CN104629699B - A kind of heat-resistant salt-resistant frozen glue of low cross-linking agent consumption - Google Patents
A kind of heat-resistant salt-resistant frozen glue of low cross-linking agent consumption Download PDFInfo
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- CN104629699B CN104629699B CN201510025766.XA CN201510025766A CN104629699B CN 104629699 B CN104629699 B CN 104629699B CN 201510025766 A CN201510025766 A CN 201510025766A CN 104629699 B CN104629699 B CN 104629699B
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- 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
- 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
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/588—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific polymers
Abstract
The invention provides a kind of heat-resistant salt-resistant frozen glue of low cross-linking agent consumption, frozen glue mass percent composition is as follows：The methyl propane sulfonic acid copolymer 0.6%~1.2% of acrylamide/2 acrylamido 2, resorcinol 0.02%~0.04%, polyethyleneimine 0.02%~0.05%, metaformaldehyde 0.02%~0.04%, alkoxy silane 0.03%~0.1%, thiocarbamide 0.2%~0.4%, surplus are water, each component sum is 100%, and the salinity of the water is 22.4 × 104Mg/L, calcium ions and magnesium ions content is 1.3 × 104mg/L.Frozen glue dosage of crosslinking agent≤0.1% provided by the present invention, 100 days no broken glue phenomenons of aging, heat-resistant salt-resistant excellent performance under the conditions of 130 DEG C.
Description
Technical field：
The present invention relates to a kind of Polymer Plugging Agent, more particularly to a kind of heat-resistant salt-resistant frozen glue of low cross-linking agent consumption, belong to
Technical field of oilfield chemistry.
Background technology：
Water flood recovery is the Main Means of new block Efficient Development and old filed adjustment and tap, due to injection water, side water with
And the continuous breakthrough of bottom water, cause well water in production process to rise rapidly, oil production drastically declines, therefore closure water breakthrough is
As the key for improving oil recovery factor.Polymer gel is because its is cheap, preparation simple, construction effect is good and turns into current
The most widely used water shutoff agent.However, for the western high temperature and high salt oil deposit of China, its reservoir temperature is up to 130 DEG C, mineralising
Degree is more than 22 × 104Mg/L, because common polyacrylamide is easily degraded under the conditions of high temperature and high salt, causes frozen glue to break
Glue is dehydrated so that plugging effect is deteriorated.Therefore, plain polypropylene amide-type frozen glue is not suitable for being applied to high temperature and high salt oil deposit, nothing
Machine grain-type water shutoff agent and lignin/tannin extract class gel plugging agent turn into current the most widely used heat-resistant salt-resistant water shutoff agent.It is inorganic
Grain-type water shutoff agent is primarily referred to as, using inorganic particles such as cement, flyash as main component, it being injected into the form of suspended substance
The blocking agent of plugging action is played in stratum, the blocking agent has the advantages that shut-off capacity is strong, but the protrusion defect of grain-type water shutoff agent is
Closure to stratum is rigid, and plugging action is easily damaged without selectivity to whole reservoir.Moreover, comparatively
Construction has certain difficulty, and operability is poor, limits its application, is only applicable to block the reservoir layer position of Thief zone macropore.It is right
In lignin/tannin extract class gel plugging agent, because tannin extract, lignin molecule are rigid molecule, its frozen glue formed has stronger
Temperature tolerance, but the crosslinking agent that uses at present of lignin/tannin extract class frozen glue is the aldehyde crosslinking agent of high concentration (generally higher than 1%)
And Phenolic crosslinkers, because two kinds of crosslinking agents are respectively provided with stronger toxicity, therefore the application of such frozen glue is unfavorable for holding for oil field
Supervention exhibition.Therefore a kind of water outlet of salt-tolerance frozen glue of low cross-linking agent consumption for solution harsh conditions oil reservoir is developed
Problem has great importance.
The content of the invention：
In view of the shortcomings of the prior art, the invention aims to provide a kind of heat-resistant salt-resistant jelly of low cross-linking agent consumption
Glue, for blocking water breakthrough.
