CA2883078C - System for increasing swelling efficiency by ion removal - Google Patents
System for increasing swelling efficiency by ion removal Download PDFInfo
- Publication number
- CA2883078C CA2883078C CA2883078A CA2883078A CA2883078C CA 2883078 C CA2883078 C CA 2883078C CA 2883078 A CA2883078 A CA 2883078A CA 2883078 A CA2883078 A CA 2883078A CA 2883078 C CA2883078 C CA 2883078C
- Authority
- CA
- Canada
- Prior art keywords
- ions
- group
- fluid
- groups
- swellable
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 230000008961 swelling Effects 0.000 title claims description 12
- 239000000463 material Substances 0.000 claims abstract description 86
- 150000002500 ions Chemical class 0.000 claims abstract description 44
- 239000012530 fluid Substances 0.000 claims abstract description 41
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 31
- 229910021389 graphene Inorganic materials 0.000 claims description 24
- 150000001768 cations Chemical class 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 14
- -1 cyclopropenylium cations Chemical class 0.000 claims description 12
- 125000000524 functional group Chemical group 0.000 claims description 12
- 150000001450 anions Chemical class 0.000 claims description 10
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- 239000013536 elastomeric material Substances 0.000 claims description 6
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 6
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 5
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 4
- 125000002228 disulfide group Chemical group 0.000 claims description 4
- 239000003446 ligand Substances 0.000 claims description 4
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 125000005496 phosphonium group Chemical group 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium group Chemical group [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 150000001457 metallic cations Chemical class 0.000 claims 4
- 125000003277 amino group Chemical group 0.000 claims 2
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims 2
- 230000002745 absorbent Effects 0.000 description 9
- 239000002250 absorbent Substances 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 5
- 230000002411 adverse Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000012267 brine Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- FHJGDBAWMRVKAB-LBPRGKRZSA-N (2s)-6-(6-aminohexanoylamino)-2-[bis(carboxymethyl)amino]hexanoic acid Chemical group NCCCCCC(=O)NCCCC[C@@H](C(O)=O)N(CC(O)=O)CC(O)=O FHJGDBAWMRVKAB-LBPRGKRZSA-N 0.000 description 1
- WCZMNYCRLMMYAM-UHFFFAOYSA-N 2-[2-aminooxyethyl(carboxymethyl)amino]acetic acid Chemical group NOCCN(CC(O)=O)CC(O)=O WCZMNYCRLMMYAM-UHFFFAOYSA-N 0.000 description 1
- SYFQYGMJENQVQT-UHFFFAOYSA-N 6-amino-2-[bis(carboxymethyl)amino]hexanoic acid Chemical group NCCCCC(C(O)=O)N(CC(O)=O)CC(O)=O SYFQYGMJENQVQT-UHFFFAOYSA-N 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000004375 physisorption Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 229920000247 superabsorbent polymer Polymers 0.000 description 1
- SLEOTGKREMTOTD-MRXNPFEDSA-N tert-butyl (2r)-6-amino-2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]hexanoate Chemical group CC(C)(C)OC(=O)CN(CC(=O)OC(C)(C)C)[C@H](CCCCN)C(=O)OC(C)(C)C SLEOTGKREMTOTD-MRXNPFEDSA-N 0.000 description 1
- QOQRIMZKEURTGL-NRFANRHFSA-N tert-butyl (2s)-6-(6-aminohexanoylamino)-2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]hexanoate Chemical group CC(C)(C)OC(=O)CN(CC(=O)OC(C)(C)C)[C@H](C(=O)OC(C)(C)C)CCCCNC(=O)CCCCCN QOQRIMZKEURTGL-NRFANRHFSA-N 0.000 description 1
Classifications
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B33/00—Sealing or packing boreholes or wells
- E21B33/10—Sealing or packing boreholes or wells in the borehole
- E21B33/12—Packers; Plugs
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B33/00—Sealing or packing boreholes or wells
- E21B33/10—Sealing or packing boreholes or wells in the borehole
- E21B33/12—Packers; Plugs
- E21B33/1208—Packers; Plugs characterised by the construction of the sealing or packing means
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B33/00—Sealing or packing boreholes or wells
- E21B33/10—Sealing or packing boreholes or wells in the borehole
- E21B33/12—Packers; Plugs
- E21B33/127—Packers; Plugs with inflatable sleeve
- E21B33/1277—Packers; Plugs with inflatable sleeve characterised by the construction or fixation of the sleeve
Landscapes
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mining & Mineral Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Fluid Mechanics (AREA)
- Physics & Mathematics (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Filtering Materials (AREA)
- Treatment Of Water By Ion Exchange (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Non-Portable Lighting Devices Or Systems Thereof (AREA)
Abstract
A swellable system reactive to a flow of fluid including an article having a swellable material operatively arranged to swell upon exposure to a flow of fluid containing ions therein. A filter material is disposed with the swellable material and operatively arranged to remove the ions from the flow of fluid before exposure to the swellable material.
