Présentation PowerPoint - PTRC

Présentation PowerPoint - PTRC

Controlled CO2 | Diversified fuels | Fuel-efficient vehicles | Clean refining | Extended reserves Associative Polymers for EOR: towards a better understanding and control of their adsorption in porous media IFP D. Rousseau, R. Tabary, Z. Xu, G. Dupuis (IFP) S. Paillet, B. Grassl, J. Desbrires (EPCP/IPREM) IEA Collaborative Project on EOR 30th Annual Workshop and Symposium 21-23 September 2009, Canberra, Australia Outline Introduction Associative polymers chemistry Adsorption in porous media Conclusion Additional results IFP

2 IEA Collaborative Project on EOR - 30th Annual Workshop and Symposium - 21-23 September 2009, Canberra, Australia Introduction 1/3 Polymers in IOR/EOR : polymer flooding and well treatments Polymer flooding: aqueous polymer solutions aqueous phase viscosity reduction of mobility ratio R = (kw/w)/(koil/oil) areal sweep efficiency improvement vertical sweep efficiency improvement (k2 > k3 > k1 ) minimum adsorption is required Well treatments: aqueous polymeric gels or microgels controlled adsorption selective permeability reduction producing wells: water shutoff IFP injecting wells: profile/conformance control

3 kW IEA Collaborative Project on EOR - 30th Annual Workshop and Symposium - 21-23 September 2009, Canberra, Australia Introduction 2/3 Advantages of (hydrophobically) associative polymers for IOR/EOR (Hydrophobically) Associative Polymers = polymers with hydrophilic backbone bearing hydrophobic groups along the chains, capable of creating physical links between each other "Super" thickeners viscosity (Pa.s) a) Higher viscosities above cac associative nonassociative concentration (g/mL) less polymer needed to achieve a given viscosity b) Mechanical stability high viscosities with short chains (e.g. 1.106 g/mol) ( standard polyacrylamides: 18.106 g/mol) less sensitivity to shear degradation (surface facilities + near wellbores) c) Salt tolerance

salinity hydrophobic bonds viscosity (standard polyacrylamides) high permeability reductions associative polymers likely adsorb as multilayers (well treatments) IFP Strong adsorption on surfaces 4 IEA Collaborative Project on EOR - 30th Annual Workshop and Symposium - 21-23 September 2009, Canberra, Australia Introduction 3/3 Associative polymers for IOR/EOR: literature review Associative polymers static adsorption Volpert et al. -- Langmuir, 14, 1870-1879 (1998) Li -- Oilfield Chemistry, Vol. 23, No. 4, 349-351 (2006) Associative polymers flooding suggested in the 1980's patents: Evani et al. (1984), Landoll (1985), Bock et al. (1987), Ball et al. (1987) review by Taylor & Nasr-el-Din (1998, updated 2007 Can. Int. Petr. Conf. paper 2007-016) renewed interest in the 2000's CNOOC's offshore polymer flooding pilot in Bohai bay: Zhou et al. (IPTC 11635 - 2007, paper B7 - 2008 IEA/EOR, Beijing) Associative polymers for well treatments IFP Eoff, Dalrymple & Reddy (2000's) Halliburton's "Waterweb" process

5 Injectivity? Adsorption? What makes a associative polymer more suitable for polymer flooding or well treatment operations ? IEA Collaborative Project on EOR - 30th Annual Workshop and Symposium - 21-23 September 2009, Canberra, Australia Outline Introduction Associative polymers chemistry Adsorption in porous media Conclusion Additional results IFP 6 IEA Collaborative Project on EOR - 30th Annual Workshop and Symposium - 21-23 September 2009, Canberra, Australia Associative polymers chemistry

Synthesis methods Post-modification = grafting hydrophobic groups on a pre-existing hydrophilic backbone Micellar copolymerization = simultaneous polymerization in aqueous solutions of the hydrophilic monomers and of the hydrophobic monomers, solubilized in micelles Present study Polymers type 1: sulfonated polyacrylamides with alkyl hydrophobic groups; (micellar copolymerization) AP + equivalent non-AP IFP Polymers type 2: polyacrylic acids with alkyl hydrophobic groups ; 7 (post-modification) AP + equivalent non-AP IEA Collaborative Project on EOR - 30th Annual Workshop and Symposium - 21-23 September 2009, Canberra, Australia Outline Introduction Associative polymers chemistry Adsorption in porous media

