CN110079286A - Delayed crosslinking gel composition for plugging and preparation method thereof - Google Patents
Delayed crosslinking gel composition for plugging and preparation method thereof Download PDFInfo
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- CN110079286A CN110079286A CN201910457305.8A CN201910457305A CN110079286A CN 110079286 A CN110079286 A CN 110079286A CN 201910457305 A CN201910457305 A CN 201910457305A CN 110079286 A CN110079286 A CN 110079286A
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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
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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
- C09K8/46—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)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
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- Inorganic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Soil Conditioners And Soil-Stabilizing Materials (AREA)
- Sealing Material Composition (AREA)
Abstract
The invention discloses a delayed crosslinking gel composition for plugging and a preparation method thereof, wherein the composition comprises the following components in parts by weight: 100 parts of water, 0.5-1 part of a gelling agent, 0.3-0.6 part of a cross-linking agent, 0.05-2 parts of a retardant, 10-20 parts of a reinforcing agent, 10-20 parts of a toughening agent and 0-10 parts of a high-temperature protective agent. The delayed crosslinking gel composition provided by the invention is not limited by a leakage channel when leaking stoppage, and the gelling agent and the crosslinking agent are subjected to crosslinking reaction in a mixed and flowing state and are retained in a leakage layer to form a viscoelastic body with a three-dimensional network structure, so that the aim of self-adaption or broad-spectrum leakage stoppage is fulfilled; the additive has good anti-dilution performance and is difficult to be mixed with formation water to be diluted; the leakage passage can be effectively blocked, and the bearing strength is higher. The method is widely applied to geological drilling and oil drilling plugging operation, and can solve the problems of fracture type leakage, malignant leakage and aquifer leakage at different depths.
Description
Technical field
The present invention relates to the leakage stopping technology field during geological drilling, oil gas drilling and Science Drilling, in particular to one
Kind leak stopping delay cross-linked gel and preparation method thereof.
Background technique
Formation leakage is the common issue frequently encountered in the probing such as metallic ore, oil gas, underground heat.Formation leakage not only causes
A large amount of wastes of mud are significantly increased drilling cost, can also bring the drilling accident of a series of complex, influence drilling efficiency.It is right
In severe mud losses such as large fracture, Caves, conventional pons hematoma is difficult to form the occluding body of sufficient intensity around pit shaft, blocks up
It is lower to leak one-time success rate, and the method can not be implemented under the conditions of slim-hole, small annular space.And cement slurry leak stopping is usually because logical
Road is lost greatly and can not play a role or be diluted and can not be solidified by underground water, and leak stopping is caused to fail.Crosslinking polymer is solidifying
As one of chemical plugging technology common in petroleum drilling engineering, when leak stopping, is not limited by leakage channel for glue leak stopping, is polymerize
Object and crosslinking agent mix and flow regime under cross-linking reaction occurs, and be detained to be formed in drop ply there is three-dimensional net structure
Viscoelastic body is to realize the purpose of leak stopping.Thus, crosslinking polymer gel leak stopping can be further improved leak stopping adaptability and
Plugging effect has broad application prospects in terms of solving severe mud losses and drop ply containing underground water.
In crosslinking polymer gel of the existing technology, gelatinizing agent used is mainly polyacrylamide, polyethylene
Alcohol, guar derivative, sesbania gum and xanthan gum etc..Existing crosslinking polymer gel is used as plugging material and asks there is also following
Topic: (1) polyacrylamide cross-linked gel be Weak Gels system, be used for water plugging and profile controlling when crosslinking time it is too long, unsuitable use
In leak stopping;(2) cold water-soluble polyvinyl alcohol is selected to prepare gel, polyvinyl alcohol easily blisters when stirring, and foam is not easy to disappear
It removes.In addition, polyvinyl alcohol crosslinked gel bearing capacity is insufficient, separately as sealing agent, its plugging effect is less obvious;(3) existing
Natural plant gum cross-linked gel is primarily used to fracturing fluid, and crosslinking time is generally shorter (being less than 10min), can go out when being used for leak stopping
Existing pumping procedure plastic system is crosslinked in drilling rod, is led to pumping difficulties, also it can not be made to enter drop ply in the best condition, is sealed
Leak stopping layer is ineffective.Such as:
105778874 A of Chinese patent CN discloses a kind of drilling well underground cross-linked gel sealing agent and its blocking method, institute
State sealing agent include high molecular polymer 10%~30%, crosslinking agent 10%~30%, coagulant or retarder 0%~20%,
Macromolecular fibre 10%~30%, toughener 2%~10% and dispersing agent 10%~30%.Crosslinker component adds in the sealing agent
Amount is big, and the solidified forming time of sealing agent is 1~8h at 100 DEG C~150 DEG C.
