Laboratory core flooding experiments using Bio-surfactant and molasses: Implications for Microbial EOR Mohammad Bahar, Keyu Liu, Abdul Rashid,Xiaofang Wei, Tara Sutherland, Xiaoyi Wang, Manzur Ahmed, Phil Hendry, Dongmei Li, Se Gong, Herbert Volk, S. Razak, Wan Ata, A Azhan,M.Rizal CSIRO Wealth from Ocean Flagship and Petronas Research

30th IEA Annual Workshop and symposium on EOR -Canberra Outline Background Objectives Materials and methods Results and discussion Conclusions

30th IEA Annual Workshop and symposium on EOR -Canberra Oil Recovery Mechanisms CONVENTIONAL RECOVERY EOR TERTIARY RECOVERY TERTIARY RECOVERY SECONDARY RECOVERY SECONDARY RECOVERY PRIMARY RECOVERY PRIMARY RECOVERY Natural Flow Natural Flow Artificial Lift (Pump, Gas Lift, etc.) Artificial Lift (Pump, Gas Lift, etc.) Waterflood Pressure Maintenance (Water, Gas Reinjection) Pressure Maintenance (Water, Gas Reinjection) Thermal Solvent Chemical MEOR Adapted from the Oil & Gas Journal, Apr 23, 1990 Other

30th IEA Annual Workshop and symposium on EOR -Canberra EOR vs. Permeability Hydrocarbon Miscible Nitrogen and Flue Gas CO 2 Miscible Surfactant Polymer Alkaline Fireflood Steam Drive EOR Method Not critical if uniform High enough for good injection Permeability (md) ,000 GoodPossibleFairDifficultNot Feasible MEOR Dr. Larry Lake, Oilfield Review (Jan. 1992)

30th IEA Annual Workshop and symposium on EOR -Canberra Oil Gravity vs. EOR Methods Oil Gravity o API N 2 & Flue Gas Hydrocarbon CO 2 - Miscible Immiscible Gas Alkaline/Surfactant/Polymer Polymer Flooding Gel Treatments MEOR Steam Flooding Mining (Modified from J.J. Taber, F.D. Martin & R.S. Seright, 1997)

30th IEA Annual Workshop and symposium on EOR -Canberra Microbes can be introduced into oil reservoirs, and/or indigenous microbes can be stimulated with nutrients. Potentials: Changing fluid properties such as Density, Viscosity, composition and IFT Changing the rock properties such as wettability, permeability and relative permeability Changing conditions of system (pressurize, What is MEOR and its Potential on EOR?

30th IEA Annual Workshop and symposium on EOR -Canberra Background: Can MEOR be a successful method for EOR? With biosurfactant (above CMC) S.M. Farouq Ali- University of Calgary-2003 Initial

30th IEA Annual Workshop and symposium on EOR -Canberra Overview of CSIRO’s MEOR project Microbiology Microbial physiology Microbial metabolisms Isolation and culture before and after Microorganisms treatments Measuring fluid physical properties, such as density, viscosity and IFT Measuring rock physical properties K, Krw, Kro, Measuring EOR Organic Geochemistry Develop analytical protocol identify/quantify metabolites Modelling Analyse/verify experimental results Build predictive model for MEOR Build reservoir model for field trial

30th IEA Annual Workshop and symposium on EOR -Canberra Monitor changes in oil and water physical properties after culture experiments Detect and quantify various by-products - Gases - Bio-surfactants - Acids - Co-biosurfactants - Polymer - Oil Degradation Select suitable nutrients to stimulate microbial growth and production of metabolites leading to MEOR Undertake core flooding experiments Objectives

30th IEA Annual Workshop and symposium on EOR -Canberra Reservoir fluids from Off-shore Malaysian oil- field - Depth: ~ 720 m - Temperature:50ºC - Salinity:2.3 % - Mature, high water cut - Reservoir Pressure: 940 Psia Material and methods

30th IEA Annual Workshop and symposium on EOR -Canberra Experiment : Core Flooding Setup

30th IEA Annual Workshop and symposium on EOR -Canberra Experimental sequences Oil Water Molasses Water Measuring volume of Water Oil Gas Core Holder

