Tài liệu Luận văn thạc sĩ design of stable graphene oxide copolymer nanocomposite dispersion orientated for eor application in high temperature offshore reservoirs

HOANG ANH QUAN MINISTRY OF EDUCATION AND TRAINING VIETNAM ACADEMY OF SCIENCE AND TECHNOLOGY GRADUATE UNIVERSITY OF SCIENCE AND TECHNOLOGY ORGANIC CHEMISTRY Hoang Anh Quan DESIGN OF STABLE GRAPHENE OXIDE-COPOLYMER NANOCOMPOSITE DISPERSION ORIENTATED FOR EOR APPLICATION IN HIGH-TEMPERATURE OFFSHORE RESERVOIRS Major : Organic Chemistry Code: 8440114 MASTER THESIS ORGANIC CHEMISTRY 2021 Ho Chi Minh City - 2021 MINISTRY OF EDUCATION VIETNAM ACADEMY OF AND TRAINING SCIENCE AND TECHNOLOGY GRADUATE UNIVERSITY OF SCIENCE AND TECHNOLOGY Hoang Anh Quan DESIGN OF STABLE GRAPHENE OXIDE-COPOLYMER NANOCOMPOSITE DISPERSION ORIENTATED FOR EOR APPLICATION IN HIGH-TEMPERATURE OFFSHORE RESERVOIRS Major: Code: Organic Chemistry 8440114 MASTER THESIS SCIENTIFIC SUPERVISOR: Dr. Luu Anh Tuyen Assoc. Prof. Dr. Nguyen Phuong Tung Ho Chi Minh City - 2021 ASSURANCE FOR MASTER THESIS I assure you that the data and research results in this master thesis are my research work based on documents and data that I have researched myself. Therefore, the research results ensure the most honesty and objective. At the same time, this result has never appeared in any other study. Any help in this thesis was thanked and reference information such as method, data, figures, and pictures was cited clearly. The data and results stated in the thesis are honest, if wrong, I will take full responsibility. Ho Chi Minh city, October 31st, 2021 Learner Hoang Anh Quan ACKNOWLEDGMENT Throughout the writing of this dissertation, I have received a great deal of support and assistance. I would first like to thank my scientific supervisors, Assoc. Prof. Dr. Nguyen Phuong Tung and Dr. Luu Anh Tuyen, whose expertise were invaluable in formulating the research questions and methodology. Your insightful feedback pushed me to sharpen my thinking and brought my work to a higher level. I would like to acknowledge my research group from Materials for enhanced oil recovery and energy conversion Lab - Institute of Applied Materials Science, who were always interested and enthusiastically supported me during the study period and completed this thesis experiment. I would also like to thank lecturers from Graduate University of Science and Technology, for their valuable guidance throughout my studies. You provided me with the knowledge and tools that I needed to choose the right direction and complete my dissertation. In addition, I would like to thank my parents for their wise counsel and sympathetic ear. You are always there for me. Finally, I could not have completed this dissertation without the support of my friends, who provided stimulating discussions and happy distractions to rest my mind outside of my research. ABSTRACT Thermostable and highly water-soluble polymers are essential for polymer flooding — one of the most effective methods used in the enhanced oil recovery (EOR) in hightemperature (HT) offshore reservoirs. In this research, the copolymerization reaction of acrylamide (AM) and N-vinylpyrrolidone (NVP) monomers were performed via a freeradical mechanism induced by gamma-rays (γ-rays) irradiation. The impact of input data (the ratio and the concentration of the monomer to product-solution viscosity) was scanned in detail and used to optimize the copolymerization conditions. The optimal viscosity values of the polymer concentration were 0.5 wt.%. Therefore, the optimal conditions for copolymerization were obtained at 1.7 for AM/NVP monomer ratios and 23.2 wt.% for monomers concentration. The copolymerization induced by γ-rays irradiation in optimized conditions was then carried out, and the obtained viscosity of 0.5 wt.% of produced copolymers solutions was 5.02 cP. These results were in good agreement with the calculated values. The obtained copolymers were then covalently coupled with graphene oxide (GO) synthesized from natural graphite using the modified Hummer’s method. The product nanocomposites, called GO–P(AM-NVP), were characterized by Fourier transform infrared spectroscopy, Raman spectroscopy, scanning electron microscopy, and gel permeation chromatography. The thermal and chemical stabilities of brine-dispersed P(AM-NVP) copolymers annealed at 123 °C (the WT Miocene reservoir temperature) and GO–P(AM-NVP) nanocomposite dispersion annealed at 135 °C (the WT Oligocene reservoir temperature) for 31 days were observed via visual inspection and viscosity testing. Results indicated that the dispersions of P(AM-NVP) copolymers and P(AM-NVP) copolymers conjugated on GO nanosheets have excellent thermal and chemical stabilities and hence became a promising agent for EOR in HT offshore reservoirs. GRAPHICAL ABSTRACT Hoang Anh Quan – Master thesis Contents CONTENTS CONTENTS .........................................................................................................i LIST OF FIGURES ............................................................................................ iv LIST OF TABLES............................................................................................. vii LIST OF ABBREVIATION.............................................................................. viii INTRODUCTION ............................................................................................... 1 Chapter 1: Literature Review .............................................................................. 3 1.1. Enhanced oil recovery (EOR) ........................................................................ 3 1.1.1. Introduction to Enhanced oil recovery ...................................................... 3 1.1.2. Mechanism of enhanced oil recovery ....................................................... 4 1.1.3. Enhanced oil recovery methods ............................................................... 7 1.2. Polymers ..................................................................................................... 8 1.2.1. Introduction ........................................................................................... 8 1.2.2. Polymers in EOR ................................................................................... 9 1.2.2.1. Biologically produced polymer (biopolymer) ...................................... 9 1.2.2.1. Synthetic polymer........................................................................... 10 1.2.3. Synthesis of EOR polymers ................................................................... 11 1.2.5. Mechanism of polymer flooding in EOR process..................................... 14 1.2.5.1. Capillary Number (Nc ) .................................................................... 14 1.2.5.2. Polymer flooding in EOR ................................................................ 15 1.2.6. Gamma-rays irradiation-induced copolymerization.................................. 17 1.2.6.1. Free radical copolymerization .......................................................... 17 1.2.6.2. Radiation-initiated polymerization ................................................... 18 1.3. GO–Polymer materials ............................................................................... 19 1.3.1. P(N-vinylpyrrolidone–Acrylamide) copolymers ...................................... 19 1.3.1.1. Acrylamide .................................................................................... 19 i Hoang Anh Quan – Master thesis Contents 1.3.1.2. N-vinylpyrrolidone ......................................................................... 20 1.3.2. Graphene oxide in EOR ........................................................................ 21 1.3.3. The researches about GO–Polymers materials ......................................... 22 1.3.4. The researches about GO–Popolymers materials in EOR ......................... 23 Chapter 2: Experimental ................................................................................... 25 2.1. Chemical and materials ............................................................................... 25 2.2. Equipment, instruments, software ................................................................ 27 2.3. Procedure .................................................................................................. 30 2.3.1. Graphene oxide (GO) preparation .......................................................... 30 2.3.2. Gamma-rays irradiation-induced copolymerization of AM and NVP monomers ..................................................................................................... 31 2.3.3. Optimization ...................................................................................... 32 2.3.4. Synthesis of GO–P(AM-NVP) nanocomposite .................................... 33 2.4. Determination of the effect of the monomer composition and concentration on copolymers yield ........................................................................................ 34 2.5. Characterization measurements ................................................................. 35 2.6. Thermal and chemical stabilities of P(AM-NVP) and GO–P(AM-NVP) dispersions ...................................................................................................... 35 Chapter 3: Results and Discussion ..................................................................... 