KR101366297B1 - Treating method of byproduct - Google Patents

Abstract

The by-product treatment method according to the present invention is a process for preparing a solvent containing at least one of SO ₄ (sulphate) and SO ₃ (sulfite), by dipping slag in the solvent, BaSO ₄ (barium sulfate) and BaSO ₃ (sulfuric acid Barium), and separating the solvent and the precipitate.
Therefore, according to embodiments of the present invention, Ba (barium) contained in the slag can be easily treated in the form of BaSO ₄ (barium sulfate) or BaSO ₃ (barium carbide). Therefore, the possibility of causing the environmental pollution by elution of Ba (barium) can be suppressed, and slag can be processed safely.

Description

Treating method of byproduct

The present invention relates to a by-product treatment method, and more particularly to a by-product treatment method for minimizing the dissolution of the water-soluble Ba (barium) contained in the slag.

A general process for producing ferro manganese is prepared by charging manganese ore and reducing agent coke and slag forming agent (Flux) into an electric furnace and reducing the manganese ore in oxide form using carbon of coke. As such, ferro-manganese produced in an electric furnace using coke is obtained in the form of high-carbon ferro-manganese in which carbon is saturated in a product due to coke as a reducing agent. In addition, the content of phosphorus (P) in ferro-manganese is mostly high as 0.4% or less, and the phosphorus (P) content in ferro-manganese, which is frequently used for steelmaking, is relatively high as 0.1-0.2%.

On the other hand, since phosphorus (P) is present as an impurity in steel and impairs the quality of steel products, such as causing high temperature brittleness, a process of lowering the content of phosphorus (P) in molten steel is carried out except in special cases. That is, the phosphorus (P ₃ ) in phosphorus (Ba ₃ (PO ₄ ) or phosphorus (P ₄ ) in ferro-manganese is reduced or dephosphorization process in which phosphorus (P) in ferro manganese is removed in the form of phosphide (Ca ₃ P ₂ , Mg ₃ P _2, etc.). ₂ ) to lower the content of phosphorus (P) by the deoxidation process such as removing in the form of. In the case of the deoxidation process, BaCO ₃ , BaO, BaF ₂ , BaCl ₂ , CaO, CaF ₂ , Na ₂ CO ₃ , Li ₂ CO _3, or the like is used as the dephosphorizing agent. Here, since the Ca-based dephosphorizer has low dephosphorization efficiency and Na and Li-based dephosphorizer have a high vapor pressure, the ablation phenomenon occurs, and a Ba-based dephosphorizer such as BaCO ₃ or BaO is mainly used for dephosphorization of ferro manganese.

However, when deferring ferro manganese using Ba-based dephosphorization agents such as BaCO ₃ or BaO, Ba is inevitably contained in slag generated after dephosphorization treatment. However, since Ba is a water-soluble substance, when the slag is disposed of in landfill, Ba is eluted from rainwater, groundwater, and the like and contaminates the environment. Therefore, the development of a slag treatment method capable of effectively recovering Ba contained in the slag of ferro-manganese is required.

Korean Patent No. 1036317 uses ferro-manganese which uses BaCO3 as a dephosphorizing agent and a material in which at least one solvent selected from Al2O3, NaF, and cryolite (Na3AlF4) is mixed, and recycles dust generated in the dephosphorization step as dephosphorization agent for steelmaking. Disclosed is a method for recycling tallin by-products.

Korean Patent Registration No. 1036317

One technical problem of the present invention is to provide a by-product treatment method for minimizing the dissolution of Ba (barium) contained in the slag.

Another technical problem of the present invention is to provide a by-product treatment method for converting BaSO ₄ (barium sulfate) or BaSO ₃ (barium carbide) of water-soluble Ba (barium) contained in the Tallinn slag of ferro-manganese.

The by-product treatment method according to the present invention is a process for preparing a solvent containing at least one of SO ₄ (sulphate) and SO ₃ (sulfite), by dipping slag in the solvent, BaSO ₄ (barium sulfate) and BaSO ₃ ( Barium sulfite), and a process of separating the solvent and the precipitate.

The slag is produced in the process of dephosphorizing ferro manganese using a dephosphorizing agent containing Ba (barium).

