KR102293624B1 - Neutralized gypsum composition for cement, method for producing the neutralized gypsum for cement, and cement comprising the neutralized gypsum - Google Patents

Abstract

The present invention relates to the recycling of waste sulfuric acid and non-adherent desulfurization slag, and more particularly, waste sulfuric acid; and non-adhering desulfurization slag, wherein the spent sulfuric acid and non-charging desulfurization slag are mixed in a weight ratio of 0.7:1.0 to 1.3:1.0, a neutralized gypsum composition for cement and a cement containing neutralized gypsum for cement thereby providing a cement .

Description

Neutralized gypsum composition for cement, method for producing the neutralized gypsum for cement, and cement comprising the neutralized gypsum

The present invention relates to a technology for recycling desulfurized slag and spent sulfuric acid, and more particularly, to a neutralized gypsum composition for cement, a method for producing neutralized gypsum for cement, and a cement containing neutralized gypsum for cement by the same.

In general, when manufacturing cement, gypsum is mixed and used to control the reactivity of clinker powder or fine powder of blast furnace slag or to impart expandability. The amount of gypsum used by domestic cement companies reaches 2.5 to 3 million tons per year, but the supply is insufficient compared to domestic demand.

Furthermore, some of the domestically used gypsum emits radon, and some gypsum is discontinued, which is a reality that requires more eco-friendliness. In addition, except for natural gypsum, most gypsum is manufactured using limestone, quicklime, or slaked lime. Since a significant amount of CO ₂ gas is emitted during the production of gypsum, it is necessary to use a raw material that does not generate _{CO 2 .}

On the other hand, when a raw material containing a Cr component is used for manufacturing cement clinker, there is a risk that the ^{Cr 6+} component is eluted from the cement clinker because _{CaCrO 4 crystal phase is generated at around 800° C. when calcined in an oxidizing atmosphere.} For this reason, the cement company manages the Cr ⁶⁺ content to 20 mg/kg or less as its own quality control standards, and efforts to reduce the ^{Cr 6+ elution in cement are continuing.}

As part of an effort to reduce this Cr ⁶⁺ _{elution, a technique for mixing a small amount of FeSO 4} 7H ₂ O into cement is disclosed. Since the Fe ²⁺ component _{in FeSO 4·} 7H ₂ ^{O reduces the Cr 6+} component in the ^{cement to Cr 3+} and stabilizes it, ^{the elution of Cr 6+} can be suppressed. However _{, due to the iron component of FeSO 4·} 7H ₂ O, it can cause defects in cement, so it is necessary to mix a small amount compared to 100 parts by weight of cement, so it is a process that needs to be careful in the quantitative input method or the uniform mixing part.

An object of the present invention is to provide an eco-friendly neutralized gypsum for cement using wastes such as spent sulfuric acid and non-adhering desulfurization slag in order to solve the above problems.

In one aspect of the present invention, the present invention includes spent sulfuric acid and non-attached desulfurization slag, wherein the spent sulfuric acid and non-attached desulfurization slag are mixed in a weight ratio of 0.7:1.0 to 1.3:1.0, neutralized gypsum for cement A composition is provided.

In another aspect of the present invention, the present invention comprises the steps of selecting a non-desulfurization slag from the desulfurization slag; preparing a mixture by mixing spent sulfuric acid and the desulfurized slag in a weight ratio of 0.7:1.0 to 1.3:1.0; And it provides a method for producing neutralized gypsum for cement, comprising the step of drying the mixture.

In another aspect of the present invention, the present invention provides a cement comprising neutralized gypsum for cement formed from the neutralized gypsum composition for cement of the present invention.

According to the present invention, desulfurized slag used as a landfill or low-grade filling material can be used as a neutralizing agent for waste sulfuric acid, and when the waste sulfuric acid is neutralized with the desulfurized slag and used as a cement gypsum, it is possible to convert the waste into a high value-added resource. do.

In addition, when manufacturing gypsum with desulfurization slag, _{since there is no CO 2} generation, the desulfurization slag can be used as an eco-friendly neutralizer.

Furthermore, since H ₂ O ₂ in spent sulfuric acid can be removed by utilizing the metallic iron component in desulfurization slag, expensive platinum catalyst and high-temperature heating evaporation process are not required for _{H 2} O _{2 removal, so it is economical and process} This is simple.

In addition, by mixing and using the neutralized gypsum according to the present invention with cement, it is possible to reduce the elution ^{of Cr 6+} components contained in cement, so it is possible to reduce the elution ^{of Cr 6+} components in cement without using a ^{separate Cr 6+ reducing agent.} .

