KR960003607B1 - Manufacturing method of solution-liquid for mno2 - Google Patents

Manufacturing method of solution-liquid for mno2 Download PDF

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KR960003607B1
KR960003607B1 KR1019920025812A KR920025812A KR960003607B1 KR 960003607 B1 KR960003607 B1 KR 960003607B1 KR 1019920025812 A KR1019920025812 A KR 1019920025812A KR 920025812 A KR920025812 A KR 920025812A KR 960003607 B1 KR960003607 B1 KR 960003607B1
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solution
manganese oxide
gas
hydrogen peroxide
sludge
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KR940014158A (en
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한상남
우용택
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포항종합제철주식회사
정명식
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/96—Regeneration, reactivation or recycling of reactants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/54—Nitrogen compounds
    • B01D53/56—Nitrogen oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/73—After-treatment of removed components

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Abstract

This relates to manufacturing of manganese oxide dissolvent solution occurred during dissolving manganese oxide sludge which is formed from KMnO4 and NOx. This solution is composed of the mixture of 0.5-3% hydrogen peroxide solution and 2-10% sulfuric acid solution in the volume ratio of 1:1. This dissolvent solution is useful for NOx scrubbing plant.

Description

망간산화물 용해액 제조방법Manganese Oxide Solution

본 발명은 질소산화물(NOX)을 제거할 때 생성되는 망간산화물 슬러지(sludge)를 분해, 용해시키는데 사용하는 망간산화물 용해액 제조방법에 관한 것이다.The present invention relates to a method for preparing a manganese oxide solution for use in decomposing and dissolving manganese oxide sludge generated when removing nitrogen oxide (NO X ).

일반적으로 금속표면 처리공정, 보일러, 가열로, 소결로등의 연소설비와 질산제조 관련설비에서는 NO, NO2등의 질소산화물(이하 NOX라 함)이 발생하는데, 이러한 NOX가스가 대기중에 그대로 배출될 경우 심각한 환경오염을 야기시키게 되므로 현재 환경청에서는 NOX가스의 배출허용기준치를 200ppm 이하로 설정하여 관리하고 있지만 환경보호 측면에서 NOX가스 배출기준치는 향후 더 강화될 것으로 예상된다.During the generally metal surface treatment process, boiler, heating, it is to occur (hereinafter referred to as NO X d) the combustion equipment and the nitric acid production-related equipment, such as NO, nitrogen oxide NO 2, such as by sintering, this NO X gas atmosphere If the discharge so as serious pollution and cause the current environmental protection Agency in the nO X emission threshold value, but in view of environmental protection and management by setting a reference value of the nO X emission gas to less than 200ppm are expected to be further more enhanced.

따라서, 배기가스중의 NOX의 함유량을 낮추거나 제거하는 기술에 대한 연구가 현재 활발히 진행중에 있다. 그러나 이러한 기술은 금속표면처리 및 질산 제조시의 배기가스와 같이 NOX가스의 함유량이 많을 경우에는 유용하지만, 보일러 가열로, 소결로 등의 연소설비에서 발생되는 배기가스는 NOX가스의 농도가 낮고 산소함유량도 낮기 때문에 상기한 기술 즉, NOX의 함유량을 낮추거나 제거하는 기술을 실용화하는데 많은 어려움이 따르고 있다.Therefore, research on the technology of lowering or removing the content of NO x in the exhaust gas is actively underway. However, this technique is useful when there are many content of NO X gas, such as exhaust gas at the time of treatment and nitric acid manufacturing metal surface, but the boiler is heated, the exhaust gas generated in combustion equipment such as sintering is the concentration of NO X gas Because of its low oxygen content and low oxygen content, there are many difficulties in the practical use of the above-described technique, that is, a technique for lowering or removing the content of NO X.