The purpose of the present invention is realized by following technical scheme：
A kind of salt-tolerance frozen glue of low cross-linking agent consumption, its mass percent composition is as follows：Acrylamide with
Copolymer 0.6%~1.2%, resorcinol 0.02%~0.04%, the polyethyleneimine of 2- acrylamide-2-methylpro panesulfonic acids
Amine 0.02%~0.05%, metaformaldehyde 0.02%~0.04%, alkoxy silane 0.03%~0.1%, thiocarbamide 0.2%~
0.4%th, surplus is water, and each component sum is 100%.
The relative molecular mass of the acrylamide and 2- acrylamide-2-methylpro panesulfonic acid copolymers is 500 × 104
~800 × 104, 2- acrylamide-2-methylpro panesulfonic acids content of monomer is 15%~30%.
The salinity of the water is 22.4 × 104Mg/L, calcium ions and magnesium ions content is 1.3 × 104mg/L。
The preparation method of above-mentioned frozen glue is as follows：
1st, Acrylamide/2-acrylamido-2-methyl-propanesulfonic Acid Copolymer is fully dissolved in simulated formation water, it is standby
With；By proportioning by amine cross-linking agent, Phenolic crosslinkers, aldehyde crosslinking agent, alkoxy silane, polymer stabilizer and surplus mould
Intend stratum water to be mixed evenly；Above two solution is mixed evenly and obtains plastic liquid.
2nd, it will be placed in into glue in ampoule bottle, and be sintered and sealed with alcohol blast burner, and be placed in the baking oven of certain temperature aging i.e.
Obtain the frozen glue.
The frozen glue gelation time of the present invention is adjustable for 5~24h.
The beneficial effects of the invention are as follows：
1st, the crosslinking agent that heat-resistant salt-resistant gel plugging agent is typically used is has virose phenols and aldehydes organic crosslinking agent, so
And, existing heat-resistant salt-resistant gel plugging agent crosslinking agent usage amount higher (＞ 1%, such as CN 102807849B, CN 103232839A
It is described).Crosslinking agent polyethyleneimine used in the present invention is polymeric crosslinker, with crosslinking points are more, crosslinking active high
The characteristics of, low concentration has excellent cross-linking properties；In addition, the crosslinking agent used in the present invention is crosslinked for amine
Agent, Phenolic crosslinkers, aldehyde crosslinking agent multiple crosslinking agent system, cross-linker molecules amount high level matches with low level are more beneficial for frozen glue netted
The formation of structure, therefore frozen glue dosage of crosslinking agent provided by the present invention is extremely low (≤0.1%), this not only lowers making for frozen glue
With cost, moreover it is possible to mitigate to the pollution of construction environment and reduce in injection process with crosslinking agent in follow-up sewage disposal process
The injury that volatilization is caused to human body.
2nd, frozen glue excellent in stability provided by the present invention, aging 100 days, can be without broken glue phenomenon under the conditions of 130 DEG C
Temperature is 130 DEG C, salinity is 22.4 × 104The stifled effect of tune is played in mg/L reservoir media.
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：
Added in 50g Tahe simulated formation water 0.02g metaformaldehydes, 0.02g polyethyleneimines, 0.02g resorcinols,
0.05g alkoxy silanes, 0.3g thiocarbamides, stir, it is fully dissolved, then by 50g mass concentrations be 1.2% acryloyl
Amine/2- acrylamide-2-methylpro panesulfonic acids copolymer is mixed with above-mentioned solution, is stirred, that is, obtains the plastic of the present invention
Liquid.Into glue, the gelation time at 130 DEG C is 9h for this, and the gel strength of acquisition is that aging does not have for 100 days at 0.072MPa, 130 DEG C
There is broken glue phenomenon.
Embodiment 2：
Added in 50g Tahe simulated formation water 0.03g metaformaldehydes, 0.02g polyethyleneimines, 0.02g resorcinols,
0.05g alkoxy silanes, 0.3g thiocarbamides, stir, it is fully dissolved, then by 50g mass concentrations be 1.4% acryloyl
Amine/2- acrylamide-2-methylpro panesulfonic acids copolymer is mixed with above-mentioned solution, is stirred, that is, obtains the plastic of the present invention
Liquid.Into glue, the gelation time at 130 DEG C is 11h for this, and the gel strength of acquisition is that aging does not have for 100 days at 0.074MPa, 130 DEG C
There is broken glue phenomenon.
