Low molecular weight polyacrylates for EOR

Abstract

The disclosure is directed to low molecular weight polyelectrolyte complex nanoparticles that can be used to deliver agents deep into hydrocarbon reservoirs. Methods of making and using said polyelectrolyte complex nanoparticles are also provided.

Claims

1. A composition comprising a polyelectrolyte complex nanoparticle having a polyalkylenimine and a polyanion, said nanoparticle having a size of less than one micron, wherein said polyanion is equal to or less than 10,000 Da, wherein said polyelectrolyte complex nanoparticle is mixed with a multivalent cation crosslinker.

2. The composition of claim 1, wherein said polyalkylenimine is polyethylenimine.

3. The composition of claim 1, wherein said polyalkylenimine is less than 26,000 Da.

4. The composition of claim 1, wherein said polyanion is selected from ammonium, sodiated or potassiated polyacrylate, polyvinyl sulfonate, poly(styrene sulfonate), copolymers of acrylate with acrylamide, vinylsulfonate or styrene sulfonate, dextran sulfate, and anionic surfactants.

5. The composition of claim 4, wherein said polyanion is an anionic surfactant selected from the group consisting of sodium dodecyl sulfate, sodium lauryl sulfate, alcohol propoxy sulfate, olefin sulfonates, and alpha olefin sulfonates.

6. The composition of claim 1, wherein said polyanion is sodium polyacrylate, potassium polyacrylate, or ammonium polyacrylate.

7. The composition of claim 1, wherein said multivalent cation crosslinker is a compound selected from the group consisting of zirconium acetate, sodium zirconium lactate, zirconium sulfate, zirconium tetrachloride, zirconium orthosulfate, zirconium oxychloride, zirconium carbonate, zirconium ammonium carbonate, zirconium acetylacetonate, chromium acetate, chromium propionate, chromium malonate, chromium malate, chromium chloride, aluminum chloride, aluminum sulfate, aluminum citrate, tin chloride, tin sulfate, iron (III) chloride, iron (III) nitrate, iron (III) sulfate, iron (III) acetate, iron (III) citrate, titanium chloride, and titanium sulfate.

8. The composition of claim 1, wherein said polyanion is 5,100 Da.

9. The composition of claim 1, wherein said polyanion is 5,100 Da and said multivalent cation crosslinker is Cr(III), Fe(III), or complexes of same.

10. An improved method of sweeping a reservoir, wherein an injection fluid is injected into a reservoir to mobilize and produce oil, the improvement comprising injecting a composition comprising i) the composition of claim 1, plus ii) a polymer, plus iii) a fluid into a reservoir, aging said composition at 85° C. for 1 day before its viscosity increases and becomes a gel, injecting additional injection fluid into said reservoir to mobilize oil, and producing said oil.

11. The improved method of claim 10, wherein said polymer is partially hydrolyzed polyacrylamide, a polymer or copolymers of acrylate with acrylamide, N,N-dimethyacrylamide, tert-butyl acrylate, acryamido-2-methylpropane sulfonic acid, sodium 2-acryamido-2-methylpropane sulfonate, or N,N, dimethyl acrylamide.

12. The improved method of claim 10, wherein fluid is brine or seawater.

13. The improved method of claim 10, wherein said polyanion is a sodium, ammonium or potassium polyvinyl sulfonate.

14. The improved method of claim 10, wherein said polyelectrolyte complex nanoparticle has an average particle size of about 100 to 500 nm in diameter.

15. A composition comprising: i. a delayed gelling agent comprising a polyelectrolyte complex nanoparticle comprising a polyethylenimine of less than 26,000 Da and a sodium, ammonium or potassium polyvinyl sulfonate equal to or less than 10,000 Da intimately associated with at least one multivalent cation crosslinker, said nanoparticle having a size of less than one micron, ii. a polymer having anionic sites that can be crosslinked with said at least one multivalent cation crosslinker, and iii. a fluid.

16. A composition comprising: i. a delayed gelling agent comprising a polyelectrolyte complex nanoparticle comprising a polyethylenimine of less than 26,000 Da and an ammonium polyacrylate, sodium polyacrylate or potassium polyacrylate of equal to or less than 10,000 Da intimately associated with at least one multivalent cation crosslinker, wherein said multivalent cation crosslinker is Cr(III), Fe(III), or complexes of same, said nanoparticle having a size of less than one micron, ii. a partially hydrolyzed polyacrylamide polymer having anionic sites that can be crosslinked with said at least one multivalent cation crosslinker, and iii. a fluid.

17. A method of improving sweep efficiency of a fluid flood of a reservoir, said method comprising: a. injecting the composition of claim 15 into a reservoir: b. aging the composition at 85° C. for about 1 day before its viscosity increases and becomes a gel; c. injecting an injection fluid into said reservoir to mobilize the oil; and d. producing said mobilized oil.

18. A method of improving sweep efficiency of a fluid flood of a reservoir, said method comprising: a. injecting the composition of claim 16 into a reservoir: b. aging the composition at 85° C. for 1 day before its viscosity increases and becomes a gel; c. injecting an injection fluid into said reservoir to mobilize the oil; and d. producing said mobilized oil.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1A-B. Water flooding wherein water bypasses oil, travelling the thief zones (FIG. 1A). However, the thief zones can be blocked by polymers, gels, foams, and the like, thus forcing water to sweep the reservoir and producing more of the original oil in place. (FIG. 1B).

(2) FIG. 2. Characterization of PEI/PAA/Cr(III)-PEC0 made with PAA of different molecular weights.

(3) FIG. 3. Characterization of PEI/PAA/Cr(III)-PEC0 with different concentrations of PAA with a molecular weight of 5.1 kDa.

(4) FIG. 4. Viscosity profiles of AC24 and PEC gelants with different molecular weights of PAA measured at 25° C. The gelants contain 5000 ppm AC24 and 100 ppm Cr(III) in Brine A incubated at 65° C. Gelation slightly slower with higher molecular weight PAA [Mw=5.1 kDa].

(5) FIG. 5. Viscosity profiles of PEI/PAA/Cr(III)-PEC0 [+] in RO water and Brine A and PEI/PVS/Cr(III)-PEC2 [+] in Brine A incubated at 65° C. and measured at 25° C. Gelant contains 5000 ppm AC24 and 100 ppm Cr(III).

(6) FIG. 6A. Viscosity profiles of PEI/PAA/Cr(III)-PEC39 [+] in Brine A incubated at 65° C. and measured at 25° C.

(7) FIG. 6B. Reproducibility of gelation tests of PEI/PAA/Cr(III)-PEC39 [+] in Brine A measured at 25° C. Gelant contains 5000 ppm EOR204 and 100 ppm Cr(III) supplied as PEI/PAA/Cr(III)-PEC39 [+].