37 3.1. Effect of monomer composition and concentration on product yield, molecular weight, and product viscosity............................................................................. 37 3.2. Optimization .............................................................................................. 40 3.3. Characterization of P(AM-NVP) and GO–P(AM-NVP) ................................. 42 3.3.1. FTIR of GO, P(AM-NVP) and GO–P(AM-NVP) .................................... 42 3.3.2. Raman spectra of GO and GO–P(AM-NVP) ........................................... 45 3.3.3. SEM analysis of P(AM-NVP) and GO–P(AM-NVP) ............................... 46 ii Hoang Anh Quan – Master thesis Contents 3.4. Evaluation of thermal and chemical stabilities of P(AM-NVP) copolymers and GO-P(AM-NVP) dispersions ............................................................................. 48 3.4.1. Observing the appearance after being annealing ...................................... 49 3.4.2. The viscosity of annealed samples ......................................................... 50 Chapter 4: Conclusions and Recommendations .................................................. 52 4.1. Conclusions ............................................................................................... 52 4.2. Recommendations ...................................................................................... 53 LIST OF PUBLISHED PAPERS RELATED TO LEARNER ............................ 54 REFERENCES.................................................................................................... a APPENDIX ......................................................................................................... e A.1. Pictures of the equipments and instruments .................................................... e A.2. Pictures of the softwares ...............................................................................i iii Hoang Anh Quan – Master thesis List of Figures LIST OF FIGURES Figure 1.1. Oil recovery categories ......................................................................... 4 Figure 1.2. Target for different crude oil systems ..................................................... 5 Figure 1.3. Effect of Nc on residual oil saturation..................................................... 6 Figure 1.4. Enhanced oil recovery methods ............................................................. 8 Figure 1.5. Suitable monomers for free radical polymerization................................ 12 Figure 1.6. The mechanism of free radical formation of KPS .................................. 12 Figure 1.7. Mechanism of pre-irradiation polymerization ....................................... 13 Figure 1.8. Mechanism of direct irradiation polymerization .................................... 14 Figure 1.9. Effect of capillary number on residual oil saturation and oil recovery ..... 15 Figure 1.10. Water breakthrough can be delayed and sweep efficiency improved by increasing the viscosity of the injected fluid with polymer ....................................... 16 Figure 1.11. Acrylamide powder (a), structure of acrylamide (b) and polyacrylamide (c) .......................................................................................................................... 19 Figure 1.12. Reaction formula of hydrolysis of polyacrylamide............................... 20 Figure 1.13. Structure of N-vinylpyrrolidone ......................................................... 21 Figure 1.14. Structure of graphene and graphene oxide .......................................... 21 Figure 2.1. Synthesis procedure of GO ................................................................. 31 Figure 2.2. Shortened steps of the γ-ray induced free radical P(AM-NVP) copolymerization ................................................................................................. 32 Figure 2.3. Synthesis procedure of GO–P(AM-NVP) nanocomposite ...................... 34 Figure 3.1. P(AM-NVP) copolymers after purifying (a) and P(AM-PVP) copolymers disperse in brine (b) ............................................................................................ 37 Figure 3.2. Response surface of viscosity of 0.5 wt.% copolymers solution .............. 41 Figure 3.3. FTIR spectra of (a) P(AM-NVP), (b) NVP and (c) AM ......................... 43 Figure 3.4. FTIR spectra of (a) GO–P(AM-NVP), (b) P(AM-NVP) and (c) GO........ 44 Figure 3.5. Raman spectra of (a) GO and (b) GO–P(AM-NVP)............................... 46 iv Hoang Anh Quan – Master thesis List of Figures Figure 3.6. SEM images of P(AM-NVP) copolymers [(a) and (b)] and GO–P(AM-NVP) nanocomposite (c) ............................................................................................... 