CN109666467A - Controllable time delay expands sealing agent and preparation method thereof - Google Patents
Controllable time delay expands sealing agent and preparation method thereof Download PDFInfo
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- CN109666467A CN109666467A CN201710954505.5A CN201710954505A CN109666467A CN 109666467 A CN109666467 A CN 109666467A CN 201710954505 A CN201710954505 A CN 201710954505A CN 109666467 A CN109666467 A CN 109666467A
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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
- C09K8/426—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells for plugging
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- 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
- C09K8/46—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement
- C09K8/467—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement containing additives for specific purposes
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Sealing Material Composition (AREA)
Abstract
The present invention relates to a kind of leak stopping auxiliary agents for oil drilling field, can especially regulate and control the Bulking Time of plugging material, inhibit its water swelling speed, improve the success rate of expansion plugging material construction.It include: 5 parts to 10 parts of water uptake expansion resin, 15 parts to 80 parts of Alcoholic modifier, 0.05 part to 0.4 part of solid acid catalyst.The invention has the advantages that 150 DEG C of (1) heatproof, significantly improves the heatproof and salt resistant character of sealing agent；(2) it when room temperature, hardly expands in water, with the raising of water temperature, water swelling speed becomes faster, and has obvious delay expansion characteristics, and expansion is slow in the wellbore, it can continue to expand after reaching lost-circulation zone, so as to effectively improve leakage stratum, achieve the effect that reparation.
Description
Technical field
The present invention relates to one kind for a kind of leak stopping auxiliary agent used in oil drilling field, can especially regulate and control leak stopping
The Bulking Time of material inhibits the purpose of its water swelling speed, improves the success rate of expansion plugging material construction, expands water suction
Expand application of the sealing agent in terms of the leak stopping of oil field.
Background technique
Leakage is existing challenge during drilling well, well cementation, well logging, well workover, it leaks into drilling fluid from wellbore
Channel is lost, a large amount of mud and plugging material is not only expended, but also may cause well slough, bit freezing, blowout, even results in wellbore report
The major accidents such as useless, cause huge economic loss.Since leakage incidence is higher, according to statistics, whole world leakage incidence is accounted for
The 20% ~ 25% of drilling well sum, and the processing of leakage is the difficult point in oil drilling, especially complicated circulation problems are particularly troublesome,
Severe well leakage loss accounts for 50% or more of leakage total losses, and leak stopping is difficult success, therefore the prevention and treatment for needing to reinforce severe well leakage is ground
Study carefully.Slot Handling is improper, may cause pernicious down-hole accident, causes serious environmental pollution.It is bored during drilling well leakproof
The plugging material of well is a kind of essential material, and the success rate of drilling well leak-proof leak-stopping directly depends on plugging material performance
Superiority and inferiority.
For a long time, engineers and technicians are directed to the leakage of different situations, carry out in practice to various plugging materials
It is preferred that the research of country's sealing agent and leakage stopping technology has been made significant headway at present, solve many practical problems, but still
There are some shortcomings, the common defects of these materials are: first is that the deformability of its own in Process of Leaking Stoppage is poor, slightly larger than leakage
Layer or is just not easily accessible hole crack with the unmatched particle of drop ply hole fracture shape, is formed and is accumulated on drop ply surface, and
Do not go deep into drop ply；Second is that most of plugging material does not have dilatancy or only small swell increment, in the work of applied external force
It is not easy steadily to be trapped in drop ply under.When using these material processing leakages due to the above reasons, often easily cause stifled
Repeatability leakage occurs after leaking ineffective and leak stopping.Although expandable plugging additives has in terms of solving above-mentioned two problems
Certain advantage, but conventional expansion its speed of expansion of plugging material is generally difficult to control, it is usually logical to leakage is entered by ground
The process in road needs several hours, but excellent water uptake expansion material can absorb water at a high speed within the time period, and volume is substantially swollen
It is swollen, affect actual plugging effect.
How to control water-absorbing resin not expand in pumping procedure, reaches leakage stratum and water swelling is occurring later
A problem, in order to make water-absorbing resin plugging material preferably play expansion blockage effect, surround its time lagged swelling, mainly by
The methods of pack, non-aqueous carrying liquid and grafted hydrophobic monomer.Pack main problem is: (1) coating material selects model
It is with limit；(2) water absorbing resin particle is small, and package difficulty is big, and package is uneven；(3) packing technology is complicated, it is difficult to realize industry
Change.Non-aqueous carrying of liquids main problem is: the ionic strength of external solution electrolyte is big, influences the water absorbing capacity of water-absorbing resin
Power.And grafted hydrophobic monomer advantage is: hydrophobic monomer is entered inside water-absorbing resin by grafting, enters suction to hydrone
There is inhibiting effect inside water-resin, the water swelling of water-absorbing resin can be slowed down.Consider from production technology and site operation angle,
Reaching water-absorbing resin delay water swelling by grafted hydrophobic monomer is most simple most efficient method.
Summary of the invention
The technical problem to be solved by the present invention is to conventional expanding material in the wellbore rapid expanding and enter loss horizon
Expansion character reduces afterwards, develops the sealing agent with certain time-delay expansion character, makes plugging material maximum limit in leakage channel
Playing a role for degree, improves the practical application effect of plugging material.
