CN113788915B - Degradable rubber plug liquid for geothermal well - Google Patents
Degradable rubber plug liquid for geothermal well Download PDFInfo
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- CN113788915B CN113788915B CN202111064600.0A CN202111064600A CN113788915B CN 113788915 B CN113788915 B CN 113788915B CN 202111064600 A CN202111064600 A CN 202111064600A CN 113788915 B CN113788915 B CN 113788915B
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- rubber plug
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- oil pipe
- geothermal well
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
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- 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
- C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
- C09K8/44—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing organic binders only
Abstract
The invention discloses a geothermal well degradable rubber plug liquid which comprises the following raw materials in parts by weight: 40 parts of isophorone diisocyanate, 100 parts of polycaprolactone polyol, 4 parts of 2,2-dimethylolpropionic acid, 5 parts of butanediol, 3 parts of triethylamine, 2 parts of ethylenediamine, 1300 parts of distilled water, 100-150 parts of acrylamide, 1 part of ammonium persulfate and 1 part of N, N-methylene bisacrylamide. The rubber plug liquid has better bonding strength with a shaft, and can meet the requirement of a sealing layer. The solidified rubber plug can be broken under the action of the hydrogen peroxide solution.
Description
Technical Field
The invention relates to a degradable rubber plug liquid for a geothermal well.
Background
In well repair and fracturing operations, because the formation pressure and the internal pressure of a shaft are not balanced, a target layer position needs to be plugged. The liquid rubber plug can realize the plugging of a target layer, and can break rubber and discharge out of a shaft after the construction is finished, so that the liquid rubber plug is widely concerned. The existing liquid rubber plug mainly aims at the field of oil and gas wells, and is hydrogel in nature. The hydrogel system is formed by mainly using guar gum, polyacrylamide and other substances as polymer matrixes through crosslinking. The liquid rubber plug has the problem that the wall-grabbing force of the rubber plug is not strong. The oil-gas wells mostly contain a large amount of combustible and explosive substances such as crude oil, natural gas and the like, so that the selection of the gel-forming substance and the corresponding gel breaker is limited to a certain extent in the design process of the rubber plugs.
Disclosure of Invention
The invention aims to provide a geothermal well degradable rubber plug liquid, which realizes that a cured rubber plug has good plugging capability and can be quickly broken and discharged out of a shaft in a short time. Therefore, the technical scheme of the invention is as follows: the geothermal well degradable rubber plug liquid comprises the following raw materials in parts by weight: 40 parts of isophorone diisocyanate, 100 parts of polycaprolactone polyol, 2,2-dimethylolpropionic acid 4 parts, 5 parts of butanediol, 3 parts of triethylamine, 2 parts of ethylenediamine, 1300 parts of distilled water, 100-150 parts of acrylamide, 1 part of ammonium persulfate and 1 part of N, N-methylene bisacrylamide.
The average molecular weight of the polycaprolactone is 1800-2000.
The invention also provides a preparation method of the oil and gas well plugging fluid, which comprises the following steps:
(1) Adding 100 parts of polycaprolactone polyol into a reaction kettle in parts by weight, heating to 75 ℃, and preserving heat for 0.5h. Further heating the reaction system to 110 ℃, vacuumizing and dehydrating for 0.5h under 250Pa, and then cooling to 65 ℃;
(2) Adding 4 parts of 2,2-dimethylolpropionic acid, 5 parts of butanediol and 40 parts of isophorone diisocyanate into a reaction kettle under the condition of stirring, heating the temperature of a reaction system to 80 ℃, and reacting for 5 hours;
(3) And cooling the temperature of the reaction system to 50 ℃, adding 3 parts of triethylamine, and reacting for 0.5h. Then adding 300 parts of distilled water and 2 parts of ethylenediamine into the system, continuously stirring for reacting for 2 hours, and cooling the reaction system to 25 ℃;
(4) Adding 1000 parts of distilled water, 100-150 parts of acrylamide, 1 part of ammonium persulfate and 1 part of N, N-methylene-bisacrylamide into the reaction system, continuously stirring for 0.1 hour, and stopping stirring to obtain the degradable rubber plug liquid for the geothermal well.
The invention has the beneficial effects that: the invention introduces the polyester urethane material into the polyacrylamide hydrogel to form an interpenetrating network structure, thereby greatly enhancing the mechanical strength of the formed polymer gel. The invention is suitable for the temperature range of a target layer of 90-110 ℃, and the rubber plug liquid can rapidly generate polymerization reaction in a shaft to form hydrogel. Acrylamide after polymerization can restrict water molecules which originally move freely in the system, and at the moment, polyurethane molecules can show excellent bonding performance, so that the bonding strength of the rubber plug and a shaft is greatly improved, and the rubber plug is endowed with good pressure bearing performance. Meanwhile, polyester polyurethane molecules contain a large number of ester bonds which are easy to degrade, the degradation performance of the polyester polyurethane molecules is far better than that of polyether polyurethane, and the polyester polyurethane can be degraded under the action of hydrogen peroxide at a target stratum temperature. The polyacrylamide molecules in the rubber plug can also be subjected to macromolecular chain fracture under the action of hydrogen peroxide, so that the rubber plug is endowed with degradable performance.
