CN106634906A - Gel with high temperature resistance - Google Patents
Gel with high temperature resistance Download PDFInfo
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- CN106634906A CN106634906A CN201610829185.6A CN201610829185A CN106634906A CN 106634906 A CN106634906 A CN 106634906A CN 201610829185 A CN201610829185 A CN 201610829185A CN 106634906 A CN106634906 A CN 106634906A
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- agent
- water
- high temperature
- gel
- frozen glue
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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
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/504—Compositions based on water or polar solvents
- C09K8/506—Compositions based on water or polar solvents containing organic compounds
- C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/512—Compositions based on water or polar solvents containing organic compounds macromolecular compounds containing cross-linking agents
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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
- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
- C08F8/36—Sulfonation; Sulfation
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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
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/504—Compositions based on water or polar solvents
- C09K8/506—Compositions based on water or polar solvents containing organic compounds
- C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/5083—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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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
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
- C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/882—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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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
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
- C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/887—Compositions based on water or polar solvents containing organic compounds macromolecular compounds containing cross-linking agents
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- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides gel with high temperature resistance. The gel is prepared by the following components in percentages by mass: 0.2-0.4% of a main agent, 0.5-1% of a cross-linking agent, 0.2-0.4% of a stabilizing agent, 0.2-0.3% of a pH conditioning agent, and the balance being water; the sum of each component is 100%, wherein the main agent is modified cationic sulfonated polyacrylamide which is generated by reaction between cationic polyacrylamide as well as triethanolamine and sodium bisulfite, and relative molecular mass is 700x10<4>-800x10<4>; the cross-linking agent is combination of hydroquinone and urotropine; a stabilizing agent is thiourea; a pH conditioning agent is sodium hydroxide. The gel is generation by a sulfonation reaction in a high temperature highly basic condition with excellent temperature toleration, and the gel has effective plugging effects in a high temperature oil reservoir environment at 150 DEG C.
Description
Technical field：
The present invention relates to a kind of high temperature resistant frozen glue, belongs to technical field of oilfield chemistry.
Background technology：
Well water is common problem in waterflooding oil field development process.Due to stratum is primary and rear life it is non-
Homogenieity, fluid mobility difference and other reasonses, form in the earth formation current predominant pathway, cause water cone, water breakthrough, water to refer to
Enter, make some oil well premature water breakthroughs or water logging, water drive is poorly efficient or inefficient cycle.Profile control and water plugging technology is always oil field improves water filling
Development effectiveness, the effective means for realizing oil reservoir stable yields.But as the exploitation in oil field, characteristics of reservoirs and environment are continually changing, especially
It is that long-period water drive makes oil reservoir development contradiction increasingly complex, existing profile control and water plugging technology, especially after oil reservoir enters the High water cut productive life
Be can effectively using technology always lag behind the needs of oil field development.For some high temperature deep well oil reservoirs of China, oil reservoir temperature
Up to 150 DEG C of degree, because common polyacrylamide is susceptible under the high temperature conditions degraded, causes frozen glue syneresis, makes
Obtain plugging effect to be deteriorated.Therefore, plain polypropylene amide-type frozen glue is not suitable for being applied to high-temperature oil reservoir.At present, artificial synthesized height
Molecularly Imprinted Polymer frozen glue has become the study hotspot of domestic and international temperature resistance frozen glue.In artificial synthesized heat-resistant polymer, mainly
It is to improve its heat and salinity tolerance ability, but the sulfonic group of AMPS by introducing the methyl propane sulfonic acid salt (AMPS) of 2- acrylamidos -2
It is to be connected on macromolecule by amido link, under high temperature and acid-base condition, amide groups can in a large number be hydrolyzed and made on macromolecular chain
Sulfonic quantity is reduced, and affects stablizing for polymer performance.Therefore a kind of new heatproof blocking agent is developed for solution high temperature
The well water problem of oil reservoir has great importance.
The content of the invention：
For the deficiencies in the prior art, the purpose of the present invention is, by MOLECULE DESIGN, to draw in PAMC
Enter the sulfonic group that is connected with carbon atom to improve sulfonic stability, so as to provide a kind of high temperature resistant frozen glue, be mainly used in
High-temperature oil reservoir blocks water breakthrough.