(8) FIG. 7. Gelation of PEI/PAA/Cr(III)-PEC39 [+] in Brine A at 65° C. with a gelant containing 5000 ppm EOR204 and 100, 85, 75, 68, 60, or 50 ppm Cr(III) supplied as PEI/PAA/Cr(III)-PEC39 [+].

(9) FIG. 8. Gelation of PEI/PAA/Cr(III)-PEC39 [+] in Brine A at 65° C. with different sources of HPAM. Gelants contain 5000 ppm HPAM from EOR204, AN907, and Alcomer 24; and 100 ppm Cr(III) supplied as PEI/PAA/Cr(III)-PEC39 [+].

(10) FIG. 9. Gelation of re-suspended PEI/PAA/Cr(III)-PEC0 [+] and AC24 incubated at 65° C. in Brine A following vacuum drying to different concentration factors. Gelation was delayed at higher concentration factors, which is consistent with higher salinity following re-suspension.

(11) FIG. 10. Characterization of PEI/PAA/Cr(III)-PEC39 [+] after concentration at various temperatures and re-suspension in Brine A.

(12) FIG. 11. Viscosity profile of 5000 ppm AC24 in Brine A with PEI/PAA/Cr(III)-PEC39 [+] (concentrated 20 times and reconstituted to final Cr(III) concentration of 100 ppm) incubated at 65° C. and measured at 25° C. to determine feasibility of concentrating PEI/PAA/Cr(III)-PEC39.

(13) FIG. 12. Sydansk Gel Code of 5000 ppm AC24 and 100 ppm Cr(III) as PEI/PAA/Cr(III)-PEC39 [+] in SW, incubated at 65° C. and observed at room temperature. PEC suspensions were concentrated in a rotary evaporator to 5% of their original volume and resuspended in Brine A.

(14) FIG. 13. Pressure drop profile during injection of PEI/PAA/Cr(III)-PEC0 [+] and AC24 gelant in Brine A into a Berea sandpack at 65° C. showed pressure drops consistent with the gelant viscosity.

(15) FIG. 14. Effluent components for PEI/PAA/Cr(III)-PEC0 [+] and AC24 injected in Brine A through a Berea sandpack held at 65° C. did not show significant retention.

(16) FIG. 15. Viscosity profile of equivalent PEI/PAA/Cr(III)-PEC0 [+] and PEI/PAA/Fe-PEC0 [+] with AC24 incubated at 65° C. in Brine A. Measurements were taken at 25° C.

(17) FIG. 16. Viscosity profile of PEI/PAA/Fe-PEC0 [+] and AC24 over time and incubated at two different temperatures. Measurements were taken at 25° C.

(18) FIG. 17. Viscosity profile of PEI/PAA/Fe-PEC0 [+] with different sources of HPAM incubated in Brine A at 65° C. Gelants contain 5000 ppm HPAM from AC24, and AN907.

(19) FIG. 18. Viscosity profile of PEI/PAA/Fe-PEC0 [+] and AC24 in different brines incubated at 65° C. Measurements were taken at 25° C. Gelation time is longer at higher salinity.

(20) FIG. 19. Viscosity development of gelants with different concentrations of PEI/PAA/Fe-PEC39 [+] and HPAMs incubated at 85° C. in synthetic seawater. Measurements were taken at 25° C.

(21) FIG. 20. Sydansk gel code of gelants with different concentrations of PEI/PAA/Fe-PEC39 [+] and HPAMs incubated at 85° C. in synthetic seawater.

(22) FIG. 21. Viscosity profiles of PEI/PVS/Cr-2 containing 100 ppm Cr(III) and 5000 ppm EOR204 HPAM in Brine A incubated both at 65° C. and 85° C. All components were commercial grade materials.

(23) FIG. 22. Cytotoxicity of PEI 800D and PEI 25,000 D. The lower molecular weight PEI is much less toxic than the PEI of larger average molecular weight.

DETAILED DESCRIPTION

(24) The disclosure provides novel polymer compositions that delay gelling under the conditions typical of water flooding in situ and have particular utility in blocking thief zones of reservoirs, but other uses are possible, especially in the agriculture, remediation and drug delivery arts.

(25) Low molecular weight PEI or PEI derivatives are used together with a low molecular weight polyanion to hold multivalent cations in a nanoparticle, allowing the gradual release of the multivalent cations. These nanoparticles plus a polymer that can be crosslinked with the multivalent cations, and an injection fluid are injected into a reservoir. As time passes, multivalent cations are released from the nanoparticles and crosslink the polymer. Thus, the multivalent cations release (and consequent gel formation) can be delayed until the injection fluid has reached the target zones deep into the reservoir.

(26) The disclosed compositions and methods comprises one or more of the following embodiments, in any combination thereof: A composition comprising a polyelectrolyte complex nanoparticle less than one micron in size having a polyalkylenimine of less than 26,000 Da, and a polyanion of less than 10,000 Da. A composition comprising a polyelectrolyte complex nanoparticle less than one micron in size having a polyalkylenimine of less than 26,000 Da, and a polyanion of less than 40,000 Da. A composition comprising a polyelectrolyte complex nanoparticle less than one micron in size having a polyalkylenimine of less than 26,000 Da, and a polyanion of less than 10,000 Da. A composition comprising a polyelectrolyte complex nanoparticle between 100 and 500 nm in size, a polyalkylenimine of less than 26,000 Da, and a polyanion of less than 10,000 Da. A composition comprising a polyelectrolyte complex nanoparticle less than one micron in size having a polyalkylenimine and sodium polyacrylate. A composition comprising a polyelectrolyte complex nanoparticle between 100 and 500 nm in size having a polyalkylenimine and sodium polyacrylate. A composition comprising a polyelectrolyte complex nanoparticle having an average size of less than one micron that facilitates delivery of an oil and gas chemical to a reservoir, wherein a polyethylenimine of less than 26,000 Da and a polyanion of less than 10,000 Da are intimately associated with an oil and gas field chemical to form the polyelectrolyte complex nanoparticle. A composition for controlled release of an oil and gas field chemical comprising a polyanion of less than 10,000 Da and a polyethylenimine of less than 26,000 Da forming a polyelectrolyte complex with an average particle size of less than 1000 nm wherein the polyelectrolyte complex is intimately associated with an oil and gas chemical consisting of (a) a gel-forming or cross-linking agent, (b) a scale inhibitor, (c) a corrosion inhibitor, (d) an inhibitor of asphaltene or wax deposition, (e) a hydrogen sulfide scavenger, (f) a hydrate inhibitor (g) a gel breaking agent, and (h) a surfactant.

(27) In any of the above compositions, the preferred polyalkylenimine can be polyethylenimine. The polyanion can be sodium polyacrylate, sodium polyvinyl sulfonate, poly(sodium styrene sulfonate), copolymers of sodium acrylate with acrylamide, sodium vinylsulfonate or sodium styrene sulfonate, dextran sulfate, or anionic surfactants. Examples of possible anionic surfactant for use in the invention including sodium dodecyl sulfate, sodium lauryl sulfate, alcohol propoxy sulfate, olefin sulfonates, and alpha olefin sulfonates. In some embodiments, the preferred polyacrylate is sodium polyacrylate.

