Sulfur dioxide capture by absorption process using amino acids from coal-fired power plant flue gas|RISS 상세보기

다국어 초록 (Multilingual Abstract)

The World Health Organization (WHO) recently warned that the world is facing a global climate crisis owing to rapidly deteriorating air quality. Nevertheless, rapid industrialization and population growth have led to a dramatic increase in the consumption of fossil fuels. Sulfur dioxide (SO2), a combustion product of fossil fuels, can threaten human health and ecosystems in the form of acid rain and smog, and can be converted into sulfate aerosols through photochemical reactions, harming human respiratory systems. The amount of SO2 emitted from coal-fired power plants is significant because coal has a higher sulfur content than other fossil fuels. However, coal-fired power plants still provide a significant portion of the world's electricity supply. Therefore, flue gas desulfurization (FGD) technology to reduce SO2 emissions is a realistic alternative, with wet FGD technology being widely used owing to its superior SO2 removal efficiency. However, the use of limestone, a traditional absorbent in wet FGD technology, is problematic as it generates large amounts of wastewater and fouling, and Korea is facing depletion of high quality limestone owing to the demand for desulfurization. Therefore, in this study, the SO2 absorption/desorption properties of amino acids, which are eco-friendly and highly biodegradable, were investigated to identify their potential as novel SO2 absorbents. In Chapter 3 of this thesis, the SO2 absorption/desorption performance of 14 different amino acid absorbers was evaluated; and in Chapter 4, the effect of molecular structure on SO2 capture was studied by investigating the SO2 absorption/desorption performance of materials with increasing alkyl chain length from the structure of glycine. Chapter 5 investigated the optimal absorbent applicable to the membrane contactor process for desulfurization by adding amino acids to ammonia solution to solve the problem of ammonia escape; and to create a synergistic effect to improve SO2 absorption performance. In Chapter 6, a study was conducted on corrosion inhibition for the application of carbon steel in FGD facilities by using eco-friendly corrosion inhibitors in the absorbent selected in Chapter 5. In conclusion, this study has identified the potential of amino acids as novel SO2 absorbers and we believe that they will make a significant contribution to the commercialization of novel of FGD technology.

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국문 초록 (Abstract)

최근 세계보건기구(WHO)는 급격히 악화되는 대기질로 인해 전 세계가 기후 위기에 직면하고 있다고 경고했다. 특히, 급속한 산업화와 인구 증가로 인해 화석 연료의 소비가 급격히 증가하면서 연소 산물인 SO2 가 산성비, 스모그 등의 형태로 인간의 건강과 생태계를 위협하며 광화학 반응을 통해 황산염 에어로졸로 전환되어 인간의 호흡기에 해를 끼치고 있다. 따라서 SO2 배출을 저감하기 위한 FGD 기술이 현실적인 대안이며, 습식 FGD 기술은 SO2 제거 효율이 가장 높은 기술로 널리 사용되고 있다. 그러나 기존의 흡수제인 석회석은 다량의 폐수 발생과 배관 막힘 등의 문제가 있으며, 우리나라는 탈황용 석회석의 고갈 문제에 직면하고 있다. 따라서 본 연구에서는 친환경적이고 생분해성이 높은 아미노산의 이산화황 흡착/탈거 특성을 탐구하여 새로운 SO2 흡수제로서의 가능성을 확인하고자 하였다. 먼저, 14 가지 아미노산 흡수제의 SO2 흡수/탈거 성능을 종합적으로 평가하였고, 반응 메커니즘을 규명하였다. 그리고 분자 구조적 차이에 따른SO2 흡수/탈거 성능을 조사하여 분자 구조가 SO2 포집에 미치는 영향을 연구하였다. 또한, SO2/CO2 경쟁 반응 속에서 높은 SO2 선택도를 가져 CO2 포집 공정에 유리한 특성을 확인하였다. 이러한 연구 결과를 통해 아미노산이 재생 가능한 SO2 흡수제로서 차세대 흡수제인 이온성액체 (ILs) 와 공융용매 (DESs)보다 우수함이 확인되었다. SO2 흡수제로서 아미노산의 활용 방안을 확장하기 위해 우수한 SO2 제거 효율로 주목받고 있는 암모니아수의 첨가제로 활용하였다. 이는 암모니아수의 가장 큰 단점인 암모니아 탈출 문제를 해결하고, 아미노산과의 시너지 효과를 통해 SO2 흡수 성능을 향상시켰다. 또한, 흡수제의 물리적 특성을 향상시켜 SO2 포집 기-액 접촉분리막 공정에 적합한 최적의 흡수제를 개발하였다. 그리고 그 최적의 흡수제에 친환경 부식 억제제를 사용하여 FGD 설비에 탄소강 적용을 위한 부식 억제에 대한 연구를 수행하였다. 이러한 다양한 연구를 통해 아미노산이 새로운 SO2 흡수제로서의 역할과 가능성을 확인하였으며, 향후 FGD 기술 발전에 큰 기여할 수 있을 것으로 기대된다.