Description
SYSTEM FOR INCREASING SWELLING EFFICIENCY BY ION REMOVAL
BACKGROUND
[0001/2] Isolation of downhole environments depends on the deployment of a downhole tool that effectively seals the entirety of the borehole or a portion thereof, for example, an annulus between a casing wall and production tube. Swellable packers, for example, are particularly useful in that they automatically expand to fill the cross-sectional area of a borehole in response to one or more downhole fluids. Consequently, swellable packers can be placed in borehole locations that have a smaller inner diameter than the cross-sectional area of the fully expanded swellable packer. However, certain downhole conditions, such as the presence of monovalent and polyvalent cations (e.g., Ca2+, Zn2F, etc.) in the aqueous downhole fluids contacting the swellable packer, tend to decrease both the amount of swelling and the rate at which the packer swells, and may also accelerate degradation of the packer. In order to overcome these issues and to continually improve upon swelling efficiency under a variety of conditions, the industry is always desirous of new and alternate swelling systems.
SUMMARY
[0003] A swellable system reactive to a flow of fluid, including an article including a swellable material operatively arranged to swell upon exposure to a flow of fluid, the flow of fluid containing ions therein; and a filter material disposed with the swellable material and operatively arranged to remove the ions from the flow of fluid before exposure to the swellable material.
[0004] A method of operating a swellable system including filtering ions from a flow of fluid with a filter material; and swelling a swellable material responsive to the flow of fluid upon exposure to the fluid.
BRIEF DESCRIPTION OF THE DRAWINGS
[0005] The following descriptions should not be considered limiting in any way.
With reference to the accompanying drawings, like elements are numbered alike:
[0006] Figure 1 is a cross-sectional view of a swellable article in an initial configuration;
[0007] Figure 2 is a cross-sectional view of the swellable article of Figure 1 in a swelled configuration;
[0008] Figure 3 is a swellable system according to an embodiment disclosed herein where a swellable article is disposed with a filter material in a shell covering a swellable core;
and [0009] Figure 4 is a swellable system according to another embodiment disclosed herein where a filter material is separately disposed from a swellable article.
DETAILED DESCRIPTION
[0010] A detailed description of one or more embodiments of the disclosed apparatus and method are presented herein by way of exemplification and not limitation with reference to the Figures.
[0011] Referring now to Figure 1, a system 10 including a tubular or string 12 and a downhole article 14, e.g., a packer or sealing element, disposed thereon is illustrated. The downhole article 14 includes, for example, a base composition and a filter component, discussed in more detail below. The base composition comprises an elastomeric material and/or an absorbent material. Due to fluid absorption by the absorbent material, e.g.
absorption of water, brine, hydrocarbons, etc., the article 14 expands or swells to a second configuration shown in Figure 2. Various absorbent materials are known and used in the art.
For example, with respect to water swellable embodiments any so-called Super Absorbent Polymer could be used, or those marketed by Nippon Shokubai Co., Ltd. under the name AQUALICO CS-65. The elastomeric material is included, for example, to provide a seal against a downhole structure 16, e.g., a borehole in a subterranean formation 18, shown in Figure 2. Of course, the structure 16 could be any other tubing, casing, liner, etc. located downhole and engagable by the article 14. The elastomeric material could be any swellable or non-swellable material. In some embodiments, the elastomeric material is absorbent with respect to one or more downhole fluids thus also encompassing the absorbent material. In this way, for example, the article 14 can be run-in having an initially radially compressed configuration, exposed to fluids once located downhole, and expanded to engage between the
BACKGROUND
[0001/2] Isolation of downhole environments depends on the deployment of a downhole tool that effectively seals the entirety of the borehole or a portion thereof, for example, an annulus between a casing wall and production tube. Swellable packers, for example, are particularly useful in that they automatically expand to fill the cross-sectional area of a borehole in response to one or more downhole fluids. Consequently, swellable packers can be placed in borehole locations that have a smaller inner diameter than the cross-sectional area of the fully expanded swellable packer. However, certain downhole conditions, such as the presence of monovalent and polyvalent cations (e.g., Ca2+, Zn2F, etc.) in the aqueous downhole fluids contacting the swellable packer, tend to decrease both the amount of swelling and the rate at which the packer swells, and may also accelerate degradation of the packer. In order to overcome these issues and to continually improve upon swelling efficiency under a variety of conditions, the industry is always desirous of new and alternate swelling systems.
SUMMARY
[0003] A swellable system reactive to a flow of fluid, including an article including a swellable material operatively arranged to swell upon exposure to a flow of fluid, the flow of fluid containing ions therein; and a filter material disposed with the swellable material and operatively arranged to remove the ions from the flow of fluid before exposure to the swellable material.
[0004] A method of operating a swellable system including filtering ions from a flow of fluid with a filter material; and swelling a swellable material responsive to the flow of fluid upon exposure to the fluid.
