TREATMENT OF REFINERY OILY SLUDGE USING ULTRASOUND, BIO-SURFACTANT, AND ADVANCED OXIDATION PROCESSES by Ju Zhang B. S., Agricultural University of Hebei, 2005 M. S., Being Normal University, 2008 THESIS SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF SCIENCE IN NATURAL RESOURCES AND ENVIRONMENTAL STUDIES (ENVIRONMENTAL SCIENCE) UNIVERSITY OF NORTHERN BRITISH COLUMBIA September 2012 © Ju Zhang, 2012 1+1 Library and Archives Bibliotheque et Canada Archives Canada Published Heritage Direction du Branch Patrimoine de I'edition 395 Wellington Street 395, rue Wellington Ottawa ON K1A0N4 Ottawa ON K1A 0N4 Canada Canada Your file Votre reference ISBN: 978-0-494-94115-7 Our file Notre reference ISBN: 978-0-494-94115-7 NOTICE: AVIS: The author has granted a non­ L'auteur a accorde une licence non exclusive exclusive license allowing Library and permettant a la Bibliotheque et Archives Archives Canada to reproduce, Canada de reproduire, publier, archiver, publish, archive, preserve, conserve, sauvegarder, conserver, transmettre au public communicate to the public by par telecommunication ou par I'lnternet, preter, telecommunication or on the Internet, distribuer et vendre des theses partout dans le loan, distrbute and sell theses monde, a des fins commerciales ou autres, sur worldwide, for commercial or non­ support microforme, papier, electronique et/ou commercial purposes, in microform, autres formats. paper, electronic and/or any other formats. The author retains copyright L'auteur conserve la propriete du droit d'auteur ownership and moral rights in this et des droits moraux qui protege cette these. Ni thesis. Neither the thesis nor la these ni des extraits substantiels de celle-ci substantial extracts from it may be ne doivent etre imprimes ou autrement printed or otherwise reproduced reproduits sans son autorisation. without the author's permission. In compliance with the Canadian Conformement a la loi canadienne sur la Privacy Act some supporting forms protection de la vie privee, quelques may have been removed from this formulaires secondaires ont ete enleves de thesis. cette these. While these forms may be included Bien que ces formulaires aient inclus dans in the document page count, their la pagination, il n'y aura aucun contenu removal does not represent any loss manquant. of content from the thesis. Canada ABSTRACT Oil refinery sludge can be generated throughout the oil production process. It consists of a large amount of petroleum hydrocarbons (PHCs) and other hazardous materials which should be disposed of appropriately. In order to find effective methods to treat the oily sludge, three different approaches were investigated in this research, including bioremediation, oil recovery, and advanced oxidation processes (AOPs). In terms of the bioremediation approach, the oily sludge was mixed with soil, and a screened bacterium strain was then introduced with the supplement of nutrients and the addition of bio-surfactant. The reduction rate of total petroleum hydrocarbons (TPH) in oily sludge spiked soil was up to 50.8% after 40 days of biodegradation. With regard to recovering oil from the oily sludge, three processes were investigated, including ultrasonic treatment alone, freeze/thaw treatment alone, and the combined ultrasonic and freeze/thaw treatment. The experimental results revealed that the combined process could achieve satisfactory performance of oil recovery. In terms of the advanced oxidation processes (AOPs), the ultrasonic treatment alone, the Fenton process alone, and the combination of ultrasound and Fenton’s reagents, were examined for their abilities to reduce petroleum hydrocarbons (PHCs) content in oily sludge. The Taguchi experimental results indicated that the combination of ultrasound and Fenton reagents achieved the best effect, with the highest TPH reduction rate of 88.1% being observed in the experimental conditions. TABLE OF CONTENTS ABSTRACT..............................................................................................................................................ii TABLE OF CONTENTS.......................................................................................................................iii LIST OF TABLES...................................................................................................................................vi LIST OF FIGURES.............................................................................................................................viii LIST OF ABBREVIATIONS...............................................................................................................xi ACKNOWLEDGEMENT...................................................................................................................xii Chapter 1 General Introduction...........................................................................................................1 Chapter 2 Remediation of refinery oily sludge using isolated strain and biosurfactant.. 6 Abstract.....................................................................................................................................................7 1. Introduction........................................................................................................................................ 8 2. Materials and Methods...................................................................................................................10 2.1. Oily sludge and soil sample.................................................................................................10 2.2. Chemicals.................................................................................................................................11 2.3. Bacteria isolation and identification..................................................................................11 2.4. Bioremediation experiment..................................................................................................14 2.5. Analysis of total petroleum hydrocarbon (TPH)...........................................................15 3. Results and discussion...................................................................................................................17 3.1. TPH biodegradation...............................................................................................................17 3.2. Analysis of optimal bioremediation conditions...............................................................19 4. Conclusion.......................................................................................................................................25 Chapter 3 Oil recovery from refinery oily sludge via ultrasound and freeze/thaw 26 Abstract..................................................................................................................................................27 1. Introduction......................................................................................................................................28 2. Materials and methods..................................................................................................................31 2.1. Oily sludge...............................................................................................................................31 