CN110105933A - Gel particle sealing agent and its preparation method and application - Google Patents
Gel particle sealing agent and its preparation method and application Download PDFInfo
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- CN110105933A CN110105933A CN201910403161.8A CN201910403161A CN110105933A CN 110105933 A CN110105933 A CN 110105933A CN 201910403161 A CN201910403161 A CN 201910403161A CN 110105933 A CN110105933 A CN 110105933A
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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
- C09K8/44—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing organic binders only
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Abstract
The present invention relates to drilling fluid leak stopping to lead field, discloses a kind of gel particle sealing agent and its preparation method and application.The gel particle sealing agent has nucleocapsid structure, wherein core is gel particle, and shell is thermoplastic resin；The gel particle carries out reaction by non-ionic monomer, crosslinking agent, initiator, alginate, filling particle and water and is made.The gel particle sealing agent has excellent heat-resisting quantity, and has excellent plugging effect to high temperature leakage stratum.
Description
Technical field
The present invention relates to drilling fluid leak stopping fields, and in particular to a kind of gel particle sealing agent and preparation method thereof and answers
With.
Background technique
Leakage is one of most common borehole problems in current drilling process, is that one kind seriously affects drilling engineering and applies
The accident of work safety, can not only bring the extension of drilling period, bring unnecessary loss to unit in charge of construction, also can be to underground
The exploration of oil-gas reservoir resource bring great negative effect.So being always domestic and international petroleum work about drilling fluid leak-proof leak-stopping
Journey field hot issue of interest.Cross-linked polymer gel class is the processing common plugging material of severe mud losses.Simple is poly-
Conjunction object gel mechanical strength is in contrast relatively low, and the mechanical strength of the multi-functional gel of NEW TYPE OF COMPOSITE is then relatively high, but anti-height
Warm nature can be usually no more than 160 DEG C, and high-temperature long term stability is poor, and in deep, the use of bad ground high temperature well is limited, difficult
To form the closure barrier of high pressure-bearing in leakage channel.
Therefore, it is necessary to research and develop a kind of GEL USED FOR PLUGGING WELL LOST CIRCULATION suitable for high-temperature stratum, the height to high temperature leakage stratum is realized
Effect blocks.
Summary of the invention
The purpose of the invention is to overcome high temperature resistance existing for sealing agent in the prior art poor, to leakage channel
The low problem of plugging effect provides a kind of high temperature gel particle sealing agent and the preparation method and application thereof, the gel particle leak stopping
Agent has excellent heat-resisting quantity, and has excellent plugging effect to high temperature leakage stratum.
To achieve the goals above, first aspect present invention provides a kind of gel particle sealing agent, wherein the gel
Grain sealing agent has nucleocapsid structure, wherein core is gel particle, and shell is thermoplastic resin；The gel particle passes through nonionic
Monomer, crosslinking agent, initiator, alginate, filling particle and water carry out reaction and are made.
Preferably, on the basis of the total weight of the gel particle, the content of the non-ionic monomer is 5-20%, described
The content of crosslinking agent is 0.5-3%, and the content of the initiator is 0.05-0.5%, and the content of the alginate is 5-
20%, the content of the filling particle is 1-5%.
It is highly preferred that the content of the non-ionic monomer is 10-15% on the basis of the total weight of the gel particle,
The content of the crosslinking agent is 1.5-2.5%, and the content of the initiator is 0.2-0.4%, and the content of the alginate is
The content of 10-15%, the filling particle are 2-3%.
Preferably, the non-ionic monomer includes acrylamide and/or Methacrylamide.
Preferably, the crosslinking agent includes N, N- methylene-bisacrylamide and/or N hydroxymethyl acrylamide.
Preferably, the initiator includes potassium peroxydisulfate and/or ammonium persulfate.
Preferably, the alginate includes at least one of potassium alginate, sodium alginate and ammonium alginate.
Preferably, the filling particle includes at least one of nano silica, sodium bentonite and diatomite.
Preferably, the preparation method of the gel particle, comprising the following steps:
(1) lipophilic emulsifier, hydrophilic emulsifier and oil phase solvent are stirred evenly, obtains solution a；
(2) non-ionic monomer and crosslinking agent are add to deionized water, stir to being completely dissolved, obtains mixed liquor b；
(3) alginate is added in mixed liquor b, stirs to being completely dissolved, obtains mixed liquor c；
(4) filling particle is added in the mixed liquor c, dispersing aid is added, stirred to being completely dissolved, mixed
Liquid d；
(5) mixed liquor d is slowly added into the solution a, stirs to get mixed liquor e；
(6) initiator is add to deionized water, stirs to being completely dissolved, obtains solution f；
(7) solution f is added drop-wise in mixed liquor e, after carrying out the first reaction, carries out first time standing, obtain microemulsion g；
(8) calcium chloride brine is added dropwise in microemulsion g, after carrying out the second reaction, carries out second and stand, obtain micro emulsion
Liquid h；
(9) precipitating reagent is mixed with the microemulsion h, solid matter, washing is precipitated, obtains the gel particle.
