Comparison Study on The Degradation of Hazardous Benzene Derivatives by Ferrate(VI)
- Abstract
- The degradation of hazardous benzene derivatives by ferrate(VI) have been demonstrated in this experiment. These result prove to be effective in the treatment of selected benzene derivatives such as bromobenzene, chlorobenzene, and toluene in aqueous solutions.
Ferrate (VI) has been studied as an alternative chemical to disinfect water and wastewater in recent years. The Coagulation and oxidation/disinfection effectiveness of two different type of ferrate(VI) (sodium ferrate and potassium ferrate) in wastewater have also been evaluated. Ferrate(VI) is synthesized by addition of ferric oxide and sodium peroxide to the mixture of calcium hypochlorite and sodium hydroxide (refer to U.S. Patent 8961921B2) with some modification steps.
Degradation of chlorobenzene by ferrate(VI) has been demonstrated and several parameters experiment were investigated. Chlorobenzene was removed effectively in the reactor. Complete degradation of chlorobenzene was achieved at molar ratio of 8/1. The degradation of chlorobenzene follows the second order reaction kinetics. The activation energy calculated from the Arrhenius expression is 80.5 KJ/mol. Degradation of chlorobenzene produces 3-methylbut-1-ene and 2,2-dichloroacetic as identified intermediate products. Then further decomposition of chlorobenzene intermediates led to end products like carbon dioxide.
Degradation of bromobenzene by ferrate(VI) has been demonstrated. Bromobenzene were removed rapidly in reactor within 10 minutes of reaction time. The degradation of bromobenzene follows the second order reaction kinetics. The activation energy calculated from the Arrhenius expression are 81.1 KJ/mol. The proposed pathway of bromobenzene degradation resulted product such as isobutyraldehyde and etahane-1,2-diol.
Toluene removal was performed effectively by solid and liquid ferrate(VI). Several parameters experiment were also investigated and both ferrates(VI) showed similar pattern. The degradation of toluene by both ferrates also followed the second order reaction kinetics. The activation energy calculated from the Arrhenius expression are 79.8 KJ/mol (liquid) and 76.8 KJ/mol (solid). Both ferrates produced similar react by-products. The possible pathway for the degradation of toluene can be described by electron transfer, oxygen transfer, and opening of an aromatic ring.
Halogenated benzene, bromobenzene and chlorobenzene were degraded rapidly by ferrate(VI) in aqueous solutions. The degradation efficiency and kinetic rate of chlorobenzene were higher than bromobenzene. The electronegativity of the substituents (-Br and -Cl) play very defined role in the potential degradation by ferrate. The activation energy values are 81.1 KJ/mol and 80.5 KJ/mol for bromobenzene and chlorobenzene, respectively.
Organic pollutants, toluene, chlorobenzene, and bromobenzene were degraded rapidly by ferrate(VI). The degradation efficiency and kinetic rate of toluene were higher than chlorobenzene and bromobenzene. The functional groups (-CH3, -Cl, and -Br) play very defined role in the potential degradation by ferrate. The activation energy values are 79.4 KJ/mol, 80.5 KJ/mol, and 81.16 KJ/mol for toluene, chlorobenzene, and bromobenzene, respectively.
Based on the investigation for the ferrate reaction of bromobenzene, chlorobenzene, and toluene, the application of ferrate appears to be a promising in both water and wastewater industries in the future.
본 연구에서는ferrate(VI) 공정으로 유해 벤젠 유도체가 분해됨을 입증하였다. 이러한 결과는 수용액에서 브로모 벤젠, 클로로 벤젠 및 톨루엔과 같은 선택된 벤젠 유도체의 처리에 효과적이라는 것을 증명한다.
Ferrate(VI)는 최근 몇 년간 물과 폐수를 소독하는 대체 화학 물질로 연구되었으며, 폐수에서 두 가지 유형(고상, 액상) ferrate(VI)의 산화/소독 및 응고 효과에 대해서도 평가된 바 있다. Ferrate(VI)는 일부 수정 단계를 포함하여 칼슘 하이포클로라이트와 수산화 나트륨의 혼합물에 철 산화물과 과산화수소를 첨가하여 합성된다(미국 특허 제 8961921B2 호 참조).
Ferrate (VI)에 의한 클로로 벤젠과 브로모 벤젠의 분해를 증명하기 위해 몇 가지 매개 변수 실험이 수행되었다. 그 결과, 반응기에서 클로로 벤젠을 효과적으로 제거하였으며 몰비 8/1에서 클로로 벤젠의 완전한 분해가 달성되었다. 클로로 벤젠의 분해는 2차 반응 속도를 따랐으며 Arrhenius 식에서 계산 된 활성화 에너지는 80.5 KJ/mol이었다. 브로모 벤젠은 반응 시간 10 분 이내에 반응기에서 제거되었으며, 브로모 벤젠의 분해는 역시 2 차 반응 속도를 따랐다. Arrhenius 식에서 계산 된 활성화 에너지는 81.1 KJ/mol이었다.
유해 유기 오염물질인 톨루엔도 고상 및 액상 Ferrate (VI)에 의해 효과적으로 제거되었으며, 이에 대한 몇 가지 매개 변수 실험을 수행하였다. 두 가지 유형의 ferrate에 의한 톨루엔의 분해는 역시 2차 반응 속도론을 따랐으며, Arrhenius 식에서 계산 된 활성화 에너지는 각각 79.8 KJ/mol (액상) 과 76.8 KJ/mol (고상)이었다. 두 ferrate는 모두 유사한 반응 부산물을 생성하였으며, 톨루엔 분해는 전자 전달, 산소 전달 및 방향족 고리의 개방에 의해 분해되는 것으로 판단된다.