46 Figure 3.7. Scanning electron microscopy energy-dispersive X-ray spectroscopy (SEMEDX) of GO-copolymer ....................................................................................... 47 Figure 3.8. SEM mapping pictures of fracture surfaces of (a) GO–P(AM-NVP) and elemental mapping images of GO–P(AM-NVP) for (b) oxygen, (c) carbon, (d) nitrogen .......................................................................................................................... 48 Figure 3.9. GO–P(AM-NVP) nanocomposite after free-drying (a) GO–P(AM-NVP) disperse in brine (b) ............................................................................................. 48 Figure 3. 10. Viscosity of (a) 0.5 wt.% P(AM-NVP) copolymers in brine annealed at 123 °C and (b) 1.0 wt.% GO–P(AM-NVP) nanocomposite in brine annealed at 135 °C during 31 days..................................................................................................... 51 Figure A.1. Powersonic 603 Hwashin Technology .................................................. e Figure A.2. Drying/Oven – Shellap ........................................................................ e Figure A.3. Digital Temperature Control Hotplate with Magnetic Stirrer ................... e Figure A.4. Ultrasonic Hielscher UP 100H.............................................................. f Figure A.5. FreeZone 6L Benchtop Freeze Dry Systems .......................................... f Figure A.6. pH/ORP Mettler Hana HI 3220............................................................. f Figure A.7. Brookfield DV-III Ultra ....................................................................... g Figure A.8. Stuart RE300 Rotary Evaporator........................................................... g Figure A.9. Fourier transform infrared spectroscopy (FT-IR) PerkinElmer frontier ..... g Figure A.10. DSC-3/TGA Mettler Toledo ............................................................... h Figure A.11. Raman Horiba Xplora One ............................................................... h Figure A.12. StatGraphics 18–X64 software.............................................................i Figure A.13. Origin 8.5 software .............................................................................i Figure A.14. Mendeley Desktop..............................................................................j Figure A.15. MathType 7 software ..........................................................................j v Hoang Anh Quan – Master thesis List of Figures Figure A.16. Chemdraw Professional 16.0 software ................................................. k vi Hoang Anh Quan – Master thesis List of Tables LIST OF TABLES Table 2.1. Chemical and materials used for experiments ......................................... 25 Table 2.2. The ingredient and properties of brine ................................................... 27 Table 2.3. Characteristics of WT Miocene and Oligocene Reservoirs [58]................ 27 Table 2.4. Equipment, instruments, and software used for characterizing/researching the obtained materials................................................................................................ 28 Table 2.5. Result of P(AM-NVP) polymerization at different irradiation dose .......... 31 Table 2.6. Experimental conditions for optimization of polymerization .................... 33 Table 3.1. Effect of monomer composition and concentration on product yield and molecular weight ................................................................................................. 38 Table 3.2. Effect of monomer composition and concentration on product viscosity ... 39 Table 3.3. The viscosity value of 0.5 wt.% polymer solution at different polymerization conditions ........................................................................................................... 40 Table 3.4. Results of optimization ........................................................................ 41 Table 3.5. Viscosity of optimal-condition polymer solutions at different concentrations .......................................................................................................................... 42 Table 3.6. FTIR results of (a) P(AM-NVP), (b) NVP and (c) AM............................ 43 Table 3.7. FTIR results of (a) GO–P(AM-NVP), (b) P(AM-NVP) and (c) GO.......... 45 Table 3.8. Viscosity of GO–P(AM-NVP) nanocomposite dispersed in brine at different concentrations ..................................................................................................... 49 Table 3.9. Appearance of P(AM-NVP) 0.5 wt.% and GO–P(AM-NVP) 1.0 wt.