CA2257028C - Liquid co2/hydrocarbon oil emulsion fracturing system - Google Patents
Liquid co2/hydrocarbon oil emulsion fracturing system Download PDFInfo
- Publication number
- CA2257028C CA2257028C CA002257028A CA2257028A CA2257028C CA 2257028 C CA2257028 C CA 2257028C CA 002257028 A CA002257028 A CA 002257028A CA 2257028 A CA2257028 A CA 2257028A CA 2257028 C CA2257028 C CA 2257028C
- Authority
- CA
- Canada
- Prior art keywords
- surfactant
- diesel
- fluid
- liquid
- hydrocarbon
- 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.)
- Expired - Fee Related
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/66—Compositions based on water or polar solvents
- C09K8/68—Compositions based on water or polar solvents containing organic compounds
- C09K8/685—Compositions based on water or polar solvents containing organic compounds containing cross-linking agents
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S507/00—Earth boring, well treating, and oil field chemistry
- Y10S507/922—Fracture fluid
Abstract
A fracturing fluid is disclosed consisting of an emulsion having a continuous phase of a liquified gas, a discontinuous phase of a hydrocarbon, and a surfactant soluble in the two phases. The surfactant is preferably a hydrofluoroether.
Description
LIQUID COZ/HYDROCARBON OIL EMULSION FRACTURING SYSTEM
Field of the Invention The present invention relates to a novel formulation for a fracturing fluid for use in fracturing subterranean formations such as oil and gas wells.
Background of the Invention It is known to utilize an emulsion consisting of water or water with a polymer therein as the continuous phase, and from about 50% to about 80% oil (crude or refined) as the discontinuous phase, with a surfactant such as sodium tallate or a quaternary amine in the aqueous phase. This is shown in Polymer Emulsion Fracturing (Sinclair et al), a 1973 publication ofthe Society of Petroleum Engineers. It is also known, as shown in U.S. Patent No.
4,233,165, to utilize a water-in-oil emulsion as a fracturing fluid. In that case, a surfactant soluble in oil is utilized to maintain an aqueous internal phase in a continuous diesel phase.
Moreover, stable foams have been developed where the external phase is water and the internal phase is COz and the foam is stabilized by selective chemical foamers. It has been found that the internal phase (COz) in such foam has to be a minimum of 53%. The Western Company of North America has developed two foams, the first one where a combination of CO, and Nitrogen is used to create a stable foam with the addition of chemical foamers. The combined internal phase of gas is still over 52% by volume. The second foam involves stabilizing the CO~
foam with a crosslinker without the use of foamer. By using less CO,, the produced gas from a well can be put on a pipe-line faster without flaring for a long time to meet pipeline CO~
content regulations. Moreover, all the above systems use gelling agents from guar to CMHPG
to stabilize the foams. There have also been attempts made to foam CO, in diesel or crudes with limited success because of the natural antifoam ability of these oils.
Conventionally, instead oil gels have been used. However, with the potential for downstream problems of the phosphate esters used in gelling oils, there is a need for alternatives.
Attempts have been made to pump CO~ with gelled oils, mainly to use the energy of the phase change from liquid to CO, gas to clean up wells efficiently. However, most phosphate ester , based oil gels are not compatible with CO,; when these systems are made to survive under CO, conditions, breaking with conventional breakers for these systems, which tend to be high pl-1 buffers tend to be neutralized by the CO, or in the presence of any water, will chelate the aluminum or iron crosslinkers (complexers) and cause precipitation resulting in formation change.
The approach of the present invention is to provide an emulsion of oil in liquid CO,. This is possible with the selection of an appropriate surfactant, in particular methoxy-or ethoxy nonafluorobutane. This approach provides an emulsion of high sustained permeability, without the need or gelling and breaking, and the costs associated therewith. The amount of CO, required is less than 48%, which results in cost effectiveness, and the inherent ability of COz simply to gasify and escape to the atmosphere indicates simplified clean-up after fracturing.
The object of the present invention, is to provide a fracturing fluid consisting of an emulsion of hydrocarbon in a liquified gas such as liquid CO,.