BRIEF DESCRIPTION OF THE DRAWINGS
[0005] The following descriptions should not be considered limiting in any way.
With reference to the accompanying drawings, like elements are numbered alike:
[0006] Figure 1 is a cross-sectional view of a swellable article in an initial configuration;
[0007] Figure 2 is a cross-sectional view of the swellable article of Figure 1 in a swelled configuration;
[0008] Figure 3 is a swellable system according to an embodiment disclosed herein where a swellable article is disposed with a filter material in a shell covering a swellable core;
and [0009] Figure 4 is a swellable system according to another embodiment disclosed herein where a filter material is separately disposed from a swellable article.
DETAILED DESCRIPTION
[0010] A detailed description of one or more embodiments of the disclosed apparatus and method are presented herein by way of exemplification and not limitation with reference to the Figures.
[0011] Referring now to Figure 1, a system 10 including a tubular or string 12 and a downhole article 14, e.g., a packer or sealing element, disposed thereon is illustrated. The downhole article 14 includes, for example, a base composition and a filter component, discussed in more detail below. The base composition comprises an elastomeric material and/or an absorbent material. Due to fluid absorption by the absorbent material, e.g.
absorption of water, brine, hydrocarbons, etc., the article 14 expands or swells to a second configuration shown in Figure 2. Various absorbent materials are known and used in the art.
For example, with respect to water swellable embodiments any so-called Super Absorbent Polymer could be used, or those marketed by Nippon Shokubai Co., Ltd. under the name AQUALICO CS-65. The elastomeric material is included, for example, to provide a seal against a downhole structure 16, e.g., a borehole in a subterranean formation 18, shown in Figure 2. Of course, the structure 16 could be any other tubing, casing, liner, etc. located downhole and engagable by the article 14. The elastomeric material could be any swellable or non-swellable material. In some embodiments, the elastomeric material is absorbent with respect to one or more downhole fluids thus also encompassing the absorbent material. In this way, for example, the article 14 can be run-in having an initially radially compressed configuration, exposed to fluids once located downhole, and expanded to engage between the
2 tubular 12 and the structure 16. In one embodiment, the structure 16 is isolated by expansion of the article 14 such that fluids (e.g., from the formation 18) are substantially prevented from flowing past the article 14 once the article 14 is expanded.
[0012] Downhole fluids typically comprise an aqueous component, which more accurately is a brine containing various ions, e.g., metal cations from dissolved salts. As noted above, monovalent and polyvalent cations can interact with the absorbent material, and decrease the overall rate and ratio of expansion of the absorbent material, thereby hindering the sealing efficacy of the article. It has been generally found that polyvalent cations such as Ca 2+, Zn2+5 etc. have a more profound effect on the performance of swellable materials, particularly in water swellable articles, than monovalent cations and are thus usually more desirable to be removed. It is to be appreciated that while water-swellable materials are discussed as an exemplary embodiment that is adversely affected by the presence of cations, other materials may be swellable in response to different fluids and/or adversely affected by anions. For example, in one embodiment the swellable material is adversely affected (e.g., reduced swelling, shorter life span, slower swelling rate, etc.) by the presence of anions. For this reason, the term "ions" as used herein will refer to any cation or anion that has a negative effect on the performance of a corresponding swellable material.
[0013] To mitigate the deleterious effect of such ions on the absorbent material, the filter material acts to remove or filter ions from the downhole fluids before they interact with the swellable material. By remove or filter, it is meant that the filter material captures or holds the ions in, at, or proximate a capture site or location proximate to the filter material, or otherwise neutralizes the ions such that the flow of fluid is at least partially relatively devoid of ions downstream of the filter material. Thus, while the ions are still technically in the fluid, they are prevented from adversely affecting the swelling of the swellable material and therefore considered to be removed or filtered. The removal, filtering, or capture may be done by chemical or physical bonding between the filter material and the ions, physisorption or chemisorption at or by the filter material or a surface thereof, electrostatic and/or van der Waals attraction between the filter material or an atomic structure thereof (e.g., functionalized group) and the ions, etc., examples of which are discussed in more detail below.
[0014] In the embodiment of Figures 1 and 2, the filter material, the elastomeric material, and/or the absorbent material can all be mixed together, e.g., homogeneously, then formed into the article 14. An alternate embodiment for a system 22 is shown in Figure 3, the system 22 including an article 24 on a tubular or string 26. The article 24 is formed from a
[0012] Downhole fluids typically comprise an aqueous component, which more accurately is a brine containing various ions, e.g., metal cations from dissolved salts. As noted above, monovalent and polyvalent cations can interact with the absorbent material, and decrease the overall rate and ratio of expansion of the absorbent material, thereby hindering the sealing efficacy of the article. It has been generally found that polyvalent cations such as Ca 2+, Zn2+5 etc. have a more profound effect on the performance of swellable materials, particularly in water swellable articles, than monovalent cations and are thus usually more desirable to be removed. It is to be appreciated that while water-swellable materials are discussed as an exemplary embodiment that is adversely affected by the presence of cations, other materials may be swellable in response to different fluids and/or adversely affected by anions. For example, in one embodiment the swellable material is adversely affected (e.g., reduced swelling, shorter life span, slower swelling rate, etc.) by the presence of anions. For this reason, the term "ions" as used herein will refer to any cation or anion that has a negative effect on the performance of a corresponding swellable material.