Preferably, on the basis of the total weight of microemulsion h, the dosage of the oleophilic emulsifier is 4-10wt%, the parent
The dosage of water emulsifier is 8-18wt%, and the dosage of the oil phase solvent is 40-65wt%.
Preferably, the oil emulsifier is the mixture of Span60 and Span80, the mass ratio of Span60 and Span80
For (0.1-0.8): 1.
It is highly preferred that the mass ratio of Span60 and Span80 is (0.4-0.6): 1.
Preferably, the hydrophilic emulsifier is the mixture of Tween60 and Tween80, the matter of Tween60 and Twee80
Amount is than being (1-5): 1.
It is highly preferred that the mass ratio of Tween60 and Tween80 is (1.5-2.5): 1.
Preferably, the oil phase solvent is at least one of hexamethylene, kerosene and atoleine.
Preferably, in step (8), the mass concentration of the calcium chloride brine is 0.5-3%.
It is highly preferred that the mass concentration of calcium chloride brine is 1.5-2.5%.
Preferably, in step (9), the precipitating reagent is dehydrated alcohol, and detergent is dehydrated alcohol and/or acetone.
Preferably, in step (7), it is 50-80 DEG C that the condition of first reaction, which includes: reaction temperature, and the reaction time is
1-6h；Preferably, reaction temperature is 60-70 DEG C, reaction time 2-4h.
Preferably, the time that the first time stands is 0.5-2h, preferably 1-1.5h.
Preferably, in step (7), the rate of addition of the solution f is 1-5 drop/s；Preferably 1-3 drop/s.
Preferably, in step (8), it is 50-80 DEG C that the condition of second reaction, which includes: reaction temperature, and the reaction time is
0.5-2.5h；Preferably, reaction temperature is 55-65 DEG C, reaction time 1-1.5h.
Preferably, described second time stood is 12-24h, preferably 16-20h.
Preferably, in step (8), the rate of addition of the calcium chloride brine is 1-5 drop/s；Preferably 1-3 drop/s.
Second aspect of the present invention provides a kind of method for preparing the gel particle sealing agent, comprising the following steps:
(a) thermoplastic resin is heated to melting completely, obtains thermoplastic resin melting liquid；
(b) after being uniformly mixed gel particle and the thermoplastic resin melting liquid, cooling processing is carried out, consolidate
Phase mixture；
(c) solid-phase mixture is subjected to grinding and makes powder, obtain gel particle sealing agent.
Preferably, the mass ratio of the gel particle and thermoplastic resin is 1:(0.5-2.0)；It is highly preferred that gel
The mass ratio of grain and thermoplastic resin is 1:(1-1.5).
Preferably, the softening point of thermoplastic resin is 90-240 DEG C.
Preferably, the thermoplastic resin is C5 Petropols, in C9 Petropols, polyurethane resin, terpene resin
It is at least one.
Preferably, the partial size of the gel particle is 200-400 μm, more preferably 250-350 μm.
Preferably, the partial size of the gel particle sealing agent is 300-800 μm, more preferably 400-600 μm.
Preferably, in step (b), the mixing time being stirred is no more than 0.5h, preferably 0.2-0.4h；
Preferably, in step (b), the rate of temperature fall of the cooling processing is not less than 10 DEG C/min；Preferably 15-20
℃/min。
Third aspect present invention provides a kind of gel particle sealing agent of the present invention or is made by the method for the invention
Gel particle sealing agent application, wherein the application be drilling fluid leak stopping.
Through the above technical solutions, gel particle sealing agent provided by the invention and preparation method, have beneficial below
Effect:
(1) gel particle sealing agent provided by the present invention has " core shell " structure, thermoplastic resin outer cladding shell tool
There is the characteristic of high softening-point, is in solid phase in low temperature formation condition, it can be by the case where formation temperature is more than the hot conditions of its softening point
It is viscous pill phase that solid phase, which slowly melts variation, therefore the gel particle sealing agent of the present invention with " core shell " structure has
The similar high temperature resistant property of thermoplastic resin, the leak stopping suitable for high-temperature stratum.