Embodiment 3：
Added in 50g Tahe simulated formation water 0.03g metaformaldehydes, 0.03g polyethyleneimines, 0.02g resorcinols,
0.05g alkoxy silanes, 0.3g thiocarbamides, stir, it is fully dissolved, then by 50g mass concentrations be 1.6% acryloyl
Amine/2- acrylamide-2-methylpro panesulfonic acids copolymer is mixed with above-mentioned solution, is stirred, that is, obtains the plastic of the present invention
Liquid.Into glue, the gelation time at 130 DEG C is 14h for this, and the gel strength of acquisition is that aging does not have for 100 days at 0.077MPa, 130 DEG C
There is broken glue phenomenon.
Embodiment 4：
Added in 50g Tahe simulated formation water 0.03g metaformaldehydes, 0.03g polyethyleneimines, 0.03g resorcinols,
0.08g alkoxy silanes, 0.3g thiocarbamides, stir, it is fully dissolved, then by 50g mass concentrations be 2% acryloyl
Amine/2- acrylamide-2-methylpro panesulfonic acids copolymer is mixed with above-mentioned solution, is stirred, that is, obtains the plastic of the present invention
Liquid.Into glue, the gelation time at 130 DEG C is 18h for this, and the gel strength of acquisition is that aging does not have for 100 days at 0.079MPa, 130 DEG C
There is broken glue phenomenon.
Embodiment 5：
Added in 50g Tahe simulated formation water 0.04g metaformaldehydes, 0.02g polyethyleneimines, 0.04g resorcinols,
0.1g alkoxy silanes, 0.3g thiocarbamides, stir, it is fully dissolved, then by 50g mass concentrations be 2.4% acryloyl
Amine/2- acrylamide-2-methylpro panesulfonic acids copolymer is mixed with above-mentioned solution, is stirred, that is, obtains the plastic of the present invention
Liquid.Into glue, the gelation time at 130 DEG C is 23h for this, and the gel strength of acquisition is that aging does not have for 100 days at 0.085MPa, 130 DEG C
There is broken glue phenomenon.
Embodiment 6：
So that " frozen glue obtained in embodiment 5 " investigates the shut-off capacity of frozen glue provided by the present invention as research object.Tool
Body experimentation is as follows：The obtained simulation core of two fill out sand tube filling quartz sand grain that by internal diameter be 2.5cm, length is 20cm,
Original permeability k is obtained after being denoted as 1# and 2#, water drive to pressure stability1, then will " in embodiment 5 " into glue inverse injection
In fill out sand tube, injected slurry volume is 0.3PV (rock pore volume), is then injected into 0.3PV water and is replaced, afterwards puts fill out sand tube
Aging 10 days and 100 days is distinguished in 130 DEG C of baking ovens, finally water drive to pressure stability, is oozed after measuring the blocking up of simulation core respectively
Saturating rate k2, and by formula E=(k1-k2)/k1* 100%, reservoir core plugging rate E is calculated, the experimental results are shown inthe following table.
Above test result indicates that：The frozen glue that the present invention is provided has excellent sealing characteristics under the high temperature conditions, can have
The high permeability formation occurred during effect closure water drive crude oil, is conducive to the raising of oil recovery factor.
The solvent that frozen glue provided by the present invention is used when preparing is 22.4 × 104Mg/L simulated formation water, it is therefore, right
It for system in Tahe Oilfield, can be prepared with the system in Tahe Oilfield Produced Liquid after purified treatment, help to solve lacking for system in Tahe Oilfield
Water problems.
Claims (3)
1. a kind of heat-resistant salt-resistant frozen glue of low cross-linking agent consumption, it is characterised in that mass percent composition is as follows：Acrylamide/2-
Acrylamide-2-methylpro panesulfonic acid copolymer 0.6%~1.2%, resorcinol 0.02%~0.04%, polyethyleneimine
0.02%~0.05%, metaformaldehyde 0.02%~0.04%, alkoxy silane 0.03%~0.1%, thiocarbamide 0.2%~
0.4%th, surplus is water, and each component sum is 100%.
