Networked polymeric gels and use of such polymeric gels in hydrocarbon recovery

a polymeric gel and network technology, applied in fluid removal, chemistry apparatus and processes, borehole/well accessories, etc., can solve the problems of difficult implementation of the above definition in practice, and it is almost impossible to measure the total dissolving material in practice, so as to increase the amine content and stiffen the resultant gel

Inactive Publication Date: 2008-07-03
UNIVERSITY OF PITTSBURGH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Benefits of technology

[0009]The surprising stability of networked polymeric gels of the present invention in waters having high salt content / salinity makes the networked polymeric gels useful for injection into subterranean or underground formations to alter the permeability thereof in, for example, the recovery of oil and / or other hydrocarbons. Moreover, because of environmental concerns as well as cost for disposing of a produced brine (that is, water of relatively high salinity co-produced with oil and gas, which is generally contaminated with some oil, or gas, or both) it may be desirable to utilize produced brine as the liquid / water used for the networked polymeric gels of the present invention. Use of produced brines eliminates the cost associated with acquiring fresh water for use as the liquid and the disposal cost for the produced brine. Although the networked polymeric compositions of the present invention may be particularly suited for use in hydrocarbon recovery, the networked polymeric compositions of the present invention can be used in virtually any device, system or method in which it is desirable to form a crosslinked polymer network in water of relatively high salinity.
[0013]Moreover, unlike many networking polymeric systems currently use in hydrocarbon recovery, the networked polymeric gels of the present invention are inherently thermally stable at the temperatures (often in excess of 90° C. or even 110° C.) found in subterranean formations from which such materials are recovered. Indeed, gelation of the networked polymeric gels of the present invention occurs best at temperatures above 80° C. The temperature dependence of the compositions of the present invention can also assist in preventing gelation prior to or too early during injection, thereby reducing or eliminating the necessity of delaying agents and the costs and other problems associated therewith.
[0016]In one embodiment, the hydrophilic polymer is at least one of poly(diallyl dimethyl ammonium chloride), diallyl dimethyl ammonium chloride / acrylamide copolymer, diallyl dimethyl ammonium chloride / diallyl amine copolymer, or diallyl dimethyl ammonium chloride / allyl amine copolymer. In the case that the hydrophilic polymer is diallyl dimethyl ammonium chloride / acrylamide copolymer, diallyl dimethyl ammonium chloride / diallyl amine copolymer, or diallyl dimethyl ammonium chloride / allyl amine copolymer, the content of diallyl dimethyl ammonium chloride in the copolymer can be at least 50 weight percent. A relatively high concentration of diallyl dimethyl ammonium chloride generally increases water solubility. The content of diallyl dimethyl ammonium chloride in the copolymer can also be at least 70 weight percent. Moreover, the content of diallyl dimethyl ammonium chloride in the copolymer can further be at least 80 weight percent. Of the above diallyl dimethyl ammonium chloride copolymers, preferred copolymer are diallyl dimethyl ammonium chloride / diallyl amine copolymer and diallyl dimethyl ammonium chloride / allyl amine copolymer.
[0019]The reducible saccharides used in the present invention can be monosaccharides, disaccharides, trisaccharides etc, (for example, sugars) or polysaccharides (for example, starch or cellulose). Polysaccharides are typically a combination of nine or more monosaccharides. Reducible saccharides or reducing saccharides include a reducing group, function or functionality which is typically an aldehyde group (—C(O)H) or a hemiacetal groupwhich is another form of an aldehyde when the saccharide is in a cyclic conformation. Examples of reducing saccharides suitable for use in the present invention include, but are not limited to, the sugars glucose, lactose, and 2-deoxy-D-ribose. To decrease costs, the saccharide is preferably a monosaccharide (for example, glucose), a disaccharide (for example, lactose) or a polysaccharide (for example, starch).
[0022]A broad range of mole ratios of amine to reducing saccharide is suitable for use in the present invention. In one embodiment, the mole ratio of amine groups to reducing saccharide is in the range of approximately 1:4 to approximately 8:1. Preferably, the mole ratio of amine groups to reducing saccharide is in the range of approximately 1:2 to approximately 8:1. In general, increasing amine content results in stiffening of the resultant gel. One skilled in the art can readily determine an appropriate amine content for a desired set of properties for the resultant gel.