Field of the Invention The present invention relates to a novel formulation for a fracturing fluid for use in fracturing subterranean formations such as oil and gas wells.
Background of the Invention It is known to utilize an emulsion consisting of water or water with a polymer therein as the continuous phase, and from about 50% to about 80% oil (crude or refined) as the discontinuous phase, with a surfactant such as sodium tallate or a quaternary amine in the aqueous phase. This is shown in Polymer Emulsion Fracturing (Sinclair et al), a 1973 publication ofthe Society of Petroleum Engineers. It is also known, as shown in U.S. Patent No.
4,233,165, to utilize a water-in-oil emulsion as a fracturing fluid. In that case, a surfactant soluble in oil is utilized to maintain an aqueous internal phase in a continuous diesel phase.
Moreover, stable foams have been developed where the external phase is water and the internal phase is COz and the foam is stabilized by selective chemical foamers. It has been found that the internal phase (COz) in such foam has to be a minimum of 53%. The Western Company of North America has developed two foams, the first one where a combination of CO, and Nitrogen is used to create a stable foam with the addition of chemical foamers. The combined internal phase of gas is still over 52% by volume. The second foam involves stabilizing the CO~
foam with a crosslinker without the use of foamer. By using less CO,, the produced gas from a well can be put on a pipe-line faster without flaring for a long time to meet pipeline CO~
content regulations. Moreover, all the above systems use gelling agents from guar to CMHPG
to stabilize the foams. There have also been attempts made to foam CO, in diesel or crudes with limited success because of the natural antifoam ability of these oils.
Conventionally, instead oil gels have been used. However, with the potential for downstream problems of the phosphate esters used in gelling oils, there is a need for alternatives.
Attempts have been made to pump CO~ with gelled oils, mainly to use the energy of the phase change from liquid to CO, gas to clean up wells efficiently. However, most phosphate ester , based oil gels are not compatible with CO,; when these systems are made to survive under CO, conditions, breaking with conventional breakers for these systems, which tend to be high pl-1 buffers tend to be neutralized by the CO, or in the presence of any water, will chelate the aluminum or iron crosslinkers (complexers) and cause precipitation resulting in formation change.
The approach of the present invention is to provide an emulsion of oil in liquid CO,. This is possible with the selection of an appropriate surfactant, in particular methoxy-or ethoxy nonafluorobutane. This approach provides an emulsion of high sustained permeability, without the need or gelling and breaking, and the costs associated therewith. The amount of CO, required is less than 48%, which results in cost effectiveness, and the inherent ability of COz simply to gasify and escape to the atmosphere indicates simplified clean-up after fracturing.
The object of the present invention, is to provide a fracturing fluid consisting of an emulsion of hydrocarbon in a liquified gas such as liquid CO,.
A further object of the present invention is to provide an emulsion of liquid CO, in which is dissolved a surfactant, and in which are suspended droplets of a hydrocarbon fluid, for use in fracturing oil and/or gas well formations.
In a broad aspect, then, the present invention relates to a fracturing fluid consisting of an emulsion having a continuous phase of a liquified gas, a discontinuous phase of a hydrocarbon, and a surfactant soluble in the two phases.
Brief Description of the Drawings The present invention will be described by way of example below, and in connection with the description the following drawings are provided:
Figure 1 is a graph of Diesel / CO~ solubility;
Figure 2 is a graph of Frac Oil 200 / CO, solubility.
Detailed Descri tn ion In order to determine the solubility of COZ with two candidate hydrocarbons, labstock diesel and Frac Oil 200T"' (a hydrocarbon based fracturing oil from Amoco Canada Petroleum Company Ltd., Calgary, Alberta) the following test was conducted.
Solubility The tests were conducted with labstock diesel and Frac Oil 200. The volumes were visual within a sight glass of a known volume. Due to the small volume in the sight glass (75mL) weight % was not used. 25 mL of hydrocarbon was added to the cell at -20 °C, CO, was added until total volume was 75 mL (50 mL of CO~). Pressure in the cell was 500 psi for the diesel and 700 psi for the Frac Oil 200. The cell was then observed at various temperatures to see the volume changes in hydrocarbon and COz.