Technical scheme is as follows：
The high temperature resistant frozen glue is a kind of mixture being made up of host, crosslinking agent, stabilizer, pH adjusting agent and water, institute
Host is stated for PAMC and triethanolamine and the Modified cationic sulfonation poly- third of sodium hydrogensulfite reaction generation
Acrylamide, the crosslinking agent is the combination of hydroquinones and methenamine, and the stabilizer is thiocarbamide, and mass percent is constituted such as
Under：
Host 0.2%～0.4%, its relative molecular mass is 700 × 104～800 × 104；
Crosslinking agent 0.5%～1%, is the combination of hydroquinones and methenamine；
Stabilizer 0.2%～0.4%, is thiocarbamide；
PH adjusting agent 0.2%～0.3%, is NaOH；
Described water is salinity 22 × 104The Tahe water of mg/L, surplus；
The mass percent sum of each component is 100%.
The preparation method of above-mentioned frozen glue is as follows：
1st, polyacrylamide is modified：Relative molecular mass is 700 × 104～800 × 104PAMC with
Triethanolamine and sodium hydrogensulfite reaction generate Modified cationic sulfonated polyacrylamide.
2nd, by the Modified cationic sulfonated polyacrylamide obtained by previous step salinity be 22 × 104The Tahe of mg/L
Fully dissolve in water, it is standby；By proportioning by hydroquinones/methenamine crosslinking agent, polymer stabilizer, pH adjusting agent and remaining
Amount Tahe water mixing and stirring；Above two solution mixing and stirring is obtained into plastic liquid.
3rd, will be placed in ampoule bottle into glue, be sealed with alcohol blast burner sintering, be placed in aging in 150 DEG C of baking oven obtaining final product
State frozen glue.
The frozen glue gelation time of the present invention is 15～20h.
The invention has the beneficial effects as follows：
1st, due to present invention utilizes in cationic polymer carbocation easily occur and the combination of alkaline matter, transfer,
The characteristics of side reactions such as isomerization, triethanolamine, sodium hydrogensulfite and NaOH are with the addition of in cationic polymer,
Under high temperature, basic conditions, cationic polymer reacts first with triethanolamine, generates one that methylol instead of on amide groups
Hydrogen, product reacts again with sodium hydrogensulfite so that the hydroxyl on a part of methylol is replaced by sodium group again, most throughout one's life
Into modified cationic polymer heat resistance greatly improve, compensate for polyacrylamide frozen glue and be not suitable for being applied to high temperature oil
The deficiency of Tibetan.Therefore frozen glue heat resistance provided by the present invention is excellent, can play in 150 DEG C of high-temperature oil reservoir environment effectively
Plugging action.
2nd, it is provided by the present invention it is polymer-modified be that reaction is produced behind injection stratum, it is to avoid series of complex
Synthesis technique, reduces cost.
Specific embodiment：
In order to be more clearly understood from the present invention, now specific embodiments of the present invention are explained in detail, but this
Invention institute protection domain is not limited only to this.
Embodiment 1：
It is 22 × 10 in 50g salinities4In the Tahe water of mg/L add 0.5g hydroquinones, 0.2g sodium hydrogensulfites,
0.2g methenamines, 0.3g thiocarbamides, 0.3g NaOH, stir so as to fully dissolving, then 50g is prepared with Tahe water
Mass concentration be that 1.6% cationic sulfonated polyacrylamide mixes with above-mentioned solution, stir, by the plastic for obtaining
Liquid is placed in ampoule bottle, is sealed with alcohol blast burner sintering, is placed in the aging frozen glue for obtaining the present invention in 150 DEG C of baking oven.Should
Gelation time of the frozen glue at 150 DEG C is 17h, and the gel strength of acquisition is 0.079MPa, no dehydration in aging 80 days at 150 DEG C
Phenomenon.
Embodiment 2：
It is 22 × 10 in 50g salinities4In the Tahe water of mg/L add 0.5g hydroquinones, 0.2g sodium hydrogensulfites,
0.4g methenamines, 0.1g triethanolamines, 0.3g thiocarbamides, 0.3g NaOH, stir so as to fully dissolving, then by 50g
The mass concentration prepared with Tahe water is that 1.6% cationic sulfonated polyacrylamide mixes with above-mentioned solution, is stirred,
To obtain into glue being placed in ampoule bottle, sealed with alcohol blast burner sintering, be placed in and aging in 150 DEG C of baking oven obtain this
Bright frozen glue.Gelation time of the frozen glue at 150 DEG C is 15h, and the gel strength of acquisition is 0.082MPa, aging at 150 DEG C
80 days without phenomenon of losing water.