Conclusion Additional results IFP 8 IEA Collaborative Project on EOR - 30th Annual Workshop and Symposium - 21-23 September 2009, Canberra, Australia Adsorption in porous media 1/6 Experimental set-up (cont'd) & experimental procedure Model granular packs SiC (silicon carbide) sharp-edged grains, 50m in size k = 100050 10-15 m ; = 401% hydrodynamic pore throats diameter d h 1.15 d c 1.15 2 8k / dh 10 m Polymer solutions adsorption study injection of diluted polymer solutions all solutions filtered on 3 m calibrated membranes prior to injection Experimental procedure IFP adsorption study monophasic flow conditions polymer solution injection mobility reduction (Rm) i.e. resistance factor (RF) brine injection permeability reduction (Rk) i.e. residual resistance factor (RRF) estimation of hydrodynamic adsorbed layers thicknesses h :

9 h (d h / 2) (1 Rk 1 / 4 ) IEA Collaborative Project on EOR - 30th Annual Workshop and Symposium - 21-23 September 2009, Canberra, Australia Adsorption in porous media 2/6 Polymers type 1: mobility reduction with equivalent non-AP Rm = DP(polymer) / DP(brine) 10 Polymer solution injected: 9 8 C = 0.84 g/L flow direction 7 r = 4.3 ; = 3.5 cP 6 5 2-5 cm 0-2 cm 4

3 5-10 cm 2 1 0 0 0.5 1 1.5 IFP # Pore volumes injected 10 close to piston-like in-depth propagation stabilized mobility reduction IEA Collaborative Project on EOR - 30th Annual Workshop and Symposium - 21-23 September 2009, Canberra, Australia Adsorption in porous media 3/6 Polymers type 1: mobility reduction with AP Rm = DP(polymer) / DP(brine) 10 0-2 cm 9

Polymer solution injected : 2-5 cm 8 C = 0.45 g/L 7 flow direction 6 r = 2.6 ; = 2.1 cP 5 4 3 5-10 cm 2 1 0 0 0.5 1 1.5 IFP

# Pore volumes injected 11 entry-face & internal plugging trend (?) strong polymer adsorption IEA Collaborative Project on EOR - 30th Annual Workshop and Symposium - 21-23 September 2009, Canberra, Australia Adsorption in porous media 4/6 Polymers type 1: adsorbed layers thicknesses estimations Adsorbed layer thickness, h (m) 2.0 internal section 2-5 cm only 1.5 Associative polymers 1.0 Equivalent non-associative polymers 0.5 0.0 10 -1 Wall shear rate, g (s ) IFP

equivalent non-AP 12 h does not depend on the amount of polymer solution injected h 0.2 m ~ single-chain size in solution 100 AP h depends on the amount of polymer solution injected h 1.4-1.5 m after only 1.3 PV injected likely multilayer adsorption IEA Collaborative Project on EOR - 30th Annual Workshop and Symposium - 21-23 September 2009, Canberra, Australia Adsorption in porous media 5/6 Polymers type 2: mobility reductions with equivalent non-AP and AP Rm = DP(polymer) / DP(brine) 10 internal 2-5 cm only 2-5 cm section section only 9 Associating polymers 8

20 g/L NaCl 58.4 g/L NaCl 7 flow direction 6 Polymer solutions injected : equivalent non-AP (20g/ L NaCl): C = 1.5 g/L ; r = 2.0 5 AP 20 g/L NaCl: 4 C = 1.6 g/L ; r = 2.2 3 AP 58.4 g/L NaCl: 2 1 Equivalent non-associating polymers - 20 g/L NaCl 0 0

1 2 3 # Pore volumes injected 4 C = 3.2 g/L ; r = 4.1 same volume fraction = 0.3 IFP good in-depth propagation of both equivalent non-AP and AP 13 IEA Collaborative Project on EOR - 30th Annual Workshop and Symposium - 21-23 September 2009, Canberra, Australia Adsorption in porous media 6/6 Polymers type 2: adsorbed layer thicknesses estimation Adsorbed layer thickness, h (m) 0.30 Porous medium #1 0.25 Equivalent nonassociative polymers