1 shows the results of XRD (X-Ray Diffraction) analysis of the crystalline phase of neutralized gypsum prepared according to an embodiment of the present invention.

Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings. However, the embodiment of the present invention may be modified in various other forms, and the scope of the present invention is not limited to the embodiments described below.

The present invention relates to a technology for recycling waste sulfuric acid and desulfurization slag, and more particularly, waste sulfuric acid; And it provides a neutralized gypsum composition for cement comprising non-adhesive desulfurization slag.

The waste sulfuric acid may be generated during a semiconductor process, for example, may be waste sulfuric acid generated in an etching process of a semiconductor production process. However, the waste sulfuric acid contains hydrogen peroxide (H ₂ O ₂ ) in an amount of about 2 to 3% by weight, and in order to utilize the waste sulfuric acid generated during the semiconductor production process as described above for the production of neutralized gypsum, hydrogen peroxide must be removed. This is because, when the neutralized gypsum is mixed with cement and applied to concrete, the hydrogen peroxide may cause corrosion of reinforcing bars.

In order to remove the hydrogen peroxide as described above, the present invention may use desulfurization slag generated in the desulfurization process of a steel mill. For example, the desulfurization slag may be desulfurization slag generated in a desulfurization process in molten iron in a molten iron pretreatment process such as an integrated steel mill. The desulfurization process uses CaO and CaF ₂ or aluminum dross as a desulfurization material, reacts with sulfur (S) components in the molten iron, is removed in the form of CaS, and may be contained in slag.

Since the desulfurization slag contains a CaS component, when used together with the spent sulfuric acid containing hydrogen peroxide, the hydrogen peroxide contained in the spent sulfuric acid is decomposed into _{H 2} O and 1/2O _{2 while oxidizing the CaS component in the desulfurization slag.} do. Therefore, in the present invention, hydrogen peroxide can be simply removed without using a platinum catalyst or performing processes such as evaporation and heating to remove hydrogen peroxide contained in spent sulfuric acid.

On the other hand, as described above, since desulfurization slag generated in an ironworks is desulfurized using quicklime as a main raw material, a large amount of unreacted quicklime component is contained in the desulfurization slag. Therefore, during the water cooling process, CaO component is _{hydrated to Ca(OH) 2} and most of it undergoes expansion and differentiation processes, so that most of it is generated in the form of powder. Therefore, it may exist in some lumps, but the energy consumption required for grinding is small. Therefore, when using the desulfurization slag, the desulfurization slag may be pulverized and used, but it may be used without pulverization, and if necessary, it can be used by sieving the desulfurization slag to a size of 10 mm or less in which a large amount of powder form is distributed. .

In addition, since the CaO component is mainly used as a desulfurization agent for molten iron in the ironworks, the desulfurization slag generated in the ironworks contains a large amount of the CaO component, so it can be used as a neutralizing agent for spent sulfuric acid or sulfuric acid used as a raw material for gypsum production. _{In addition, since CO 2} is already removed by a high-temperature melting reaction during the desulfurization process of a steel mill _{, CO 2} is not generated in the process of manufacturing gypsum because the desulfurization slag is a non-CO _{2 neutralizing agent.}

Therefore, since the present invention produces neutralized gypsum for cement with desulfurized slag and spent sulfuric acid, it is possible to provide an environmentally friendly neutralized gypsum without _{CO 2 generation.}

Specifically, the present invention provides a neutralized gypsum composition for cement, wherein the spent sulfuric acid and non-adherent desulfurization slag are mixed in a weight ratio of 0.7:1.0 to 1.3:1.0.

In addition, the present invention comprises the steps of selecting non-adherent desulfurization slag from desulfurization slag; preparing a mixture by mixing spent sulfuric acid and the non-attached desulfurization slag in a weight ratio of 0.7:1.0 to 1.3:1.0; And it provides a method for producing neutralized gypsum for cement, comprising the step of drying the mixture.

At this time, the spent sulfuric acid and non-adherent desulfurization slag may be mixed in a weight ratio of 0.7:1.0 to 1.3:1.0, preferably 1.0:1.0 may be mixed in a weight ratio. The ratio by weight of the waste sulfuric acid and non-complex desulfurization slag 0.7: 1.0, for not preferable because a sufficient neutralization during the neutralization gypsum produced less the amount of waste sulfuric acid occur, neutralized gypsum produced by it, the SO ₃ content of the cement is less than Problems that do not meet the gypsum standard may occur. On the other hand, if it exceeds 1.3:1.0, the amount of spent sulfuric acid is large and unreacted spent sulfuric acid remains even after the neutralization reaction, so due to the deliquescent properties of the remaining spent sulfuric acid, it has the property of adsorbing moisture even after neutralized gypsum production, which is not preferable.