Main technical schemes of the present invention: controllable time delay expands sealing agent, it is characterised in that composition is as follows: each component is by weight
Number includes: 5 parts to 10 parts of water uptake expansion resin, 15 parts to 80 parts of Alcoholic modifier, 0.05 part to 0.4 of solid acid catalyst
Part.
Generally, the water uptake expansion resin includes following components, each component according to parts by weight: 60 parts of distilled water is extremely
90 parts, 5 parts to 28 parts of acrylic acid, 1 part to 10 parts of 2- acrylamide-2-methylpro panesulfonic acid, 0.01 part to 0.5 part of crosslinking agent,
0.01 part to 0.3 part of initiator, 2 parts to 5 parts of reinforcing agent.
The crosslinking agent is N,N methylene bis acrylamide.
The initiator is ammonium persulfate, anhydrous sodium sulfite, potassium peroxydisulfate, any two kinds in sodium peroxydisulfate, mixing
Proportion is 1:1.
The reinforcing agent is sodium bentonite or kaolin, and mesh number is 100-400 mesh.
Stirring the preparation method is as follows: first fetching water to be put into reactor for water uptake expansion resin of the present invention, sequentially adds
Reinforcing agent, acrylic acid, 2- acrylamide-2-methylpro panesulfonic acid, N,N methylene bis acrylamide and crosslinking agent are put into reaction
In device, lead to N2It protects, stirs in ice-water bath to being completely dissolved, when temperature is down to 0-10 DEG C, initiator solution is slowly added dropwise, drip
After complete, continuing to stir 10-30min, stop stirring, be to slowly warm up to 30-70 DEG C, static reaction 2-5h obtains resilient gel,
It takes out, 60-90 DEG C of vacuum drying, shearing, obtains the water uptake expansion resin.
The Alcoholic modifier is n-butanol, amylalcohol, octanol, any one in lauryl alcohol.
The preparation method of controllable time delay expansion sealing agent of the present invention is put into it is characterized in that: weighing water uptake expansion resin
In Alcoholic modifier, solid acid catalyst is added, 2-8h is reacted at 60-150 DEG C, it is stifled to obtain controllable time delay expansion for filtering, drying
Leak agent.
Generally, the reaction temperature is 120-150 DEG C.
The reaction time is 3-5 h.
The present invention compared with prior art, has the advantages that (1) time lagged swelling sealing agent provided by the invention,
150 DEG C of heatproof, significantly improve the heatproof and salt resistant character of sealing agent；(2) it when room temperature, hardly expands in water, with dampening
The raising of temperature, water swelling speed become faster, and have obvious delay expansion characteristics, and expansion slowly, reaches lost-circulation zone in the wellbore
After can continue to expand, so as to effectively improve leakage stratum, achieve the effect that reparation.
Specific embodiment
The present invention is further illustrated below by specific preparation embodiment.
Embodiment 1
First weigh 6g sodium bentonite, 20g acrylic acid, 10g2- acrylamide-2-methylpro panesulfonic acid, 0.03gN, N- methylene
Bisacrylamide and 0.015g initiator ammonium persulfate are put into reactor, and 150g distilled water is added, stirs in ice-water bath to complete
Fully dissolved leads to N2Protection；When temperature is down to 5 DEG C or so, 10g initiator sodium sulfite solution (sodium sulfite is slowly added dropwise
0.015g)；After dripping off, continues to stir 20min, stop stirring, be to slowly warm up to 45 DEG C, static reaction 3h obtains elastic gel
Body；It is drawn off, 70 DEG C of vacuum drying, shears to obtain water uptake expansion resin；It weighs the 5g resin to be put into reactor, sequentially add
20g n-butanol, 0.025g solid acid catalyst, react 4h at 120 DEG C, and filtering, drying obtain controllable time delay expansion sealing agent
No. 1 product.
Embodiment 2
First weigh 5g sodium bentonite, 25g acrylic acid, 10g2- acrylamide-2-methylpro panesulfonic acid, 0.04gN, N- methylene
Bisacrylamide and 0.015g initiator ammonium persulfate are put into reactor, and 200g distilled water is added, stirs in ice-water bath to complete
Fully dissolved leads to N2Protection；When temperature is down to 5 DEG C or so, 10g initiator sodium sulfite solution (sodium sulfite is slowly added dropwise
0.015g)；After dripping off, continues to stir 20min, stop stirring, be to slowly warm up to 50 DEG C, static reaction 2h obtains elastic gel
Body；It is drawn off, 70 DEG C of vacuum drying, shears to obtain water uptake expansion resin；It weighs the 5g resin to be put into reactor, sequentially add
20g n-octyl alcohol, 0.025g solid acid catalyst, react 3h at 150 DEG C, and filtering, drying obtain controllable time delay expansion sealing agent
No. 2 products.