배기가스중의 NOX를 제거하는 방법은 크게 건식법과 습식법으로 분류할 수 있으며, 건식법에서는 중화법, 용융환원법이 있고, 습식법에는 산화흡수법과 환원법이 있다. 건식방법은 배출가스의 온도가 높으며 발생되는 NOX가스의 농도가 일정하고 1,000(mg/ℓ) 이하의 저농도일 경우에 효과적이고 경제적으로 처리할 수 있는 방법이고, NOX가스가 1,000(mg/ℓ) 이상으로 고농도이고 가스의 온도가 낮은 경우에 안정적으로 처리할 수 있는 방법이 습식방법이다.NO x in the exhaust gas can be largely classified into a dry method and a wet method. The dry method includes a neutralization method and a melt reduction method, and the wet method includes an oxidation absorption method and a reduction method. The dry method is an effective and economical method when the temperature of the exhaust gas is high, the concentration of generated NO x gas is constant and low concentration is less than 1,000 (mg / l), and the NO x gas is 1,000 (mg / Wet method is a method that can be treated stably in case of high concentration above l) and low temperature of gas.

한편, 스테인리스강은 열간압연 후 소둔(燒鈍)을 하고, 소둔시 생성된 스케일을 제거하기 위하여 질산(HNO3)과 불산(HF)을 혼합한 용액으로 산세(酸洗)를 하는데, 이때 스테인리스강의 표면에 산(酸)이 분사되어 반응할때에 NOX가스가 발생한다.On the other hand, stainless steel is subjected to annealing after hot rolling and pickling with a solution of nitric acid (HNO 3 ) and hydrofluoric acid (HF) in order to remove scale generated during annealing. and a NO X gas is generated when the acid is (酸) is injected in response to the river surface.

이 경우 NOX가스를 제거하는 방법으로는 상기에서 설명한 습식법 중에서 과망간산칼륨(KMnO4)을 이용한 산화흡수법을 주로 이용한다. 과망간산칼륨 산화흡수법은 가스 용량이 많고 가스의 온도가 낮은 경우에 많이 사용하는데, 과망간산칼륨은 NOX가스와 반응하여 하기 식(1)과 같이 반응한다.In this case, as a method of removing the NO X gas, an oxidation absorption method using potassium permanganate (KMnO 4 ) is mainly used in the above-described wet method. The potassium permanganate oxidation absorption method is used when the gas capacity is high and the temperature of the gas is low. Potassium permanganate reacts with NO x gas and reacts as in the following formula (1).

NO＋KMnO4－KNO3＋MnO2…………………………(1)NO + KMnO 4- KNO 3 + MnO 2 . … … … … … … … … … (One)

즉, NOX를 제거하는 과정은 상기 (1)식에 나타난 바와같이 정상적인 반응에서 망간산화물(MnO2) 슬러지(sludge)가 생성됨을 알 수 있다.That is, in the process of removing NO X , it can be seen that manganese oxide (MnO 2 ) sludge is produced in a normal reaction as shown in Equation (1).

망간산화물 슬러지는 NOX가스 제거설비에 고착되어 노즐이 폐쇄되거나 배관내부가 막히는 경우가 빈번하여 NOX가스를 충분히 제거하지 못하여 규정치 이상의 NOX가스가 배기되어 심한 환경공해를 일으키게 된다. NOX가스 제거 설비에 고착되는 고착물의 조성을 분석하면 하기 표-1과 같다.Manganese oxide sludge is causing severe environmental pollution is secured to the NO X gas removal system nozzle is closed or a predetermined value or more frequently to NO failure to sufficiently remove NO X gas X gas if the inner pipe is clogged exhaust. By analyzing the composition of water to be fixed secured to the NO X gas removal equipment shown in the following Table-1.

[표 1]TABLE 1

고착물의 조성분석 결과Composition Analysis Result of Fixture

표 1로부터 알 수 있는 바와같이 산화물의 대부분은 망간산화물(MnO2)과 불화나트륨(NaF)이다. 그런데 불화나트륨(NaF)은 액체이기 때문에 문제가 되지 않으며, NOX가스 제거 설비에 고착되어 노즐을 폐쇄시키거나 배관내부를 막는 것은 주로 망간산화물(MnO2)이다.As can be seen from Table 1, most of the oxides are manganese oxides (MnO 2 ) and sodium fluoride (NaF). However, sodium fluoride (NaF) is not a problem because it is liquid, it is secured to the NO X gas removal system to close the nozzle or stopping the internal pipe is mainly manganese oxide (MnO 2).