The invention also provides a method for sealing a layer by using the degradable rubber plug liquid, which comprises the following steps:
(1) After the oil pipe is lowered to a target layer, 100L-200L of degradable rubber plug liquid is pumped into the shaft from the oil pipe, and the degradable rubber plug liquid is replaced to the target layer by using clear water, wherein the temperature of the target layer is 90-110 ℃;
(2) Lifting the oil pipe to separate and contact the oil pipe and the degradable rubber plug liquid, and curing and molding the degradable rubber plug liquid after 4 hours to finish plugging; (3) After the construction is finished, an oil pipe is lowered into the shaft to a position 0.5m above the rubber plug, and a 15% hydrogen peroxide aqueous solution is pumped to the position of the rubber plug through the oil pipe to break the rubber. After the rubber plug is degraded, clear water is injected from the oil pipe, and degradation products are washed out of the shaft.
Detailed Description
The invention is described in further detail below:
example 1
Weighing the following raw materials in parts by weight: 40kg of isophorone diisocyanate, 100kg of polycaprolactone polyol (average molecular weight is 1800), 2,2-dimethylolpropionic acid 4 kg, 5kg of butanediol, 3kg of triethylamine, 2kg of ethylenediamine, 1300kg of distilled water, 100kg of acrylamide, 1kg of ammonium persulfate and 1kg of N, N-methylene bisacrylamide.
The preparation method comprises the following steps:
(1) Adding 100kg of polycaprolactone polyol into a reaction kettle, heating to 75 ℃, and keeping the temperature for 0.5h. Further heating the reaction system to 110 ℃, vacuumizing and dehydrating for 0.5h under 250Pa, and then cooling to 65 ℃;
(2) Adding 2,2-dimethylolpropionic acid 4 kg, butanediol 5kg and isophorone diisocyanate 40kg into a reaction kettle under the condition of stirring, heating the temperature of a reaction system to 80 ℃, and reacting for 5 hours;
(3) The temperature of the reaction system is reduced to 50 ℃, and then triethylamine 3kg is added for reaction for 0.5h. Then adding 300kg of distilled water and 2kg of ethylenediamine into the system, continuously stirring for reacting for 2 hours, and cooling the reaction system to 25 ℃;
(4) Adding 1000kg of distilled water, 100kg of acrylamide, 1kg of ammonium persulfate and 1kg of N, N-methylene bisacrylamide into the reaction system, continuing stirring for 0.1h, and stopping stirring to obtain the degradable rubber plug liquid for the geothermal well.
A method for liquid sealing a layer by utilizing a degradable rubber plug comprises the following steps:
(1) After the oil pipe is lowered to a target layer, 100L of degradable rubber plug liquid is pumped into the shaft from the oil pipe, and the degradable rubber plug liquid is replaced to the target layer by using clear water, wherein the temperature of the target layer is 90 ℃;
(2) Lifting the oil pipe to separate and contact the oil pipe with the degradable rubber plug liquid, and curing and molding the degradable rubber plug liquid after 4 hours to finish plugging;
(3) After the construction is finished, an oil pipe is put into the shaft to a position 0.5m above the rubber plug, and the hydrogen peroxide aqueous solution with the concentration of 15% is pumped to the position of the rubber plug through the oil pipe for rubber breaking. After the rubber plug is degraded, clear water is injected from the oil pipe, and degradation products are washed out of the shaft.
Example 2
Weighing the following raw materials in parts by weight: 40kg of isophorone diisocyanate, 100kg of polycaprolactone polyol (average molecular weight of 1900), 2,2-dimethylolpropionic acid 4 kg, butanediol 5kg, triethylamine 3kg, ethylenediamine 2kg, 1300kg of distilled water, 100kg of acrylamide, 1kg of ammonium persulfate and 1kg of N, N-methylene bisacrylamide.
The preparation method comprises the following steps:
(1) Adding 100kg of polycaprolactone polyol into a reaction kettle, heating to 75 ℃, and preserving heat for 30min. Further heating the reaction system to 110 ℃, vacuumizing and dehydrating for 30min under 250Pa, and then cooling to 65 ℃;
(2) Adding 2,2-dimethylolpropionic acid 4 kg, butanediol 5kg and isophorone diisocyanate 40kg into a reaction kettle under the condition of stirring, heating the temperature of a reaction system to 80 ℃, and reacting for 5 hours;
(3) And (3) cooling the temperature of the reaction system to 50 ℃, adding 3kg of triethylamine, and reacting for 20min. Then adding 300kg of distilled water and 2kg of ethylenediamine into the system, continuously stirring for reacting for 2 hours, and cooling the reaction system to 25 ℃;
(4) 1000kg of distilled water, 125kg of acrylamide, 1kg of ammonium persulfate and 1kg of N, N-methylene bisacrylamide are added into the system, the stirring is continued for 0.1 hour, and the stirring is stopped to obtain the degradable rubber plug liquid for the geothermal well.