(28) The PECs in the above compositions can be intimately associated with at least one multivalent cation crosslinker having Zr(IV), Cr(III), Ti(IV), Fe(III) or Al(III). Examples of such crosslinkers include zirconium acetate, sodium zirconium lactate, zirconium sulfate, zirconium tetrachloride, zirconium orthosulfate, zirconium oxychloride, zirconium carbonate, zirconium ammonium carbonate, zirconium acetylacetonate, chromium acetate, chromium propinonate, chromium malonate, chromium malate, chromium chloride, aluminum chloride, aluminum sulfate, aluminum citrate, tin chloride, tin sulfate, iron (III) chloride, iron (III) nitrate, iron (III) sulfate, iron (III) acetate, iron (III) citrate, titanium chloride, and/or titanium sulfate. In other embodiments, the PEC entraps the multivalent cation.

(29) In some embodiments, the above compositions can also include monovalent or divalent cations, such as sodium, potassium, magnesium, and calcium. A composition comprising a polyelectrolyte complex nanoparticle having a polyethylenimine (PEI) of less than 26,000 Da and a sodium polyacrylate of less than 10,000 Da intimately associated with a chromium ion crosslinker, said nanoparticle having a size of less than one micron, wherein said nanoparticle has a predominance of negative charges and the amount of sodium polyacrylate exceeds the amount of PEI. A composition comprising a polyelectrolyte complex nanoparticle having a polyethylenimine (PEI) of less than 26,000 Da and a sodium polyvinyl sulfonate of less than 10,000 Da intimately associated with a chromium ion crosslinker, said nanoparticle having a size of less than one micron, wherein said nanoparticle has a predominance of negative charges and the amount of sodium polyvinyl sulfonate exceeds the amount of PEI. A composition comprising a polyelectrolyte complex nanoparticle having a polyethylenimine (PEI) of less than 26,000 Da and sodium polyacrylate of less than 10,000 Da intimately associated with a Cr(III) or Fe(III) ion crosslinker, said nanoparticle having a size of less than one micron, wherein said nanoparticle has a predominance of positive charges and the amount of PEI exceeds the amount of sodium polyacrylate. A composition comprising a polyelectrolyte complex nanoparticle having a polyethylenimine (PEI) of less than 26,000 Da and sodium polyvinyl sulfonate of less than 10,000 Da intimately associated with a Cr(III) or Fe(III) ion crosslinker, said nanoparticle having a size of less than one micron, wherein said nanoparticle has a predominance of positive charges and the amount of PEI exceeds the amount of sodium polyvinyl sulfonate. A composition comprising a polyelectrolyte complex nanoparticle having a polyethylenimine (PEI) of less than 26,000 Da and a polyanion of less than 10,000 Da intimately associated with at least one multivalent cation crosslinker, wherein said polyanion is selected from sodium polyacrylate, sodium polyvinyl sulfonate, poly(sodium styrene sulfonate), copolymers of sodium acrylate with acrylamide, sodium vinylsulfonate or sodium styrene sulfonate, dextran sulfate, and anionic surfactants, and where the at least one multivalent cation crosslinker is selected from aluminum(III), iron(III), titanium(IV), chromium(III), zirconium(IV) and complexes of same. An improved method of sweeping a reservoir, wherein an injection fluid is injected into a reservoir to mobilize and produce oil, the improvement comprising injecting any of the above compositions plus a polymer plus a fluid into a reservoir, aging the composition and polymer to increase its viscosity, injecting additional injection fluid into said reservoir to mobilize oil, and producing said oil. A delayed gelling composition comprising any of the above compositions, a polymer that can be crosslinked with any of the above compositions and a fluid. The fluid can be brine, seawater, river or lake water, or produced water. The polymer can have anionic sites that crosslink with at least one multivalent cation crosslinker used in the above compositions. In some embodiments, the polymer is a polymer or copolymers of acrylate, acrylamide, N,N-dimethyacrylamide, tert-butyl acrylate, acryamido-2-methylpropane sulfonic acid, sodium 2-acryamido-2-methylpropane sulfonate, or N,N, dimethyl acrylamide. A method of improving sweep efficiency of a fluid flood of a reservoir, said method comprising: injecting any of the delayed gelling compositions described above into a reservoir, aging the composition to increase its viscosity, injecting an injection fluid into said reservoir to mobilize the oil, and producing said mobilized oil.

(30) The present disclosure is exemplified with respect to the examples and figures below. The following examples are intended to be illustrative only, and not unduly limit the scope of the appended claims

Materials

(31) Reagent grade chemicals were obtained from Fisher Scientific (Morris Plains, N.J.). Polyethylenimine (Mw=25 kDa & 800 Da) and polyvinyl sulfonic acid (PVS) (sodium salt, 25 wt %, Mw=4-6 kDa) were obtained from Sigma Aldrich (St. Louis, Mo.). Other polyanions (PAAs) were, Nuosperse FX605 PAA from Elementis and CrCl.sub.3 (as 12.3% Cr(III)) from McGean. Commercial grade product of PEI used in these below tests were Lupasol-WF PEI25k, obtained from BASF.

(32) Reagents were used as supplied and all aqueous solutions were prepared in 18 MΩ/cm reverse osmosis (RO) water from a WaterPro/RO/PS unit (Labconco, Kansas City, Mo.).

(33) Partially hydrolyzed polyacrylamide (HPAM) was obtained from a variety of sources (Table 1). Typically, 2% HPAM polymer stock solutions were prepared in 1.5% NaCl+400 ppm NaN.sub.3 solution and passed through a 5 μm nylon filter before use.

(34) TABLE-US-00002 TABLE 1 Identity, supplier and characteristics of HPAM used in these studies Alcoflood Alcomer24 Alcoflood Name AF935 AC24 AN907 AN905 EOR204 AF254S Provider Ciba Specialty BASF SNF SNF Tiorco Allied Chemicals Colloids M.sub.w 6 MDa 6.6 MDa 10-13 MDa 8-10 MDa 10-12 MDa 300-500 KDa Degree of 5-10% 10% 7% 5% 12% <4% Hydrolysis

Brines

(35) Synthetic field brines and seawater used in the preparation of PECs and gelants were prepared according to the recipes in Table 2. To avoid precipitation during storage, NaHCO.sub.3 was either omitted or added immediately prior to use:

(36) TABLE-US-00003 TABLE 2 Synthetic brines North Sea Brine A, g/L Brine B, g/L Water SW, g/L NaCl 26.22 35.74 22.64 KCl 0.166 0.298 0.763 CaCl.sub.2•2H.sub.2O 0.444 32.28 1.72 MgCl.sub.2•6H.sub.2O 1.414 4.35 11.24 Na.sub.2SO.sub.4 0.37 — 3.57 NaHCO.sub.3* 2.232 0.20 0.22 TDS 30,000 ppm 62,640 ppm 33,746 ppm *Omitted or added immediately before use

PEC Preparation and Characterization

(37) Polyelectrolyte complexes (PECs) were prepared by mixing dilute solutions of a polyanion (PAA), a polycation (PEI) and a multivalent cation (Cr.sup.3+ or Fe.sup.3+) in sequence while stirring vigorously with a magnetic stirrer. Typically, the larger volume of the two polyelectrolyte stock solutions was placed in a 100 mL beaker and stirred at 1200 min.sup.−1. While stirring, the oppositely-charged polyelectrolyte was added rapidly from a syringe fitted with a 16 gauge hypodermic needle. Finally, the multivalent cation stock solution was added from another syringe fitted with a 23 gauge needle.