(2) gel particle sealing agent provided by the present invention has " core shell " structure, gel particle kernel, by three kinds
The material composition of heterogeneous networks structure, first is that filling particle, second is that organic solidifying by the acrylamide that non-ionic monomer is polymerized
Glue, third is that the calcium alginate gel that ion exchange generates occurs by alginate and calcium salt.Wherein, organogel and calcium alginate
Gel forms gel particle main body in the form of interpenetrating composite network, a large amount of kernel for filling particle and being used as gel particle simultaneously,
Toughening effect is played, so that the intensity of the gel particle with " core shell " structure is high and has both hard and soft characteristic, it is logical to leakage
The plugging effect in road is more preferable.
(3) due to having the presence of thermoplastic resin outer cladding shell, the kernel of gel particle sealing agent provided by the present invention
Gel particle avoids contacting with outside water too early, caused by gel aging.When temperature is increased to the softening point of thermoplastic resin
On after, thermoplastic resin gradually melts, can be adhered with rock wall surface, enhance resident energy of the gel particle in leakage channel
Power overcomes simple gel particle temperature resistance and the insufficient defect of presence, realizes and blocks to high-temperature stratum leakage channel.
Detailed description of the invention
Fig. 1 shows be gel particle sealing agent " core/shell structure " schematic diagram；
What Fig. 2 was indicated is the transmission electron microscopy figure of gel particle in embodiment 1.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
First aspect present invention provides a kind of gel particle sealing agent, wherein the gel particle sealing agent has core-shell structure copolymer
Structure, wherein core is gel particle, and shell is thermoplastic resin；
The gel particle is carried out anti-by non-ionic monomer, crosslinking agent, initiator, alginate, filling particle and water
It should be made.
In the present invention, the gel particle sealing agent has " core shell " structure as shown in Figure 1, wherein the heat as shell
Plastic resin is in solid phase under the conditions of low temperature formation, enters ground layer gap conducive to gel particle sealing agent, and super in formation temperature
It crosses under the hot conditions of resin softening point, the resin of solid phase state, which slowly melts, becomes viscous pill phase, realizes to high-temperature stratum crack
Closure.
And as the gel particle of core by the material composition of three kinds of heterogeneous networks structures, first is that particle is filled, second is that by non-
The acrylamide organogel that ion monomer is polymerized, third is that the seaweed that ion exchange generates occurs by alginate and calcium salt
Sour calcium gel.
Wherein, as shown in Figure 1, organogel and calcium alginate gel can form gel in the form of interpenetrating composite network
Grain main body, filling particle are scattered in the gel particle being made of organogel and calcium alginate gel.Gel as shown in Figure 2
The transmission electron microscopy figure of particle is shown, is scattered in gel particle main body to filling uniform particle, is played toughening gel particle
The effect of, so that the intensity of the gel particle with " core shell " structure is high and has both hard and soft characteristic, to the envelope of leakage channel
Stifled effect is more preferable.
According to the present invention, on the basis of the total weight of the gel particle, the content of the non-ionic monomer is 5-20%,
The content of the crosslinking agent is 0.5-3%, and the content of the initiator is 0.05-0.5%, and the content of the alginate is 5-
20%, the content of the filling particle is 1-5%.
In the gel particle provided by the invention, non-ionic monomer, crosslinking agent, initiator, alginate, filling particle
Content summation with water is 100%.
In the present invention, in order to obtain with excellent gel strength and counterincision is sewed with the gel particle of excellent plugging effect, hair
Bright people studies the dosage of each component in gel particle, studies have shown that when the dosage of each component in gel particle is at this
When invention limited range, the gel particle of acquisition has excellent gel strength and counterincision is sewed with excellent plugging effect.
Further, in the present invention, inventor the study found that in the gel particle, non-ionic monomer, crosslinking agent,
The dosage of initiator, alginate and filling ion meets the nonionic list on the basis of the total weight of the gel particle
The content of body is 10-15%, and the content of the crosslinking agent is 1.5-2.5%, and the content of the initiator is 0.2-0.4%, institute
The content for stating alginate is 10-15%, and when the content of the filling particle is 2-3%, obtained GEL USED FOR PLUGGING WELL LOST CIRCULATION is blocked up
It is more excellent to leak performance.