Embodiment 3
First weigh 5g sodium bentonite, 30g acrylic acid, 18g2- acrylamide-2-methylpro panesulfonic acid, 0.05gN, N- methylene
Bisacrylamide and 0.02g initiator ammonium persulfate are put into reactor, and 200g distilled water is added, stirs in ice-water bath to complete
N is led in dissolution2Protection；When temperature is down to 5 DEG C or so, 10g initiator sodium sulfite solution (sodium sulfite is slowly added dropwise
0.02g)；After dripping off, continues to stir 20min, stop stirring, be to slowly warm up to 50 DEG C, static reaction 3h obtains elastic gel
Body；It is drawn off, 70 DEG C of vacuum drying, shears to obtain water uptake expansion resin；It weighs the 5g resin to be put into reactor, sequentially add
15g lauryl alcohol, 0.02g solid acid catalyst, react 4h at 150 DEG C, and filtering, drying obtain controllable time delay expansion sealing agent 3
Number product.
Above three product is subjected to water-swelling property detection, detection and analysis the results are shown in Table 1,1 product water swelling of table
Performance detection analyzes result
As shown in Table 1, compared with routinely expanding sealing agent, sealing agent of the present invention hardly expands at water suction initial stage, can smoothly infuse
Enter stratum, with the raising of formation temperature, water swelling speed is speeded, can be swollen rapidly in the short time when reaching loss horizon
It is swollen, enhance the actual plugging effect of sealing agent.
Claims (10)
1. a kind of controllable time delay expands sealing agent, it is characterised in that composition is as follows: each component includes: water swelling in parts by weight
5 parts to 10 parts of resin, 15 parts to 80 parts of Alcoholic modifier, 0.05 part to 0.4 part of solid acid catalyst.
2. controllable time delay according to claim 1 expands sealing agent, it is characterised in that the water uptake expansion resin include with
Lower component, each component according to parts by weight: 60 parts to 90 parts of distilled water, 5 parts to 28 parts of acrylic acid, 2- acrylamido -2- first
1 part to 10 parts of base propane sulfonic acid, 0.01 part to 0.5 part of crosslinking agent, 0.01 part to 0.3 part of initiator, 2 parts to 5 parts of reinforcing agent.
3. controllable time delay according to claim 2 expands sealing agent, it is characterised in that the crosslinking agent is N, N- methylene
Bisacrylamide.
4. controllable time delay according to claim 2 expands sealing agent, it is characterised in that the initiator is ammonium persulfate, nothing
Water sodium sulfite, potassium peroxydisulfate, any two kinds in sodium peroxydisulfate, mixing match 1:1.
5. controllable time delay according to claim 2 expands sealing agent, it is characterised in that the reinforcing agent is sodium bentonite
Or kaolin, mesh number are 100-400 mesh.
6. -5 any controllable time delays expand sealing agent according to claim 1, it is characterised in that the water uptake expansion resin
The preparation method is as follows: first water intaking is put into reactor and stirs, sequentially add reinforcing agent, acrylic acid, 2- acrylamido -2- first
Base propane sulfonic acid, N, N- methylene-bisacrylamide and crosslinking agent are put into reactor, lead to N2It protects, stirs in ice-water bath to complete
Dissolution, when temperature is down to 0-10 DEG C, is slowly added dropwise initiator solution, after dripping off, continues to stir 10-30min, stops stirring,
It is to slowly warm up to 30-70 DEG C, static reaction 2-5h, obtains resilient gel, takes out, 60-90 DEG C of vacuum drying, shearing, obtains
The water uptake expansion resin.
7. controllable time delay according to claim 1 expands sealing agent, it is characterised in that Alcoholic modifier is n-butanol, penta
Alcohol, octanol, any one in lauryl alcohol.
8. the preparation method of controllable time delay expansion sealing agent according to claim 1, it is characterized in that: weighing water swelling tree
Rouge is put into Alcoholic modifier, and solid acid catalyst is added, and 2-8h is reacted at 60-150 DEG C, and filtering, drying obtain and controllably prolong
When expand sealing agent.
9. the preparation method of controllable time delay expansion sealing agent according to claim 8, it is characterised in that reaction temperature 120-
150℃。
10. the preparation method of controllable time delay expansion sealing agent according to claim 8, it is characterised in that reaction time 3-5
h。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710954505.5A CN109666467A (en) | 2017-10-13 | 2017-10-13 | Controllable time delay expands sealing agent and preparation method thereof |
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| CN201710954505.5A CN109666467A (en) | 2017-10-13 | 2017-10-13 | Controllable time delay expands sealing agent and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112143467A (en) * | 2019-06-26 | 2020-12-29 | 中石化南京化工研究院有限公司 | Time-delay expansion plugging agent and preparation method thereof |
| CN114292633A (en) * | 2022-01-07 | 2022-04-08 | 承德石油高等专科学校 | Delayed crosslinking gel plugging agent for well drilling and preparation method thereof |
| CN114524899A (en) * | 2022-02-28 | 2022-05-24 | 中国地质大学（北京） | Acrylate base fluid, preparation method thereof, plugging agent and application thereof |
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| CN114524899A (en) * | 2022-02-28 | 2022-05-24 | 中国地质大学（北京） | Acrylate base fluid, preparation method thereof, plugging agent and application thereof |
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