[0013] To mitigate the deleterious effect of such ions on the absorbent material, the filter material acts to remove or filter ions from the downhole fluids before they interact with the swellable material. By remove or filter, it is meant that the filter material captures or holds the ions in, at, or proximate a capture site or location proximate to the filter material, or otherwise neutralizes the ions such that the flow of fluid is at least partially relatively devoid of ions downstream of the filter material. Thus, while the ions are still technically in the fluid, they are prevented from adversely affecting the swelling of the swellable material and therefore considered to be removed or filtered. The removal, filtering, or capture may be done by chemical or physical bonding between the filter material and the ions, physisorption or chemisorption at or by the filter material or a surface thereof, electrostatic and/or van der Waals attraction between the filter material or an atomic structure thereof (e.g., functionalized group) and the ions, etc., examples of which are discussed in more detail below.
[0014] In the embodiment of Figures 1 and 2, the filter material, the elastomeric material, and/or the absorbent material can all be mixed together, e.g., homogeneously, then formed into the article 14. An alternate embodiment for a system 22 is shown in Figure 3, the system 22 including an article 24 on a tubular or string 26. The article 24 is formed from a
3 core 28 and a shell 30. In this embodiment, the core 28 includes the aforementioned swellable material, while the shell 30 includes the filter material. The core 28 and the shell 30 may both, for example, include suitable elastomeric and/or filler materials to provide sealing for the article 24 and to impart chemical and physical properties to the article 24. In this way, the flow of fluid to which the swellable material in the core 28 is reactive will first be filtered of ions by the filter material in the shell 30.
[0015] A system 32 according to another embodiment is shown in Figure 4 in which a swellable article 34 is disposed with a tubular or string 36. In this embodiment, a formation 38 is separated from the article 34 by a radially disposed tubular or string 40, e.g., a casing, liner, tubing, etc. The tubular/string 40 includes at least one port or opening 42 for enabling a flow of fluid, generally designated by an arrow 44, to encounter the article 34. The filter material can be arranged in a plug 46 positioned in the opening 42, in a membrane or film 48 positioned over the opening 42, etc. The plug 46 can be formed as any suitable fluid permeable member for creating a passageway for communicating fluid to the swellable material. In this way, the flow of fluid is filtered by the filter material before it reaches the article 34. The plug 46 and/or the membrane 48 could be formed from any suitable permeable material, e.g., a porous foam, fibers, with the filter material disposed in or with the permeable material, e.g., in pores of the permeable material.
[0016] In another embodiment, essentially a combination of the above, the shell 30 could be a protective or elastomeric shell impermeable to downhole fluids and resistant to corrosion and degradation. A permeable plug, such as discussed with respect to the plug 46 could be included in the shell 30 as opposed the an outer tubular 40. In this way, the swellable article will benefit from an outer shell made of an elastomeric or other material that can be selected to provide beneficial properties such as corrosion resistance, fluid impermeability, etc., while also maintaining the advantageous ion filtering properties provided by the current invention as discussed herein.
[0017] In one embodiment, the filter material comprises one or more graphene-based compounds. By graphene-based it is meant a compound that includes or is derived from graphene, such as graphene itself, graphite, graphite oxide, graphene oxide, etc. The compounds could take any form used with such graphene-based compounds, such as sheets or nanosheets, particles, flakes, nanotubes, etc. Advantageously, the unique properties of graphene enable effective donor¨acceptor interactions between both the anions and the cations and the graphene flakes or particles. The graphene-based materials, associated oxides, or other derivatives or functionalized compounds thereof may contain a corresponding
[0015] A system 32 according to another embodiment is shown in Figure 4 in which a swellable article 34 is disposed with a tubular or string 36. In this embodiment, a formation 38 is separated from the article 34 by a radially disposed tubular or string 40, e.g., a casing, liner, tubing, etc. The tubular/string 40 includes at least one port or opening 42 for enabling a flow of fluid, generally designated by an arrow 44, to encounter the article 34. The filter material can be arranged in a plug 46 positioned in the opening 42, in a membrane or film 48 positioned over the opening 42, etc. The plug 46 can be formed as any suitable fluid permeable member for creating a passageway for communicating fluid to the swellable material. In this way, the flow of fluid is filtered by the filter material before it reaches the article 34. The plug 46 and/or the membrane 48 could be formed from any suitable permeable material, e.g., a porous foam, fibers, with the filter material disposed in or with the permeable material, e.g., in pores of the permeable material.
