that all changes and modifications derived from the equivalent concept be included within the scope of the present invention.

Claims (13)

A step of preparing a mixture comprising a mill scale, a waste denitration catalyst, an aluminum containing material, sodium chlorate (NaClO ₃ ) and a calcium compound (step 1); And
And a step (2) of reducing slag and alloy produced by subjecting the mixture thus prepared to a reduction melt treatment, and separating the generated slag and the alloy (step 2).
The method according to claim 1,
The above-
Tungsten, vanadium, and titanium. The method of separating and recovering valuable metals using the dense scale and the waste denitration catalyst.
The method according to claim 1,
The dense scale or waste denitration catalyst of the above step (1)
Wherein the catalyst is pulverized and dried at a particle size of 1 mm or less, and a method of separating and recovering valuable metals using the dense scale and the waste denitration catalyst.
The method of claim 3,
The drying process of the mill scale in the step (1)
Wherein the catalyst is carried out at a temperature of 200 ° C to 300 ° C for 20 minutes to 40 minutes.
The method of claim 3,
The drying treatment of the waste denitration catalyst of the step 1,
At a temperature of 500 to 800 DEG C for 30 to 60 minutes.
The method according to claim 1,
In the mixing of the step 1,
To 100 parts by weight of the waste denitration catalyst
43.7 parts by weight to 71.9 parts by weight of a mill scale;
61.8 parts by weight to 73.4 parts by weight of an aluminum-containing material;
Sodium chlorate (NaClO ₃₎ 12.1 parts to 20.2 parts by weight; And
And calcium compound (46.1 parts by weight to 56.1 parts by weight). The method of separating and recovering valuable metals using a dense scale and a waste denitration catalyst.
The method according to claim 1,
The reducing and melting treatment in the step (2)
Wherein 0.5 to 2.5 parts by weight of a complexing agent is added to 100 parts by weight of the mixture.
8. The method of claim 7,
The complexing agent of the step 2,
100 parts by weight of iron oxide (Fe ₂ O ₃ )
90 parts by weight to 110 parts by weight of an aluminum-containing substance; And
And 90 parts by weight to 110 parts by weight of sodium chlorate (NaClO ₃ ). The method for separating and recovering valuable metals using the dense scale and the waste denitration catalyst.
The method according to claim 1,
The reducing and melting treatment in the step (2)
Wherein the catalyst is carried out at a temperature of 1800 캜 to 2300 캜 for 2 to 10 minutes.
A method for producing an iron alloy comprising a valuable metal, comprising steps 1 and 2 of claim 1.
11. A process for the preparation of a compound according to claim 10,
33.0 wt% to 40.4 wt% of titanium;
From 30.6 wt% to 49.4 wt% of iron;
6.2 wt% to 7.6 wt% tungsten;
0.6 wt% to 0.9 wt% of vanadium;
Aluminum balance; And
Other unavoidable impurities,
An iron alloy comprising a valuable metal recovered from 70 wt% to 85 wt% titanium relative to titanium in the waste denitration catalyst of step 1 above.
12. The method of claim 11,
The iron alloy containing the above-
95.0 wt% to 99.5 wt% of tungsten or vanadium relative to tungsten or vanadium in the waste denitration catalyst of step 1 is recovered,
Wherein iron is recovered in an amount of 95.0 wt% to 99.5 wt% based on the iron of the mill scale of the step (1).
100 parts by weight of waste denitration catalyst
43.7 parts by weight to 71.9 parts by weight of a mill scale;
61.8 parts by weight to 73.4 parts by weight of an aluminum-containing material;
Sodium chlorate (NaClO ₃₎ 12.1 parts to 20.2 parts by weight; And
46.1 parts by weight to 56.1 parts by weight of a calcium compound, and a composition for separating and recovering a valuable metal through reduction melting from a mill scale.

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