105441046 B of Chinese patent CN disclose it is a kind of suitable for crack and the hydrogen bond hydrogel of solution cavity leak stopping, it is described
The raw material of hydrogen bond hydrogel is counted by ratio of weight and the number of copies is urged by 5~10 parts of polyvinyl alcohol, 10~30 parts of polyalcohol, 1~5 part
Agent, 15~25 parts of salt, 0~100 part of heavy weight additive and 100 parts of water.The presetting period of the hydrogen bond hydrogel 120~
240min etc., but its gel strength is general (maximum reaches 32.59N), is not able to satisfy deep hole leak stopping demand.
101896573 A of Chinese patent CN discloses a kind of fracturing fluid for being suitable for using under high temperature (135~171 DEG C)
Or cross-linked composition, the fracturing fluid or cross-linked composition by liquid, aqueous, salt water, thermostabilization, non-delayed property ealkaline buffer,
Organic acid, hydroxypropyl guar gum and zirconium crosslink agent composition, cross-linked composition crosslinking time under 135~171 DEG C of high temperature are less than
10min。
Therefore, need to develop it is a kind of suitable for different drilling depths, crosslinking time is controllable and the delay of higher bearing capacity
Cross-linked gel.
Summary of the invention
In order to solve drilling fluid caused by brill chance slit formation leakage stratum, severe mud losses stratum and water-bearing layer in drilling process
Leakage, drilling fluid is diluted and borehole well instability problem, the present invention provides a kind of leak stopping with delay cross-linked gel composition and its
Preparation method.Its crosslinking time of delay cross-linked gel composition of the invention is controllable, and bearing capacity is higher, and heatproof is up to 150
DEG C, the plugging operations being widely used in during geological drilling, oil gas drilling and Science Drilling.
A kind of leak stopping delay cross-linked gel composition, is grouped as by the group of following parts by weight:
100 parts of water, 0.5~1 part of gelatinizing agent, 0.3~0.6 part of crosslinking agent, 0.05~2 part of delayer, reinforcing agent 10~20
Part, 10~20 parts of toughener, 0~10 part of high temperature protection agent.
The gelatinizing agent is the mixture that hydroxypropyl guar gum is mixed with hydrophobic associated polymer according to arbitrary proportion, plastic
Agent functions as the host agent of delay cross-linked gel, for improving the viscosity of aqueous solution.
The crosslinking agent is four n-propyl zirconates, and crosslinking action is to crosslink to react with gelatinizing agent macromolecular chain,
Form the gel with three-dimensional net structure.
The delayer is one of sodium citrate, disodium ethylene diamine tetraacetate and glycolic, and delayer effect is to prolong
The crosslinking time of long crosslinking agent and gelatinizing agent.
The reinforcing agent is one of lithium magnesium silicate and aluminium-magnesium silicate, and reinforcing agent effect is to enhance the intensity of gel.
The toughener is one of sepiolite fibre, basalt fibre, polypropylene fibre and polyester fiber, toughener
Effect is to further increase the intensity and bearing capacity of gel by increasing the toughness of gel.
The high temperature protection agent is one of sodium thiosulfate and potassium sulfite, and high temperature protection agent effect is to improve gel
High-temperature stability and temperature resistant capability.
The present invention also provides a kind of leak stopping preparation methods of delay cross-linked gel composition, the steps include: (1) by water
It is mixed with reinforcing agent, obtains enhancing agent dispersing liquid;(2) by enhancing agent dispersing liquid that the step (1) obtains and toughener, delay
Agent and high temperature protection agent mixing, obtain mixed serum;(3) mixed serum that the step (2) obtains is mixed with gelatinizing agent, is obtained
To base fluid;(4) base fluid that the step (3) obtains is mixed with crosslinking agent, obtains cross-linked gel.
The delay cross-linked gel composition of leak stopping made from the method for the invention, temperature resistance up to 150 DEG C, crosslinking time 30~
120min is adjustable, pumpable 15~90min of time, gel bearing strength >=7MPa.
The beneficial effect of the present invention compared with prior art is:
(1) delay cross-linked gel composition temperature applicable range of the invention is wide, and it is pernicious to can be not only used for deep hole high temperature well section
The plugging operations such as leakage stratum can also be used for shallow bore hole low temperature leakage plugging operations.