A method for liquid sealing a layer by utilizing a degradable rubber plug comprises the following steps:
(1) After the oil pipe is lowered to a target layer, 150L of degradable rubber plug liquid is pumped into the shaft from the oil pipe, and the degradable rubber plug liquid is replaced to the target layer by clear water, wherein the temperature of the target layer is 100 ℃;
(2) Lifting the oil pipe to separate and contact the oil pipe and the degradable rubber plug liquid, and curing and molding the degradable rubber plug liquid after 4 hours to finish plugging;
(3) After the construction is finished, an oil pipe is lowered into the shaft to a position 0.5m above the rubber plug, and a 15% hydrogen peroxide aqueous solution is pumped to the position of the rubber plug through the oil pipe to break the rubber. After the rubber plug is degraded, clear water is injected from the oil pipe, and degradation products are washed out of the shaft.
Example 3
Weighing the following raw materials in parts by weight: 40kg of isophorone diisocyanate, 100kg of polycaprolactone polyol (average molecular weight of 2000), 4 kg of 2,2-dimethylolpropionic acid, 5kg of butanediol, 3kg of triethylamine, 2kg of ethylenediamine, 1300kg of distilled water, 150kg of acrylamide, 1kg of ammonium persulfate and 1kg of N, N-methylene bisacrylamide.
The preparation method comprises the following steps:
(1) Adding 100kg of polycaprolactone polyol into a reaction kettle, heating to 75 ℃, and preserving heat for 30min. Further heating the reaction system to 110 ℃, vacuumizing and dehydrating for 30min under 250Pa, and then cooling to 65 ℃;
(2) Adding 2,2-dimethylolpropionic acid 4 kg, butanediol 5kg and isophorone diisocyanate 40kg into a reaction kettle under the condition of stirring, heating the temperature of a reaction system to 80 ℃, and reacting for 5 hours;
(3) The temperature of the reaction system is reduced to 50 ℃, and triethylamine 3kg is added to react for 20min. Then adding 300kg of distilled water and 2kg of ethylenediamine into the system, continuously stirring for reacting for 2 hours, and cooling the reaction system to 25 ℃;
(4) Adding 1000kg of distilled water, 150kg of acrylamide, 1kg of ammonium persulfate and 1kg of N, N-methylene bisacrylamide into the reaction system, continuing stirring for 0.1h, and stopping stirring to obtain the degradable rubber plug liquid for the geothermal well.
A method for liquid sealing a layer by utilizing a degradable rubber plug comprises the following steps:
(1) After the oil pipe is lowered to a target layer, 200L of degradable rubber plug liquid is pumped into the shaft from the oil pipe, and the degradable rubber plug liquid is replaced to the target layer by clear water, wherein the temperature of the target layer is 110 ℃;
(2) Lifting the oil pipe to separate and contact the oil pipe and the degradable rubber plug liquid, and curing and molding the degradable rubber plug liquid after 4 hours to finish plugging;
(3) After the construction is finished, an oil pipe is put into the shaft to a position 0.5m above the rubber plug, and the hydrogen peroxide aqueous solution with the concentration of 15% is pumped to the position of the rubber plug through the oil pipe for rubber breaking. After the rubber plug is degraded, clear water is injected from the oil pipe, and degradation products are washed out of the shaft.
Claims (2)
1. The geothermal well degradable rubber plug liquid is characterized by comprising the following raw materials in parts by weight: 40 parts of isophorone diisocyanate, 100 parts of polycaprolactone polyol, 4 parts of 2,2-dimethylolpropionic acid, 5 parts of butanediol, 3 parts of triethylamine, 2 parts of ethylenediamine, 1300 parts of distilled water, 100-150 parts of acrylamide, 1 part of ammonium persulfate and 1 part of N, N-methylene-bisacrylamide.
2. The geothermal well degradable plug fluid of claim 1 wherein the polycaprolactone polyol has an average molecular weight of 1800 to 2000.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202111064600.0A CN113788915B (en) | 2021-09-11 | 2021-09-11 | Degradable rubber plug liquid for geothermal well |
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| CN202111064600.0A CN113788915B (en) | 2021-09-11 | 2021-09-11 | Degradable rubber plug liquid for geothermal well |
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| CN113788915B true CN113788915B (en) | 2022-10-04 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102182421A (en) * | 2011-03-30 | 2011-09-14 | 中国石油天然气股份有限公司 | Segmented water plugging method of liquid bridge plug of horizontal well |
| US11473006B2 (en) * | 2016-07-28 | 2022-10-18 | Halliburton Energy Services, Inc. | Excapsulation oxidizing breakers for downhole applications |
| CN113174018A (en) * | 2021-04-27 | 2021-07-27 | 岭南师范学院 | Oil and gas well plugging fluid and preparation method thereof |
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