황산암모늄 주입시 바이오매스 발전소의 오염부하 특성 연구 :A study on the characteristics of pollution load in biomass power plant with ammonium sulfate injection

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자료유형: 학위논문

저자정보: 이창열 (호서대학교, 호서대학교 대학원)

지도교수: 정진도

발행연도: 2019

저작권: 호서대학교 논문은 저작권에 의해 보호받습니다.

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이 논문의 연구 히스토리 (3)

2019

황산암모늄 주입시 바이오매스 발전소의 오염부하 특성 연구

이창열 에너지기후융합기술학과 2019.01 학위논문

2018

황산암모늄 주입시 CFBC 보일러의 오염물질 특성 연구

이창열 , 정복화 , 정진도 한국폐기물자원순환학회지 2018.01 학술저널

황산암모늄 주입시 바이오매스 발전소의 오염부하 특성 연구

이창열 , 김성후 , 정진도 한국폐기물자원순환학회지 2018.01 학술저널

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국제사회는 산업의 급진적인 발전과 더불어 환경오염과 온실가스 배출량이 증가하고, 기후변화로 인한 자연재해 발생에 대해 적극적으로 대응하고자 신 기후체제인 파리협정을 체결(2015년)하였다. 우리나라는 온실가스배출량을 2030년까지 전망치(BAU) 대비 37%를 감축하겠다고 발표하였다. 국내의 에너지 산업도 정부의 에너지전환 정책을 반영한 제8차 전력수급기본계획(2017년)에 따르면 신재생에너지를 중심으로 친환경에너지를 대폭 확대하고 원전과 석탄을 단계적으로 줄여 나가 겠다는 것이다. 정부는 태양광, 풍력 위주로 확대할 예정이지만 바이오매스도 향후 2030년까지 설비용량을 1GW 증대할 계획을 발표하였다. 그러나 바이오매스 연료 연소시 알칼리 염화물이 과열기 튜브에 융착하여 고온부식을 유발하고 있다. 과열기 튜브의 고온부식은 보일러의 안정적인 운전을 저해하여 운전 및 유지관리비용을 증가시키고 설비의
수명을 단축시키는 큰 문제점을 가지고 있다. 이 문제를 해결하기 위해 황산암모늄 주입으로 고온부식 저감 효용성이 47～93% 정도 방지효과가 있는 것으로 연구 보고되고 있으나 국내 바이오매스 발전소에 적용된 사례가 거의 없는 실정이다. 따라서 본 논문에서는 고온부식 방지기술중 하나인 황산암모늄을 주입하여 바이오매스 발전소의 고온부식에 문제가 되는 오염부하 특성 연구를 통해 다음과 같은 결과를 얻었다. 첫째, 황산암모늄 주입량에 비례하여 염화칼륨(KCl) 농도가 감소되었다. 그 이유는 황산암모늄 주입시 염화칼륨(KCl)의 발생량을 줄여서 고온부식을 저감하는데 효과가 있는 것으로 판단되었다. 둘째, 황산암모늄 주입위치에 따라 SO2의 농도가 각각 126.9 ppm, 87.2 ppm 이 증가되었고 황산암모늄 주입량 비례하여 증가되었다. 그 이유는 황산암모늄이 염화칼륨(KCl)과 반응하면서 보일러 내에서 SO2 가 증가한 것으로 사료된다. 셋째, 황산암모늄 주입량에 따라서 염화수소(HCl)의 농도가 증가되었다. 그 이유는 황산암모늄을 주입하면 염화칼륨KCl)와 반응하여 염화수소(HCl)를 생성하고 황화합물(K2SO4)로 전환되어 염화수소(HCl)가 증가한 것으로 판단되었다. 넷째, 황산암모늄 주입량이 증가함에 따라 NOx 발생량은 23 ppm 저감되었고, CO의 발생량은 6.8 ppm증가되었다. 그 이유는 황산암모늄에서 분리된 NH3 에 의한 NOx 제거효과에 의한 것으로 사료된다. 다섯째, 황산암모늄 주입시 보일러 과열기 튜브의 부식이 약 87%～ 93% 감소되는 것을 확인하였다. 여섯째,1등급 연료의 혼합비율을 높혀서 실험한 결과 염화칼륨(KCl) 농도가 낮고 SOx, NOx, CO도 낮게 나타났으나 염화수소(HCl)은 높아졌다. 이 결과는 연료혼합 비율에 따라 연료성분이 다르기 때문인 것으로 판단되었다. 일곱째, 고온부식 Probe 시험에서 16Mo3 재료는 다른 재료에 비해 염화물 부식에 대해 가장 적은 민감도를 가짐에도 불구하고 13CrMo4-5 및 10CrMo9-10 합금보다 장기간 Creep 저항에 약하여 국내 바이오매스 발전소의 높은 과열기 온도 때문에 16Mo3 소재는 바람직하지 않다고 판단되었다. 본 연구결과 황산암모늄 주입량에 따라 염화칼륨(KCl)를 감소시켜 고온부식 방지에 효과가 있었으며 NOx 저감효과를 가져왔다. 황산암모늄의 불충분한 주입은 튜브의 부식을 초래하고 과도한 주입량은 HCl 및 SOx의 증가를 초래하여 연료성분에 따라 적정한 주입량을 결정해야 할 것으로 판단된다.