The process of preparing the solvent is prepared by dissolving an additive for producing at least one of BaSO ₄ (barium sulfate) and BaSO ₃ (barium sulfite) in a solution, using water as the solution.

Preferably, the water is at least 3 ml per gram of slag.

In preparing a solvent containing the sulfate (SO ₄ ), an additive is added to contain 0.03 g to 0.55 g of SO ₄ ^2- (sulfate ion) per 1 g of Ba included in the slag.

In preparing a solvent containing the sulfate (SO ₄ ), an additive is added so that 0.7 g or more of SO ₄ ^2- (sulfate ion) is contained per 1 g of the water-soluble Ba contained in the slag.

In preparing a solvent containing the sulfate (SO ₄ ), at least one of M ₂ SO ₄ , MSO ₄ and Alum-based materials may be used as the additive.

One of K ₂ SO ₄ and NaSO ₄ is used as the M ₂ SO ₄ material.

In preparing a solvent containing the sulfite (SO ₃ ), an additive is added so as to contain 0.02 g to 0.4 g of SO ₃ ^2- (sulfite ion) per 1 g of Ba included in the slag.

In preparing a solvent containing the sulfite (SO ₃ ), an additive is added so that 0.6 g of SO ₃ ^2- (sulfite ion) is contained per 1 g of water-soluble Ba contained in the slag.

In preparing a solvent containing the sulfite (SO ₃ ), a substance of M ¹ SO ₃ series (M ¹ = monovalent metal) is used as the additive.

As the material of the M ¹ SO ₃ series (M ¹ = monovalent metal), any one of K ₂ SO ₃ and NaSO ₃ is used.

In immersing slag in the solvent, the slag is immersed for at least 24 hours in a static bath without stirring.

In immersing slag in the solvent, the solvent in which the slag is immersed is stirred.

By-product treatment method according to embodiments of the present invention, Ba (barium) contained in the slag can be easily treated in the form of BaSO ₄ (barium sulfate) or BaSO ₃ (barium carbide). Therefore, the possibility of causing the environmental pollution by elution of Ba (barium) can be suppressed, and slag can be processed safely.

1 is a flow chart sequentially showing the by-product recovery process according to the present invention
2 is an XRD graph of ferro manganese slag
3 is an XRD graph when ferro manganese slag is immersed in a solvent containing SO ₄ .
4 is an XRD graph when ferro manganese slag is immersed in a solvent containing SO ₃ .

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. It will be apparent to those skilled in the art that the present invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, It is provided to let you know. Wherein like reference numerals refer to like elements throughout.

The by-product treatment method according to the present invention is a method for recovering Ba contained in the slag, wherein the water-soluble Ba (barium) contained in the slag of ferro manganese (FeMn) is replaced with BaSO ₄ (barium sulfate) or BaSO ₃ After the conversion to (barium sulfite), a by-product treatment method for treating the slag containing BaSO ₄ (barium sulfate) or BaSO ₃ (barium sulfite) will be described.

In general, a Ba-based dephosphorizing agent having an excellent delineation effector is used in a delineation process for removing phosphorus (P) in ferro manganese. When the ferro-manganese is treated with delineation, the slag generated after the delineation treatment by the Ba-based dephosphorizing agent may contain Ba. However, since Ba is a water-soluble substance, when the slag is disposed of in landfill, Ba is eluted from rainwater or groundwater, causing a problem of polluting the environment.

Accordingly, embodiments of the present invention provide a by-product treatment method capable of effectively recovering Ba contained in ferro manganese slag.

1 is a flow chart sequentially showing the by-product recovery process according to the present invention. 2 is an XRD graph of ferro manganese slag. 3 is an XRD graph when ferro manganese slag is immersed in a solvent containing SO ₄ . 4 is an XRD graph when ferro manganese slag is immersed in a solvent containing SO ₃ .

Referring to Figure 1, the by-product recovery process is sulfate (SO ₄ , A process for preparing a solvent containing SO 4) or sulfite (SO ₃ , hereinafter SO ₃ ) (S100), by immersing slag in the solvent to convert the water-soluble Ba (barium) from the slag into BaSO ₄ (barium sulfate) or BaSO ₃ ( Barium sulfite) process (S200), the process of separating the solvent and the precipitate (S300) and the process of treating the precipitate (S400). Here, the slag according to the embodiment is generated in the process of delineating ferro manganese using a dephosphorization agent containing Ba, for example.