(38) Particle size & zeta potential: Particle size was estimated from dynamic light scattering using a Brookfield NanoBrook Omni instrument. Four drops of the PEC complexes were diluted with RO water in a 1 cm square polystyrene cuvette. Three one minute measurements of light scattering at 90° were taken to calculate the particle size distribution, mean effective diameter and polydispersity.

(39) Zeta potential is a measure of the magnitude of the electrostatic or charge repulsion/attraction between particles, and is one of the fundamental parameters known to affect stability. The magnitude of the zeta potential indicates the degree of electrostatic repulsion between adjacent, similarly charged particles in a dispersion. For molecules and particles that are small enough, a high zeta potential will confer stability, i.e., the solution or dispersion will resist aggregation. When the potential is small, attractive forces may exceed this repulsion and the dispersion may break and flocculate. So, colloids with high zeta potential (negative or positive) are electrically stabilized while colloids with low zeta potentials tend to coagulate or flocculate, as shown in the table:

(40) TABLE-US-00004 Zeta potential [mV] Stability behavior of the colloid from 0 to ±5, Rapid coagulation or flocculation from ±10 to ±30 Incipient instability from ±30 to ±40 Moderate stability from ±40 to ±60 Good stability more than ±61 Excellent stability

(41) Zeta potential was measured in the same instrument. Two to four drops of the PEC complexes were diluted to 1.4 mL with 1 mMol/L KCl solution in a cuvette. Electrophoretic mobility was used to calculate zeta potential using the Smoluchowski approximation. Three consecutive measurements were averaged for each sample.

(42) Multivalent cations entrapment efficiency: A sample of the PEC complex was centrifuged at 14,000 G for 30-90 minutes. The concentrations of multivalent cations were measured in the whole suspension and in the supernatant and the entrapment efficiency calculated from:

Equation 1: Entrapment Efficiency

(43)
EE=(M.sub.0−M.sub.s)/[M].sub.0

(44) Where EE is the entrapment efficiency (expressed as a fraction or multiplied by 100 to give %), [M].sub.0 is the concentration of multivalent cations in the PEC suspension, and [M].sub.s is the concentration of multivalent cations in the supernatant.

(45) For the multivalent cation determination, samples were analyzed by inductively-coupled plasma optical emission spectrometry (ICP-OES) using the following procedure: 1. Add 400 μL 30% hydrogen peroxide to a 200 μL sample of PEC 2. Heat to 70-75° C. for 3 h 3. Add 1000 μL concentrated nitric acid 4. Heat to 70-75° C. for 1 h 5. Dilute to 10 mL with RO water (50× dilution factor)

(46) The chromium and/or iron concentration was determined using a PerkinElmer (Waltham, Mass.) ICP-OES instrument according to standard operating procedures, wherein the presence of Cr(III) was detected at 276.7 nm and Fe(III) at 238.2 nm.

(47) Alternatively, for the multivalent cations determination of chromium, samples were analyzed colorimetrically by oxidizing Cr(III) to Cr(VI) using the following procedure: 1. Weigh 0.5-1 mL sample and add 1 mL 30% hydrogen peroxide 2. Heat to 70-75° C. for 30 minutes 3. Add 1 mL of 1N KOH and 5-10 mL RO water and weigh to find dilution factor 4. Determine optical absorbance at 373 nm

(48) For the Total organic carbon/total nitrogen (TOC/TN) characterization, PEC samples were analyzed as follows: 1. Prepare phosphoric acid stock solution (as used in the TOC/TN instrument) by mixing 18 mL concentrated phosphoric acid and 94 mL RO water. 50× diluted phosphoric acid was prepared by mixing 20 mL of the stock solution with 1000 mL of RO water. 2. Prepare samples by adding 200 mL PEC sample to an EPA vial and diluting to 20 g with diluted phosphoric acid (from 1 above to give 50× dilution factor)

(49) TOC and TN were measured in a Teledyne Tekmar Torch instrument according to standard operating procedures.

Gelation of HPAM by PECs

(50) After characterizations, the PECs were mixed with a HPAM source and a brine to form a gelant according to some embodiments of the present disclosure.

(51) Gelant preparation: PECs, HPAM stock solution and synthetic brine were mixed together in an anaerobic chamber to a predetermined concentration of HPAM and PEC to form a “gelant”. Typically, the PEC concentration is expressed as ppm multivalent cations, though the PEI also plays a substantial role in the gelation process.

(52) The gelant was aliquoted into a number of glass vials and sealed by crimping the foil and PTFE caps. The vials were placed in ovens or heating blocks at the desired incubation temperature and incubated under anaerobic conditions to prevent oxidative degradation of the polymer. The initial viscosity was measured and vials were opened at aging intervals to test the viscosity development.

(53) Viscosity measurement: Viscosity profiles of the gelants were measured using a Brookfield DV-II+ Pro viscometer (Brookfield Engineering, Middleboro, Mass.) fitted with a CP40 cone and plate. Viscosity was measured at 25° C. at the lowest shear rate that gave a reliable reading (i.e. >10% of available torque and <maximum viscosity available at that shear rate). Gelation was considered to have occurred when the viscosity exceeded 1032 cp at 2.25 s.sup.−1, which is the highest value that can be measured by the instrument in this configuration.

(54) Gel strength: After the gelant had gelled according to the viscosity measurement, it generally continued to develop a stronger gel structure. To capture this behavior, the gels were also assigned a score on the Sydansk Gel Code scale (SPE 153241 Advanced Technology Series, Vol. 1). To facilitate a graphical representation of this information, a numeric code, displayed in Table 3 was also used, where A=0, B=1 . . . J=9.