[0016] In another embodiment, essentially a combination of the above, the shell 30 could be a protective or elastomeric shell impermeable to downhole fluids and resistant to corrosion and degradation. A permeable plug, such as discussed with respect to the plug 46 could be included in the shell 30 as opposed the an outer tubular 40. In this way, the swellable article will benefit from an outer shell made of an elastomeric or other material that can be selected to provide beneficial properties such as corrosion resistance, fluid impermeability, etc., while also maintaining the advantageous ion filtering properties provided by the current invention as discussed herein.
[0017] In one embodiment, the filter material comprises one or more graphene-based compounds. By graphene-based it is meant a compound that includes or is derived from graphene, such as graphene itself, graphite, graphite oxide, graphene oxide, etc. The compounds could take any form used with such graphene-based compounds, such as sheets or nanosheets, particles, flakes, nanotubes, etc. Advantageously, the unique properties of graphene enable effective donor¨acceptor interactions between both the anions and the cations and the graphene flakes or particles. The graphene-based materials, associated oxides, or other derivatives or functionalized compounds thereof may contain a corresponding
4 relatively large number of capture sites for attracting and binding ions via van der Waals and/or Coulombic interactions. Of course, other materials with electron-rich surfaces can be used for similarly filtering cations, while highly electron deficient materials may be utilized with respect to anions.
[0018] To further increase the ability of graphene-based filter materials to capture the aforementioned polyvalent cations, the filter materials can be functionalized to include one or more functional groups. The process of forming graphite or graphene oxide, for example, results in the inclusion of various functional groups that are relatively negatively charged (e.g., carboxylic acid groups) or polar (e.g., carbonyl groups). Polyvalent cations will be attracted to and captured by these groups. In one embodiment the filter material is covalently modified with thiol groups according to known diazonium chemistry procedures.
Thiol groups are naturally excellent at capturing positively charged ions, notably doubly charged mercury cations, although other metallic cations ions such as the aforementioned Ca2 ', Zn2 ', etc., contained in downhole brines will also be readily captured by thiol groups. Other functional groups such as disulfide groups, carboxylic acid, sulfonic acid groups may also be used for their ability to capture polyvalent cations, particularly doubly charged cations. Other functional groups include chelating ligand groups, such as iminodiacetic acid, iminodiacetic acid group,N45-amino-1-carboxy-(t-butyppentyl]iminodi-t-butylacetate) group, N-(5-amino-1-carboxypentyl)imino-diacetic acid group, N-(5-amino-1-carboxypentyl)iminodiacetic acid tri-t-butyl ester group, aminocaproic nitrilotriacetic acid group, aminocaproic nitrilotriacetic acid tri-tert-butylester group, 2-aminooxyethyliminodiacetic acid group, and others that would be recognized by those of ordinary skill in the art in view of the disclosure herein.
[0019] The graphene-based materials could also be functionalized to filter anions, e.g., with quaternary ammonium, quaternary phosphonium, ternary sulfonium, cyclopropenylium cations, or primary, secondary, ternary amino, or other groups. These groups are either positively charged or become protonated in acidic environments and thus require anions to compensate for the charge. In some situations, the anion can be exchanged with another anion while preserving charge. For example, in one embodiment, the graphene-based material is functionalized with a quaternary ammonium group, the positive charge of which is balanced by hydroxide anions. In this example, in brine containing S042- anions, one S042- anion will be captured and two hydroxide anions (OH-) will be released. In an embodiment, a mixture of graphene-based material functionalized with sulfonic acid groups and graphene-based material functionalized with quarternary ammonium groups balanced by hydroxide anions is used to neutralize a CaC12 brine. In the cation-exchange process, Ca2 ' cations are captured with a simultaneous release of two H ' ions for each Ca2' cation. In the anion-exchange process, Cl- ions are captured by the quaternary ammonium group with a simultaneous release of OH- anion for each a ion. Recombination of released H
' and Off ions results in the formation of water molecules, which may contribute to the swelling process of water-swellable materials.
[0020] While the invention has been described with reference to an exemplary embodiment or embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this invention, but that the invention will include all embodiments falling within the scope of the claims. Also, in the drawings and the description, there have been disclosed exemplary embodiments of the invention and, although specific terms may have been employed, they are unless otherwise stated used in a generic and descriptive sense only and not for purposes of limitation, the scope of the invention therefore not being so limited.
Moreover, the use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another. Furthermore, the use of the terms a, an, etc. do not denote a limitation of quantity, but rather denote the presence of at least one of the referenced item.
[0018] To further increase the ability of graphene-based filter materials to capture the aforementioned polyvalent cations, the filter materials can be functionalized to include one or more functional groups. The process of forming graphite or graphene oxide, for example, results in the inclusion of various functional groups that are relatively negatively charged (e.g., carboxylic acid groups) or polar (e.g., carbonyl groups). Polyvalent cations will be attracted to and captured by these groups. In one embodiment the filter material is covalently modified with thiol groups according to known diazonium chemistry procedures.