The observed results are shown in Figures 1 and 2.
The volume change could be caused by a number of factors: CO, volume increases with lower temperature and the solubility of CO, in hydrocarbon decreases with lower temperature.
The volume ofthe hydrocarbons both increased about the same, 25 mL to 36-38 mL, indicating both the fluids had similar COz solubility. Both fluids match up well in solubility and volume changes at the various temperatures. The pressure of the cell in both tests did not increase until the temperature was 10°C and vapor was created. When the vapor is created then the fluid changes from a polyemulsion into a CO, foam. However, since the volume of CO, may not be above 53 quality, there will be little viscosity to this foam. If the pressure exceeds 500 psi at -20 °C the emulsion will be formed until the temperature increases to 5-I 0 °C or enough pressure is applied to keep the CO~ in a liquid phase.
The emulsions of the present invention were then created, using labstock diesel, liquid COz and hydrofluoroether surfactant HFE 7200 and HFE 7100 from 3M Chemicals.
(C4F90CZH5) consists oftwo inseparable isomers with essentially identical properties. These are (CF3)ZCFCFZOCZHS (CAS No. 163702-06-5) and CF3CF,CF,CF,H, (CAS No. 163702-0~-4).
HFE-7100 (C4F90CH;) consists of two inseparable 1 isomers with essentially identical properties.
These are (CF3)~CFCF~OCH3 (CAS No. 163702-08-7) and CF;CF,CF~CF,OCH; (CAS No.
163702-07-6). Both surfactant are soluble in liquid CO, and diesel, and both produced similar results.
The surfactant is added at a rate of from about 1 to 30, preferably about 4 L/m' to diesel.
The diesel/surfactant solution is then mixed with liquid CO, at a rate of about 5% - 48% CO, , preferably ;about 30 - 40% COz . The mixture is then vigorously agitated or subject to shear, resulting in a stable emulsion (stability increasing with shear), with appropriate viscosity for use as a fracturing fluid.
In a broad aspect, then, the present invention relates to a fracturing fluid consisting of an emulsion having a continuous phase of a liquified gas, a discontinuous phase of a hydrocarbon, and a surfactant soluble in the two phases.
Brief Description of the Drawings The present invention will be described by way of example below, and in connection with the description the following drawings are provided:
Figure 1 is a graph of Diesel / CO~ solubility;
Figure 2 is a graph of Frac Oil 200 / CO, solubility.
Detailed Descri tn ion In order to determine the solubility of COZ with two candidate hydrocarbons, labstock diesel and Frac Oil 200T"' (a hydrocarbon based fracturing oil from Amoco Canada Petroleum Company Ltd., Calgary, Alberta) the following test was conducted.
Solubility The tests were conducted with labstock diesel and Frac Oil 200. The volumes were visual within a sight glass of a known volume. Due to the small volume in the sight glass (75mL) weight % was not used. 25 mL of hydrocarbon was added to the cell at -20 °C, CO, was added until total volume was 75 mL (50 mL of CO~). Pressure in the cell was 500 psi for the diesel and 700 psi for the Frac Oil 200. The cell was then observed at various temperatures to see the volume changes in hydrocarbon and COz.
The observed results are shown in Figures 1 and 2.
The volume change could be caused by a number of factors: CO, volume increases with lower temperature and the solubility of CO, in hydrocarbon decreases with lower temperature.
The volume ofthe hydrocarbons both increased about the same, 25 mL to 36-38 mL, indicating both the fluids had similar COz solubility. Both fluids match up well in solubility and volume changes at the various temperatures. The pressure of the cell in both tests did not increase until the temperature was 10°C and vapor was created. When the vapor is created then the fluid changes from a polyemulsion into a CO, foam. However, since the volume of CO, may not be above 53 quality, there will be little viscosity to this foam. If the pressure exceeds 500 psi at -20 °C the emulsion will be formed until the temperature increases to 5-I 0 °C or enough pressure is applied to keep the CO~ in a liquid phase.
