07/ This document is the property of SNF. It must not be reproduced or transfered without prior consent Enhanced Oil Recovery Optimizing Molecular Weight in Polymer Flood

07/ This document is the property of SNF. It must not be reproduced or transfered without prior consent Fluid viscosity in a polymer flood It is surprising to find that, regardless the initial molecular weight of the polymer injected, the molecular weight of the polymer in the produced water is low, around 4 to 10 million. The questions that leap to our minds are: –What is the viscosity of the brine inside the reservoir ? –What is the efficiency of the motor fluid ? –Which are the parameters affecting this efficiency ? –How can the polymer flood be optimized ?

07/ This document is the property of SNF. It must not be reproduced or transfered without prior consent Average molecular weight Polyacrylamides are formed of very long chain of polymers, several million Daltons, and the average molecular weight does not represent the length of the chain. A polymer is a mixture of long and short chains. In fact, even with very different average MW, a part of the molecules are the same. Number of molecules Molecular weight (10^6 Daltons) 15M25M20M

07/ This document is the property of SNF. It must not be reproduced or transfered without prior consent Chemical degradation The mechanism of chemical degradation is the formation of free radicals that cut the chain These free radicals are formed by the reaction of an oxidizer with a reducer (redox) The high molecular weight chains are more sensitive to chemical degradation, especially those above 15 million MW The best polyacrylamide stability is found in a reducing media OxydizerReducer O2O2 H2SH2S Fe 2+, Fe 3+ Scavenger HydrocarbonFe 2+ PeroxydesSulfato reducing bacteria NH 3

07/ This document is the property of SNF. It must not be reproduced or transfered without prior consent Example of chemical degradation

07/ This document is the property of SNF. It must not be reproduced or transfered without prior consent Mechanical degradation High shear will cut the polymer chains in pieces High MW giving a certain viscosity with few chains will be more sensitive to shear than a low MW providing the same viscosity with more chains This shear degradation is amplified by the formation of free radicals as a mechanism of degradation

07/ This document is the property of SNF. It must not be reproduced or transfered without prior consent Example of mechanical degradation Low MW polymers are less sensitive to shearing

07/ This document is the property of SNF. It must not be reproduced or transfered without prior consent Example of mechanical degradation

07/ This document is the property of SNF. It must not be reproduced or transfered without prior consent Influence of time on shear The shear at the injection side is normally very limited in time (seconds to minutes) It is also dependent, at the beginning of the injection, on the structure of the reservoir During injection time, solids come from the injected water or are precipitated – (CaCO 3, MgOH, FeS, S 2 or biological molds) The solids increase the shearing time by forming channels, where the polymer solution can be under high degradation conditions for a length of time

07/ This document is the property of SNF. It must not be reproduced or transfered without prior consent Low stability for high MW The stability of high molecular weight molecules is very low Number of molecules Molecular weight (10^6 Daltons) 15M25M20M Very high stability Poor stability Low stability Very low stability

07/ This document is the property of SNF. It must not be reproduced or transfered without prior consent Injection time & mechanical degradation At the beginning of the injection, the shear is given by –The flow of polymer solution –The area of injection –The area of the front surface of the reservoir –The permeability Each polymer contains a certain amount of insoluble particles which swell in the brine about 50 times forming a large amount of gels, increasing with time and coating the injection surface There are two types of gels –Soft gels which are degraded to soluble polymers at a certain pressure; and at this pressure, there is an equilibrium between injected gels and degraded gels and the injection well is permanently cleaned –Hard gels which are not sensitive to pressure and plug the injection surface With time, due to coating of the injection surface, the area of injection decreases till the injection pressure from the gel is achieved, then the mechanical degradation becomes stable (in the range of 1 to 7 bar) But the injection pressure increases with the MW as the amount of gel and hardness of gel increases with MW

07/ This document is the property of SNF. It must not be reproduced or transfered without prior consent Final viscosity The mechanical degradation is generated directly at the injection point The chemical degradation happens a few hours after injection and polymer solution is then stable Viscosity cps Time Factors Brine (TDS) Temperature Oxydo reduction equilibrium Oxydo reduction reactions Flow Differential pressure, Shear Permeability Precipitation (salts, sulfur, SRB, Fe) Viscosity of injection Viscosity at different steps of degradation Mechanical degradation Chemical degradation Stable fluid

07/ This document is the property of SNF. It must not be reproduced or transfered without prior consent Polymer choice Choosing the best polymer for polymer flooding is a very complex question. The efficiency of the polymer depends on: –The amount of oxygen at the injection and the addition of a scavenger in large amounts will not correct it. Oxygen and scavengers form free radicals –The stable pressure of injection which depends on the flow, permeability, polymer, viscosity… –The quality of the polymer For the same injected viscosity the high MW products will give a lower viscosity in the reservoir Harder are the gels, more the pressure of injection is high and the mechanical degradation The absorption of the polymer will depend on the anionicity –A copolymer with very narrow distribution of anionicity will absorb less than a co-hydrolyzed polymer and less than a post hydrolyzed polymer. The absorption will take place mainly near the injection points

07/ This document is the property of SNF. It must not be reproduced or transfered without prior consent How to correct these parameters There are solutions to improve these parameters –Addition of free radical scavengers. ITW (isopropylalcohol+thiourea) is presently the best but expensive and difficult to handle (flash point, volume) –Increase of concentration of high MW products to match the same viscosity in the reservoir as the medium MW. But this will decrease injectivity and it is necessary to decrease the flow to avoid fracturation. It is easier to adapt the MW to the field conditions –Avoid oxygen in the polymer dissolution system by a very careful conception of the equipment –Keep all water circuit in reducing status –Decrease to a minimum all chemical injections –Avoid H 2 S formation by SRB by biological control

07/ This document is the property of SNF. It must not be reproduced or transfered without prior consent New types of polymers Many types of polymers are known from the 70s in laboratory developments. Some of them are now produced in pilot or industrial quantities. The main ones are: –Thermostable polymers which increase the stability of the polyacrylamides from 75°C to 90°C with new monomers FLOPAAM AN –Associative polymers with a main polyacrylamide chain and statistic repartition of hydrophobic groups. There is an association of these hydrophobic groups in a specific brine to give a high viscosity SUPERPUSHER –Star polymers with 3 or more branches on a central polymer group. These polymers are normally associative to have a high viscosity ST5030 –Comb and T shape polymers with a main hydrophobic chain and end hydrophobic chain –Block associative polymers with multiple hydrophobic groups inside an hydrophylic chain –Structured polymers with hydrophilic branches in a main hydrophilic chain –Soft or Movable gels are totally insoluble yet injectable gels mainly used in profile modification but with high potential in EOR FLOPERM 2000

07/ This document is the property of SNF. It must not be reproduced or transfered without prior consent EOR problems solved? The new polymers bring as many questions as they solve problems –Size of associative polymers compared with the permeability of the reservoir –Association with oil –Absorption on the oil wetted parts –Very high variation viscosity against the salinity of the reservoir with possibility of plugging with salinity increase –Very quick loss of viscosity by dilution –Sensitivity to Calcium, Magnesium and precipitation –Thermal stability –Mechanical stability –Dissolution problems –Very high viscosities before dilution –… Today the potential is high and depends on the risks taken

07/ This document is the property of SNF. It must not be reproduced or transfered without prior consent Thank you for your attention Optimizing Polymer Molecular Weight not Maximizing it, to Achieve the Highest Efficiency in EOR Polymer Flooding