Thiol groups are naturally excellent at capturing positively charged ions, notably doubly charged mercury cations, although other metallic cations ions such as the aforementioned Ca2 ', Zn2 ', etc., contained in downhole brines will also be readily captured by thiol groups. Other functional groups such as disulfide groups, carboxylic acid, sulfonic acid groups may also be used for their ability to capture polyvalent cations, particularly doubly charged cations. Other functional groups include chelating ligand groups, such as iminodiacetic acid, iminodiacetic acid group,N45-amino-1-carboxy-(t-butyppentyl]iminodi-t-butylacetate) group, N-(5-amino-1-carboxypentyl)imino-diacetic acid group, N-(5-amino-1-carboxypentyl)iminodiacetic acid tri-t-butyl ester group, aminocaproic nitrilotriacetic acid group, aminocaproic nitrilotriacetic acid tri-tert-butylester group, 2-aminooxyethyliminodiacetic acid group, and others that would be recognized by those of ordinary skill in the art in view of the disclosure herein.
[0019] The graphene-based materials could also be functionalized to filter anions, e.g., with quaternary ammonium, quaternary phosphonium, ternary sulfonium, cyclopropenylium cations, or primary, secondary, ternary amino, or other groups. These groups are either positively charged or become protonated in acidic environments and thus require anions to compensate for the charge. In some situations, the anion can be exchanged with another anion while preserving charge. For example, in one embodiment, the graphene-based material is functionalized with a quaternary ammonium group, the positive charge of which is balanced by hydroxide anions. In this example, in brine containing S042- anions, one S042- anion will be captured and two hydroxide anions (OH-) will be released. In an embodiment, a mixture of graphene-based material functionalized with sulfonic acid groups and graphene-based material functionalized with quarternary ammonium groups balanced by hydroxide anions is used to neutralize a CaC12 brine. In the cation-exchange process, Ca2 ' cations are captured with a simultaneous release of two H ' ions for each Ca2' cation. In the anion-exchange process, Cl- ions are captured by the quaternary ammonium group with a simultaneous release of OH- anion for each a ion. Recombination of released H
' and Off ions results in the formation of water molecules, which may contribute to the swelling process of water-swellable materials.
[0020] While the invention has been described with reference to an exemplary embodiment or embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this invention, but that the invention will include all embodiments falling within the scope of the claims. Also, in the drawings and the description, there have been disclosed exemplary embodiments of the invention and, although specific terms may have been employed, they are unless otherwise stated used in a generic and descriptive sense only and not for purposes of limitation, the scope of the invention therefore not being so limited.
Moreover, the use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another. Furthermore, the use of the terms a, an, etc. do not denote a limitation of quantity, but rather denote the presence of at least one of the referenced item.
Claims (29)
1. A swellable system reactive to a flow of fluid, comprising:
an article including a swellable material operatively arranged to swell upon exposure to a flow of fluid, the flow of fluid containing ions therein; and a filter material disposed with the swellable material and operatively arranged to remove the ions from the flow of fluid before exposure to the swellable material.
an article including a swellable material operatively arranged to swell upon exposure to a flow of fluid, the flow of fluid containing ions therein; and a filter material disposed with the swellable material and operatively arranged to remove the ions from the flow of fluid before exposure to the swellable material.
2. The system of claim 1, wherein the filter material exerts at least one of van der Walls forces and Coulombic forces on the ions.
3. The system of claim 1 or 2, wherein attraction between the filter material and the ions is formed by functional groups attached to the filter material.
4. The system of claim 3, wherein the functional groups are at least one of thiol groups, disulfide groups, carboxylic acid groups, sulfonic acid groups and chelating ligand groups.
5. The system of claim 3, wherein the functional groups are at least one of quaternary ammonium groups, quaternary phosphonium groups, ternary sulfonium groups, cyclopropenylium cations, groups which can be protonated in an acidic environment, primary amino groups, secondary amino groups and ternary amino groups.
6. The system of any one of claims 1 to 5, wherein the ions are cations.
7. The system of any one of claims 1 to 5, wherein the ions are anions.
8. The system of any one of claims 1 to 5, wherein the ions are polyvalent ions.
9. The system of any one of claims 1 to 5, wherein the ions are polyvalent cations.
10. The system of claim 8, wherein the polyvalent cations are di-valent metallic cations.
11 . The system of any one of claims 1 to 10, wherein the fluid is aqueous.
12. The system of claim 1, wherein the filter material comprises a graphene-based material.
13. The system of claim 11, wherein the graphene-based material is at least one of graphene, graphite, graphene oxide and graphite oxide.
14. The system of claim 12, wherein the graphene-based material further comprises at least one functional group operatively arranged to capture the ions.
15. The system of claim 13, wherein the at least one functional group is at least one of a thiol group, a disulfide group, a carboxylic acid group, a sulfonic acid group and a chelating ligand group.