Specifically, the content of the non-ionic monomer preferably can be on the basis of the total weight of the gel particle
The arbitrary value in range constituted such as any two in 11%, 12%, 13%, 14% and these numerical value；The crosslinking
In the range that the content of agent can preferably be constituted for any two in such as 1.8%, 2%, 2.3% and these numerical value
Arbitrary value；The content of the initiator preferably can be any in such as 0.25%, 0.3%, 0.35% and these numerical value
Arbitrary value in two ranges constituted；The content of the alginate can preferably such as 11%, 12%, 13%,
14% and these numerical value in the range that is constituted of any two in arbitrary value；The content of the filling particle can be preferred
The arbitrary value in range constituted for any two in such as 2.2%, 2.6%, 2.8% and these numerical value.
According to the present invention, the non-ionic monomer includes acrylamide and/or Methacrylamide.
In the present invention, the non-ionic monomer is preferably acrylamide.
According to the present invention, the crosslinking agent includes N, N- methylene-bisacrylamide and/or N hydroxymethyl acrylamide.
According to the present invention, the initiator includes potassium peroxydisulfate and/or ammonium persulfate.
According to the present invention, the alginate includes at least one of potassium alginate, sodium alginate and ammonium alginate.
According to the present invention, the filling particle includes at least one in nano silica, sodium bentonite and diatomite
Kind.
According to the present invention, the gel particle preparation method the following steps are included:
(1) lipophilic emulsifier, hydrophilic emulsifier and oil phase solvent are stirred evenly, obtains solution a；
(2) non-ionic monomer and crosslinking agent are add to deionized water, stir to being completely dissolved, obtains mixed liquor b；
(3) alginate is added in mixed liquor b, stirs to being completely dissolved, obtains mixed liquor c；
(4) filling particle is added in the mixed liquor c, dispersing aid is added, stirred to being completely dissolved, mixed
Liquid d；
(5) mixed liquor d is slowly added into the solution a, stirs to get mixed liquor e；
(6) initiator is add to deionized water, stirs to being completely dissolved, obtains solution f；
(7) solution f is added drop-wise in mixed liquor e, after carrying out the first reaction, carries out first time standing, obtain microemulsion g；
(8) calcium chloride brine is added dropwise in microemulsion g, after carrying out the second reaction, carries out second and stand, obtain micro emulsion
Liquid h；
(9) precipitating reagent is mixed with the microemulsion h, solid matter, washed dose of washing is precipitated, obtains the gel
Grain.
In the present invention, the gel particle is preferably prepared using method as described above, specifically, using the above method
When preparing gel particle, so that the acrylamide organogel in gel particle and interacting between calcium alginate gel
To improve, and the two is capable of forming effective inierpeneirating network structure, and fills particle and good can be scattered in by acryloyl
In the gel particle that amine organogel and calcium alginate gel are constituted, and then gel strength height is obtained, had to leakage channel excellent
The gel particle of different plugging effect.
According to the present invention, on the basis of the total weight of microemulsion h, the dosage of the lipophilic emulsifier is 4-10wt%,
The dosage of the hydrophilic emulsifier is 8-18wt%, and the dosage of the oil phase solvent is 40-65wt%.
According to the present invention, the lipophilic emulsifier is the mixture of Span60 and Span80, Span60 and Span80's
Mass ratio is (0.1-0.8): 1.
Preferably, the mass ratio of Span60 and Span80 is (0.4-0.6): 1
According to the present invention, the hydrophilic emulsifier is the mixture of Tween60 and Tween80, Tween60 and Twee80
Mass ratio be (1-5): 1.
Preferably, the mass ratio of Tween60 and Tween80 is (1.5-2.5): 1.
According to the present invention, the oil phase solvent is at least one of hexamethylene, kerosene and atoleine.
According to the present invention, it is 0.5-3% that the calcium chloride brine, which is mass concentration,.
Preferably, the mass concentration of calcium chloride brine is 1.5-2.5%.
According to the present invention, the precipitating reagent is dehydrated alcohol, and detergent is dehydrated alcohol and/or acetone.
In the present invention, the dispersing aid is surfactant, to improve dispersion of the filling particle in mixed liquor
Property.
According to the present invention, in step (7), it is 50-80 DEG C, when reaction that the condition of first reaction, which includes: reaction temperature,
Between be 1-6h；Preferably, reaction temperature is 60-70 DEG C, reaction time 2-4h.
According to the present invention, in step (7), the time that the first time stands is 0.5-2h, preferably 1-1.5h.
According to the present invention, in step (8), it is 50-80 DEG C, when reaction that the condition of second reaction, which includes: reaction temperature,
Between be 0.5-2.5h；Preferably, reaction temperature is 55-65 DEG C, reaction time 1-1.5h.
According to the present invention, in step (8), described second time stood is 12-24h, preferably 16-20h.