The emulsions of the present invention were then created, using labstock diesel, liquid COz and hydrofluoroether surfactant HFE 7200 and HFE 7100 from 3M Chemicals.
(C4F90CZH5) consists oftwo inseparable isomers with essentially identical properties. These are (CF3)ZCFCFZOCZHS (CAS No. 163702-06-5) and CF3CF,CF,CF,H, (CAS No. 163702-0~-4).
HFE-7100 (C4F90CH;) consists of two inseparable 1 isomers with essentially identical properties.
These are (CF3)~CFCF~OCH3 (CAS No. 163702-08-7) and CF;CF,CF~CF,OCH; (CAS No.
163702-07-6). Both surfactant are soluble in liquid CO, and diesel, and both produced similar results.
The surfactant is added at a rate of from about 1 to 30, preferably about 4 L/m' to diesel.
The diesel/surfactant solution is then mixed with liquid CO, at a rate of about 5% - 48% CO, , preferably ;about 30 - 40% COz . The mixture is then vigorously agitated or subject to shear, resulting in a stable emulsion (stability increasing with shear), with appropriate viscosity for use as a fracturing fluid.
Claims (6)
1. A fracturing fluid comprising an emulsion having a continuous phase of liquified CO2, a discontinuous phase of a hydrocarbon, a proppant and a surfactant soluble in the two phases.
2. A fluid as claimed in claim 1, wherein said surfactant is selected from the group consisting of C4F9OC2H5, comprising the isomers (CF3)2CFCF2OC2H5 and CF3CF2CF2CF2H5 and C4F9OCH3, comprising the isomers (CF3)2CFCF2OCH3 and CF3CF2CF2CF2OCH3.
3. A fluid as claimed in claim 2, wherein said hydrocarbon is diesel fuel.
4. A fluid as claimed in claim 3, wherein said surfactant is present in said diesel fuel in an amount from 1 to 30 liters per cubic meter.
5. A fluid as claimed in claim 4, wherein diesel/surfactant is mixed with said CO2 in a ratio of 95% to 52% of said diesel/surfactant and 5% to 48% of said CO2.
6. A fluid as claimed in claim 4, wherein said diesel/surfactant solution is prepared by mixing 4 liters of surfactant per cubic meter of diesel, and said diesel/surfactant is mixed with said CO2 in a ratio of 60% to 70% of said diesel/surfactant and 30% to 40% of said CO2.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002257028A CA2257028C (en) | 1998-12-24 | 1998-12-24 | Liquid co2/hydrocarbon oil emulsion fracturing system |
| US09/469,428 US6509300B1 (en) | 1998-12-24 | 1999-12-23 | Liquid CO2/hydrocarbon oil emulsion fracturing system |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002257028A CA2257028C (en) | 1998-12-24 | 1998-12-24 | Liquid co2/hydrocarbon oil emulsion fracturing system |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2257028A1 CA2257028A1 (en) | 2000-06-24 |
| CA2257028C true CA2257028C (en) | 2003-11-18 |
Family
ID=4163126
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002257028A Expired - Fee Related CA2257028C (en) | 1998-12-24 | 1998-12-24 | Liquid co2/hydrocarbon oil emulsion fracturing system |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US6509300B1 (en) |
| CA (1) | CA2257028C (en) |
Families Citing this family (29)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7405188B2 (en) * | 2001-12-12 | 2008-07-29 | Wsp Chemicals & Technology, Llc | Polymeric gel system and compositions for treating keratin substrates containing same |
| US7183239B2 (en) * | 2001-12-12 | 2007-02-27 | Clearwater International, Llc | Gel plugs and pigs for pipeline use |
| US8273693B2 (en) * | 2001-12-12 | 2012-09-25 | Clearwater International Llc | Polymeric gel system and methods for making and using same in hydrocarbon recovery |
| WO2005074528A2 (en) * | 2004-01-30 | 2005-08-18 | Great Lakes Chemical Corporation | Compositions, halogenated compositions, chemical production and telomerization processes |