The international community has concluded a new climate regime, the Paris Agreement, to cope with natural disasters caused by climate change as the greenhouse gas emissions increase along with the radical evelopment of the industry. The Korean government announced its goal to reduce greenhouse gas emission by 37% compared to the forecast by 2030. According to the eighth power supply basic plan, which reflects the government’s energy conversion policy, the domestic energy industry will significantly expand eco-friendly energy and reduce nuclear power plants and coal gradually, centering on renewable energy. The government plans to expand the solar power and wind power, but biomass power also announced plans to increase 1GW of capacity by 2030. However, during the combustion of biomass fuel, alkali chloride is deposited in the superheater tube, causing high-temperature corrosion. The high-temperature corrosion of the superheater tube has a major problem that hinders the stable operation of the boiler, thus increasing the operation and maintenance cost and shortening the lifetime of the power plant. In order to solve this problem, it has been reported that the injection of ammonium sulfate has the effect of preventing the high-temperature corrosion reduction by 47% to 93%, but there are few cases applied to domestic biomass power plants. therefore, in this thesis, the following results were obtained from the study on the characteristics of pollution loads, which
are problematic for the high-temperature corrosion of biomass power plants by injecting ammonium sulfate, one of the techniques to prevent high-temperature corrosion. First, the concentration of potassium chloride
was reduced in proportion to the amount of ammonium sulfate injected. The reason is believed to be effective in reducing high-temperature corrosion by reducing the amount of potassium chloride when ammonium sulfate is injected. Second, depending on the position of ammonium sulfate injection.
the concentration of SO2 increased 126.9ppm and 87.2ppm respectively and increased in proportion to the amount of ammonium sulfate injected. The reason is that SO2 increased in the boiler while ammonium sulfate reacted with potassium chloride. Third, the concentration of hydrogen chloride was increased according to the injection amount of ammonium sulfate. The reason is that when ammonium sulfate is injected, it reacts with potassium chloride to produce hydrogen chloride and convert it to a sulfur compound. It is considered that hydrogen chloride is increased by this reaction. Fourth, as the injection amount of ammonium sulfate increased, the NOx concentration was reduced by 23 ppm and the CO concentration was increased by 6.8ppm. The reason is attributed to NOx removal effects by NH3 separated from ammonium sulfate. Fifth, it was confirmed that the corrosion of the boiler superheater tube decreases by 87% to 93% upon injection of ammonium sulfate. Sixth, increasing the mixing ratio of first-class fuels resulted in lower potassium chloride and lower SOx, NOx, CO but increased HCl. This result is considered to because the fuel component varies according to the fuel mixture ratio. Seventh, the 16Mo3 has the least sensitivity to
Chlorine-corrosion of the three materials analyzed. Nevertheless one has to consider that the 16Mo3 material has a weaker long period creep resistance than the 10CrMo9-10 and 13CrMo4-5 alloys, which makes the 16Mo3 material very unfavorable for the relatively high superheater temperatures in the biomass power plant boiler. The results of this study showed that potassium chloride was reduced according to the injection amount of ammonium sulfate, which helped prevent high-temperature corrosion and resulted in NOx
reduction. Inadequate injection of ammonium sulfate causes corrosion in tubes and excessive injection results in increased HCl and SOx, so it is considered necessary to determine the appropriate injection amount depending on the fuel component.

목 차
Ⅰ. 서 론 ························································································ 1
1. 연구의 배경 및 목적 ··································································· 1
2. 연구의 방법과 범위 ····································································· 3
Ⅱ. 이론적 배경 및 문헌조사 ····························································· 4
1. 순환유동층 보일러 개요 ································································ 4
2. 바이오매스의 분류 및 연료 특성 ·················································· 16
3. 바이오매스 REC 현황 ································································· 23
4. 바이오매스 보일러의 부식현상 ··················································· 24
5. 고온부식의 발생 메커니즘 ··························································· 35
6. 고온부식방지 기술 ····································································· 40
7. 황산암모늄의 특성 ······································································ 49
Ⅲ. 실험장치 및 방법········································································· 51
1. 실험 Pilot Plant ··········································································· 51
2. 실험장치의 구성 ·········································································· 52
가. 과열기튜브외면 Scale, Clinker, Ash분석장치 ······························ 52
나. 황산암모늄 주입시험장치 ···························································· 52
다. 고온부식 Probe 시험장치 ··························································· 54
3. 실험방법 및 측정 ········································································ 56
가. 과열기튜브 외면 Scale 및 Clinker, Ash분석방법 ·························· 56
나. 예비시험 1차 황산암모늄 주입방법 ·············································· 56
다. 예비시험 2차 황산암모늄 주입방법 ·············································· 58
라. 연료혼합 비율에 따른 황산암모늄 주입방법 ··································· 60
마. 고온부식 Probe 시험방법 ····························································· 61
Ⅳ. 연구결과 및 고찰 ·········································································· 64
1. 과열기튜브 외면 Scale 및 Clinker, Ash 분석결과 ···························· 64
2. 예비시험 1차 황산암모늄 주입 분석결과 ········································· 70
3. 예비시험 2차 황산암모늄 주입 분석결과 ········································· 77
4. 연료혼합 비율에 따른 황산암모늄 주입 분석결과 ····························· 82
5. 황산암모늄 주입시 과열기튜브 부식 분석결과 ································· 96
6. 고온부식 Probe 시험 분석결과 ····················································· 99
Ⅴ. 결 론 ························································································ 104
참고문헌 ·························································································· 106
Abstract ························································································· 113

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