ABSTRACT
Undoped and doped goethite catalysts were synthesized and applied in the Fentondepuration of Kaduna refinery wastewater. The of copper in the doped was 0.2 wt% copper in Cu-doped (A), 1.6 wt% copper in Cu-doped (B), and 3.3 wt% copper in Cu-doped (C), respectively.
Characterization of the catalysts was done using X-ray (XRD), Scanning Electron Microscopy (SEM), Atomic Spectrophotometer (AAS), and Surface Area Analysis.
An experimental design matrix was used to evaluate the individual and combined effects of the process variables. Response surface methodology (RSM) was applied with a central composite design (CCD), and models were developed.
The optimal conditions are pH of 3, 360 minutes reaction time, catalyst loading of 55mg/L, and hydrogen peroxide dosage of 1.1g/L.Astonishingly,
appreciable depuration percentage was achieved at near-neutral pH, 67.44% was achieved by the undoped catalyst, 79%, 82.56%, and 83.72% were by the Cu-doped A, B, and C goethite catalysts, respectively.
The obtained models for the undoped and doped catalysts gave R-square (R2) values of 0.9471, 0.9794, 0.9371, and 0.9407, respectively which showed that the experimental data fitted the model fairly well, depicting the viability and reliability of the model.
It was observed that the Cu-doped goethite catalysts yielded improved depuration, confirming that the doped catalysts have great potential as an efficient tool for Fenton depuration of petroleum refinery wastewater.
TABLE OF CONTENTS
COVER PAGE ………………………………………………………………………………………………….. i
TITLE PAGE ……………………………………………………………………………………………………. ii
DECLARATION ……………………………………………………………………………………………… iii
CERTIFICATION …………………………………………………………………………………………….. iv
ACKNOWLEDGEMENT……………………………………………………………………………………. v
ABSTRACT …………………………………………………………………………………………………….. vi
TABLE OF CONTENTS ………………………………………………………………………………….. vii
LIST OF TABLES ……………………………………………………………………………………………. xi
LIST OF FIGURES …………………………………………………………………………………………. xii
LIST OF ABBREVIATIONS ……………………………………………………………………………. xv
CHAPTER ONE: INTRODUCTION ……………………………………………………………………. 1
1.1 Preamble ………………………………………………………………………………………………………. 1
1.2 Problem Statement …………………………………………………………………………………………. 3
1.3 Aim and Objectives ………………………………………………………………………………………… 3
1.4 Scope ……………………………………………………………………………………………………………. 4
1.5 Justification …………………………………………………………………………………………………… 4
CHAPTER TWO: LITERATURE SURVEY………………………………………………………….. 5
2.1 Petroleum Refinery Wastewater ………………………………………………………………………. 5
2.1.1Wastewater composition and effect…………………………………………………. 6
2.1.2 Sources of refinery wastewater…………………………………………………………… 8
2.1.3 Refinery wastewater characterization………………………………………………….. 8
2.2 Wastewater Treatment Methods …………………………………………………………………….. 13
2.2.1 Primary treatment methods ……………………………………………………………… 14
2.2.2 Secondary treatment methods …………………………………………………………… 15
2.3 Advanced Oxidation Processes ………………………………………………………………………. 21
2.3.1 Adsorption treatment methods ………………………………………………………….. 24
2.3.2 Activated carbon treatment method …………………………………………………… 24
2.3.3 Zeolites ………………………………………………………………………………………….. 25
2.3.4 Natural materials …………………………………………………………………………….. 26
2.3.5 Photocatalysis …………………………………………………………………………………. 26
2.4 Fenton Oxidation ………………………………………………………………………………………….. 27
2.4.1 History of Fenton https://innaija.com.ng/current-projects/depuration-studies-on-kaduna-refinery-wastewater-using-modified-cu-doped-goethite-catalyst/oxidation ……………………………………………………………… 28
2.4.2 Fenton process ……………………………………………………………………………….. 29
2.4.3 PRWdepuration by Fenton https://innaija.com.ng/current-projects/depuration-studies-on-kaduna-refinery-wastewater-using-modified-cu-doped-goethite-catalyst/oxidation ………………………………………………… 31
2.4.4 Sludge generation in Fenton https://innaija.com.ng/current-projects/depuration-studies-on-kaduna-refinery-wastewater-using-modified-cu-doped-goethite-catalyst/oxidation ……………………………………………….. 33
2.5 Goethite Catalyst …………………………………………………………………………………………. 34
2.5.1 Composition and properties of goethite ……………………………………………… 35
2.5.2 Occurrence of goethite …………………………………………………………………….. 38
2.5.3 Uses of goethite ………………………………………………………………………………. 39