(55) TABLE-US-00005 TABLE 3 Sydansk Gel Codes used to describe strength of HPAM-PEC gels (SPE 153241) Sydansk Numeric Gel Code Equivalent Description A 0 No detectable gel formed B 1 Highly flowing gel C 2 Flowing gel D 3 Moderately flowing “tonguing” gel E 4 Barely flowing gel F 5 Highly deformable non-flowing gel G 6 Moderately deformable non-flowing gel H 7 Slightly deformable non-flowing gel I 8 Rigid gel J 9 Ringing rigid gel

(56) Retention in sandpacks: Sandpack trials were carried out using crushed Berea outcrop material. The sand was dry sieved and the fraction between 48 and 270 mesh was retained for use. Glass sandpack holders with heated water jackets were used for temperature control.

(57) Before injection of gelant, sandpacks were flooded with Brine A at 5 ml/min and pressure drop across the sandpack was measured to determine permeability to brine under constant head using Darcy's law:

Equation 2: Calculating Permeability According to Darcy's Law

(58)
k=(μ×L×Q)/(A×ΔAP) where: μ=viscosity, centipoise (cP); L=length of sandpack, cm; Q=flow rate, cm.sup.3/s; A=cross-sectional area of sandpack, cm.sup.2; AP=pressure drop across sandpack, atm

(59) Homogeneity and pore volume of sandpacks was confirmed by injecting tracer (brine+1% KNO.sub.3) and plotting tracer concentration versus volume injected. The nitrate tracer was detected in the effluent by measuring optical absorbance at 302 nm. Prior to further use of the sandpack, the tracer was displaced by brine.

(60) For the gelant injection, sandpacks were connected to a circulating water bath and were allowed to reach the target temperature of 65° C. Gelant was prepared as described above and loaded into a 60 mL plastic syringe with a polyethylene plunger. The gelant was injected into the sandpack at 5 mL/min using a programmable syringe pump. The pressure drop profile was recorded across the sandpack to allow apparent viscosity to be calculated. During injection, effluent fractions were collected in numbered 2 mL polypropylene microcentrifuge tubes for further analysis.

(61) Post-gelant brine flood: After an overnight shut-in at 65° C. temperature, the sandpack was flooded with brine at constant flow of 5 mL/min.

(62) Effluent analysis: Injected gelant and representative effluent samples were analyzed for multivalent cations concentration by ICP-OES as previously described. Concentration was normalized to the injected concentration and plotted against number of pore volumes injected, along with the previously measure tracer breakthrough curve. The shape of the breakthrough curve is an important indicator of the degree of retention and adsorption. Any delay in breakthrough is easily seen by comparing to the tracer curve.

(63) A mass balance calculation was performed by summing the mass of multivalent cations injected and produced (interpolating samples that were not measured) and dividing by the mass of sand in the sandpack. This retention value was expressed as μg of multivalent cations per gram of sand.

(64) Cr(III)-PEC concentration and re-suspension: Since the PEC formulation method requires the reagents to be dissolved in fresh water at relatively low concentrations, it is desirable to concentrate the final PEC suspension for ease of storage, transportation and use.

(65) Two methods were used to concentrate the samples. The initial trials were performed in a vacuum oven without temperature control. Later trials were performed with the rotary evaporator at elevated temperature. The rotary evaporator method has the advantage of being much quicker, especially at higher temperatures; however, either method works.

(66) Concentration Method 1: Samples were placed in 20 mL glass vials or 50 mL polypropylene centrifuge tubes in a vacuum oven at ambient temperature. The sample containers were covered with Parafilm, which was pierced multiple times with a 23 gauge hypodermic needle to allow the escape of water vapor without loss of liquid during boiling. Temperature was neither controlled nor monitored, but was below room temperature due to latent heat of evaporation.

(67) Concentration Method 2: 40 mL samples were dried in a rotary evaporator under vacuum at elevated temperature.

(68) Re-suspension: Following the concentration step, samples were diluted back to their original volume with brine.

(69) Re-suspended samples were studied (size, zeta potential, gelation behavior with HPAM) and characterized according to the methods described above.

Results

PEI/PAA/Cr PEC

(70) The initial approach to incorporating PAA into PECs was to recreate the stoichiometric charge ratio seen in a previously developed PEI/PVS/Cr(III) formulation in US20140209305 by multiplying the polyanion stock concentration by the ratio of the formula weights of vinylsulfonate (VS) and sodium acrylate (AA) to maintain and keep stoichiometric ratios of PEI, polyanion and multivalent cation without changing the overall mass. The formula weights are VS=130.1, AA=94.05; PVS:PAA=1.38:1=1:0.723 and the concentration of PAA in stock solution was thus reduced to 0.6125×0.723=0.443%.

(71) For later formulations, the PEI concentration and pH, PAA concentration and multivalent cation concentration were varied. Some representative formulations (Cr(III)-PEC0 and Cr(III)—PEC39) were selected for further study based on results of particle characterization (size, zeta potential and entrapment efficiency). Tables 4 and 5 detail the formulation and initial PEC characterization studies for Cr(III)-PEC0 and Cr(III)—PEC39.

(72) TABLE-US-00006 TABLE 4 Cr(III)-PEC formulations 0.443% 1% PEI 19.5k ppm PAA 25 kDa Cr(III) as 10% 5.1 kDa pH 10.5 CrCl.sub.3•6H.sub.2O Cr(III)-PEC0 3.48 g 21.0 g 0.72 g 0.222% 0.5% PEI 19.5k ppm PAA 25 kDa Cr(III) (from 5.1 kDa pH 9.55 12.3%) Cr(III)-PEC39 3.48 15.2 0.49

(73) TABLE-US-00007 TABLE 5 Typical PEC characterizations Zeta Entrapment [Cr(III)], ppm pH Size, nm potential, mV Efficiency, % Cr(III)-PEC0 560 8.9 89 32 >90 Cr(III)-PEC39 499 7.5 333 49.8 98

(74) Effect of PAA molecular weights: To examine the effect of PAA molecular weight on the PECs, the PEI/PAA/Cr-0 formulation initially made with 5.1 kDa of PAA was replicated using equivalent concentration of PAA at different molecular weights. Stock concentrations were manipulated to account for whether the PAA was supplied as the acid or as the sodium salt and recipes for which are in Table 6.

(75) TABLE-US-00008 TABLE 6 PEC formulations using different molecular weight PAA PAA PAA stock PAA 1% PEI 10% Polyanion stock viscosity, stock, 25 kDa CrCl.sub.3•6H.sub.2O, stock pH cp g pH 10.5, g g 0.335% PAA 3.0 1.03 3.48 21.0 0.72 2 kDa 0.443% PAA-Na 8.1 1.04 3.48 21.0 0.72 5.1 kDa * 0.335% PAA 2.9 1.19 3.48 21.0 0.72 100 kDa 0.335% PAA 3.1 1.48 3.48 21.0 0.72 250 kDa 0.335% PAA 3.2 >1032 3.48 21.0 0.72 1.25 MDa * 0.443% PAA = 0.335% as acid

(76) FIG. 2 displays the characterization data for each PECs such as size, zeta potential, multivalent cation entrapment efficiency and pH. As can be seen, the multivalent cation entrapment efficiency and pH did not vary much. However, the lowest zeta potential was seen in the smallest PECs, which had a PAA molecular weight of approximately 2-500 kDa.