Problems solved by technology

However, for a number of reasons it is almost impossible to measure the total dissolved materials in practice (for example, volatile materials such as gases cannot be accurately measured and chlorides are lost in drying).
The above definition is still difficult to implement in practice.

Method used

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  • Networked polymeric gels and use of such polymeric gels in hydrocarbon recovery
  • Networked polymeric gels and use of such polymeric gels in hydrocarbon recovery
  • Networked polymeric gels and use of such polymeric gels in hydrocarbon recovery

Examples

Experimental program
Comparison scheme
Effect test

example 1

[0047]An aqueous solution was prepared by dissolving 7.5 g D-glucose and 2.5 g poly(vinylalcohol) (PVOH) into distilled, deionized water in a 25 mL volumetric flask. The solution was clear with some undissolved polymer. It was, however, pourable. The solution was transferred to a round bottom flask and heated to 80° C. in an oil bath. Heating was done with constant stirring and under reflux conditions. Upon completion the solution remained clear with all polymer dissolved and was still pourable.

example 2

[0048]Prior studies suggest that an aqueous solution of PVOH and D-glucose could be used to form hydrogels by using freezing / thawing cycles. See Yamaura, K.; Fukada, M.; Tanaka, T.; Tanigami, T. J. of Applied Polymer Science. 1999, 74, 1298-1303. To study this effect, a solution was prepared as in example 1. Heating was carried out using the same procedure as in example 1, but was allowed to reach a temperature of 90° C. The aqueous solution was then placed in a −10° C. freezer over 48 hours. After thawing the solution at room temperature for 1 hour a weak, white hydrogel had formed. The gel was then placed back in the freezer for 24 hours and then thawed at room temperature for 1 hour. After which, the gel appeared visibly stronger. This gel was found to be soluble in water heated up to 49° C. Neither swelling nor dissolution was noted when placed in 1M HCl.

example 3

[0049]Prior studies further suggest that D-glucose was not necessary for the gelation of poly(vinylalcohol) using the process in example 2. See Yamaura, K.; Karasawa, K. I.; Tanigami, T.; Matsuzawa, S. J. of Applied Polymer Science. 1994, 51, 2041-2046. To study such gelation, a 2.5 g of PVOH was dissolved in distilled, deionized water in a 25 mL volumetric flask. Heating was carried out using the same procedure as in example 1, but was allowed to reach a temperature of 95° C. The solution was then placed in the freezer at −25° C. for 48 hours. After 1 hour of thawing at room temperature a gel, similar in appearance to the gel in Example 2, was produced. The inability of PVOH to form hydrogels without the freezing / thawing cycle indicated that the amine groups on copolymers of PVOH and Poly(vinylamine) in the compositions of the present invention are responsible for gelation.

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Abstract

A composition includes water having a salinity of at least 1 ppt, at least one hydrophilic polymer containing primary (—NH2) and / or secondary (—NHR) amine groups and at least one saccharide containing a reducible function. A method of changing the permeability of a subterranean formation includes the step of injecting into a subterranean formation a composition comprising water, at least one hydrophilic polymer containing at least two groups which are independently the same or different a primary amine group or a secondary amine group and at least one saccharide containing a reducible function.

Description

CROSS-REFERENCE TO RELATED APPLICATION[0001]The present application claims the benefit of U.S. Provisional Patent Application Ser. No. 60 / 548,300, filed Feb. 27, 2004, the disclosures of which are incorporated herein by reference.BACKGROUND OF THE INVENTION[0002]The present invention relates to crosslinked or networked polymeric gels and to methods of hydrocarbon production or recovery from underground formations using such networked polymeric gels, and, especially, to networked polymeric gels that are suitable to withstand high temperatures and / or high salt content / salinity (for example, commonly experienced in hydrocarbon / oil production and recovery) and to methods of using such gels in hydrocarbon / oil production or recovery.[0003]Gelled or crosslinked water-soluble polymers have been widely used in enhanced oil recovery operations. For example, such gelled polymers can be used to alter the permeability of underground formations to enhance the effectiveness of water flooding opera...

Claims

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Application Information

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Patent Type & Authority Applications(United States)
IPC IPC(8): C09K8/68C08J3/075C08L101/14C09K8/512E21B43/00E21B43/27
CPCC08L101/14Y10S507/903
Inventor BECKMAN, ERIC J.LOSASSO, RONALD A.LOSASSO, JANICE E.
Owner UNIVERSITY OF PITTSBURGH
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