Embodiment 3：
It is 22 × 10 in 50g salinities4In the Tahe water of mg/L add 0.5g hydroquinones, 0.2g sodium hydrogensulfites,
0.4g methenamines, 0.2g triethanolamines, 0.3g thiocarbamides, 0.3g NaOH, stir so as to fully dissolving, then by 50g
The mass concentration prepared with Tahe water is that 1.6% cationic sulfonated polyacrylamide mixes with above-mentioned solution, is stirred,
To obtain into glue being placed in ampoule bottle, sealed with alcohol blast burner sintering, be placed in and aging in 150 DEG C of baking oven obtain this
Bright frozen glue.Gelation time of the frozen glue at 150 DEG C is 18h, and the gel strength of acquisition is 0.076MPa, aging at 150 DEG C
80 days without phenomenon of losing water.
Embodiment 4：
It is 22 × 10 in 50g salinities4In the Tahe water of mg/L add 0.5g hydroquinones, 0.2g sodium hydrogensulfites,
0.5g methenamines, 0.2g triethanolamines, 0.3g thiocarbamides, 0.3g NaOH, stir so as to fully dissolving, then by 50g
The mass concentration prepared with Tahe water is that 1.6% cationic sulfonated polyacrylamide mixes with above-mentioned solution, is stirred,
To obtain into glue being placed in ampoule bottle, sealed with alcohol blast burner sintering, be placed in and aging in 150 DEG C of baking oven obtain this
Bright frozen glue.Gelation time of the frozen glue at 150 DEG C is 17h, and the gel strength of acquisition is 0.080MPa, aging at 150 DEG C
80 days without phenomenon of losing water.
Embodiment 5：
It is 22 × 10 in 50g salinities4In the Tahe water of mg/L add 0.4g hydroquinones, 0.2g sodium hydrogensulfites,
0.6g methenamines, 0.2g triethanolamines, 0.3g thiocarbamides, 0.3g NaOH, stir so as to fully dissolving, then by 50g
The mass concentration prepared with Tahe water is that 1.6% cationic sulfonated polyacrylamide mixes with above-mentioned solution, is stirred,
To obtain into glue being placed in ampoule bottle, sealed with alcohol blast burner sintering, be placed in and aging in 150 DEG C of baking oven obtain this
Bright frozen glue.Gelation time of the frozen glue at 150 DEG C is 20h, and the gel strength of acquisition is 0.082MPa, aging at 150 DEG C
80 days without phenomenon of losing water.
Embodiment 6：
It is 22 × 10 in 50g salinities4In the Tahe water of mg/L add 0.4g hydroquinones, 0.3g sodium hydrogensulfites,
0.6g methenamines, 0.2g triethanolamines, 0.3g thiocarbamides, 0.3g NaOH, stir so as to fully dissolving, then by 50g
The mass concentration prepared with Tahe water is that 1.6% cationic sulfonated polyacrylamide mixes with above-mentioned solution, is stirred,
To obtain into glue being placed in ampoule bottle, sealed with alcohol blast burner sintering, be placed in and aging in 150 DEG C of baking oven obtain this
Bright frozen glue.Gelation time of the frozen glue at 150 DEG C is 19h, and the gel strength of acquisition is 0.077MPa, aging at 150 DEG C
80 days without phenomenon of losing water.
Shut-off capacity is investigated：
The frozen glue obtained with " embodiment 1-6 " investigates the shut-off capacity of frozen glue provided by the present invention as research object.
Specific experiment process is as follows：The six roots of sensation fill out sand tube filling quartz sand grain that internal diameter is 2.5cm, length is 20cm is obtained into simulation rock
The heart, is denoted as respectively 1#, 2#, 3#, 4#, 5# and 6#, and original permeability k is obtained after water drive to pressure stability1, then by " embodiment
Distinguishing in the above-mentioned six roots of sensation fill out sand tube of inverse injection into glue in 1-6 ", injected slurry volume is 0.25PV (rock pore volume), so
0.25PV water is injected afterwards to be replaced, and afterwards six roots of sensation fill out sand tube is placed in into 150 DEG C of baking ovens aging 20 days and 90 days respectively, finally
Respectively water drive measures stifled rear permeability k of simulation core to pressure stability2, and by formula E=(k1-k2)/k1* 100%, calculate
Reservoir core plugging rate E, experimental result is as shown in the table.
Above test result indicate that：The frozen glue that the present invention is provided has excellent sealing characteristics under 150 DEG C of hot conditions.