(77) Effect of PAA 5.1 kDa concentration: Multiple batches of Cr(III)-PEC0 (21 g of 1% PEI+3.48 g of PAA stock+0.72 g of 10% CrCl.sub.3.6H.sub.2O) were assembled with different final concentrations of PAA 5.1 kDa to determine how the PAA concentration affected the PECs. To maintain the final volume and concentrations of PEI and Cr(III), the PAA stock solution concentrations were varied according to Table 7.

(78) TABLE-US-00009 TABLE 7 Dilutions of PAA stock solution used to maintain final concentration of PEI and Cr(III) in PECs PAA [PAA] stock solution stock, ppm 1x dilution 3345 2x dilution 1673 5x dilution 669 10x dilution 334 25x dilution 133

(79) FIG. 3 displays the characterization data for each of these PECs, such as size, zeta potential, multivalent cation entrapment efficiency and pH. As can be seen, the multivalent cations entrapment efficiency and pH did not vary much and are not considered to be affected by the PAA. However, both size and zeta potential decreased with increasing final concentrations of PAA at 5.1 kDa.

(80) Once PECs were assembled, they were combined with various sources of an exemplary oilfield polymer, partially hydrolyzed polyacrylamide (HPAM), to monitor viscosity and gelation.

(81) Gelation of PEI/PAA/Cr(III)-PEC0 and AC24: FIGS. 4 and 5 display viscosity profiles of PECs mixed with AC24 as the source for HPAM and 100 ppm Cr(III) in either RO water or Brine A to form a gelant. The gelant was incubated at 65° C.

(82) In FIG. 4, PECs with differing concentrations of PAA at both 5.1 kDa and 1.25 MDa were studied. The average gelation time was only 1 day for these gelants. In FIG. 5, the gelation time increased by using brine A instead of water as the injection fluid in the gelant. Furthermore, switching the PAA to PVS saw an increase in gelation time.

(83) Gelation of PEI/PAA/Cr(III)-PEC39 [+] and EOR204 in Brine A at 65° C.: Cr(III)—PEC39 was found to be suitable for use with a wider range of HPAMs than Cr(III)-PEC0, at the cost of a lower chromium loading. Further work is being conducted to mitigate this limitation on chromium loading by concentrating the PEC suspension to allow for ease of handling, transportation and use.

(84) FIG. 6A shows the initial viscosity profile of PEI/PAA/Cr-39 [+] mixed with EOR204 as the HPAM source in Brine A. The final concentration of Cr(III) in the gelant was 100 ppm. As expected, the PECs delayed the gelation by four days. To confirm the reproducibility of the gelation for PEI/PAA/Cr-39 [+] and EOR204 in Brine A at 65° C., a total of three gelation tests were carried out using independently-prepared batches of Cr(III)-PEC39 to ensure that the gelation delay was repeatable. The results are shown in FIG. 6B.

(85) The effects on gelation time of varying concentration of chromium, i.e. by changing the amount of PECs, was examined and the results are shown in FIG. 7. As expected, gelation was delayed with decreasing chromium concentration.

(86) The effects on gelation time of using different sources of HPAM were also examined and the results are shown in FIG. 8. Gelation time for EOR204, AN907, and Alcomer 24 are 4, 5.8, and 8 days respectively. EOR204 has the shortest gelation time due to its higher molecular weight (10-12 MDa) and high degree of hydrolysis (˜12%). Gelation time of AN907 is shorter than Alcomer 24 because the molecular weight of AN907 (10-13 MDa) is higher than that of Alcomer 24 (6.6 MDa).

(87) Concentration and Re-Suspension of Cr(III)-PECs

(88) Concentrating PEI251c/PAA5.1k/Cr(III)-PEC0—Initial Trial

(89) PEI(25 kDa)/PAA(5.1 kDa)/Cr-0 PECs were concentrated by drying to lower water content, and then re-suspended in Brine A. Several samples were evaporated at ambient temperature in 20 mL glass vials in a vacuum oven. The vials were covered with Parafilm, which was pierced multiple times with a 23 gauge hypodermic needle to allow the escape of water vapor without loss of liquid during boiling.

(90) Samples that had been concentrated to different final masses were re-suspended in Brine A (no bicarbonate) to their original concentration. At the highest concentration factor, no free water was visible before the addition of brine and the PECs formed a blue film on the inside of the glass vial. Re-suspended PECs were characterized (size, zeta potential) and the results are shown in Table 8.

(91) TABLE-US-00010 TABLE 8 Characterization of Cr(III)-PEC0 after vacuum concentration and re-suspension to original volume in Brine A Mass Zeta Dilution Factor Reduction Size, nm potential, mV EE As prepared (1×) — 162.9 ± 9.6  30.2 ± 0.55 ND 1.97× 49% 153.2 ± 14.5 29.2 ± 1.14 ND 7.5×  87% 156.0 ± 9.7  29.2 ± 1.16 ND All liquid 99% 231.7 ± 23.3 21.1 ± 1.35 ND removed (79.1×)

(92) Concentration, re-suspension and HPAM gelation with PEI25 kDa/PAA5.1 kDa/Cr(III)-PEC0

(93) Multiple batches of Cr(III)-PEC0 were prepared (21 g 1% PEI−25 kDa (pH10)+3.48 g 0.443% PAA—5.1 kDa+0.72 g 10% CrCl.sub.3.6H.sub.2O) and 40 mL samples were dried under vacuum at ambient temperature in 50-mL polypropylene centrifuge tubes. Tubes were covered with Parafilm, which was pierced multiple times with a 23 gauge hypodermic needle to allow the escape of water vapor without loss of liquid during boiling. Samples that had been concentrated to different final masses were re-suspended in Brine A to their original concentration.

(94) The re-suspended Cr(III)-PEC0 were characterized (size, zeta potential) and used to form gels with AC24. Characterization data is provided below in Table 9 and viscosity profiles are displayed in FIG. 9. The larger particles have the lowest zeta potential and longer gelation times.

(95) TABLE-US-00011 TABLE 9 Characterization of Cr(III)-PEC0 after vacuum concentration and re-suspension to original volume in Brine A Mass Zeta Dilution Factor Reduction Size, nm potential, mV EE As prepared (1×) — 105.1 ± 0.5 15.9 ± 2.0 83% 1.96× 49% 106.3 ± 1.8 13.4 ± 1.0 82% 4.48× 78% 105.5 ± 0.3 13.9 ± 2.1 87% 10.0×  90% 115.4 ± 0.5 14.3 ± 0.7 83% 20.82×  95% 133.8 ± 0.7 11.9 ± 1.6 88%

(96) Multiple batches of PEC39 prepared with commercial components (15.2 g 1% PEI−25 kDa (pH=9.55)+3.48 g 0.443% PAA−4.9 kDa+0.49 g 1.95% Cr) at single and double scale. No significant differences were seen between the batches and so they were pooled for further study.