2.2. Chemicals and Bio-surfactant.............................................................................................32 2.3. Experiments on oil recovery using three different processes......................................32 2.4. Experiments on factors affecting the combined treatment process.............................35 2.5. Sample extraction and analysis............................................................................................36 2.5.1. TPH concentration in the recovered oil layer............................................................36 2.5.2. TPH concentration in separated aqueous phase.........................................................38 2.5.3. PHCs analysis...................................................................................................................39 3. Results and discussion..................................................................................................................41 3.1. Comparison of methods.......................................................................................................41 3.2. Effects of different factors on the combined treatment process...................................46 3.2.1. Effects of ultrasonic power and treatment duration..................................................46 3.2.2. Effects of sludge/water ratio..........................................................................................48 3.2.3. Effects of bio-surfactant (rhamnolipids).....................................................................49 3.2.4. Effects of salt addition (sodium chloride)...................................................................51 3.3. PHC fraction analysis for recovered oil..............................................................................52 4. Conclusion.......................................................................................................................................54 Chapter 4 Treatment of oily sludge through advanced oxidation processes......................57 Abstract..................................................................................................................................................58 1. Introduction......................................................................................................................................59 2. Materials and methods.................................................................................................................. 66 2.1. Oily sludge and chemicals................................................................................................... 66 2.2. Ultrasonic apparatus..............................................................................................................67 2.3. Experiment on oxidation of PHCs in oily sludge by three different processes 67 2.4. Experiment on factors affecting the combined process (US/Fenton)..........................70 2.5. Sample extraction after advanced oxidation processes..................................................72 2.6. PHCs analysis.........................................................................................................................75 3. Results and discussions.................................................................................................................76 3.1. Comparison of methods.........................................................................................................76 3.1.1. TPH reduction using ultrasonic irradiation alone...................................................76 3.1.2 TPH reduction through Fenton’s reaction process....................................................79 3.1.3 TPH reduction through the combination of ultrasound and Fenton’s reaction process (US/Fenton).........................................................................................................84 3.1.4 Petroleum hydrocarbons distribution in samples and fractional analysis after oxidation processes.......................................................................................................... 88 3.2. Degradation of petroleum hydrocarbons after different treatments through US/Fenton process...........................................................................................................90 iv 3.3. Impact of factors on TPH degradation through the combined (US/Fenton) process94 3.2.1. The effect of sludge content...........................................................................................97 3.2.2. The effect of ultrasonic treatment time......................................................................100 3.2.3. The effect of the ratio of H O to Fe2+.......................................................................101 2 2 3.4. Impact of factors on degradation of PHCs in different fractions through the combined (US/Fenton) process.........................................................................................102 4. Conclusion .......................................................................................................................Ill Chapter 5 General Conclusion...................... 113 Limitations and future research.......................................................................................................115 REFERENCE........................................................................................................................................117 v LIST OF TABLES Table 2.1 Summary of clean soil properties...............................................................................10 Table 2.2 Summary of oily sludge properties.............................................................................10 Table 2.3 Taguchi experimental design..................................................................................15 Table 2.4 ANOVA for bioremediation of TPH.........................................................................20 Table 2.5 ANOVA for F3 fraction degradation.........................................................................22 Table 2.6 ANOVA for F4 fraction degradation.........................................................................22 Table 3.1 Characteristics of the oily sludge................................................................................32 Table 3.2 Influencing factors and their corresponding levels.................................................36 Table 3.3 Summary of oil recovery results using different methods.....................................42 Table 3.4 PHCs fraction distribution for samples before and after US+F/T treatment... 