(2) hydroxyl crosslinking rate on zirconium ion and hydroxypropyl guar gum, hydrophobic polymer chain is regulated and controled by addition delayer,
The technical problem for breaking through the crosslinking time universal too short (being no more than 10min) of existing hydroxypropyl guar gum cross-linked gel, is realized big
Width extends the crosslinking time of hydroxypropyl guar glue gel at room temperature.Delay cross-linked gel composition crosslinking time of the invention can
It controls, gelation time can be controlled in 30~120min at 25 DEG C.
(3) postpone cross-linked gel composition in gelatinizing agent and crosslinking agent dosage it is small, but crosslinking after gel gel strength compared with
Height, bearing capacity is also relatively strong, can meet 5000m with the severe mud losses leak stopping requirement that shallowly drills.
(4) gel rubber system is biodegradable, will not remain underground and cause environmental pollution.
Specific embodiment
The present invention is further explained in the light of specific embodiments, so that those skilled in the art can be preferably
Understand the present invention and can be practiced, but illustrated embodiment is not as a limitation of the invention.
Material used in embodiment commercially obtains.Hydroxypropyl guar gum is bought in Kunshan Beijing-Kunming oil field
Subject skill development company, hydrophobic associated polymer GRF-1H are bought in Sichuan Guangya Polymer Chemical Co., Ltd., four n-propyls
Zirconate purchase is bought in Huangshan Ke Beirui Chemical Co., Ltd., sodium citrate in the outstanding Chemical Co., Ltd. in Suzhou, ethyl alcohol
Acid purchase in the rich Chemical Co., Ltd. of Quzhou City's riel, lithium magnesium silicate purchase in hundred benefit of Nanjing can new material Science and Technology Ltd.,
Aluminium-magnesium silicate purchase adds in this new material Science and Technology Ltd. of Nanjing hamming, sepiolite fibre purchase in Lingshou County perseverance stone ore product
Factory, basalt fibre purchase are bought in Changzhou Zhu Wei construction material Co., Ltd, polyacrylonitrile fibre in the strong engineering in Tai'an road
Materials Co., Ltd, sodium thiosulfate purchase moisten chemical products production Co., Ltd in Zhengding County hundred, and potassium sulfite is bought in black
Bo Diminde Chemical Co., Ltd..
Embodiment 1
30g lithium magnesium silicate is added in 200g water and is mixed to get lithium magnesium silicate dispersion liquid, 40g basalt fibre is then added
And 0.16g sodium citrate is mixed to get mixed serum, and 1.2g hydroxypropyl guar gum is then added and is mixed to get base fluid, is eventually adding
Tetra- n-propyl zirconate of 0.6g is mixed to get delay cross-linked gel.
Embodiment 2
40g aluminium-magnesium silicate is added in 200g water and is mixed to get lithium magnesium silicate dispersion liquid, it is fine that 20g sepiolite is then added
Dimension, 2g glycolic and 1g potassium sulfite are mixed to get mixed serum, and 1.1g hydroxypropyl guar gum is then added and 0.9g is hydrophobic forms
It closes mixed with polymers and obtains base fluid, be eventually adding tetra- n-propyl zirconate of 0.8g and be mixed to get delay cross-linked gel.
Embodiment 3
20g aluminium-magnesium silicate is added in 200g water and is mixed to get lithium magnesium silicate dispersion liquid, it is fine that 40g polypropylene is then added
Dimension, 4g glycolic and 2g sodium thiosulfate are mixed to get mixed serum, and 1.6g hydroxypropyl guar gum then is added and 0.4g is hydrophobic
Association polymer is mixed to get base fluid, is eventually adding tetra- n-propyl zirconate of 1.0g and is mixed to get delay cross-linked gel.
Leak stopping delay cross-linked gel composition properties test:
(a) crosslinking time measures: using method is hung, i.e., crosslinking agent being added into base fluid under 25 DEG C of water-baths, uses glass
Stick is stirred continuously, can be needed for the class solid viscoelastic object (frozen glue) that glass bar is hung to postpone the formation of cross-linked gel composition
Time is as crosslinking time.
(b) gel bearing capacity measures: using GGS71-B type high pressure high temperature filter tester as closing leak-off tester
A piece of strainer (aperture 0.60mm) is placed in filter-pressing cauldron bottom by device, adds the quartz sand that 100g partial size is different meshes,
It fills and leads up as far as possible, then slowly, equably along the addition of kettle wall, just prepared gel combination adds 150mL after standing 4h
5% bentonite base slurry cover after at 7MPa pressure (the maximum pressure resistance 7.5MPa of the matched rubber tube of filtration device) leak-off 30min, remember
Record the volume of remaining bentonite base slurry in filtrate volume and kettle.