Claims (1)
1. a kind of high temperature resistant frozen glue, is characterized in that being made up of following components and its mass percent：Host 0.2%～0.4%, friendship
Connection agent 0.5%～1%, stabilizer 0.2%～0.4%, pH adjusting agent 0.2%～0.3% and excess water, each component quality percentage
It is 100% than sum, wherein, the host is that PAMC is generated with triethanolamine and sodium hydrogensulfite reaction
Modified cationic sulfonated polyacrylamide, its relative molecular mass is 700 × 104～800 × 104；Crosslinking agent is hydroquinones
With the combination of methenamine；Stabilizer is thiocarbamide；PH adjusting agent is NaOH.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610829185.6A CN106634906A (en) | 2016-09-18 | 2016-09-18 | Gel with high temperature resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610829185.6A CN106634906A (en) | 2016-09-18 | 2016-09-18 | Gel with high temperature resistance |
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| Publication Number | Publication Date |
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| CN106634906A true CN106634906A (en) | 2017-05-10 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610829185.6A Pending CN106634906A (en) | 2016-09-18 | 2016-09-18 | Gel with high temperature resistance |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108531153A (en) * | 2018-05-03 | 2018-09-14 | 中国石油大学(华东) | A kind of high temperature resistant Petropols dispersion blocking agent and the preparation method and application thereof |
| CN109666468A (en) * | 2018-10-31 | 2019-04-23 | 中国石油大学(华东) | Skid-mounted type frozen glue dispersion process units and frozen glue dispersion and preparation method and application |
| CN109679604A (en) * | 2019-01-28 | 2019-04-26 | 中国石油大学(华东) | A kind of salt tolerant high-temperature resistant water gel and the preparation method and application thereof |
| CN113249103A (en) * | 2021-06-01 | 2021-08-13 | 中国石油大学(华东) | Seawater-based polyacrylamide high-temperature jelly profile control system |
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| CN101892037A (en) * | 2010-07-19 | 2010-11-24 | 中国海洋石油总公司 | Novel salt-resistant gel selective water shutoff agent |
| CN102559158A (en) * | 2010-12-24 | 2012-07-11 | 中国石油天然气股份有限公司 | Acidic gel plugging agent for oil well |
| CN102807849A (en) * | 2012-04-06 | 2012-12-05 | 中国石油大学(华东) | Gel plugging agent for deep profile control of higher temperature oil reservoir and preparation method of gel plugging agent |
| CN104629699A (en) * | 2015-01-19 | 2015-05-20 | 中国石油大学(华东) | Low-crosslinking-agent-consumption temperature-resistant salt-resistant gel |
| CN104629697A (en) * | 2015-01-19 | 2015-05-20 | 中国石油大学(华东) | Temperature-resistant jelly |
-
2016
- 2016-09-18 CN CN201610829185.6A patent/CN106634906A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101892037A (en) * | 2010-07-19 | 2010-11-24 | 中国海洋石油总公司 | Novel salt-resistant gel selective water shutoff agent |
| CN102559158A (en) * | 2010-12-24 | 2012-07-11 | 中国石油天然气股份有限公司 | Acidic gel plugging agent for oil well |
| CN102807849A (en) * | 2012-04-06 | 2012-12-05 | 中国石油大学(华东) | Gel plugging agent for deep profile control of higher temperature oil reservoir and preparation method of gel plugging agent |
| CN104629699A (en) * | 2015-01-19 | 2015-05-20 | 中国石油大学(华东) | Low-crosslinking-agent-consumption temperature-resistant salt-resistant gel |
| CN104629697A (en) * | 2015-01-19 | 2015-05-20 | 中国石油大学(华东) | Temperature-resistant jelly |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108531153A (en) * | 2018-05-03 | 2018-09-14 | 中国石油大学(华东) | A kind of high temperature resistant Petropols dispersion blocking agent and the preparation method and application thereof |
| CN108531153B (en) * | 2018-05-03 | 2020-09-22 | 中国石油大学(华东) | High-temperature-resistant petroleum resin dispersoid blocking agent and preparation method and application thereof |
| CN109666468A (en) * | 2018-10-31 | 2019-04-23 | 中国石油大学(华东) | Skid-mounted type frozen glue dispersion process units and frozen glue dispersion and preparation method and application |
| CN109666468B (en) * | 2018-10-31 | 2019-11-05 | 中国石油大学(华东) | Skid-mounted type frozen glue dispersion process units and frozen glue dispersion and preparation method and application |
| CN109679604A (en) * | 2019-01-28 | 2019-04-26 | 中国石油大学(华东) | A kind of salt tolerant high-temperature resistant water gel and the preparation method and application thereof |
| CN109679604B (en) * | 2019-01-28 | 2021-01-05 | 中国石油大学(华东) | Salt-resistant and high-temperature-resistant hydrogel and preparation method and application thereof |
| CN113249103A (en) * | 2021-06-01 | 2021-08-13 | 中国石油大学(华东) | Seawater-based polyacrylamide high-temperature jelly profile control system |
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