16. The system of any one of claims 1 to 15, further comprising an elastomeric material operatively arranged to enable the article to seal against another structure after swelling.
17. The system of any one of claims 1 to 16, wherein the swellable material and the filter material are mixed homogeneously in the article.
18. The system of any one of claims 1 to 16, wherein the article is formed from a shell surrounding a core, with the filter material included in the shell and the swellable material included in the core.
19. The system of any one of claims 1 to 16, wherein the article is formed from a fluid impel meable shell surrounding a core, with the swellable material included in the core and the filter material formed as a fluid permeable plug or passageway permitting fluid through the shell into the core.
20. The system of any one of claims 1 to 16, wherein the filter material is separate from the article and disposed with an opening through which the fluid must flow to reach the article.
21. The system of claim 1, wherein the filter material is operatively arranged to at least one of remove the ions by capturing the ions and capture the ions while simultaneously releasing one or more other ions in order to preserve a charge balance.
22. A method of operating a swellable system comprising:
removing ions from a flow of fluid with a filter material; and swelling a swellable material responsive to the flow of fluid upon exposure to the fluid.
removing ions from a flow of fluid with a filter material; and swelling a swellable material responsive to the flow of fluid upon exposure to the fluid.
23. The method of claim 21, wherein the fluid is aqueous and the ions are metallic cations from dissolved salts.
24. The method of claim 22, wherein the metallic cations are polyvalent metallic cations.
25. The method of any one of claims 21 to 24, wherein the filter material comprises at least one of a graphene-based material being graphene, graphite, graphene oxide and graphite oxide.
26. The method of claim 24, wherein the graphene-based material further comprises at least one functional group operatively arranged to capture the ions.
_
_
27. The method of claim 25, wherein the at least one functional group is at least one of a thiol group, a disulfide group, a carboxylic acid group, a sulfonic acid group and a chelating ligand group.
28. The method of claim 25, wherein the at least one functional group is at least one of a quatemary ammonium group, a quatemary phosphonium group, a temary sulfonium group, a cyclopropenylium cation, a group configured to be protonated in an acidic environment, a primary amino group, a secondary amino group and a temary amino group.
29. The system of any one of claims 21 to 28, wherein removing the ions includes at least one of capturing the ions and capturing the ions while simultaneously releasing one or more other ions in order to preserve a charge balance.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/646,028 | 2012-10-05 | ||
US13/646,028 US9284812B2 (en) | 2011-11-21 | 2012-10-05 | System for increasing swelling efficiency |
PCT/US2013/063501 WO2014055891A1 (en) | 2012-10-05 | 2013-10-04 | System for increasing swelling efficiency |
Publications (2)
Publication Number | Publication Date |
---|---|
CA2883078A1 CA2883078A1 (en) | 2014-04-10 |
CA2883078C true CA2883078C (en) | 2017-03-21 |
Family
ID=50435478
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA2883078A Active CA2883078C (en) | 2012-10-05 | 2013-10-04 | System for increasing swelling efficiency by ion removal |
Country Status (7)
Country | Link |
---|---|
CN (1) | CN104704193B (en) |
AU (1) | AU2013326895B2 (en) |
CA (1) | CA2883078C (en) |
GB (1) | GB2525323B (en) |
NO (1) | NO347100B1 (en) |
RU (1) | RU2617815C2 (en) |
WO (1) | WO2014055891A1 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR102311838B1 (en) | 2017-12-27 | 2021-10-14 | 주식회사 파멥신 | Anti-PD-L1 Antibody and Use Thereof |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3385367A (en) * | 1966-12-07 | 1968-05-28 | Kollsman Paul | Sealing device for perforated well casing |
JPH08501653A (en) * | 1990-06-11 | 1996-02-20 | ザ ダウ ケミカル カンパニー | Ion exchange membranes with increased efficiency in the proton exchange method. |
US5164060A (en) * | 1990-06-11 | 1992-11-17 | The Dow Chemical Company | Ion exchange membrane having increased efficiency in proton exchange processes |
GB2248255B (en) * | 1990-09-27 | 1994-11-16 | Solinst Canada Ltd | Borehole packer |
RU2186196C1 (en) * | 2000-11-03 | 2002-07-27 | ОАО НПО "Буровая техника" | Composition for filling packer sealing member |
GB2428058B (en) * | 2004-03-12 | 2008-07-30 | Schlumberger Holdings | Sealing system and method for use in a well |