(c) temperature and shearing sustainability is tested: the delay cross-linked gel composition after will be fully crosslinked is packed into FANN50 high temperature
High pressure rheometer is heated sample with 3.0 DEG C/min ± 0.2 DEG C/min heating rate, rotates rotor, shear rate 3s-1,
Start to measure when sample reaches 150 DEG C of temperature.Increase rotor speed, when shear rate reaches 170s-1(i.e. 100 turns/min)
When continuous shear stress, record shearing 2h after apparent viscosity numerical value.
Leak stopping see the table below shown in 1 with delay cross-linked gel composition properties test result.
Table 1 postpones cross-linked gel performance test
Table 1 statistics indicate that, delay cross-linked gel composition of the present invention is resistant to 150 DEG C of high temperature, have it is stronger resistance to
Warm endurance of cutting and bearing capacity, and there is good plugging effect for different type crack.
Embodiment described above is only to absolutely prove preferred embodiment that is of the invention and being lifted, protection model of the invention
It encloses without being limited thereto.Those skilled in the art's made equivalent substitute or transformation on the basis of the present invention, in the present invention
Protection scope within.Protection scope of the present invention is subject to claims.
Claims (8)
1. the invention discloses a kind of leak stopping delay cross-linked gel compositions, which is characterized in that by the group of following parts by weight
It is grouped as:
100 parts of water, 0.5~1 part of gelatinizing agent, 0.3~0.6 part of crosslinking agent, 0.05~2 part of delayer, 10~20 parts of reinforcing agent, increase
Tough dose 10~20 parts, 0~10 part of high temperature protection agent.
2. leak stopping according to claim 1 delay cross-linked gel composition, it is characterized in that: the gelatinizing agent is hydroxypropyl
The mixture that guar gum is mixed with hydrophobic associated polymer according to arbitrary proportion.
3. leak stopping according to claim 1 delay cross-linked gel composition, it is characterized in that: the crosslinking agent is four positive third
Base zirconate.
4. leak stopping according to claim 1 delay cross-linked gel composition, it is characterized in that: the delayer is citric acid
One of sodium, disodium ethylene diamine tetraacetate and glycolic.
5. leak stopping according to claim 1 delay cross-linked gel composition, it is characterized in that: the reinforcing agent is magnesium silicate
One of lithium and aluminium-magnesium silicate.
6. leak stopping according to claim 1 delay cross-linked gel composition, it is characterized in that: the toughener is sepiolite
One of fiber, basalt fibre, polypropylene fibre and polyester fiber.
7. leak stopping according to claim 1 delay cross-linked gel composition, it is characterized in that: the high temperature protection agent is sulphur
One of sodium thiosulfate and potassium sulfite.
8. a kind of preparation method of leak stopping as described in claim 1 delay cross-linked gel composition, comprising the following steps:
(1) water and reinforcing agent are mixed, obtains enhancing agent dispersing liquid;(2) the enhancing agent dispersing liquid and toughening obtained the step (1)
Agent, delayer and high temperature protection agent mixing, obtain mixed serum;(3) mixed serum and gelatinizing agent for obtaining the step (2)
Mixing, obtains base fluid;(4) base fluid that the step (3) obtains is mixed with crosslinking agent, after the crosslinking time of 30~120min
Obtain cross-linked gel.
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CN111205839A (en) * | 2020-01-17 | 2020-05-29 | 中国石油天然气股份有限公司 | Elastic gel temporary plugging well killing fluid used in combination with gas well and construction process |
CN111303849A (en) * | 2020-04-02 | 2020-06-19 | 中国石油大学(华东) | Temporary plugging agent, preparation method thereof and high-temperature reservoir temporary plugging diversion fracturing method |
CN112280543A (en) * | 2020-10-29 | 2021-01-29 | 中国石油化工集团有限公司 | Composite gel plugging material and composite gel plugging slurry |
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CN112280543A (en) * | 2020-10-29 | 2021-01-29 | 中国石油化工集团有限公司 | Composite gel plugging material and composite gel plugging slurry |
CN113501910A (en) * | 2021-09-09 | 2021-10-15 | 中国石油大学(华东) | Non-covalent-bond synergistic self-healing gel plugging agent and preparation method and application thereof |
CN114477880A (en) * | 2022-04-08 | 2022-05-13 | 郑州大学 | Geopolymer-based waterproof and leak-stopping material for heat distribution pipeline and preparation method of material |
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