When the ferro manganese slag is immersed in a solvent containing SO ₄ or SO ₃ , the water-soluble Ba existing in the slag is dissolved, and Ba ²⁺ (barium ion) is generated as in the following equation (1). At this time, the solvent is by an ionic bond by reacting with the SO ₄ ^2- to the Ba ²⁺ as in the case of the solvent, the following reaction formula (2) containing SO ₄ is present in the solvent, and BaSO ₄ is produced, the resulting BaSO ₄ is Precipitates. Further, the solvent when the solvent, to ion reacts with SO ₃ ^2- present in a Ba ²⁺ a solvent as shown in the reaction formula (3) bonds, including SO _3, BaSO ₃ is generated, the generated BaSO ₃ Is precipitated.

^{_{Ba (OH) 2 = Ba 2+}} + 2OH - --------------------- formula (1)

Ba ²⁺ + SO ₄ ^2- = BaSO ₄ --------------------- Scheme (2)

Ba ²⁺ + SO ₃ ^2- = BaSO ₃ --------------------- Scheme (3)

In the reaction by the same water-soluble Ba contained in the slag is changed into or BaSO ₄ BaSO _3, BaSO ₄ or BaSO ₃ produced has a very low solubility in water characteristic. Thus, BaSO even ₄ or embedded in the slag containing BaSO _3, because of the BaSO ₄ or BaSO ₃ has a very low solubility in water, is eluted, for example, from rain or underground water as in the prior art can be minimized that may pollute the environment.

Hereinafter, the by-product recovery process according to the embodiment will be described in more detail with reference to FIG. 1.

First, after completing the dephosphorization treatment of ferro manganese using a Ba-based dephosphorization agent such as BaCO ₃ , Ba and the like, the produced slag is prepared. Slag is present in about 20 to 50 wt% Ba, of which the amount of water soluble Ba is about 3 to 30%. Referring to FIG. 2, there is no BaSO ₄ or BaSO ₃ in the slag before penetrating into the solvent containing SO ₄ (sulphate) or SO ₃ (sulphite). Then, the prepared slag is crushed, and it is preferable to crush the particles so as to be 2 mm or less or 0.5 mm or less.

In addition, a solvent containing SO ₄ (sulphate) or SO ₃ (sulfite) is prepared (S100). To this end, a solution, for example, water is prepared, and an additive is added to the water to dissolve, thereby preparing a solvent containing SO ₄ or SO ₃ . At this time, the water is preferably prepared more than 3ml per 1g of ferro manganese slag mixed in the subsequent process.

The solvent containing SO ₄ is prepared by adding one of M ₂ SO ₄ , MSO ₄ and Alum to the water as an additive and dissolving it. In an embodiment, one of K ₂ SO ₄ and Na ₂ SO ₄ is used as the M ₂ SO ₄ -based material. The additive of any one of M ₂ SO ₄ , MSO ₄ and Alum is dissolved in water. As the additive is dissolved, SO ₄ ^2- ions are generated, and the SO ₄ ^2- ions are then reacted with water-soluble Ba of ferro manganese slag, resulting in very low solubility BaSO ₄ . Accordingly, the solvent should contain a sufficient amount of SO ₄ ^2- ions to BaSO ₄ Ba contained in the ferro manganese slag.

On the other hand, as a Ba-based dephosphorization agent, for example, when using a dephosphorization agent mixed with BaCO3 and NaF, slag that completed the dephosphorization process is BaMn ₂ O ₃ , Ba ₂ SiO ₄ , MnO, BaO, BaCO ₃ (unreacted Flux), BaMnO A reactant of ₂ , MnO ₂ , SiO ₂ , Na ₂ CO ₃ , Na ₂ O, BaF ₂ is produced. Among them, a substance such as BaO is combined with moisture in the known to form Ba (OH) ₂ , and H ₂ O is attached thereto to form a hydrate such as Ba (OH) ₂ H ₂ O. Thus, in the slag generated during the delineation process using a dephosphorization agent mixed with BaCO 3 and NaF, water-soluble substances of BaO, Ba (OH) ₂ , and Ba (OH) ₂ + H ₂ O exist. As another example, when BaCl ₂ is used as the Ba-based dephosphorizing agent, BaCl ₂ is present in the slag, and BaCl ₂ is a water-soluble material. The amount of Ba contained in the slag can be detected by dissolving the slag in water and measuring the amount of Ba eluted in the water.