RU2413836C2 (en) * | 2006-09-11 | 2011-03-10 | Хэллибертон Энерджи Сервисиз, Инк. | Procedure for forming circular barrier in underground well, procedure for making well packer and design of well packer |
US9018144B2 (en) * | 2007-10-01 | 2015-04-28 | Baker Hughes Incorporated | Polymer composition, swellable composition comprising the polymer composition, and articles including the swellable composition |
US8181708B2 (en) * | 2007-10-01 | 2012-05-22 | Baker Hughes Incorporated | Water swelling rubber compound for use in reactive packers and other downhole tools |
US20090178800A1 (en) * | 2008-01-14 | 2009-07-16 | Korte James R | Multi-Layer Water Swelling Packer |
US8685900B2 (en) * | 2009-04-03 | 2014-04-01 | Halliburton Energy Services, Inc. | Methods of using fluid loss additives comprising micro gels |
GB2471330B (en) * | 2009-06-26 | 2012-01-04 | Swelltec Ltd | Improvements to swellable apparatus and materials therefor |
US8302680B2 (en) * | 2009-08-12 | 2012-11-06 | Halliburton Energy Services, Inc. | Swellable screen assembly |
US9470058B2 (en) * | 2009-12-10 | 2016-10-18 | Schlumberger Technology Corporation | Ultra high temperature packer by high-temperature elastomeric polymers |
US8490707B2 (en) * | 2011-01-11 | 2013-07-23 | Schlumberger Technology Corporation | Oilfield apparatus and method comprising swellable elastomers |
US20120202047A1 (en) * | 2011-02-07 | 2012-08-09 | Baker Hughes Incorporated | Nano-coatings for articles |
US8459366B2 (en) * | 2011-03-08 | 2013-06-11 | Halliburton Energy Services, Inc. | Temperature dependent swelling of a swellable material |
US9403115B2 (en) * | 2011-03-18 | 2016-08-02 | William Marsh Rice University | Graphite oxide coated particulate material and method of making thereof |
-
2013
- 2013-10-04 CN CN201380052768.7A patent/CN104704193B/en active Active
- 2013-10-04 CA CA2883078A patent/CA2883078C/en active Active
- 2013-10-04 WO PCT/US2013/063501 patent/WO2014055891A1/en active Application Filing
- 2013-10-04 RU RU2015114317A patent/RU2617815C2/en active
- 2013-10-04 NO NO20150297A patent/NO347100B1/en unknown
- 2013-10-04 GB GB1507423.0A patent/GB2525323B/en active Active
- 2013-10-04 AU AU2013326895A patent/AU2013326895B2/en active Active
Also Published As
Publication number | Publication date |
---|---|
WO2014055891A1 (en) | 2014-04-10 |
GB2525323A (en) | 2015-10-21 |
RU2617815C2 (en) | 2017-04-27 |
AU2013326895B2 (en) | 2016-11-10 |
RU2015114317A (en) | 2016-11-27 |
CA2883078A1 (en) | 2014-04-10 |
NO20150297A1 (en) | 2015-03-05 |
GB2525323B (en) | 2016-10-26 |
GB201507423D0 (en) | 2015-06-17 |
CN104704193A (en) | 2015-06-10 |
CN104704193B (en) | 2017-09-05 |
AU2013326895A1 (en) | 2015-03-12 |
NO347100B1 (en) | 2023-05-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US9284812B2 (en) | System for increasing swelling efficiency | |
US9518211B2 (en) | Method for recovering oil | |
CA2950089C (en) | Surfactant formulations for reduced and delayed adsorption | |
US20110221137A1 (en) | Sealing method and apparatus | |
RU2601636C2 (en) | Amines of glycolic esters for use as agents for prevention of dispersion of plate and clay rocks for drilling industry | |
WO2014052238A1 (en) | High water and brine swell elastomeric compositions and method for making and using same | |
CA2883078C (en) | System for increasing swelling efficiency by ion removal | |
CN103773335B (en) | Acidificable consolidation type plugging agent | |
AU2007255128B2 (en) | Apparatus for sealing and isolating pipelines | |
US11661812B2 (en) | Fluid barriers for dissolvable plugs | |
CN104048086B (en) | Water-leakage protection valve | |
US9556702B2 (en) | Compositions and methods for well completions | |
EP3640517B1 (en) | Method for curing leakages in pipes | |
CN202927128U (en) | Floating sleeve type combined sealing valve seat | |
CN203383775U (en) | Filling permanent-solidification type sleeve-outside packer | |
GB2532656A (en) | Method and apparatus for back-flow prevention | |
WO2013070082A1 (en) | Use of swellable elastomeric polymer materials | |
WO2012050687A2 (en) | Swellable member, swell controlling arrangement and method of controlling swelling of a swellable member background | |
US9828834B2 (en) | Water removal from anti-agglomerate LDHIs | |
CN104404525A (en) | Method and special-purpose preparation for preventing oil gas pipeline and equipment from being corroded | |
CN205841181U (en) | Discharge opeing plunger and liquid discharging apparatus | |
Vorderbruggen et al. | To the Barricades! Using a Self-Assembled Wall to Protect Ordinary Portland Cement from Acidic Corrosion | |
EP3735452A1 (en) | Capsule design for the capture of reagents |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
EEER | Examination request |
Effective date: 20150224 |