2.5.4 The concept of doping in goethite ……………………………………………………. 40
2.6 Depuration of PRW using copper doped goethite catalyst ………………………………… 41
2.6.1 Goethite as an adsorbent …………………………………………………………………. 42
2.6.2 Cation adsorption ……………………………………………………………………………. 44
2.6.3 Anion adsorption ……………………………………………………………………………. 45
CHAPTER THREE: MATERIALS AND METHODS …………………………………………… 46
3.1 Materials ……………………………………………………………………………………………………… 46
3.2 Apparatus …………………………………………………………………………………………………….. 46
3.3 Equipment ……………………………………………………………………………………………………. 47
3.4 Experimental Procedures ………………………………………………………………………………. 47
3.4.1 Catalyst preparation …………………………………………………………………………. 48
3.4.2 Sample Characterization …………………………………………………………………… 49
3.5 Depuration Experiments ………………………………………………………………………………… 50
3.6 Analysis of the Raw and Treated Water Samples ……………………………………………… 52
3.6.1 Measurement of COD and BOD ………………………………………………………. 52
3.6.2 Measurement of pH …………………………………………………………………………. 52
3.6.3 Measurement of TDS ………………………………………………………………………. 52
3.6.4 Measurement of soluble iron content …………………………………………………. 52
CHAPTER FOUR: RESULTS AND DISCUSSION ………………………………………………. 53
4.1 Characterization of the Synthesized Catalysts …………….……………………………….. 53
4.1.1 XRD analysis of the synthesized undoped and doped goethite catalysts …. 53
4.1.2 Composition of the synthesized undoped and doped goethite catalysts ….. 56
4.1.3 Surface area analysis of the synthesized catalysts ………………………………… 56
4.1.4Particle size analysis of the synthesized catalysts ………………………………… 57
4.1.5 Morphology of the synthesized catalysts ……………………………………………. 58
4.2 Depuration of Kaduna Refinery Wastewater ……………………………………………………. 58
4.2.1 Effect of time on COD reduction ………………………………………………………. 72
4.2.2 Effect of doping on depuration percentage …………………………………………. 74
4.3 Stability Test of the Synthesized Samples ……………………………………………………….. 74
CHAPTER FIVE: CONCLUSIONS AND RECOMMENDATIONS ………………………. 76
5.1 Conclusions …………………………………………………………………………………………………. 76
5.2 Recommendations ………………………………………………………………………………………… 77
REFERENCES …………………………………………………………………………………………………. 78
APPENDICES ………………………………………………………………………………………………….. 87
APPENDIX A: Surface Area Determination…………………………………………………………. 87
APPENDIX B: Particle Size Analysis Using XRD………………………………………………… 88
INTRODUCTION
The petroleum refining process is associated with the generation of voluminous wastewater(0.4-1.6 times the volume of the oil processed) (Diya’uddeen et al., 2012).
The wastewater is predominantly o and recalcitrant ic compounds such as , toluene, ethylbenzene, and xylene which are among the most hazardous compounds released into the environment (Aranda et al.,2010).
Environmental deterioration and the increase in demand for water consumption in the industry necessitate the development of wastewater treatment technologies for the petroleum industry (Diya’uddeen et al., 2012).
The conventional wastewater treatment methods (primary and secondary) used for treating refinery effluents include mechanical and physiochemical processes such as oil-water separation, sedimentation, coagulation, and dissolved air flotation with further biological treatment (Diya’uddeen et al., 2011).
However, biological processes are not efficient for treating wastewater with high toxicity and bio-refractory compounds (Saien and Nejati2007). Therefore, it is imperative to introduce newer treatment technologies capable of effectively treating petroleum refinery wastewater.
The newer technologies include advanced https://innaija.com.ng/current-projects/depuration-studies-on-kaduna-refinery-wastewater-using-modified-cu-doped-goethite-catalyst/oxidation processes (AOP), filtration, nutrient removal, and toxic elements or chemicals removal among others (Chunli, 2013).
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Andreozzi, R., Caprio, V., Insola, A. and Marotta, R. (1999). Advanced https://innaija.com.ng/current-projects/depuration-studies-on-kaduna-refinery-wastewater-using-modified-cu-doped-goethite-catalyst/oxidationprocesses (AOP)for water purification and recovery.Catalysis Today, 53:51-59.
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