Therefore, in the present embodiment, the content of Ba in slag, more preferably, and adjusting the amount of SO ₄ ^2- ions depending on the amount of soluble Ba, controlled by adjusting the amount of the SO ₄ ^2- ions in the amount of additive to be added can do. That is, this SO ₄ ^2- ions per 1g of Ba slag 0.03g to 0.55g, more preferably SO ₄ ^2- ions per 1g of soluble Ba present in the slag to be not less than 0.70g. For example, SO ₄ ^2- or the amount of the ions is less than 0.03g per 1g Ba within the slag, if water-soluble is less than 0.70g per 1g Ba, SO ₄ ^2- ion, the amount of Ba is too small, the amount of BaSO ₄ is less anger . For example, at least 10% Ba may be eluted with respect to the total slag content (mg / L) when the slag is embedded. On the contrary, when the amount of SO ₄ ^2- ions exceeds 0.55 g per 1 g of Ba in the slag, the amount of the additive added is too large compared to the amount of Ba, and the consumption of the additive is increased.

Therefore, in the embodiment of the present invention, the SO ₄ ^2- ion per Ba 1 contained in the slag is 0.03 g to 0.55 g, more preferably, the SO ₄ ^2- ion per 0.7 g of water-soluble Ba present in the slag is 0.70 g or more. Add the additive so that it contains. Thus, a large amount of Ba contained in the slag can be easily converted to BaSO ₄ without the consumption of the additive, and the amount of Ba eluted during the slag landfill can be 10% or less with respect to the total slag.

In the case of a solvent containing SO ₃ as well, the amount of SO ₃ ^2- ions is adjusted according to the content of Ba in the slag, more preferably, the amount of water-soluble Ba, and the amount of SO ₃ ^2- ions is added to the additive. It can be controlled by adjusting the amount of. That is, this SO ₃ ^2- ions per 1g of Ba slag 0.02g to 0.4g, more preferably SO ₃ ^2- ions per 1g of soluble Ba present in the slag to be not less than 0.6g. For example, if the amount of SO ₃ ^2- ions is less than 0.02 g per 1 g of Ba in the slag or less than 0.6 g per 1 g of water-soluble Ba, the amount of SO ₃ ^2- ions is too small so that the amount of Ba converted to BaSO ₃ is small. . For example, at least 10% Ba may be eluted with respect to the total slag content (mg / L) when the slag is embedded. On the contrary, when the amount of SO ₃ ^2- ions is greater than 0.4 g per 1 g of Ba in the slag, the amount of the additive added is too large compared to the amount of Ba, and the consumption of the additive is increased.

Therefore, in the embodiment of the present invention, the SO ₃ ^2- ion per Ba 1 contained in the slag is 0.02 g to 0.4 g, more preferably 0.6 g or more SO ₃ ^2- ion per 1 g of water-soluble Ba present in the slag. Add the additive so that it contains. Thus, a large amount of Ba contained in the slag can be easily converted to BaSO ₃ without a large consumption of the additive, and the amount of Ba eluted during the slag embedding can be 10% or less with respect to the total slag.

When a solvent containing SO ₄ or SO ₃ is prepared, the ferro manganese slag is immersed in the solvent to convert BaSO ₄ (barium sulfate) or BaSO ₃ (barium sulfite) into water-soluble Ba in the slag. At this time, the slag to be immersed is preferably at room temperature or 25 ℃ to 40 ℃. When the slag is immersed in the solvent, it is preferable to immerse the slag for 1 day (24 hours) or more in a condition without stirring, that is, a standing bath.

For example, when reacting slag and additives in a standing bath, if the reaction time is less than 24 hours, the reaction time is too short to be sufficient for the large amount of water-soluble Ba contained in the slag to be BaSO ₄ or BaSO ₃ . Thus, more than 10% Ba may be eluted with respect to the total slag content (mg / L) when the slag is embedded.