2. the heat-resistant salt-resistant frozen glue of low cross-linking agent consumption according to claim 1, it is characterised in that the acrylamide/2-
The relative molecular mass of acrylamide-2-methylpro panesulfonic acid copolymer is 500 × 104~800 × 104, 2- acrylamidos-
2- methyl propane sulfonic acids content of monomer is 15%~30%.
3. the heat-resistant salt-resistant frozen glue of low cross-linking agent consumption according to claim 1, it is characterised in that the salinity of the water
For 22.4 × 104Mg/L, calcium ions and magnesium ions content is 1.3 × 104mg/L。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510025766.XA CN104629699B (en) | 2015-01-19 | 2015-01-19 | A kind of heat-resistant salt-resistant frozen glue of low cross-linking agent consumption |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510025766.XA CN104629699B (en) | 2015-01-19 | 2015-01-19 | A kind of heat-resistant salt-resistant frozen glue of low cross-linking agent consumption |
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| Publication Number | Publication Date |
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| CN104629699A CN104629699A (en) | 2015-05-20 |
| CN104629699B true CN104629699B (en) | 2017-11-03 |
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| CN201510025766.XA Expired - Fee Related CN104629699B (en) | 2015-01-19 | 2015-01-19 | A kind of heat-resistant salt-resistant frozen glue of low cross-linking agent consumption |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106634906A (en) * | 2016-09-18 | 2017-05-10 | 中国石油大学(华东) | Gel with high temperature resistance |
| CN106800921B (en) * | 2016-12-02 | 2019-06-07 | 长江大学 | The stifled frozen glue of wide temperature high salinity tune |
| CN106590560A (en) * | 2016-12-05 | 2017-04-26 | 中国石油大学(华东) | Gel temporary plugging agent |
| CN106905940A (en) * | 2017-03-31 | 2017-06-30 | 西南石油大学 | A kind of middle-high density elastic liquid plug and method for well fixing |
| CN111019619A (en) * | 2019-11-26 | 2020-04-17 | 中国石油集团川庆钻探工程有限公司长庆井下技术作业公司 | Liquid rubber plug temporary plugging slug for shaft isolation and preparation method |
| CN113528104B (en) * | 2020-04-21 | 2022-12-16 | 中国石油化工股份有限公司 | Jelly liquid and application thereof as suspension partition board water shutoff agent |
| CN111808585B (en) * | 2020-07-15 | 2022-12-27 | 中国石油大学(华东) | Slow-crosslinking temperature-resistant salt type high-strength gel and preparation method and application thereof |
| CN115703959B (en) * | 2021-08-04 | 2024-01-30 | 中国石油化工股份有限公司 | Method for preparing composite gel |
Citations (3)
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|---|---|---|---|---|
| CN102382241A (en) * | 2010-08-30 | 2012-03-21 | 中国石油化工股份有限公司 | Long-branched chain polyacrylamide copolymer and preparation method thereof |
| CN102850488A (en) * | 2012-09-25 | 2013-01-02 | 西南石油大学 | Low-density double expansion gel particle |
| CN103614123A (en) * | 2013-10-21 | 2014-03-05 | 中国石油大学(华东) | Polyethyleneimine jelly profile-control water-blocking agent |
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2015
- 2015-01-19 CN CN201510025766.XA patent/CN104629699B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102382241A (en) * | 2010-08-30 | 2012-03-21 | 中国石油化工股份有限公司 | Long-branched chain polyacrylamide copolymer and preparation method thereof |
| CN102850488A (en) * | 2012-09-25 | 2013-01-02 | 西南石油大学 | Low-density double expansion gel particle |
| CN103614123A (en) * | 2013-10-21 | 2014-03-05 | 中国石油大学(华东) | Polyethyleneimine jelly profile-control water-blocking agent |
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Granted publication date: 20171103 Termination date: 20180119 |