(97) 40 mL samples of the Cr(III)-PEC39 were dried to about 5% of their original volume in a rotary evaporator under vacuum at several different temperatures and re-suspended in synthetic seawater or Brine A to their original concentration. Re-suspended PECs were characterized (size, zeta potential—Table 10) and used to form gelants with HPAM at 85° C. in synthetic seawater.

(98) TABLE-US-00012 TABLE 10 Formulation and characterization of multiple batches of Cr(III)-PEC39 before concentration in a rotary evaporator 0.5% PEI 0.2215% 1.95% 25 kDa PAA Cr(III) Zeta pH 9.55 4.9 kDa (from Size, potential, Loading, (Lupasol WF) (FX605) 12.3%) pH nm mV ppm EE, % Single 15.2 g 3.48 g 0.49 g 7.45 578 47.6 496 98.1 Batch 7.41 646 44.4 515 98.2 7.50 760 55.3 473 98.2 Double 30.4 g 6.96 g 0.98 g 7.46 394 41.4 540 98.3 Batch 7.47 548 53.3 535 98.3 7.43 522 52.2 510 98.3 7.48 865 50.3 515 98.0

(99) The Cr(III)-PEC39 were concentrated at drying temperatures of 35, 45, 55, and 65° C. Characterization data is shown in FIG. 10 and viscosity profiles of the concentrated and re-suspended PECs during gelation with AC24 are shown in FIG. 11. Longer gelation times were seen with the higher drying temperatures. However, the difference of one day in gelation time between the control and three of the four concentrated samples is most likely within experimental error.

(100) Summary—Concentration of Cr(III)-PEC

(101) Vacuum concentration at ambient temperature is very time-consuming. The time required can be reduced by elevating the temperature but this is associated with increasing flocculation and there are technical challenges associated with boiling at higher temperature under reduced pressure.

(102) Concentration to 5% of the original volume does not appear to disrupt the particles, and they can be successfully resuspended in synthetic field brine, as shown in FIG. 12. Any changes in particle size and zeta potential, along with slight increases in gelation delay can be attributed to the salinity of the brine.

(103) Retention of Cr(III)-PEC0 and AC24 Gelant in Berea Sand

(104) It is important that the gelant does not suffer from excessive filtration, retention or chromatographic separation of its components during injection into high permeability subsurface features. A simple injection experiment was performed using a Berea sand pack as described above to test the retention of the gelant.

(105) A batch of Cr(III)-PEC0 was assembled and characterized (results shown in Table 11) mixed with AC24 to form a gelant for the sand pack experiments. Final concentrations were 100 ppm Cr(III) as PEC and 5000 ppm AC24 in Brine A.

(106) TABLE-US-00013 TABLE 11 Characterization of Cr(III)-PEC0 nanoparticles used in sandpack test Zeta Entrapment Polyanion [Cr(III)], ppm pH Size, nm potential, mV Efficiency, % PAA 5.1 kDa 20140328 574 ± 13.6 9.0 ± 0.02 86.9 ± 0.56 40.1 ± 1.69 92.6 ± 0.47 Mean ± SE (N = 3)

(107) FIGS. 13 and 14 displays the results for the sandpack trials. FIG. 13 shows the pressure drop profile wherein the drops correspond to the injection of several portions of gelant. This was done using a syringe pump of limited capacity. The points at which the pressure falls to zero correspond to the recharge of the syringe pump of the gelant. FIG. 14 shows the breakthrough of effluent concentration curve of the gelant, which matches the tracer. This shows that the gelant is not separating after injection. The TOC and TN results are also displayed.

(108) Only a single formulation of PECs has been tested so far using the sand pack, but both the shape of the breakthrough curve compared to the tracer, and the material balance suggest that this formulation will not suffer from retention during injection into high permeability underground formations.

PEI/PAA/FE(III) PECS

(109) The use of chromium is problematic in some environmentally-sensitive fields. The Applicants were interested in whether Cr(III) in PEC formulations can be replaced with other multivalent cations, such as Fe(III), while still retaining the delayed gelation features exemplified above. Thus, PEC formulations similar to Cr(III)-PEC0 and Cr(III)—PEC39 were prepared using iron.

(110) Gelation of PEI/PAA/Fe and AC24

(111) Cr(III) was replaced with Fe(III) on a stoichiometric basis. To maintain the overall volume and masses of the other components, the Fe stock solution concentration was reduced compared to the Cr(III) stock concentration. PECs were made with 21 g 1% PEI (pH10)+3.48 g 0.445% PAA-Na, 5.1 kDa+0.72 g multivalent cation stock and characterized. Table 12 compares the data for Cr(III)-PEC0 and Fe-PEC0.

(112) TABLE-US-00014 TABLE 12 Characteristics of PEC0 made with Cr(III) and Fe(III) Multivalent cations Measured [X] in PECs, Zeta stock solution ppm (Target = 558) pH Size, nm potential, mV EE 10% CrCl.sub.3•6H.sub.2O 585 8.9 88.7 31.9 ≥89% 9.5% FeCl.sub.3•6H.sub.2O 589 9.1 None None ≥40% Detected Detected

(113) As shown in Table 12, it proved difficult to detect any particles made with Fe(III), however—a pellet was formed following centrifugation and an orange-colored supernatant, indicating that at least some of the Fe was associated with the polyelectrolytes, but that a fraction either remained in solution, or was associated with PECs that were too small to be separated at the acceleration used. This was confirmed by measuring an entrapment efficiency of approximately 40%. The hypothesis that there may be a population of very small particles was supported by the fact that gelation behavior with AC24 was similar to that seen with an equivalent PEI/PAA/Cr PEC (Cr(III)-PEC0). FIG. 15 displays the viscosity profile for Cr(III)-PEC0 and Fe-PEC0 gelled with AC24. Similar gelation delays were obtained for both the Cr(III) and Fe PECs.

(114) Similar to the Cr(III)-PECs, different variables in the Fe-PEC0 gelant were adjusted to determine their effect on the viscosity profiles.

(115) Fe-PEC0 was gelled with AC24 at two different temperatures, 40 and 65° C., and the viscosity plot is shown in FIG. 16. While Fe-PEC0 gelled within a few days at 65° C., no gelation occurred at 40° C. The non-gelation at 40° C. is not unexpected as similar systems have not gelled under 45° C. because there is not enough energy at this temperature.

(116) Different sources of HPAM, AC24, AN907 and AF254, were mixed with the Fe-PEC0 to obtain a final concentration of 5000 ppm HPAM and the viscosity profiles are shown in FIG. 17. While AC24 and AN907 gelled as expected, the Fe-PEC0 formulation was not found to be compatible with AF254.