In addition, when the slag is immersed in the solvent, the solvent may be stirred, for example, there is an effect that the reaction time can be shortened compared to the stagnation bath when stirring using a stirrer such as an impeller (impeller).

For example, when ferro-manganese slag is immersed in a solvent containing SO ₄ , the water-soluble Ba existing in the slag is dissolved while the slag is deposited, and Ba ²⁺ is generated as in the equation (1). And BaSO _{4 is} produced by reacting Ba ²⁺ with SO ₄ ^2- present in the solvent and reacting with ions as shown in Scheme (2) and FIG. At this time, as described above, the solvent contains 0.03 g to 0.55 g per 1 g of Ba, preferably 0.70 g or more SO ₄ ^2- per 1 g of water-soluble Ba. Thus, most of the large amount of water-soluble Ba present in the slag becomes BaSO ₄ .

As another example, immersion of ferro-manganese slag in a solvent containing sulfite (SO3), while dissolving the water-soluble Ba present in the slag, Ba ²⁺ is generated as in Scheme (1). And BaSO ₃ is produced by reacting Ba ²⁺ with SO ₃ ^2- present in the solvent and reacting with ions as shown in Scheme (3) and FIG. 4. At this time, as described above, the solvent contains 0.02 g to 0.4 g per Ba, preferably 0.6 g or more SO ₃ ^2- per 1 g of water-soluble Ba. As a result, most of the large amount of water-soluble Ba present in the slag becomes BaSO ₃ .

And, generated BaSO ₄ or BaSO ₃ is Due to its high specific gravity compared to water, it precipitates.

When the process of converting the water-soluble Ba in the slag BaSO ₄ or BaSO ₃ is completed, the solvent and the precipitate is separated (S300). In the examples, a filter is used to separate the precipitate and the solution. That is, the solvent is filtered through a filter to separate the precipitate, ie slag and BaSO ₄ or BaSO ₃ from the solvent. Since the sulfuric acid component or water-soluble Ba may remain in the solvent, it is preferable to proceed with the separation process while washing with water. At this time, the water used in the washing process depends on the amount of slag, it is effective to use more than 0.1ml of water per 1g of slag in the washing process.

Thereafter, the separated precipitate is treated (S400). That is, the separated slag and BaSO ₄ or BaSO ₃ is dried and then landfilled. At this time, since the amount of water-soluble Ba is less than 10% compared to the total amount of slag, and BaSO ₄ or BaSO ₃ has very low solubility in water, the amount of Ba eluted even when the slag is embedded is total slag. Less than 10% by volume. Therefore, it is possible to minimize the occurrence of environmental pollution compared to the prior art.

The separated solution may be treated by repeating the second, third and fourth steps described above. At this time, it is preferable to repeat the treatment under the condition that the cations in the solution do not reach the SO ₄ ^2- ion or the SO ₃ ^2- ion-bonding saturation solubility in water. And when the cation binding with SO ₄ ^2- ions or SO ₃ ^2- ions reaches a saturation concentration during the reuse of the solution, the solution is sent to a wastewater treatment plant to treat the solution.

Table 1 is a table showing the elution amount and ratio of Ba in the slag according to the by-product recovery conditions according to the examples and comparative examples of the present invention. Here, the slag of the 1st-8th Example and the slag of the 1st-4th Comparative Example are the same in the characteristic. In other words, the slag of the first to eighth examples and the first slag amount of the first to fourth comparative examples is 24000 mg / L, the amount of Ba in the slag is 42 wt%, the amount of water-soluble Ba in the slag is 24wt%. In recovering such slag, the first to eighth embodiments and the first to fourth embodiments depend on the type of the additive, the amount of the additive added (g), the amount of the solution in the preparation of the solvent (ml), the reaction time (hr) and the presence / absence of stirring. It divided into the comparative example.