% dispersions after annealing ................................................................................... 49 vii Hoang Anh Quan – Master thesis List of Abbreviation LIST OF ABBREVIATION EOR Enhanced oil recovery IOR Improved oil recovery OOIP Original oil in place IFT Interfacial tension APP 1-(3-aminopropyl)pyrrole COPAM Copolymers of acrylamide HPAM Hydrolyzed polyacrylamide HTHS High temperature and high salinity ATBS Tertiary butyl sulfonic acid TAP Thermoassociative copolymers AM Acrylamide NVP N-vinylpyrrolidone PAM Polyvinylpyrrolidone APS Ammonium persulfate GO Graphene oxide rGO Reduced graphene oxide GONs Graphene oxide nanosheets NMP N-methylpyrrolidone RSM Response surface methodology FTIR Fourier transform infrared spectroscopy SEM Scanning electron microscopy GPC Gel permeation chromatography TGA Thermogravimetric analysis WT White Tiger P(AM-NVP) Poly(acrylamide-N-vinylpyrrolidone) copolymers GO–P(AM-NVP) P(AM-NVP) copolymers covalently couple with graphene oxide nanocomposite viii Hoang Anh Quan – Master thesis Introduction INTRODUCTION Energy is one of the most critical problems in the development and sustainability of human life. Substantial amounts of energy are supplied to human life every year by the oil industry. The world oil production is projected to peak in 2022, with the production level being increased to 3.861 million tons and decreasing after that [1,2]. After the primary and secondary exploitation stages, approximately 70% to 75% of the original oil in place is left trapped in the reservoir [3]; because of the compressibility of fluids and initial pressure of the reservoir, but recovering it is always a difficult task. While in Vietnam, many major oil fields in Vietnam, such as White Tiger, Dragon, and Dawn, have passed the peak harvesting period and their production is rapidly declining; therefore, enhanced oil recovery (EOR) processes (physical and chemical) should be applied to recover a part of these trapped oils to solve this problem. Chemical EOR is a technology that involves the injection into reservoir solutions of chemical agents, such as alkalis, surfactants, polymers or their combinations, and recently some smart nanofluids. Among them, polymer injection is considered to be the most effective method, which has been widely used in EOR technology. Over time, exploiting oilfields has become increasingly tricky as offshore reservoirs have high temperatures and injection seawater has high salinity and hardness. Accordingly, the polymers to be used as EOR agents must be highly soluble in seawater and highly stable at high temperatures. Polymer testing and consultancy for plastic have automotive, aerospace, packaging, electronics, and medical devices applications. Polymers are incredibly diverse elements representing such engineering fields from avionics through biomedical applications, drug delivery systems, tissue engineering, biosensor devices, cosmetics, etc. The application of polymers and their ensuing composites is still advancing and going up rapidly since their ease regarding manufacturing. To be mindful that these are some of the industries in which you would see the use and application of various polymeric materials and polymers themselves: In aircraft, aerospace [4]; 3D printing plastics [5]; biopolymers in molecular recognition [6]; organic polymers used in water purification [7]; printed circuit board substrates [8]; green Chemicals: Polymers and Biopolymers [9]; polymers that are used in the operation of bulletproof vests and fire-resistant jackets [10]. Polymers, together with surfactants, are the chemicals that play an important role in oilfield operations, especially 1 Hoang Anh Quan – Master thesis Introduction in EOR. In EOR, surfactant solution is injected into the reservoir to reduce the interfacial tension between oil and water to wipe out the trapped oil from the reservoir rock and thence increase the oil production. While an injection of polymer solution into the reservoir for increasing the driving fluid viscosity to improve sweeping efficiency, and due to that, the oil production rises. The acrylamide-based polymers have been the most commonly used for this application. Recently, graphene oxide is also studied in EOR because it can increase the water viscosity, reduce the interfacial tension, and considerably emulsify the oil droplets in water [11]. In the present work, the irradiation-induced copolymerization of the AM and NVP monomers was investigated to explore the optimal reaction conditions. The conjugation of synthesized P(AM-NVP) copolymers on thermo-resisted GO nanosheets was then performed to obtain GO–copolymer nanocomposites with high viscosity, solubility in seawater, and stability at high temperature (135 °C). Moreover, the proportion of monomers and their total content in the reaction mixture were optimized during the material fabrication to produce a polymer product with suitable viscosity and stability for high-temperature offshore reservoirs, which has never been reported so far. These features render them suitable for EOR application in HT offshore reservoirs. 