따라서 본 발명은 과망간산칼륨(KMnO4)과 NOX가스에 의해 생성된 망간산화물 슬러지를 분해, 용해시킴으로써 NOX제거 설비의 막힘현상을 제거할 수 있는 망간산화물 용해액 제조방법을 제공하는데 그 목적이 있다.Accordingly, an object of the present invention is to provide a method for preparing a manganese oxide dissolving solution capable of eliminating clogging in an NO x removal plant by decomposing and dissolving manganese oxide sludge produced by potassium permanganate (KMnO 4 ) and NO x gas. have.

상기 목적은 황산(H2SO4)과 과산화수소(H2O2)를 적정농도로 배합하여 망간산화물 용해액을 제조함으로써 달성된다.The object is achieved by formulating sulfuric acid (H 2 SO 4 ) and hydrogen peroxide (H 2 O 2 ) at an appropriate concentration to produce a manganese oxide solution.

이하, 실시예를 참조하여 본 발명을 설명한다.Hereinafter, the present invention will be described with reference to Examples.

[실시예]EXAMPLE

본 발명은 과망간산칼륨(KMnO4)이 NOX가스와 반응하여 망간산화물 슬러지를 형성한다는 점을 고려하여 과망간산칼륨(KMnO4)에 대한 산화력이 큰 황산(H2SO4)과 과산화수소(H2O2)를 사용하여 실험하였다.In the present invention, considering that potassium permanganate (KMnO 4 ) reacts with NO x gas to form manganese oxide sludge, sulfuric acid (H 2 SO 4 ) and hydrogen peroxide (H 2 O) having high oxidizing power against potassium permanganate (KMnO 4 ) 2 ) was used.

첫째로, 1~40% 농도의 황산용액 200ml를 사용하여, 5g의 망간산화물 슬러지의 용해 상태를 분석하였다.First, the dissolution state of 5 g of manganese oxide sludge was analyzed using 200 ml of a 1-40% sulfuric acid solution.

이 경우 황산의 농도와 용해시간에 관계없이 슬러지는 완전히 용해되지 않았다. 둘째로, 1~15% 농도 과산화수소 용액 200ml를 사용하여 5g의 망간산화물 슬러지의 용해상태를 분석하였으나, 이 경우도 과산화수소(H2O2)의 농도와 용해시간에 관계없이 완전히 용해되지 않았다. 세째로 0.5~3% 농도의 과산화수소(H2O2) 200ml와 2~10% 농도의 황산(H2SO4) 200ml를 혼합한 용액으로 망간산화물 슬러지 5g의 용해상태를 분석하고, 그 결과를 표-2에 나타냈다.In this case, the sludge did not dissolve completely regardless of sulfuric acid concentration and dissolution time. Second, the dissolved state of 5 g of manganese oxide sludge was analyzed using 200 ml of a 1-15% hydrogen peroxide solution, but in this case, it was not completely dissolved regardless of the concentration of hydrogen peroxide (H 2 O 2 ) and the dissolution time. Third, a solution of 200 ml of hydrogen peroxide (H 2 O 2 ) at a concentration of 0.5 to 3% and 200 ml of sulfuric acid (H 2 SO 4 ) at a concentration of 2 to 10% was analyzed, and the dissolved state of 5 g of manganese oxide sludge was analyzed. Table 2 is shown.

[표 2]TABLE 2

황산과 과산화수소의 농도에 따른 슬러지 용해시간Sludge Dissolution Time According to Concentration of Sulfuric Acid and Hydrogen Peroxide

표 2로부터 황산(H2SO4)과 과산화수소(H2O2)가 미량으로 혼합된 용액이더라도 시간이 흐름에 따라 망간산화물 슬러지는 완전히 용해됨을 알 수 있다.It can be seen from Table 2 that even with a solution in which sulfuric acid (H 2 SO 4 ) and hydrogen peroxide (H 2 O 2 ) are mixed in a small amount, manganese oxide sludge is completely dissolved with time.

상기 시험결과, 첫번째, 두번째 경우에서와 같이 황산이나 과산화수소 용액만을 이용했을 때는 망간산화물 슬러지를 완전히 용해시킬 수 없었으며, 과산화수소가 5% 이상일 때에는 격렬하게 반응하여 온도가 상승(5%일때 10℃ 이상)하여 안전성에 문제가 있었다.As a result of the above test, when only sulfuric acid or hydrogen peroxide solution was used as in the first and second cases, the manganese oxide sludge could not be completely dissolved, and when the hydrogen peroxide was 5% or more, it reacted violently to increase the temperature (at 10% or more when 5%). ), There was a safety problem.