In addition, the non-attached desulfurization slag can select a powder having a particle size of 10 mm or less in which a large amount of powder form is distributed in the desulfurization slag. Therefore, the non-attached desulfurization slag may be selected into a powder of 10 mm or less through sieve classification, and a separate crushing process may not be required.

In this case, based on the total weight of the non-magnetic slag, the non-magnetic slag may contain 30 to 60 wt% of CaO and 0.1 to 5.0 wt% of metallic iron (M-Fe).

Furthermore, the non-adherent desulfurization slag may be obtained in the following process. First, the molten desulfurization slag is put in a pot, poured into the slag cooling field, and cooled by spraying. In order to sort the grain iron, which is a valuable component, contained in the cooled desulfurization slag, magnetic and non-magnetizing materials and dust-collected powder are separated through processes such as drying, sieving, crushing, and magnetic separation. Although kish carbon is concentrated in the dust collection powder, there is a small amount of kish carbon in the desulfurization slag of non-magnetized matter.

Therefore, a small amount of metallic iron powder contained in the non-desorbed desulfurization slag reacts with _{a small amount of H 2} O ₂ contained in the waste sulfuric acid generated in the semiconductor process to act as a catalyst for decomposition _{into H 2} O and 1/2O ₂ . Therefore, in the present invention, heating and evaporating processes using a platinum catalyst to decompose and remove _{H 2} O _{2 in spent sulfuric acid may be omitted. Therefore, in the present invention, H 2} O ₂ in the spent sulfuric acid can be simply removed by simply mixing the non-attached desulfurization slag and the spent sulfuric acid.

However, since the iron component in the desulfurization slag is impregnated in the slag, it is difficult to completely remove it by magnetic lines as described above. However, the present invention, the iron content a small amount of contained non-tinted desulfurization slag and a neutralization reaction when the iron content of the spent sulfuric acid is directly reacted with the sulfuric acid, the precipitation and crystallization of the dissolved and FeSO ₄ of iron proceeds rapidly FeSO _{4 ·} Since 7H ₂ O is generated, it is possible to prepare a neutralized gypsum in _{which FeSO 4·} 7H _{2 O is mixed in the prepared gypsum.}

Since FeSO _4· 7H ₂ ^{O thus formed can serve as a reducing agent for reducing Cr 6+} contained in cement, the neutralized gypsum for cement prepared by the neutralized gypsum composition for cement of the present invention can be utilized as a functional gypsum. .

Accordingly, the present invention provides a cement comprising neutralized gypsum for cement formed by drying the neutralized gypsum composition for cement of the present invention, and the neutralized gypsum for cement _{may be one in which FeSO 4·} 7H ₂ O is formed.

At this time, the neutralized gypsum for cement of the present invention prepared as described above may contain _{0.5 to 25% by weight of FeSO 4·} 7H _{2 O based on the total weight of the neutralized gypsum for cement.} This is when the M-Fe contained in the non-desorption desulfurization slag reacts with sulfuric acid to become FeSO _4· 7H ₂ O, the weight increases by about 5 times, and therefore, M-Fe 0.1-5 in the non-desorption desulfurization slag This is because 0.5 to 25% by weight of FeSO _4· 7H ₂ O is produced when all of the weight % reacts with sulfuric acid to form FeSO _4· 7H _{2 O.}

Hereinafter, the present invention will be described in more detail through specific examples. The following examples are merely examples to help the understanding of the present invention, and the scope of the present invention is not limited thereto.

Example

The slag generated in the desulfurization process of the molten iron pretreatment process of the integrated steelworks is cooled through the spray cooling process, and the large-scale granulated iron is removed through a sieve and then crushed, dried, and magnetically separated through processes such as dust collection, magnetic and non-magnetic materials. Among those classified by , non-magnetic materials were selected, and spent sulfuric acid generated during the semiconductor process was used. indicated.

Category (unit: wt%) CaO SiO ₂ MgO Al ₂ O ₃ T-Fe M-Fe S C Degassing slag dust collection powder 61.2 10.6 2.6 1.4 9.2 0.5 1.5 5.0 Non-adhesive desulfurization slag
(10mm or less) 41.2 14.0 2.1 1.6 19.3 2.0 0.5 1.0

T-Cr Cu CD As Pb Si Ti 0.1 mg/l or less 0.1 mg/l or less 0.1 mg/l or less 0.2 mg/l or less 0.1 mg/l or less 0.2 mg/l or less 0.31 mg/l Hg F Cl SO ₄ (%) H ₂ O ₂ (%) importance non-detection non-detection 302 mg/l 64.8 0.77 1.51

Among the non-bonding desulfurization slag, the non-bonding desulfurization slag having a particle size of 10 mm or less was mixed with the spent sulfuric acid, and the spent sulfuric acid and the non-bonding desulfurization slag were mixed while changing the weight ratio of the spent sulfuric acid. The mixing weight ratio is summarized in Table 3.