In the present invention, in step (5), mixed liquor d is slowly added into solution a, it can be ensured that microemulsion particle obtained
Diameter is uniform, and excessive velocities, which are added, causes mixed liquor d to be difficult to carry out good dispersibility in solution a, eventually leads to obtained solidifying
The sealing characteristics of glue particle reduces.
At the same time, inventor to solution f in step (7) and step (8) and the rate of addition of calcium chloride brine into
Row research, the study found that control solution f is added dropwise to mixed liquor e respectively and calcium chloride brine is added dropwise to dropwise addition in microemulsion g
Speed can guarantee that solution f and calcium chloride brine can obtain good dispersion in mixed liquor e and microemulsion g, in turn
So that gel particle obtained has more excellent sealing characteristics.
Specifically, according to the present invention, in step (7), the rate of addition of the solution f is 1-5 drop/s；Preferably 1-3 drop/
s。
According to the present invention, in step (8), the rate of addition of the calcium chloride brine is 1-5 drop/s；Preferably 1-3 drop/s.
Second aspect of the present invention provides a kind of method for preparing gel particle sealing agent of the present invention, wherein including with
Lower step:
(a) thermoplastic resin is heated to melting completely, obtains thermoplastic resin melting liquid；
(b) after being uniformly mixed gel particle and the thermoplastic resin melting liquid, cooling processing is carried out, consolidate
Phase mixture；
(c) solid-phase mixture is subjected to grinding and makes powder, obtain the gel particle sealing agent.
In the present invention, the gel particle sealing agent preferably uses the above method to be prepared, and use is of the present invention
Gel particle sealing agent, which is made, in method has nucleocapsid structure, and the gel particle sealing agent with nucleocapsid structure is with excellent resistance to
It is high temperatures, and there is excellent plugging effect to high temperature leakage stratum.
At the same time, inventor studies the mass ratio of gel particle and thermoplastic resin, the study found that when solidifying
It is 1:(0.5- that glue particle and thermoplastic resin particle, which meet gel particle defined by the present invention and the mass ratio of thermoplastic resin,
2), preferably 1:(1-1.5) range when, the plugging effect of obtained gel particle sealing agent is more excellent.
According to the present invention, the softening point of the thermoplastic resin is 90-180 DEG C.
According to the present invention, the thermoplastic resin is C5 Petropols, C9 Petropols, polyurethane resin, terpene resin
One of or combination of the above.
In the present invention, the thermoplastic resin preferably uses polyurethane resin.
According to the present invention, the partial size of the gel particle is 200-400 μm, preferably 250-350 μm.
According to the present invention, the partial size of the gel particle sealing agent is 300-800 μm, preferably 400-600 μm.
In the present invention, inventor is the study found that pass through the side quickly stirred for gel particle and thermoplastic resin melting liquid
Formula after mixing, can obtain heat-resisting quantity and the more excellent gel particle sealing agent of plugging effect.Specifically, step
(b) in, the mixing time being stirred is no more than 0.5h, preferably 0.2-0.4h.
In the present invention, after gel particle is mixed with thermoplastic resin melting liquid, fast cooling processing is carried out, fast prompt drop is passed through
Temperature processing, it can be ensured that there is excellent binding performance between gel particle and thermoplastic resin, and then obtain with excellent envelope
The gel particle sealing agent with " core shell " structure of stifled performance.
Specifically, according to the present invention, the rate of temperature fall of the cooling processing is not less than 10 DEG C/min；Preferably 15-20
℃/min。
Third aspect present invention provides a kind of gel particle sealing agent of the present invention or is made by the method for the invention
Gel particle sealing agent application, wherein the application be drilling fluid leak stopping.
The present invention will be described in detail by way of examples below.
The high temperature plugging effect of GEL USED FOR PLUGGING WELL LOST CIRCULATION: stifled using LHKYDL-3 type high temperature and pressure leak stopping test device test gel
Agent is leaked to the plugging effect of porous media, is used the quartz sand of 20-40 mesh as evaluation casting bed, is simulated leakage channel.It is specific to survey
Method for testing: 500mL GEL USED FOR PLUGGING WELL LOST CIRCULATION solution (initiator is added) is poured into device for plugging dehydration cylinder；It is put at an upper portion thereof removable
Then piston screws cover sealing；240 DEG C after its solidification, are pressurizeed using huge discharge advection pump priming, control pressurization
Speed, every 10min increase 1MPa, are pressurized to 10MPa, observe and record the wastage of fractured model outlet.