In addition, in the first to eighth embodiments, the SO ₄ ^2- ion contained in the solvent is 0.7g or more per 1g of water-soluble Ba, and the content of SO ₃ ^2- ion is 0.6g or more per 1g of water-soluble Ba containing the slag. The amount of the additive (Na ₂ SO ₄ or Na ₂ SO ₃ ) was adjusted so that 100 ml or more of a solution, that is, water, was added and the reaction time was 24 hours or more. Here, the first to sixth and eighth embodiments did not proceed with stirring when the slag penetrated into the solvent, and the seventh embodiment proceeded with stirring.

The 1st comparative example and the 2nd comparative example are the case where it progressed for 12 hours whose reaction time is less than 24 hours. The third comparative example is a case where an input amount of Na ₂ SO _{4 as} an additive is 18 g, and SO ₄ ^2- ions are added at less than 0.7 g per 1 g of water-soluble Ba. In addition, the fourth comparative example is a case where the input amount of Na ₂ SO _{3 as} an additive is 15 g, and SO ₃ ^2- ions are added at less than 0.6 g per 1 g of water-soluble Ba.

And each of the precipitates by the method according to the first to eighth and the precipitates according to the first to fourth comparative examples were immersed in water to detect the amount of Ba eluted.

division
Tallinn Slag Properties Slag content (g)

Additive input amount (g)
Solution amount (ml)
Reaction time (hr)
Stirring
The presence or absence
Ba elution amount (mg / L)
Ba elution rate (%) Ba (wt%) in slag Water soluble Ba (wt%) in slag 1st
Example











42











24











100 Na ₂ SO ₄
25 g 100 168 radish
Stirring 497 2.0 Second
Example Na ₂ SO ₄
25 g 500 168 radish
Stirring 260 1.0 Third
Example Na ₂ SO ₄
25 g 1000 168 radish
Stirring 186 0.7 Fourth
Example Na ₂ SO ₃
23 g 100 72 radish
Stirring 1125 4.6 Fifth
Example Na ₂ SO ₃
23 g 100 96 radish
Stirring 964 4.0 6th
Example Na ₂ SO ₃
23 g 1000 96 radish
Stirring 1860 7.7 Seventh
Example Na ₂ SO ₄
25 g 500 12
Stirring 296 1.2 Eighth
Example Na ₂ SO ₄
25 g 500 12 radish
Stirring 867 3.6 1st
Comparative Example Na ₂ SO ₄
25 g 500 12 radish
Stirring 6574 27.3 Second
Comparative Example Na ₂ SO ₃
23 g 500 12 radish
Stirring 3241 13.5 Third
Comparative Example Na ₂ SO ₄
: 18 g 500 168 radish
Stirring 9840 41.0 Fourth
Comparative Example Na ₂ SO ₃
: 15 g 500 168 radish
Stirring 8924 37.1

Referring to Table 1, according to the by-product treatment method according to the first to eighth embodiments, the amount of Ba eluted (mg / L) relative to the amount of initial slag (24000 mg / L) is 10% or less. Comparing the second and seventh embodiments, when the additive was used in the same amount as Na ₂ SO ₄ , when the slag was penetrated into the solvent and reacted, the seventh embodiment proceeded to the stirring process. The reaction time is short compared with the 2 examples. That is, when stirring is carried out as in the seventh example, the reaction time is shorter than the second example so that the amount of Ba eluted is 10% or less. From this, it can be seen that in the reaction of the solvent and the slag, accompanying the stirring operation has the effect of increasing the reaction efficiency.

In the case of the first comparative example, Na ₂ SO ₄ was used as an additive, and the reaction time was 12 hours. When the reaction time is shortened to less than 24 hours as in the first comparative example, even if the amount of the additive Na ₂ SO ₄ is sufficient, the reaction time is too short, so that the eluted Ba exceeds about 10% to about 27%. In the case of the second comparative example, Na ₂ SO ₃ was used as the additive, and the reaction time was 12 hours. Similarly, when the reaction time is shortened to less than 24 hours as in the second comparative example, even if the amount of the additive Na ₂ SO ₃ is sufficient, the reaction time is too short, so that the eluted Ba is about 27% to 10%. Exceed.