(117) The brine used in the gelant was also tested and results are given in FIG. 18. Higher salinity brines results in longer delays in gelation.

(118) Fe-PEC39

(119) Fe-PEC39 was formulated by replacing Cr(III) in Cr(III)-PEC39 with Fe to overcome the incompatibility of Fe-PEC0 with some HPAMs. Formulation and characterization information is in Table 13.

(120) TABLE-US-00015 TABLE 13 Characteristics of Fe-PEC39 made at two different batch sizes to show repeatabilty of formulation 0.5% 1.95% PEI 25k 0.2215% Fe(III) Zeta pH 9.55 PAA 4.9k (from Size, potential Loading, (Lupasol WE) (FX605) solid) pH nm mV ppm Single 15.2 g 3.48 g 0.49 g 7.44 49.5 NA 476 Batch 7.50 50.8 503 7.48 50.9 506 Double 30.4 g 6.96 g 0.98 g 7.46 59.4 NA 518 Batch 7.43 57.1 537 7.41 54.5 558

(121) Small but statistically significant differences in particle sizes were seen between single/double batches. It was confirmed by examining the particle size distribution data that the artificially low entrapment efficiency observed was due to inability to centrifuge small particles (approximately 10 nm). These small particles do not contribute strongly to the calculated effective diameter because this is based on intensity data and the larger particles contribute disproportionally to this measurement. Plotting the distribution on a volume basis makes the population of small particles more obvious. The instrument was unable to measure zeta potential.

(122) As with Fe-PEC0, different gelants were prepared by varying the source of HPAM, the concentration of the HPAM and the final concentration of the Fe to determine how the gelation was affected and hopefully overcome the gelation issues that Fe-PEC0 encountered with the various HPAM sources. The different formulations are given in Table 14.

(123) TABLE-US-00016 TABLE 14 Gelant formulations to control gelation of Fe- PEC39 and HPAM at 85° C. in synthetic seawater Fe-PEC39 2% 2% 20% (523 ppm AC24, AN907, AF254S, Synthetic Total, Fe(III), HPAM, Fe), g g g g SW, g g ppm ppm 8.03 12.5 — — 29.47 50 84 5000 8.03 — 12.5 — 29.47 50 84 5000 8.03 — — 12.5 29.47 50 84 50,000 8.03 25.0 — — 29.47 62.5 67.2 8000 8.03 — 25.0 — 29.47 62.5 67.2 8000 8.03 — — 25.0 29.47 62.5 67.2 80,000 4.78  7.5 — — 37.72 50 50 5000 4.78 —  7.5 — 37.72 50 50 5000 4.78 — — 12.5 32.72 50 50 50,000

(124) FIG. 19 displays the viscosity profiles for the gelants in Table 14. Unlike Fe-PEC0, Fe-PEC39 formed gels with the AN254S. However, it should be noted that the Sydansk Gel Code data, shown in FIG. 20, indicates that gelants containing AF254S act as viscous liquids with viscosity>1032 cp (nominal gelation) and so the effective gelation delay is longer than would be inferred from the viscosity data alone. For the remaining compositions, delays of 2-3 days were experienced.

(125) Based on these results, a range of concentrations are being studied to achieve a gelation delay of about four days under similar reaction conditions.

(126) Additional lab tests on PEI/PVS polyelectrolyte complexes were performed with commercial grade components as described here. Polyethyleneimine, Lupasol WF (Mw=25 kDa) was obtained from BASF. Poly (sodium vinylsulfonate) (PVS) (25-35%, Mw=3-7 kDa) was obtained from Monomer-Polymer & Dajac Laboratories, Inc. Chromium (III) chloride solution 12.3% Cr(III))) was obtained from McGean. It is expected that a PVS molecular weight of less than 40,000 Da will demonstrate utility. However, focus was on the preferred range of less than 10,000 Da, and most preferably will be on PVS in the 3,000-7000 Da range.

(127) Tables 15 details the formulation for one such PEI/PVS/Cr-2 PEC. The initial PEC characterization studies for this PEC are found in Table 16.

(128) TABLE-US-00017 TABLE 15 PEI/PVS/Cr-2 PEC formulations 1% PEI Adjusted 0.6125% 1.95% pH = 10.69 PVS Cr(III) 21.0 g 3.48 g 0.72 g

(129) TABLE-US-00018 TABLE 16 PEI/PVS/Cr-2 PEC Characterization results Zeta Cr(III) Cr(III) Particle potential Loading Entrapment Size (nm) pH (mV) (ppm) Efficiency (%) 106.3 ± 1.1 9.0~9.2 28.6 ± 1.8 558 93.3 ± 0.6

(130) Concentration and Re-Suspension of PECs

(131) Several batches of the PEI/PVS/Cr-2 PEC were made and pooled together. PEC was concentrated to ˜5% of original mass and then re-suspended in Brine A to the original concentration. The re-suspended PEC was characterized and the results are shown in Table 17.

(132) TABLE-US-00019 TABLE 17 Characterization of PEI/PVS/Cr-2 PEC after vacuum concentration and re-suspension to original volume in Brine A Zeta Cr Size, nm potential, mV loading, ppm EE, % pH Mean of separate 106.3 ± 1.06 28.58 ± 1.80 535.3 ± 5.04 93.3 ± 0.56 9.23 ± 0.01 batches (N = 8) Pooled (Control) 103.5 ± 0.21 26.98 ± 1.15 531 88.5 9.15 Concentrated 230.1 ± 1.16 18.51 ± 0.26 504 92.4 Nd and re-suspended in Brine A

(133) Gelation of PEI/PVS/Cr-2 PEC and EOR204: FIG. 21 displays viscosity profiles of PEC (containing 100 ppm Cr(III)) mixed with 5000 ppm EOR 204 in Brine A to form a gelant. The gelant was incubated at both 65° C. and 85° C. The average gelation time was 1 day at 85° C. and 5 days at 65° C. Concentration and re-suspension of the PEC did not change the gelation behavior.

(134) Each of the following references is incorporated herein in their entirety for all purposes. US2010056399, US2008058229, U.S. Pat. No. 7,644,764, US20140209305 Cordova, M.; Cheng, M.; Trejo, J.; Johnson, S. J.; Willhite, G. P.; Liang, J.-T.; Berkland, C., Delayed HPAM gelation via transient sequestration of chromium in polyelectrolyte complex nanoparticles. Macromolecules 2008, 41 (12), 4398-4404. Johnson, S. J.; Trejo, J.; Veisi, M.; Willhite, G. P.; Liang, J.-T.; Berkland, C., Effects of divalent cations, seawater and formation brine on positively charged polyethylenimine/dextran sulfate/Cr(III) polyelectrolyte complexes and HPAM/Cr(III) gelation. Journal of Applied Polymer Science 2010, 115 (2), 1008-1014.