| WO2005074639A2 (en) * | 2004-01-30 | 2005-08-18 | Great Lakes Chemical Corporation | Production processes and systems, compositions, surfactants, monomer units, metal complexes, phosphate esters, glycols, aqueous film forming foams, and foam stabilizers |
| KR20060132888A (en) * | 2004-01-30 | 2006-12-22 | 그레이트 레이크스 케미칼 코퍼레이션 | Compositions, halogenated compositions, chemical production and telomerization processes |
| US7943567B2 (en) | 2004-01-30 | 2011-05-17 | E.I. Du Pont De Nemours And Company | Production processes and systems, compositions, surfactants, monomer units, metal complexes, phosphate esters, glycols, aqueous film forming foams, and foam stabilizers |
| US20070027349A1 (en) * | 2005-07-28 | 2007-02-01 | Stephan Brandstadter | Halogenated Compositions |
| EP1907343A2 (en) * | 2005-07-28 | 2008-04-09 | Great Lakes Chemical Corporation | Production processes and systems, compositions, surfactants, monomer units, metal complexes, phosphate esters, glycols, aqueous film forming foams, and foam stabilizers |
| US7513307B2 (en) * | 2006-02-13 | 2009-04-07 | Team Co2 Holdings Llc | Pumping system for injecting a mixture of liquids via a well into a subterranean formation |
| US20080076892A1 (en) * | 2006-08-03 | 2008-03-27 | Bruno Ameduri | Telomer compositions and production processes |
| US20080217012A1 (en) * | 2007-03-08 | 2008-09-11 | Bj Services Company | Gelled emulsions and methods of using the same |
| US8099997B2 (en) | 2007-06-22 | 2012-01-24 | Weatherford/Lamb, Inc. | Potassium formate gel designed for the prevention of water ingress and dewatering of pipelines or flowlines |
| US8065905B2 (en) | 2007-06-22 | 2011-11-29 | Clearwater International, Llc | Composition and method for pipeline conditioning and freezing point suppression |
| US8318656B2 (en) | 2007-07-03 | 2012-11-27 | E. I. Du Pont De Nemours And Company | Production processes and systems, compositions, surfactants, monomer units, metal complexes, phosphate esters, glycols, aqueous film forming foams, and foam stabilizers |
| US8691734B2 (en) | 2008-01-28 | 2014-04-08 | Baker Hughes Incorporated | Method of fracturing with phenothiazine stabilizer |
| US7718582B2 (en) * | 2008-05-29 | 2010-05-18 | Bj Services Company | Method for treating subterranean formation with enhanced viscosity foam |
| US7913762B2 (en) * | 2008-07-25 | 2011-03-29 | Baker Hughes Incorporated | Method of fracturing using ultra lightweight proppant suspensions and gaseous streams |
| US9291045B2 (en) | 2008-07-25 | 2016-03-22 | Baker Hughes Incorporated | Method of fracturing using ultra lightweight proppant suspensions and gaseous streams |
| US7956012B2 (en) * | 2009-02-04 | 2011-06-07 | Bj Services Company Llc | Oil field treatment fluids with viscosified brines |
| US20110028354A1 (en) * | 2009-02-10 | 2011-02-03 | Hoang Van Le | Method of Stimulating Subterranean Formation Using Low pH Fluid Containing a Glycinate Salt |
| US20100204069A1 (en) * | 2009-02-10 | 2010-08-12 | Hoang Van Le | METHOD OF STIMULATING SUBTERRANEAN FORMATION USING LOW pH FLUID |
| EA024769B1 (en) | 2009-10-06 | 2016-10-31 | Эм-Ай Эл.Эл.Си. | Method for hydrocarbon removal and recovery from drill cuttings |
| US8183181B1 (en) | 2010-11-19 | 2012-05-22 | Baker Hughes Incorporated | Oil field treatment fluids comprising zwitterionic betaine-group-containing polymers |
| US9580996B2 (en) | 2014-05-27 | 2017-02-28 | General Electric Company | Modular assembly for processing a flowback composition stream and methods of processing the same |