In the third comparative example, Na ₂ SO ₄ was used as an additive and the reaction time was treated for 24 hours or more. However, the amount of the additive was 18 g, which was the amount of SO ₄ ^2- ions contained in the solvent containing SO ₄ . It is 0.29 g per 1 water-soluble Ba. That is, in the third comparative example, the amount of SO ₄ ^2- ions contained in the solvent is small, less than 0.7 g per water-soluble Ba 1. Thus, the amount of SO ₄ ^2- ions to react with a large amount of water-soluble Ba ²⁺ ions was not enough, resulting in a Ba dissolution amount exceeding 10%.

The use of Na ₂ SO ₃ to 4 and the comparative example when the additive, as a treatment, but the reaction time to 24 hours or more, the amount of additive added 15g, the amount of SO ₃ ^2- ions contained in the solvent containing a SO ₃ 0.23 g per water-soluble Ba. That is, in the fourth comparative example, the amount of SO ₃ ^2- ions contained in the solvent is small, less than 0.6 g per water-soluble Ba 1. Thus, the amount of SO ₃ ^2- ions to react with a large amount of water-soluble Ba ²⁺ ions was not enough, resulting in a Ba elution amount exceeding 10%.

Thus, by treating the slag in the method according to the embodiments of the present invention, the amount of Ba dissolution can be adjusted to 10% or less. Therefore, even if the slag is subsequently buried, it is possible to reduce the elution of Ba from rainwater, groundwater, and the like to contaminate the environment, as compared with the related art.

Claims (14)

Dissolving an additive in the solution to prepare a solvent containing at least one of SO ₄ (sulfate) and SO ₃ (sulfite);
Immersing slag in the solvent to produce at least one of BaSO ₄ (barium sulfate) and BaSO ₃ (barium sulfite); And
Separating the solvent and the precipitate;
In preparing a solvent containing the sulfite (SO ₃ ), a substance of M ¹ SO ₃ series (M ¹ = monovalent metal) is used as the additive,
In preparing a solvent containing the sulfate (SO ₄ ), an additive is added to add 0.03 g to 0.55 g of SO ₄ ^2- (sulfate ion) per 1 g of Ba contained in the slag. The method according to claim 1,
The slag is a by-product treatment method generated in the process of delineating ferro manganese using a dephosphorization agent containing Ba (barium). The method according to claim 1,
The by-product treatment method using water as the solution. The method according to claim 3,
The water is a by-product treatment method of more than 3ml per 1g of slag. delete The method according to claim 1,
In preparing a solvent containing the sulfate (SO ₄ ),
The by-product treatment method for adding an additive so that 0.7g or more of SO ₄ ^2- (sulfate ion) per 1g of water-soluble Ba contained in the slag. The method according to claim 1 or 3,
In preparing a solvent containing the sulfate (SO ₄ ),
The by-product treatment method using at least one of M ₂ SO ₄ , MSO ₄ and Alum-based material as the additive. The method of claim 7,
The by-product treatment method using any one of K ₂ SO ₄ and Na ₂ SO ₄ as the M ₂ SO ₄ material . Dissolving an additive in the solution to prepare a solvent containing at least one of SO ₄ (sulfate) and SO ₃ (sulfite);
Immersing slag in the solvent to produce at least one of BaSO ₄ (barium sulfate) and BaSO ₃ (barium sulfite); And
Separating the solvent and the precipitate;
In preparing a solvent containing the sulfite (SO ₃ ), a substance of M ¹ SO ₃ series (M ¹ = monovalent metal) is used as the additive,
In preparing a solvent containing the sulfite (SO ₃ ), an additive is added to add 0.02 g to 0.4 g of SO ₃ ^2- (sulfite ion) per 1 g of Ba contained in the slag. The method of claim 9,
In preparing a solvent containing the sulfite (SO ₃ ),
The by-product treatment method of adding an additive so that 0.6g or more of SO ₃ ^2- (sulfite ion) per 1g of water-soluble Ba contained in the slag. delete The method according to claim 1 or 9,
The by-product treatment method using any one of K ₂ SO ₃ and Na ₂ SO ₃ as the material of the M ¹ SO ₃ series (M ¹ = monovalent metal). The method according to claim 1 or 9,
In immersing slag in the solvent,
The by-product treatment method for immersing the slag in a stagnation bath without stirring for more than 24 hours. The method according to claim 1 or 9,
In immersing slag in the solvent,
The by-product treatment method of stirring the solvent in which the slag is immersed.

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