Thesis Final

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  1. 1. Studies on the Characterization, Interfacial Tension and Rheology of a Novel Polymeric Surfactant Derived from Castor Oil for Enhanced Oil Recovery Dissertation submitted in partial fulfillment of requirements for the award of the degree of Master of Technology In PETROLEUM ENGINEERING By NILANJAN PAL (Admission no. 2013MT0087) Under the guidance of Dr. AJAY MANDAL Associate Professor Department of Petroleum Engineering DEPARTMENT OF PETROLEUM ENGINEERING INDIAN SCHOOL OF MINES, DHANBAD April 2015
  2. 2. DEPARTMENT OF PETROLEUM ENGINEERING INDIAN SCHOOL OF MINES UNIVERSITY Dhanbad-826004, Jharkhand (India) ________________________Address for Communication_______________________ Dept. of Petroleum Engg., Indian School of Mines University, Dhanbad-826004, Jharkhand Tel. : +91-326-2296632, 2235280, Fax : +91-326-2296632/2296563 E-mail: pe@ismdhanbad.ac.in Website : www.ismdhanbad.ac.in CERTIFICATE This is to certify that the dissertation entitled Studies on the Characterization, Interfacial Tension and Rheology of a Novel Polymeric Surfactant Derived from Castor Oil for Enhanced Oil Recovery carried out by Nilanjan Pal (Admission No. 2013MT0087) in the Department of Petroleum Engineering, Indian School of Mines, Dhanbad in partial fulfillment of the requirements for the award of the degree of Master of Technology in Petroleum Engineering is a record of bonafide research work carried out by him under my supervision and guidance. His dissertation, in my opinion, is worthy of consideration for the award of the degree of Master of Technology in accordance with regulations of the institute. To the best of my knowledge, the results embodied in this dissertation have not been submitted anywhere else for the award of degree certificate. Dr. Ajay Mandal Associate Professor Department of Petroleum Engineering Indian School of Mines Dhanbad-826004
  3. 3. Dedicated to my beloved parents
  4. 4. Page | II I It is a privilege to lay earnest thanks to my guide Dr. Ajay Mandal, Associate Professor, Department of Petroleum Engineering, Indian School of Mines Dhanbad, for his excellent guidance, caring, patience, and providing me with an motivating atmosphere for doing the dissertation. His expertise was motivation for me from the inception of this dissertation till the writing of this project report. I could not have imagined having a better advisor and mentor for my project. I am thankful to Prof. V. P. Sharma, Head of Department and distinguished faculty members of the Department of Petroleum Engineering, Indian School of Mines, Dhanbad for valuable support to help the completion of my research work in the department which has admirable facilities from every aspect as required by any researcher. It was a great time working with PhD research students, Mr. Keshak Babu, Mr. Shranish Kar and Mr. Sunil Kumar who have been helpful at the very ground level during the various stages of experiments that were undertaken for the completion of my project (thesis) work. NILANJAN PAL Admission No. 2013MT0087 Master of Technology Petroleum Engineering ACKNOWLEDGEMENT
  5. 5. Page | III II 1. "Synthesis and Characterization of new Polymeric Surfactant for Chemical Enhanced Oil Recovery", Ajay Mandal, Keshak Babu, Nilanjan Pal, V. K. Saxena. 2. Surface Tension, Dynamic Light Scattering and Rheological studies of a new Polymeric Surfactant for application in enhanced oil recovery, Nilanjan Pal, Keshak Babu, Ajay Mandal. 3. Studies on Interfacial Tension and Contact Angle of Synthesized surfactant and Polymeric from Castor Oil for Enhanced Oil Recovery, Keshak Babu, Nilanjan Pal, Achinta Bera, V.K. Saxena, Ajay Mandal. COMMUNICATED PAPERS
  6. 6. Page | IV III Various experimental studies were carried out on a novel polymeric surfactant synthesized from castor oil. FTIR analysis of polymeric surfactants with varying acrylamide-to-sulfonate weight ratios revealed similar chemical composition and bonding arrangement with different transmittance percentages. Dynamic Light Scattering (DLS) experiments were performed on all polymeric surfactants to show that hydrodynamic particle diameter generally increased with concentration due to aggregation of molecules. Addition of NaCl resulted in decrease in particle size. The effects of concentration and salt addition on interfacial studies and rheology were investigated. IFT values decreased with concentration upto a certain limit called Critical Micelle Concentration after which the IFT value increased. Addition of salt saw the same trend with the lowest IFT value obtained at optimal salinity of the salt-polymeric mixture. The values of CMC and optimal salinity were identified along with their corresponding IFT values to aid in the formulation of desired mixtures for achieving ultralow IFT. Viscosity was found to increase with increase with PMES concentration. However, reduction in viscosity was observed with temperature rise