The trade mark of polyurethane resin is HD-355, is purchased from Dongguan hongda polyurethane resin Co., Ltd；
The trade mark of C5 Petropols is A2200, is purchased from Puyang Heng Tai petrochemical industry Co., Ltd；
The trade mark of C9 Petropols is T1130, is purchased from Puyang Heng Tai petrochemical industry Co., Ltd；
Other raw materials used in the embodiment of the present invention and comparative example are commercially available product.
Preparation example 1
The preparation of gel particle
(1) lipophilic emulsifier, hydrophilic emulsifier and oil phase solvent are stirred evenly, obtains solution a；
(2) non-ionic monomer and crosslinking agent are add to deionized water, stir to being completely dissolved, obtains mixed liquor b；
(3) alginate is added in mixed liquor b, stirs to being completely dissolved, obtains mixed liquor c；
(4) filling particle is added in the mixed liquor c, dispersing aid is added, stirred to being completely dissolved, mixed
Liquid d；
(5) mixed liquor d is slowly added into the solution a, stirs to get mixed liquor e；
(6) initiator is add to deionized water, stirs to being completely dissolved, obtains solution f；
(7) solution f is added drop-wise in mixed liquor e, after carrying out the first reaction, carries out first time standing, obtain microemulsion g；
(8) calcium chloride brine is added dropwise in microemulsion g, after carrying out the second reaction, carries out second and stand, obtain micro emulsion
Liquid h；
(9) precipitating reagent dehydrated alcohol is mixed with the microemulsion h, solid matter, washed dose of washing is precipitated, obtains institute
State gel particle.
Preparation example 2
The preparation of gel particle sealing agent
(a) thermoplastic resin is heated to melting completely, obtains thermoplastic resin melting liquid；
(b) after being uniformly mixed gel particle and the thermoplastic resin melting liquid, cooling processing is carried out, consolidate
Phase mixture；
(c) solid-phase mixture is subjected to grinding and makes powder, gel particle sealing agent is made.
To guarantee that embodiment and comparative example primary condition is consistent, in following embodiment and comparative examples, " core shell " structure is coagulated
The partial size of glue particle sealing agent selects 500 μm.
Embodiment 1
Prepare gel particle according to the method for preparation example 1, wherein on the basis of the total weight of the gel particle, it is non-from
The content of sub- monomeric acrylamide is 12%, and the content of crosslinking agent N, N- methylene-bisacrylamide is 1.5%, initiator over cure
The content of sour potassium is 0.3%, and the content of sodium alginate is 12%, and the content of the filling particle nano silica is 2%.
On the basis of the total weight of microemulsion h, the dosage of lipophilic emulsifier is 8wt%, the dosage of hydrophilic emulsifier
For 13wt%, the dosage of oil phase solvent is 55wt%.Lipophilic emulsifier is the mixture of Span60 and Span80, and mass ratio is
0.5:1.Wherein, hydrophilic emulsifier is the mixture of Tween60 and Tween80, mass ratio 2:1.Oil phase solvent is hexamethylene
Alkane.The mass concentration of calcium chloride brine is 2%.Precipitating reagent is dehydrated alcohol, and detergent is acetone.
Wherein, in step (7), the reaction temperature of the first reaction is 60 DEG C, reaction time 2.5h, and time of repose is
1.5h.In step (8), the reaction temperature of the second reaction is 60 DEG C, reaction time 1h, time of repose 18h, gel obtained
The transmission electron microscopy figure of particle is as shown in Fig. 2, as seen from Figure 2, be scattered in gel particle to filling uniform particle.
Gel particle sealing agent is prepared according to the method for preparation example 2, specifically, stifled with the gel particle of " core shell " structure
On the basis of the total weight for leaking agent, the mass ratio of gel particle and thermoplastic resin is 1:1.5.
The thermoplastic resin is polyurethane resin, and softening point is 220 DEG C.
Wherein, in step (b), the time being stirred is 15min.
Gel particle sealing agent A1 is made, high temperature plugging effect is shown in Table 1.
Embodiment 2
Gel particle sealing agent is prepared using method same as Example 1, unlike: with the gel particle kernel
Total weight be the content of benchmark non-ionic monomer be 8%, the content of crosslinking agent is 1%, and the content of initiator is 0.1%, sea
The content of alginates is 5%, and the content for filling particle is 1.5%.Gel particle sealing agent A2 is made, high temperature plugging effect is shown in
Shown in table 1.
Embodiment 3
Gel particle sealing agent is prepared using method same as Example 1, unlike: gel particle and thermoplastic resin
The mass ratio of rouge is 1:0.5.Gel particle sealing agent A3 is made, high temperature plugging effect is shown in Table 1.