Category (weight ratio) spent sulfuric acid Non-adhesive desulfurization slag Comparative Example 1 0.3 1.0 Example 1 0.7 1.0 Example 2 1.0 1.0 Example 3 1.3 1.0 Comparative Example 2 1.5 1.0

As described above, a neutralized gypsum composition for cement was prepared by mixing spent sulfuric acid and non-adhering desulfurization slag. Furthermore, by naturally drying the prepared neutralized gypsum composition for cement, A neutralized gypsum for cement was prepared, and the chemical composition of the neutralized gypsum was analyzed by XRF in order to analyze the components of the prepared neutralized gypsum. The results are summarized in Table 4, among which the results of the neutralized gypsum corresponding to Examples 1 to 3 are shown in FIG.

Category (wt%) CaO SiO ₂ Al ₂ O ₃ MgO Fe ₂ O ₃ SO ₃ Comparative Example 1 34.7 10.5 1.8 2.1 23.7 24.5 Example 1 28.3 9.2 1.8 2.0 18.8 34.9 Example 2 24.7 8.1 1.6 1.9 17.0 42.4 Example 3 23.1 8.5 1.6 1.8 16.6 44.4 Comparative Example 2 21.7 8.0 1.5 1.7 15.9 47.2

As a result, as shown in Table 4, the SO ₃ content of the neutralized gypsum prepared with the composition of Comparative Example 1 was 24.5%, which was _{not suitable for the standard of SO 3} for cement gypsum of 25% or more. Comparative Example 5 for the neutralization gypsum made of the composition is in the risk present in the neutralization gypsum surface unreacted sulfuric acid in the SO ₃ content of problem, but the amount of sulfuric acid compared to the CaO content contained in the desulfurization slag increases insufficient for use in the neutralization gypsum cement did.

_{Furthermore, as shown in FIG. 1, FeSO 4·} 7H ₂ O is generated in the neutralized gypsum prepared with the compositions of Examples 1 to 3, _{and hydrogen peroxide (H 2} O ₂ ) contained in the spent sulfuric acid can be easily removed. could check

Experimental Example 1

The performance of the neutralized gypsum prepared with the composition of this example was compared with that of a conventionally used gypsum.

The test method was carried out in accordance with KS L ISO 679 (strength test method of cement), and the mutual compressive strength expression properties were comparatively evaluated.

For the used ordinary cement and fine powder of blast furnace slag, products produced by domestic company H were used. The binder mixing ratio was a mixture of 40% by weight of ordinary cement and 60% by weight of fine powder of blast furnace slag as a reference sample. The compressive strength of each gypsum was compared by substituting for weight%.

At this time, the neutralized gypsum used is neutralized gypsum prepared by mixing the non-adhering desulfurized slag fine powder (separated to a particle size of 90 μm or less) and spent sulfuric acid in a weight ratio of 1:1 and non-attached desulfurized slag (separated to a particle size of 10 mm or less). Neutralized gypsum prepared in a 1:1 weight ratio with waste sulfuric acid was dried and then pulverized to a size of 90 μm or less.

As a result, the results of measuring the compressive strength of cement for each gypsum are summarized in Table 5.

division Compressive strength (MPa) 3 days 7 days 28 days gypsum free 18.1 32.0 52.2 Natural anhydrous gypsum 3% 21.2 34.7 50.7 Neutralized gypsum 3%
Desulfurization slag (<90㎛): Waste sulfuric acid = 1:1 19.2 33.2 51.9 Neutralized gypsum 3%
Desulfurization slag (<10mm): Waste sulfuric acid = 1:1 18.9 32.3 52.7

According to the compressive strength results in Table 5, it was confirmed that the compressive strength equivalent to that of the existing gypsum was expressed even when the neutralized gypsum prepared in the present invention was mixed with ordinary cement and slag cement.

Experimental Example 2

In the cement of the neutralized gypsum prepared in the present invention, Cr ⁶⁺ elution inhibition performance was tested.