2 Hoang Anh Quan – Master thesis Chapter 1: Literature review Chapter 1 Literature Review Chapt er 1: Li te r ta ure Revi w e 1.1. Enhanced oil recovery (EOR) 1.1.1. Introduction to Enhanced oil recovery According to the method and time hydrocarbons are produced, there are three terms: primary oil recovery, secondary oil recovery, and tertiary (enhanced) oil recovery. Primary oil recovery describes the production of hydrocarbons under the natural driving mechanisms present in the reservoir without extra help from injected gas or water. Secondary oil recovery refers to the additional recovery resulting from the conventional methods of water injection and immiscible gas injection. Finally, tertiary (enhanced) oil recovery is the additional recovery over and above what could be recovered by secondary recovery methods. Various methods of enhanced oil recovery (EOR) are essentially designed to recover oil, commonly described as residual oil, left in the reservoir after both primary and secondary recovery methods have been exploited to their respective economic limits. The concept of the three recovery categories is illustrated in Figure 1.1. 3 Hoang Anh Quan – Master thesis Chapter 1: Literature review Figure 1.1. Oil recovery categories 1.1.2. Mechanism of enhanced oil recovery Improved oil recovery (IOR) is a general term that implies improving oil recovery by any means (operational strategies, such as infill drilling, horizontal wells, and improving areal and vertical sweep). Enhanced oil recovery (EOR) is a concept being more definitive and it can be considered as a section of IOR. EOR is the process of reducing oil saturation below the residual oil saturation “Sor”. The target of EOR varies considerably by different types of hydrocarbons. Figure 1.2 shows the fluid saturations and the target of EOR for typical light and heavy oil reservoirs and tar sand. For light oil reservoirs, EOR is usually applicable after secondary exploitation stages with an EOR target of approximately 45% original oil in place (OOIP). Heavy oils and tar sands respond poorly to methods in primary and secondary exploitation stages, and the majority of the production from these types of reservoirs comes from EOR methods. 4 Hoang Anh Quan – Master thesis Chapter 1: Literature review Figure 1.2. Target for different crude oil systems The magnitude of the reduction and mobilization of residual oil saturation “Sor” by an EOR process is controlled by two major factors: - Capillary number “Nc” - Mobility ratio “M” The capillary number is defined as the ratio of viscous force to interfacial tension force, or Nc  Viscous force v  Interfacial tension force  cos   k  p  Or equivalently as: N c   0        L  (1.1) (1.2) Where μ = viscosity of the displacing fluid σ = interfacial tension (IFT) between the displacing fluid and the displaced fluid (oil) v = Darcy velocity θ = the contact angle  = porosity k0 = effective permeability of the displaced fluid Δp/L = pressure gradient 5 Hoang Anh Quan – Master thesis Chapter 1: Literature review Figure 1.3. Effect of Nc on residual oil saturation Figure 1.3 is a schematic representation of the ratio of residual oil saturation (after conduction of an EOR process to residual oil saturation before the EOR process) and the capillary number. The illustration shows the reduction in the residual oil saturation with the augmentation in the capillary number. It is clear from the Eq. (1.2) that the capillary number can be increased by: - Increasing the pressure gradient Δp/L - Increasing the viscosity of the displacing fluid - Increasing displacing fluid viscosity μ - Decreasing the interfacial tension between the injection fluid and displaced fluid Another significant concept in understanding the displacing mechanism of an EOR process is the mobility ratio “M”. The mobility ratio is defined as the ratio of the displacing fluid mobility to that of the displaced fluid: M displacing ( k /  )displacing  (1.3) displaced ( k0 / 0 )displaced Where “k” is the effective permeability and “μ” is the viscosity. The mobility ratio influences the microscopic (pore-level) and macroscopic (areal and vertical sweep) displacement efficiencies. A value of M > 1 is considered unfavourable because it indicates that the displacing fluid flows more rapidly than the displaced fluid (oil). This unfavourable condition can 6