| CN105971579B (en) | 2016-07-07 | 2018-05-08 | 赵立强 | A kind of phase transformation hydraulic fracturing process |
| US10899958B2 (en) | 2016-07-22 | 2021-01-26 | Halliburton Energy Services, Inc. | Liquid gas treatment fluids for use in subterranean formation operations |
| US10457857B2 (en) * | 2016-08-11 | 2019-10-29 | General Electric Company | Method of fracking using silicone surfactants |
| CN108913116B (en) * | 2018-05-29 | 2021-04-16 | 山东大学 | Supercritical carbon dioxide reverse-phase association fracturing fluid and preparation method and application thereof |
Family Cites Families (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3396107A (en) * | 1962-08-09 | 1968-08-06 | Producers Chemical Company | Composition for fracturing process |
| US3310112A (en) | 1964-03-09 | 1967-03-21 | Dow Chemical Co | Well fracturing method |
| US3356138A (en) * | 1965-11-22 | 1967-12-05 | Marathon Oil Co | Oil recovery process utilizing liquefied petroleum gases and heavier hydrocarbons |
| US3368627A (en) | 1966-03-21 | 1968-02-13 | Dow Chemical Co | Method of well treatment employing volatile fluid composition |
| US3623552A (en) | 1969-11-13 | 1971-11-30 | Cities Service Oil Co | Recovery of oil by low-pressure miscible gas injection |
| US3664422A (en) * | 1970-08-17 | 1972-05-23 | Dresser Ind | Well fracturing method employing a liquified gas and propping agents entrained in a fluid |
| US3765488A (en) | 1972-04-06 | 1973-10-16 | Dow Chemical Co | Well treating method |
| US3954626A (en) | 1973-09-24 | 1976-05-04 | The Dow Chemical Company | Well treating composition and method |
| US3842910A (en) | 1973-10-04 | 1974-10-22 | Dow Chemical Co | Well fracturing method using liquefied gas as fracturing fluid |
| US4233165A (en) | 1978-05-24 | 1980-11-11 | Exxon Production Research Company | Well treatment with emulsion dispersions |
| US4554082A (en) * | 1984-01-20 | 1985-11-19 | Halliburton Company | Fracturing method for stimulation of wells utilizing carbon dioxide based fluids |
| US4519455A (en) | 1984-01-20 | 1985-05-28 | Halliburton Company | Fracturing method for stimulation of wells utilizing carbon dioxide based fluids |
| US4627495A (en) * | 1985-04-04 | 1986-12-09 | Halliburton Company | Method for stimulation of wells with carbon dioxide or nitrogen based fluids containing high proppant concentrations |
| CA1268325A (en) * | 1987-11-13 | 1990-05-01 | Loree, Dwight N. | Fracturing process for low permeability reservoirs employing a compatible hydrocarbon-liquid carbon dioxide mixture |
| US4921635A (en) * | 1988-11-22 | 1990-05-01 | University Of Pittsburgh | CO2 gels and methods for making |
| US5424285A (en) * | 1993-01-27 | 1995-06-13 | The Western Company Of North America | Method for reducing deleterious environmental impact of subterranean fracturing processes |
| US5312882A (en) * | 1993-07-30 | 1994-05-17 | The University Of North Carolina At Chapel Hill | Heterogeneous polymerization in carbon dioxide |
| CA2129613C (en) * | 1994-08-05 | 1997-09-23 | Samuel Luk | High proppant concentration/high co2 ratio fracturing system |
| CA2131195C (en) * | 1994-08-26 | 1997-04-29 | Dwight N. Loree | Method of improving oil and gas well productivity |
| CA2198156C (en) * | 1994-11-14 | 2001-04-24 | Robin Tudor | Nitrogen/carbon dioxide combination fracture treatment |
-
1998
- 1998-12-24 CA CA002257028A patent/CA2257028C/en not_active Expired - Fee Related
-
1999
- 1999-12-23 US US09/469,428 patent/US6509300B1/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| US6509300B1 (en) | 2003-01-21 |
| CA2257028A1 (en) | 2000-06-24 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |
Effective date: 20161228 |