20 g/L NaCl 0.20 Porous medium #2 internal section 2-5 cm only Associative polymers injection 1: polymers 20 g/L NaCl injection 3: polymers 58.4 g/L NaCl 0.15 injection 2: brine 58.4 g/L NaCl 0.10 0.05 0.00 IFP 0 14 1 2 3

# Experimental phase 4 5 AP adsorbed layer collapse when exposed to higher salinity brine over-adsorption occurs when AP are injected in higher salinity brine likely salinity-controlled multilayer adsorption IEA Collaborative Project on EOR - 30th Annual Workshop and Symposium - 21-23 September 2009, Canberra, Australia Outline Introduction Associative polymers chemistry Adsorption in porous media Conclusion Additional results IFP

15 IEA Collaborative Project on EOR - 30th Annual Workshop and Symposium - 21-23 September 2009, Canberra, Australia Conclusion Adsorption behavior in porous media of 2 types of associative polymers (AP) has been investigated adsorption appears as a key parameter governing AP propagation in porous media adsorption is a key parameter to address for EOR AP applications A control of the adsorption is and must be possible (hydrophobic bonds = low-energy bonds) control through salinity is possible control through shear-rate ? Ongoing work on this topic @ IFP various injections conditions IFP various polymer chemistries 16 modeling AP adsorption in porous media IEA Collaborative Project on EOR - 30th Annual Workshop and Symposium - 21-23 September 2009, Canberra, Australia Outline Introduction Associative polymers chemistry

Adsorption in porous media Conclusion Additional results IFP 17 IEA Collaborative Project on EOR - 30th Annual Workshop and Symposium - 21-23 September 2009, Canberra, Australia Adsorption in porous media: additional results 1/3 Polymers type 1 (micellar copolymerization): impact of molecular structure Set of associative sulfonated polyacrylamides (G. Dupuis work) same backbones: 20 mol-% AMPS ; Mw = 106 g/mol C8, C12 and C18 hydrophobic side groups 0.1, 0.2 and 0.5 mol-% hydrophobic monomers (+ equivalent non-associative polymers) Thickening ability vs. salt concentration IFP vs. polymer concentration

18 IEA Collaborative Project on EOR - 30th Annual Workshop and Symposium - 21-23 September 2009, Canberra, Australia Adsorption in porous media: additional results 2/3 Pressure taps layout Polymers type 1: long-term injections (0.5 mol-% C12) 1-5 cm Coreflood experiments: SiC granular packs (50 m grains) ; k = 1D ; = 0.4 ; PV 8 cm3 low flow rate: Q = 2 cc/h (vD 1 foot/day) ; gwall = 15 s-1 diluted polymer solution: C = 0.9 g/L ; effective = 0.2 ; rbulk = 1.7 IFP 3 Injected PV 19 viscous front propagation + polymer adsorption (Rm > rbulk) breakthrough, with C/C0 = 1 entry-face plugging trend ? flow 0-1 cm 5-9 cm 130 Injected PV "secondary adsorption" front propagation entry + internal stabilization trends (?) stable effluent concentration origin of the secondary adsorption ? IEA Collaborative Project on EOR - 30th Annual Workshop and Symposium - 21-23 September 2009, Canberra, Australia

Adsorption in porous media: additional results 3/3 Polymers type 1: re-injection test (0.5 mol-% C18) Assumption: 2 components in the polymer solutions (chemical structure heterogeneity?) vast majority of low-adsorption (weakly damaging) polymers quick effluent breakthrough, C/C0=1 minority of strong-adsorption (strongly damaging) polymers slow propagation of the "secondary front" Experimental testing: effluent collection until the secondary front reaches half of the core "cleaned" solution effluent re-injection in a fresh core IFP Practical outcomes for polymer flooding with associative polymers: towards specific in-depth filtration procedures? improvement in chemical synthesis methods? controlling the injectivity of associative polymers seems possible 20 IEA Collaborative Project on EOR - 30th Annual Workshop and Symposium - 21-23 September 2009, Canberra, Australia

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