Embodiment 4
Gel particle sealing agent is prepared using method same as Example 1, unlike: nonionic list in gel particle
Body is acrylamide and Methacrylamide, and the mass ratio of the two is 1:1.Gel particle sealing agent A4 is made, high temperature blocks
Effect is shown in Table 1.
Embodiment 5
Gel particle sealing agent is prepared using with 1 method of embodiment, unlike: thermoplastic resin is that softening point is 200
DEG C C5 Petropols and softening point be 180 DEG C of C9 Petropols, the mass ratio of the two is 1:1.Gel particle leak stopping is made
Agent A3, high temperature plugging effect are shown in Table 1.
Embodiment 6
Gel particle sealing agent is prepared using method same as Example 1, unlike: with the gel particle kernel
Total weight be the content of benchmark non-ionic monomer be 25%, the content of crosslinking agent is 3.5%, and the content of initiator is 1%, sea
The content of alginates is 25%, and the content for filling particle is 6%.Gel particle sealing agent D4 is made, high temperature plugging effect is shown in
Shown in table 1.
Comparative example 1
Gel particle sealing agent is prepared using method same as Example 1, unlike: without filling in gel particle
Particle.Gel particle sealing agent D1 is made, high temperature plugging effect is shown in Table 1.
Comparative example 2
Gel particle sealing agent is prepared using method same as Example 1, unlike: the gel of " core shell " structure
Particle sealing agent is free of thermoplastic resin, i.e., without resin outer cladding shell.Gel particle sealing agent D2, high temperature plugging effect is made
It is shown in Table 1.
Comparative example 3
Gel particle sealing agent is prepared using method same as Example 1, unlike: be free of alginate.It is made
Gel particle sealing agent D3, high temperature plugging effect are shown in Table 1.
Comparative example 4
Gel particle sealing agent is prepared using method same as Example 1, unlike: gel particle and thermoplastic resin
The mass ratio of rouge is 1:3.Gel particle sealing agent D5 is made, high temperature plugging effect is shown in Table 1.
The high temperature of 1 gel particle sealing agent A1-D5 of table blocks test effect
By data in table 1 it is found that being missed after gel particle sealing agent A1 plastic of the invention to high permeability porous media
Channel has good plugging effect, and under the conditions of 240 DEG C, the bearing capacity of GEL USED FOR PLUGGING WELL LOST CIRCULATION A1 is above 10MPa, shows when solidifying
When glue sealing agent each component concentration is in optimized scope, the drilling fluid under the conditions of 240 DEG C of high temperature, 10MPa high pressure-bearing can be met
Leak stopping requirement.
Water clock occurs in 10MPa for GEL USED FOR PLUGGING WELL LOST CIRCULATION A2, and high-temperature bearing ability is lower than GEL USED FOR PLUGGING WELL LOST CIRCULATION A1, illustrates to work as gel
When the dosage of sealing agent each component is not fallen in currently preferred range, high-temperature bearing ability decreases.
GEL USED FOR PLUGGING WELL LOST CIRCULATION A3-A6, due to the mass ratio of gel particle and thermoplastic resin, non-ionic monomer type and
The type and GEL USED FOR PLUGGING WELL LOST CIRCULATION A1-A2 of thermoplastic resin slightly have difference, the plugging effect of GEL USED FOR PLUGGING WELL LOST CIRCULATION obtained at high temperature
The drilling fluid leak stopping demand for being declined slightly, but still being able to satisfy under 240 DEG C of high temperature, 6MPa, plugging effect are better than gel significantly
Sealing agent D1-D4.
In 7MPa, 5MPa and 6MPa water clock occurs for GEL USED FOR PLUGGING WELL LOST CIRCULATION D1, D2 and D3 respectively, final that all leakages occur,
Show high temperature plugging effect difference not as good as GEL USED FOR PLUGGING WELL LOST CIRCULATION A1 and A2.
And the gel leak stopping D4 that the mass ratio of GEL USED FOR PLUGGING WELL LOST CIRCULATION and thermoplastic resin does not fall within the scope of the present invention exists
Water clock just occurs when 6MPa, it is final that all leakages occur, show that GEL USED FOR PLUGGING WELL LOST CIRCULATION D4 is unable to satisfy under high-temperature and high-pressure conditions, drilling well
The leak stopping demand of liquid.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (10)
1. a kind of gel particle sealing agent, wherein the gel particle sealing agent has nucleocapsid structure, wherein core is gel
Grain, shell is thermoplastic resin；
The gel particle carries out reaction system by non-ionic monomer, crosslinking agent, initiator, alginate, filling particle and water
?.