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최근 세계보건기구(WHO)는 급격히 악화되는 대기질로 인해 전 세계가 기후 위기에 직면하고 있다고 경고했다. 특히, 급속한 산업화와 인구 증가로 인해 화석 연료의 소비가 급격히 증가하면...

목차 (Table of Contents)

CHAPTER 1. INTRODUCTION 1
1.1 Background 1
CHAPTER 2. THEORETICAL BACKGROUND 8
2.1 FGD Technology 8
2.1.1 Wet FGD 8

CHAPTER 1. INTRODUCTION 1
1.1 Background 1
CHAPTER 2. THEORETICAL BACKGROUND 8
2.1 FGD Technology 8
2.1.1 Wet FGD 8
2.1.2 Semi-dry FGD 13
2.1.3 Dry FGD 15
2.1.4 Regenerable Wet FGD 16
CHAPTER 3. SULFUR DIOXIDE ABSORPTION CHARACTERISTICS OF AQUEOUS AMINO ACID SOLUTIONS 20
3.1 Abstract 20
3.2 Introduction 21
3.3 Experimental section 25
3.3.1 Materials 25
3.3.2 SO2 absorption and desorption 28
3.3.3 Characterization of amino acid-based absorbents via 13C-NMR, 1H-NMR, and UV-Vis spectrophotometry 31
3.4 Results and discussion 31
3.4.1 SO2 absorption performances of the aqueous amino acid solutions 31
3.4.2 SO2 desorption performances of the aqueous amino acid solutions 36
3.4.3 SO2 initial absorption and desorption rates 39
3.4.4 Amino acid dissociation constants (pKa) 42
3.4.5 NMR analysis and UV-Vis spectra 45
3.4.6 Comparison of the amino acid absorption capacities with those of other DESs and ILs 52
3.4.7 Effect of operating parameters on SO2 absorption by β-Ala 54
3.5 Conclusions 57
CHAPTER 4. REVERSIBLE SULFUR DIOXIDE CAPTURE BY AMINO ACIDS CONTAINING A SINGLE AMINO GROUP AT LOW SULFUR DIOXIDE CONCENTRATIONS 59
4.1 Abstract 59
4.2 Introduction 60
4.3 Experimental section 65
4.3.1 Materials 65
4.3.2 Reaction mechanism 67
4.3.3 SO2 absorption-desorption experiment 67
4.3.4 Calculation method 70
4.3.5 Characterization methods 70
4.4 Results and discussion 73
4.4.1 Validation of the experimental method 73
4.4.2 SO2 absorption performance 75
4.4.3 SO2 desorption performance 83
4.4.4 Effect of the amino acid dissociation constants 87
4.4.5 Absorbent reusability 89
4.4.6 SO2/CO2 selectivity 91
4.4.7 Comparison of amino acid, DES and IL absorption performance 93
4.4.8 13C-NMR analysis 95
4.5 Conclusions 97
CHAPTER 5. EFFECT OF AMINO ACID ADDITIVES IN AMMONIA SOLUTION ON SO2 ABSORPTION AND AMMONIA ESCAPE USING BUBBLING REACTOR FOR MEMBRANE CONTACTOR APPLICATIONS 99
5.1 Abstract 99
5.2 Introduction 101
5.3 Experimental section 104
5.3.1 Materials 104
5.3.2 SO2 absorption mechanism 107
5.3.3 Ammonia escape mechanism 108
5.3.4 Experimental apparatus and procedures 110
5.3.5 Data analysis 113
5.3.6 Characterization methods 113
5.4 Results and discussion 114
5.4.1 Effect of amino acids additives on the SO2 absorption performance 114
5.4.2 Ammonia escape inhibition 119
5.4.3 Surface tension and theoretical breakthrough pressure 124
5.4.4 Effect of the His additive concentration 131
5.4.5 Effect of concentration of SO2 and temperature on SO2 absorption performances using 0.3 M NH4OH + 0.1 M His 133
5.4.6 NMR analysis on 0.3 M NH4OH + 0.1 M His 136
5.5 Conclusions 138
CHAPTER 6. EFFECT OF SELECTED GREEN CORROSION INHIBITORS ON SO2 REMOVAL DURING CARBON STEEL CORROSION IN AQUEOUS SOLUTIONS OF AMMONIA AND HISTIDINE 140
6.1 Abstract 140
6.2 Introduction 141
6.3 Experimental section 144
6.3.1 Materials 144
6.3.2 SO2 absorption in NH4OH-His-SO2 system 148
6.3.3 Corrosion reaction 149
6.3.4 SO2 absorption experiment 149
6.3.5 Analysis of corrosion by the weight-loss method 152
6.3.6 Characterization 152
6.4 Results and discussion 155
6.4.1 Corrosion inhibition 157
6.4.2 SO2 absorption loading 160
6.4.3 Surface analysis of carbon steel 164
6.4.4 Mechanism of corrosion inhibition in the presence of BTA 171
6.5 Conclusions 173
CHAPTER 7. CONCLUSIONS 174
REFERENCES………………………………………………….177
KOREAN ABSTRACT……………………………………….204
BIOGRAPHY…………………………………………………...206