53 Table 4.1 Experiment factors and their three levels.................................................................71 Table 4.2 L27 array orthogonal experimental design...........................................................72 Table 4.3 TPH reduction in oily sludge through US treatment alone...................................77 Table 4.4 TPH reduction in samples under Fenton process alone.........................................80 Table 4.5 TPH content in aqueous and solid phases of samples* before and after advanced oxidation processes...............................................................................................89 Table 4.6 Remaining TPH mass in samples after different US/Fenton treatments 92 Table 4.7 Degradation of petroleum hydrocarbons in samples after different US/Fenton treatments and the S/N ratio results....................................................................................93 Table 4.8 Analysis of Variance for TPH degradation after different treatments through US/Fenton process..................................................................................................................97 Table 4.9 Analysis of variance for Fraction 2 (F2) degradation after different US/Fenton treatments................................................................................................................................103 Table 4.10 Analysis of variance for Fraction 3 (F3) degradation after different treatments through US/Fenton treatments..........................................................................................104 Table 4.11 Analysis of variance for Fraction 4 (F4) degradation after different treatments through US/Fenton treatments............................................................................................104 LIST OF FIGURES Figure 2.1 Isolation procedure for PHCs degrading microorganisms..................................12 Figure 2.2 Soil contaminated with PHCs in a land-farming site...........................................13 Figure 2.3 Enrichment of bacteria................................................................................................13 Figure 2.4 Isolated strain: Luteibacter sp....................................................................................14 Figure 2.5 A flask with soil.............................................................................................................16 Figure 2.6 Setup of the bioremediation experiments................................................................16 Figure 2.7 TPH reduction rate for different treatments...........................................................18 Figure 2.8 TPH concentration remained in soil after bioremediation..................................19 Figure 2.9 Effect of independent factors on TPH reduction...................................................21 Figure 2.10 Effect of independent factors on F3 fraction reduction.....................................21 Figure 2.11 Effect of independent factors on F4 fraction reduction.....................................23 Figure 2.12 TPH fraction distribution before and after bioremediation: “Be”- before bioremediation and “Af’- after bioremediation................................................................24 Figure 3.1 Oily sludge sample.......................................................................................................31 Figure 3.2 Ultrasonic treatment system.......................................................................................33 Figure 3.3 Ultrasonic treatment for oil recovery......................................................................34 Figure 3.4 Evaporation of extraction solution...........................................................................37 Figure 3.5 Round flask with residual after evaporation...........................................................38 Figure 3.6 Aqueous sample after oil recovery...........................................................................39 Figure 3.7 Samples for GC analysis............................................................................................40 Figure 3.8 Oil recoveries for different treatment methods (error bar represents standard deviation)..................................................................................................................................42 Figure 3.9 TPH concentrations in separated oil layer (a) and water (b) (error bar represents standard deviation)..............................................................................................43 Figure 3.10 Oil recovery versus ultrasonic power for the combined process (error bar represents standard deviation) (experimental condition: ultrasonic treatment duration of 10 min, sludge/water ratio of 1:4, without the addition of rhamnolipids and NaCl)...................................................................................................................................47 Figure 3.11 Oil recovery versus ultrasonic treatment duration for the combined process (error bar represents standard deviation) (experimental condition: ultrasonic treatment power of W, sludge/water ratio of 1:4, without the addition of 66 rhamnolipids and NaCl)..........................................................................................................48 Figure 3.12 Oil recovery versus sludge/water ratio for the combined process (error bar represents standard deviation) (experimental condition: ultrasonic power of W, 66 ultrasonic treatment duration of min, without the addition of rhamnolipids and 10 NaCl)..........................................................................................................................................49 Figure 3.13 Oil recovery versus bio-surfactant concentration for the combined process (error bar represents standard deviation) (experimental condition: ultrasonic power of W, ultrasonic treatment duration of 10 min, sludge/water ratio of 1:4, without 66 the addition of NaCl)...............................................................................................................50 Figure 3.14 Oil recovery versus NaCl concentration for the combined process (error bar represents standard deviation) (experimental condition: ultrasonic power of W, 6 6 ultrasonic treatment duration of 10 min, sludge/water ratio of 1:4, without the addition of rhamnolipids).......................................................................................................52 Figure 3.15 GC profiles of samples from oil recovery treatment (A represents oil sample after US + F/T treatment and B represents original oily sludge sample)....................53 Figure 4.1 Oxidation of oily sludge using ultrasound..............................................................67 Figure 4.2 Fenton’s reaction process for degradation of oily sludge.................................... 68 Figure 4.3 Samples after US/Fenton treatment..........................................................................69 Figure 4.4 Liquid-liquid extraction...............................................................................................73 Figure 4.5 Mechanical shaking for the extraction of PHCs from solids...............................74 Figure 4.6 Extraction solution cleanup using silica gel column............................................75 Figure 4.7 Remaining TPH mass in samples after different ultrasonic treatment durations (error bar stands for standard deviation; the value at the time of stands for the 0 initial TPH mass)....................................................................................................................77 Figure 4.8 Remaining TPH mass in samples after Fenton process alone (error bar stands for standard deviation; the value at the dosage of 0 stands for the initial TPH mass) 80