and salt addition. Analysis of rheological data showed that polymeric surfactant behaved ideally up to a critical shear rate of 50 s-1 but exhibited shear- thinning or pseudoplastic behavior at higher shear rates. Determination of viscoelastic properties were carried out by dynamic mechanical analysis in oscillatory mode. Storage modulus G' and loss modulus G'' increased with increasing PMES concentration. Specific frequency (SF) indicated by the crossing point between G' and G'' on the viscoelastic curve represents the point of transition between elastic and viscous phases of the polymeric surfactant system. Keywords: Polymeric Surfactant; Castor Oil; Fourier Transform Infrared Spectroscopy; Dynamic Light Scattering; Interfacial Tension; Viscosity; Shear Stress; Viscoelasticity ABSTRACT
  7. 7. Page | V IV 1. Investigate the effects of concentration and salt addition on the particle size profile of polymeric surfactant in aqueous solution by DLS Analysis. 2. Analyze and compare the effects of concentration, acrylamide-to-sulfonate ratio and salt addition on the interfacial tension measurements for polymeric surfactant and SMES. 3. Study the rheological properties, including viscosity, shear stress and viscoelastic properties of polymeric surfactant solutions in aqueous solution and under the effect of salt. NILANJAN PAL Admission No. 2013MT0087 Master of Technology Petroleum Engineering OBJECTIVES OF THE EXPERIMENTAL STUDY
  8. 8. Page | VI V DESCRIPTION Page No. ACKNOWLEDGEMENT COMMUNICATED PAPERS ABSTRACT OBJECTIVES OF THE EXPERIMENTAL STUDY CONTENTS II III IV V VI LIST OF FIGURES VIII 1. INTRODUCTION 2-4 2. LITERATURE REVIEW 5-10 2.1. Current Demand for oil and need for EOR 5 2.2. Prospects of Chemical flooding for EOR 6 2.3. Prominence in ASP Flooding 8 2.4. Chemical EOR challenges 9 2.5. Potential possibilities in the synthesis of a new polymeric surfactant 9 3. WORK OVERVIEW 11-12 3.1. Previous and Relevant Works 11 3.2. Focus of the Present Study 12 4. DLS CHARACTERIZATION 13-20 4.1. Principle of DLS Analysis 13 4.2. Experimental Section 14 4.2.1. Material(s) Required 14 4.2.2. Apparatus Description 14 4.2.3. Measurable Quantities 15 4.2.4. Technical Features 15 4.2.5. Zetasizer Nano S90 Specifications 16 4.2.6. Experimental Procedure 17 4.3. Results and Discussions 18 4.3.1. Effect of PMES concentration on particle size distribution profile 18 4.3.2. Effect of salt addition on particle size distribution profile 19 CONTENTS
  9. 9. Page | VII 5. INTERFACIAL TENSION STUDIES 21-40 5.1. Principle of IFT measurement by Spinning Drop Method 21 5.2. Experimental Section 23 5.2.1. Material(s) Required 23 5.2.2. Apparatus Description 23 5.2.3. Measurable Quantities 24 5.2.4. Technical Features 25 5.2.5. SVT-15 Tensiometer Specifications 27 5.2.6. Capillary Tube Specifications 28 5.2.7. Experimental Procedure 29 5.3. Results and Discussions 31 5.3.1. Effect of surfactant concentration on interfacial tension measurements for SMES solution 31 5.3.2. Effect of NaCl addition on interfacial tension measurements for SMES solution 33 5.3.3. Effect of concentration on IFT of polymeric surfactant (PMES) solutions with different acrylamide-to-surfactant ratios 34 5.3.4. Effect of NaCl addition on the most effective polymeric surfactant solution 38 5.3.5. Effect of Acrylamide-to-Sulfonate Ratios on salt-polymeric surfactant mixture with lowest IFT value 39 6. RHEOLOGICAL STUDIES 41-56 6.1. Principle of rheometry 41 6.2. Experimental Section 42 6.2.1. Material(s) Required 42 6.2.2. Apparatus Description 42 6.2.3. Measurable Quantities 43 6.2.4. Technical Features 44 6.2.5. Bohlin Gemini 2 Rheometer Specifications 44 6.2.6. Experimental Procedure 45 6.3. Results and Discussions 47 6.3.1. Effect of Temperature on PMES viscosity 47 6.3.2. Effect of PMES concentration and acrylamide-to-sulfonate ratio on viscosity and shear Stress 49 6.3.3. Effect of addition of salt on PMES viscosity 53 6.3.4. Effect of concentration on dynamic viscoelasticity 55 7. SUMMARY AND CONCLUSIONS 57-59 REFERENCES 60
  10. 10. Page | VIII VIFigure no. Description Page no. Fig 3.1 Infrared spectrum of polymeric methyl ester sulfonate 11 Fig 4.1 ZETASIZER (Nano-S90, Malvern) apparatus for DLS analysis 14 Fig 4.2 Polarizer Tube for storing sample solution during DLS Analysis 17 Fig 4.3 Effect of PMES concentration on hydrodynamic diameter of molecules in polymer ethyl ester sulfonate solution 18 Fig 4.4 Effect of PMES concentration on hydrodynamic diameter of PMES solution containing 1% NaCl 19 Fig 4.5 Effect of PMES concentration on hydrodynamic diameter of PMES solution containing 2% NaCl 19 Fig 4.6 Effect of PMES concentration on hydrodynamic diameter of PMES solution containing 3% NaCl 20 Fig 5.1 Spinning Drop in a Spinning Drop Tensiometer along the Spinning Axis 21 Fig 5.2 Spinning Drop Tensiometer SVT 15N Assembly 24 Fig 5.3 High Temperature Capillary Tube FEC 622/400-HT 25 Fig 5.4 Spinning Drop Video Tensiometer SVT 15N 27 Fig 5.5 A typ