참고문헌 (Reference)

1. Environment, t. C. C. o. M. o. t., Canadian Ambient Air Quality Standards, , 2022

2. Criteria Air Pollutants, E. P. A. o., U. States, https://www. epa. gov/criteria-air- pollutants/naaqs-table, , 2022

3. CRC handbook of Chemistry and Physics, R. R. John, CRC Press Boca Raton, FL, , 2019

4. Pandemic War and Global Energy Transitions, C. Zimm, B. Zakeri, B. Boza-Kiss, S. Pachauri, L. G. Echeverri, L. Barreto-Gomez, F. Creutzig, D., J. Rogelj, K. Paulavets, 15(17) 6114, , 2022

5. Adsorption of SOx by oxide materials: A review, J. Patarin, Y. Mathieu, M. Soulard, M. Molière, M. Vierling, L. Tzanis, Fuel Processing Technology 114 81-100, , 2013

6. Functionalized Tertiary Amines as SO2Absorbents, H. S. Kim, M. Kim, M. Cheong, Proceedings of the World Congress on Civil, Structural, and Environmental Engineering, CSEE 2016, Avestia Publishing, , 2016

7. UV spectrophotometry for monitoring toxic gases, J. Ollivier, G. Dusserre, O. Thomas, E. Dupuit, A. Dandrieux, P. Kvapil, Analusis 28(10) 966-972, , 2000

8. CRC Handbook of Chemistry and Physics (100th ed.), J. R. Rumble (Ed, CRC Press, Boca Raton, United States, , 2019

9. Coal combustion and its pollution control in China, C. a. You, X. Xu, 3511) 4467-4472, , 2010

10. International tables of the surface tension of water, L. Voljak, B. Volkov, N. Vargaftik, 12(3) 817-820, , 1983