할로겐화 벤젠, 브로모 벤젠 및 클로로 벤젠은 ferrate(VI)에 의해 빠르게 분해되었다. 클로로 벤젠의 분해 효율 및 반응속도는 브로모 벤젠보다 높았다. 이는 치환체 (-Br 및 -Cl)의 전기 음성도가 ferrate에 의한 분해에서 매우 중요한 역할을 하기 때문인 것으로 판단된다. 브로모 벤젠 및 클로로 벤젠의 활성화 에너지 값은 각각 81.1 KJ/mol, 80.5 KJ/mol이었다.
유기오염물질인 톨루엔 및 클로로 벤젠 역시 ferrate (VI)에 의해 빠르게 분해되었다. 특히 톨루엔의 분해 효율 및 반응속도는 클로로 벤젠보다 높았다. 이는 작용기 (-CH3 및 -Cl)가 Ferrate 에 의한 분해에서 매우 중요한 역할을 하는 것으로 판단된다. 톨루엔 및 클로로 벤젠의 활성화 에너지 값은 각각 79.4 KJ/mol, 80.5 KJ/mol이었다.
이러한 결과를 바탕으로 향후 물과 폐수 산업분야에서 브로모 벤젠, 클로로 벤젠 및 톨루엔의 제거에 ferrate (VI)을 적용하는 것은 매우 유망할 것으로 판단된다.
- Issued Date
- 2018
- Awarded Date
- 2018. 8
- Type
- Dissertation
- Publisher
- 부경대학교
- Affiliation
- 부경대학교 대학원
- Department
- 대학원 마린융합디자인협동과정
- Advisor
- Kim Il-Kyu
- Table Of Contents
- TABLE OF CONTENTS
Acknowledgements i
Table of Contents ii
List of Figures vi
List of Tables x
Abstract xi
Chapter I INTRODUCTION 1
1.1. Objectives 4
Chapter II LITERATURE REVIEW 6
2.1. Contaminant Compounds Overview 6
2.1.1. Toluene 6
2.1.2. Chlorobenzene 7
2.1.3. Bromobenzene 9
2.2. Ferrate(VI) 11
2.2.1. Synthesis of ferrate(VI) 11
2.2.2. Ferrate(VI) Reactions 12
2.2.3. Ferrate Chemistry 14
Chapter III FERRATE(VI) APPLICATION FOR CHLOROBENZENE DEGRADATION 17
3.1. Introduction 18
3.2. Materials and Methods 19
3.2.1. Materials 19
3.2.2. Methods 20
3.3. Result and Discussion 22
3.3.1. Synthesis of Ferrate(VI) 22
3.3.2. Effect of pH 23
3.3.3. Effect of Molar Ratio 27
3.3.4. Effect of Temperature 30
3.3.5. Intermediate Products 32
3.4. Conclusion 35
Chapter IV FERRATE(VI) APPLICATION FOR BROMOBENZENE DEGRADATION 36
4.1. Introduction 36
4.2. Materials and Methods 38
4.2.1. Materials 38
4.2.2. Methods 39
4.3. Result and Discussion 40
4.3.1. Effect of pH 40
4.3.2. Effect of Molar Ratio 43
4.3.3. Effect of Temperature 46
4.3.4. Degradation Pathways 48
4.4. Conclusion 50
Chapter V DEGRADATION OF TOLUENE BY LIQUID FERRATE(VI) AND SOLID FERRATE(VI) 51
5.1. Introduction 52
5.2. Materials and Methods 54
5.2.1. Materials 54
5.2.2. Methods 55
5.3. Results and Discussion 57
5.3.1. Synthesis of Solid and Liquid Ferrate(VI) 57
5.3.2. Effect of pH 59
5.3.3. Effect of Molar Ratio 65
5.3.4. Effect of Temperature 68
5.3.5. Intermediate Products Study and Degradation Pathways 72
5.4. Conclusion 76
Chapter VI BROMOBENZENE AND CHLOROBENZENE DEGRADATION BY FERRATE(VI) 77
6.1. Introduction 78
6.2. Materials and Methods 80
6.2.1. Materials 80
6.2.2. Methods 80
6.3. Result and Discussion 81
6.3.1. Effect of pH 81
6.3.2. Effect of Molar Ratio 83
6.3.3. Effect of Temperature 85
6.4. Conclusion 88
Chapter VII TOLUENE, CHLOROBENZENE AND BROMOBENZENE DEGRADATION BY FERRATE(VI) 89
7.1. Introduction 90
7.2. Materials and Methods 92
7.2.1. Materials 92
7.2.2. Methods 92
7.3. Result and Discussion 93
7.3.1. Effect of pH 93
7.3.2. Effect of Molar Ratio 96
7.3.3. Effect of Temperature 97
7.3.4. Degradation Pathways of Toluene and Halogenated Benzene 100
7.4. Conclusion 101
Chapter VIII CONCLUSIONS AND RECOMMENDATIONS 103
8.1. Conclusions 103
8.2. Further Recommendations 105
REFERENCES 107
- Degree
- Master
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