세번째 실험에서는 황산과 과산화수소가 미량으로 혼합, 희석된 경우라도 시간이 흐름에 따라 망간산화물 슬러지가 완전히 용해되었다.In the third experiment, manganese oxide sludge completely dissolved over time even when sulfuric acid and hydrogen peroxide were mixed and diluted in small amounts.

황산과 과산화수소가 혼합된 용액이 망간산화물을 용해하는 반응식은 다음과 같다.The reaction formula for dissolving manganese oxide in a solution of sulfuric acid and hydrogen peroxide is as follows.

MnO2＋H2O2＋H2SO4－MnSO4＋2H2O＋O2……………(2)MnO 2 + H 2 O 2 + H 2 SO 4 -MnSO 4 + 2H 2 O + O 2 ... … … … … (2)

2KMnO4＋3H2SO4＋5H2O2－K2SO4＋2MnSO4＋8H2＋5O2…(3) 2 KMnO 4 + 3H 2 SO 4 + 5H 2 O 2 -K 2 SO 4 + 2MnSO 4 + 8H 2 + 5O 2 . (3)

상기 식(2), (3)으로부터 슬러지 상태로 고착된 망간산화물(MnO2)과 과망간산칼륨(KMnO4)이 산(酸)에 용해된 상태(MnSO4)로 됨을 알 수 있다.It can be seen from the above formulas (2) and (3) that manganese oxide (MnO 2 ) and potassium permanganate (KMnO 4 ) fixed in a sludge state are in a state (MnSO 4 ) dissolved in an acid.

특히, 상기 표-2에 나타낸 바와 같이 d, e, f 경우와 같은 배율로 희석된 용액은 슬러지의 용해상태가 매우 양호하였고, 또한 과산화수소를 5% 이상으로 하면 반응이 격렬하게 진행되고 온도가 상승하여 안전도 및 설비보존에 문제가 있었으며, 과산화수소의 농도를 일정하게 하고 황산의 농도를 점점 증가시키면 어느 정도까지는 슬러지의 용해가 빠르게 진행되었으나, 황산농도 20% 이상에서는 포화 상태가 되고, 황산의 농도가 10% 이상일 경우에는 가스의 발생이 심하여 작업 효율이 떨어졌다.In particular, as shown in Table 2, the solution diluted at the same magnification as in the case of d, e, and f was very good in the state of dissolution of sludge, and when the hydrogen peroxide was 5% or more, the reaction proceeded vigorously and the temperature increased. As the concentration of hydrogen peroxide and the concentration of sulfuric acid were gradually increased, the dissolution of sludge proceeded rapidly to a certain extent, but the concentration of sulfuric acid became saturated at the sulfuric acid concentration of 20% or more. When more than 10%, the generation of gas is severe and the working efficiency is reduced.

상기 실시예에서 설명한 바와같이 본 발명의 제조방법으로 제조된 용해액은 NOX가스 제거시 과망간산칼륨(KMnO4)과 NOX가스에 의해 생성되어 NOX가스 제거설비에 고착된 망간산화물 슬러지를 분해, 용해함으로써 노즐 표면, 배관 내부등 NOX제거설비를 용이하게 세척할 수 있는 효과가 있다.The solution was prepared by the method of the present invention as described in the above embodiment, NO X gas potassium permanganate removal (KMnO 4) and NO generated by the X gas decomposing the manganese oxide sludge adhered to the NO X gas removal system dissolved by an effect capable of easily cleaning the nozzle surface, the inner pipe, such as NO X removal system.

Claims (1)

0.5~3% 농도의 과산화수소 수용액과 2-10% 농도의 황산수용액을 1 : 1의 부피비로 혼합하는 것을 특징으로 하는 망간산화물 용해액 제조방법.A method for producing a manganese oxide solution, characterized in that the aqueous solution of hydrogen peroxide at a concentration of 0.5-3% and an aqueous sulfuric acid solution at a concentration of 2-10% are mixed at a volume ratio of 1: 1.
KR1019920025812A 1992-12-28 1992-12-28 Manufacturing method of solution-liquid for mno2 KR960003607B1 (en)

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