30th IEA Annual Workshop and symposium on EOR -Canberra Effects of biosurfactant on water densities No effects

30th IEA Annual Workshop and symposium on EOR -Canberra Effects of bio-surfactant on viscosity of Bokor formation water (104LS) H2O viscosity increases with BS concentrations

30th IEA Annual Workshop and symposium on EOR -Canberra Effect of bio-surfactant (Surfactin) on IFT (104LS) at 50 ° C 940psi

30th IEA Annual Workshop and symposium on EOR -Canberra MEOR core flooding results 4.1% MEOR Sor=25.6% Swir=14%; Primary oil recovery: 74.4% Soir=25.6%; incremental EOR: 4.1%

30th IEA Annual Workshop and symposium on EOR -Canberra Which phenomena is more reliable? Injecting Molasses Increasing production 4% ?

30th IEA Annual Workshop and symposium on EOR -Canberra What types of by-products were produced? Gases Alcohols Acids Bio-surfactants Micro-emulsion

30th IEA Annual Workshop and symposium on EOR -Canberra Gases and swelling A large reduction in oil viscosity and small increase in water viscosity The Young – Laplace Equation predicts an inverse relation of pressure drop with Swelling of Oil

30th IEA Annual Workshop and symposium on EOR -Canberra Distribution of microbial gases CO 2 CH 4 C2H6C2H6 C3H8C3H8 C 4 H 10 Concentration (ppm) Stimulation by carbohydrates produced substantial amounts of CO 2 and CH 4 gases C 2 + gases desorbed from oil?

30th IEA Annual Workshop and symposium on EOR -Canberra Microbial gases Duration of culture (days) (Control) CO 2 CH 4 Concentration (ppm) Very high amounts of CO 2 and CH 4 gases produced CO 2 generation continued to increase until after 9 days CH 4 generation continued to increase until after 11 days

30th IEA Annual Workshop and symposium on EOR -Canberra Alcohols production Variable amounts of alcohols produced Generation continued to increase until after 16 days of culture A second cycle of moderate generation initiated after 18 days ng/mL of water Duration of culture (days) 2 (Control)

30th IEA Annual Workshop and symposium on EOR -Canberra ng/mL of water Duration of culture (days) 2 (Control) Acids production Variable amounts of acids produced Consistent with gases and alcohols, generation continued to increase until after 16 days of culture A second cycle of intense generation initiated after 18 days

30th IEA Annual Workshop and symposium on EOR -Canberra Micro-emulsion experiment using co- surfactant

30th IEA Annual Workshop and symposium on EOR -Canberra Low Concentration - Surfactant Adsorption High Concentration - Self-Assembled Surface Aggregates Moderate Concentration - Hemimicelle Formation Surfactants at the Solid-Liquid Interface Clay

30th IEA Annual Workshop and symposium on EOR -Canberra Water droplets Oil rim surfactants Solubility of alcohol in micelles

30th IEA Annual Workshop and symposium on EOR -Canberra w/o emulsion Micelles Bio-surfactants

30th IEA Annual Workshop and symposium on EOR -Canberra Water droplets Oil

30th IEA Annual Workshop and symposium on EOR -Canberra Water droplets with oil rim Oil droplets in water droplets 5  m

30th IEA Annual Workshop and symposium on EOR -Canberra Interfacial tension and capillary pressure Surfactant Reduce interfacial tension in small pore and reduce the capillary pressure in the system R1=2 Y=2 P=(2*2)/2=2 R2=1 Y=1 P=(2*1)/1=2

30th IEA Annual Workshop and symposium on EOR -Canberra Conclusions Microorganisms can change the threshold point of residual oil in reservoirs and to enhance oil recovery: Core flooding using 40 ppm surfactin enable 3% EOR Core flooding using 0.875% molasses enable 4.1% EOR MEOR uses a combination of mechanisms to recover residual oils in reservoirs including Gas production can reduce oil viscosity Biosurfactant production can reduce IFT Solvents and biosurfactants can promote micro or nano emulsion Produced biosurfactants may change the wettability of clay rocks MEOR could become a low cost environmental friendly EOR method in the future but more research is required

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