Ordinary cement was manufactured by Domestic Company H. ^{To improve Cr 6+} component in cement, reagent grade CaCrO ₄ was mixed with ordinary cement, and a ^{sample was prepared so that Cr 6+} component in cement was about 200 mg/kg. Specifically, 49.97 g of domestic H company cement (OPC) and _{0.03 g of reagent grade CaCrO 4} were added and mixed to prepare.

Furthermore, Cr ⁶⁺ to Cr ⁶⁺ conventional reducing agent of commercially available _{4 ·} 7H ₂ O and existing FeSO natural anhydrite was used as a comparison for the comparison of the reducing ability. The commercially available FeSO _4· 7H ₂ O and the existing natural anhydride were mixed up to 10% by weight based on 100 parts by weight of cement.

Distilled water 10 times the weight of the prepared cement was mixed, and the dissolution test was carried out by shaking for 6 hours at a solid:liquid ratio of 1:10 according to the Korean Waste Process Test Method.

After the dissolution test, the Cr ⁶⁺ content in the filtrate was measured to compare the reducing agent performance. The results are summarized in Table 6 below.

OPC+CaCrO ₄ mixture (g) Reductant mixing amount (g) reducing agent type Cr ⁶⁺ elution amount (mg/l) 25 (OPC only) 0.0 0.42 25 0.0 4.57 25 0.025 Neutralized gypsum of the present invention 4.79 natural anhydrite 4.79 FeSO ₄ 7H ₂ O 4.60 25 0.125 Neutralized gypsum of the present invention 4.48 natural anhydrite 4.52 FeSO ₄ 7H ₂ O 4.39 25 0.25 Neutralized gypsum of the present invention 4.05 natural anhydrite 4.88 FeSO ₄ 7H ₂ O 3.67 25 1.25 Neutralized gypsum of the present invention 3.33 natural anhydrite 4.81 FeSO ₄ 7H ₂ O 1.88 25 2.5 Neutralized gypsum of the present invention 3.17 natural anhydrite 4.77 FeSO ₄ 7H ₂ O 1.79

As a result, as shown in Table 6, according to the dissolution test results, it can be seen that natural anhydride does not reduce the ^{Cr 6+ component in cement.} On the other hand, it was confirmed that the neutralized gypsum prepared by the composition of the present invention can reduce the ^{Cr 6+} component to a level similar _{to that of FeSO 4·} 7H ₂ O, which is used as a ^{Cr 6+ component reducing agent in the existing cement.}

Furthermore, although the mixing ratio of the neutralized gypsum prepared with the composition of the present invention is not specified, when using the neutralized gypsum in cement companies, the _{amount of gypsum used is higher than that of the existing reducing agent FeSO 4·} 7H ₂ O, so quantitative input when mixing with cement It is easy to mix and it is advantageous to mix it uniformly with cement, so it is preferable in terms of usability compared to the existing reducing agent.

Although the embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and variations are possible within the scope without departing from the technical spirit of the present invention described in the claims. It will be apparent to those of ordinary skill in the art.

Claims (9)

spent sulfuric acid; and
Contains non-adherent desulfurization slag,
The spent sulfuric acid and non-adherent desulfurization slag are mixed in a weight ratio of 0.7:1.0 to 1.3:1.0, neutralized gypsum composition for cement.
According to claim 1,
The waste sulfuric acid is generated during the semiconductor process, neutralized gypsum composition for cement.
According to claim 1,
The non-attached desulfurization slag is generated in the desulfurization process of a steel mill, neutralized gypsum composition for cement.
According to claim 1,
Based on the total weight of the non-bonded desulfurized slag, the non-bonded desulfurized slag contains 30 to 60 wt% of CaO and 0.1 to 5.0 wt% of metallic iron (M-Fe), the neutralized gypsum composition for cement.
Selecting the non-desulfurization slag from the desulfurization slag;
preparing a mixture by mixing spent sulfuric acid and the non-attached desulfurization slag in a weight ratio of 0.7:1.0 to 1.3:1.0; and
A method for producing neutralized gypsum for cement, comprising the step of drying the mixture.
6. The method of claim 5,
The non-attached desulfurization slag is a method for producing neutralized gypsum for cement, which is selected into a powder of 10 mm or less through sieve classification.
A cement comprising neutralized gypsum for cement formed from the neutralized gypsum composition for cement of any one of claims 1 to 4.
8. The method of claim 7,
The neutralized gypsum for cement is _{to contain FeSO 4 ·} 7H ₂ O, cement.
8. The method of claim 7,
The neutralized gypsum for cement, based on the total weight of the neutralized gypsum for cement _{, containing 0.5 to 25% by weight of FeSO 4 ·} 7H ₂ O, cement.

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