2. gel particle sealing agent according to claim 1, wherein on the basis of the total weight of the gel particle, institute
The content for stating non-ionic monomer is 5-20%, and the content of the crosslinking agent is 0.5-3%, and the content of the initiator is 0.05-
0.5%, the content of the alginate is 5-20%, and the content of the filling particle is 1-5%；
Preferably, on the basis of the total weight of the gel particle, the content of the non-ionic monomer is 10-15%, the friendship
The content for joining agent is 1.5-2.5%, and the content of the initiator is 0.2-0.4%, and the content of the alginate is 10-
15%, the content of the filling particle is 2-3%.
3. gel particle sealing agent according to claim 1 or 2, wherein the non-ionic monomer include acrylamide and/
Or Methacrylamide；
The crosslinking agent includes N,N methylene bis acrylamide and/or N hydroxymethyl acrylamide；
The initiator includes potassium peroxydisulfate and/or ammonium persulfate；
The alginate includes at least one of potassium alginate, sodium alginate and ammonium alginate；
The filling particle includes at least one of nano silica, sodium bentonite and diatomite.
4. gel particle sealing agent described in any one of -3 according to claim 1, wherein the preparation side of the gel particle
Method the following steps are included:
(1) lipophilic emulsifier, hydrophilic emulsifier and oil phase solvent are stirred evenly, obtains solution a；
(2) non-ionic monomer and crosslinking agent are add to deionized water, stir to being completely dissolved, obtains mixed liquor b；
(3) alginate is added in mixed liquor b, stirs to being completely dissolved, obtains mixed liquor c；
(4) filling particle is added in the mixed liquor c, dispersing aid is added, stirred to being completely dissolved, obtain mixed liquor d；
(5) mixed liquor d is slowly added into the solution a, stirs to get mixed liquor e；
(6) initiator is add to deionized water, stirs to being completely dissolved, obtains solution f；
(7) solution f is added drop-wise in mixed liquor e, after carrying out the first reaction, carries out first time standing, obtain microemulsion g；
(8) calcium chloride brine is added dropwise in microemulsion g, after carrying out the second reaction, carries out second and stand, obtain microemulsion h；
(9) precipitating reagent is mixed with the microemulsion h, solid matter, washed dose of washing is precipitated, obtains the gel particle.
5. gel particle sealing agent according to claim 4, wherein on the basis of the total weight of microemulsion h, the oleophylic
Property emulsifier dosage be 4-10wt%, the dosage of the hydrophilic emulsifier is 8-18wt%, the dosage of the oil phase solvent
For 40-65wt%；
The lipophilic emulsifier is the mixture of Span60 and Span80, and the mass ratio of Span60 and Span80 are (0.1-
0.8):1；Preferably, the mass ratio of Span60 and Span80 is (0.4-0.6): 1；
The hydrophilic emulsifier is the mixture of Tween60 and Tween80, and the mass ratio of Tween60 and Twee80 are (1-
5):1；Preferably, the mass ratio of Tween60 and Tween80 is (1.5-2.5): 1；
The oil phase solvent is at least one of hexamethylene, kerosene and atoleine；
In step (8), the mass concentration of the calcium chloride brine is 0.5-3%；Preferably, the mass concentration of calcium chloride brine is
1.5-2.5%；
In step (9), the precipitating reagent is dehydrated alcohol, and detergent is dehydrated alcohol and/or acetone.
6. gel particle sealing agent according to claim 4 or 5, wherein in step (7), the condition of first reaction
Include: reaction temperature be 50-80 DEG C, reaction time 1-6h；Preferably, reaction temperature is 60-70 DEG C, reaction time 2-
4h；
The time that the first time stands is 0.5-2h, preferably 1-1.5h；
The rate of addition of the solution f is 1-5 drop/s；Preferably 1-3 drop/s；
In step (8), it is 50-80 DEG C that the condition of second reaction, which includes: reaction temperature, reaction time 0.5-2.5h；It is excellent
Selection of land, reaction temperature are 55-65 DEG C, reaction time 1-1.5h；
Described second time stood is 12-24h, preferably 16-20h；
The rate of addition of the calcium chloride brine is 1-5 drop/s；Preferably 1-3 drop/s.
7. a kind of method for preparing gel particle sealing agent described in any one of claim 1-6, wherein including following step
It is rapid:
(a) thermoplastic resin is heated to melting completely, obtains thermoplastic resin melting liquid；
(b) after being uniformly mixed gel particle and the thermoplastic resin melting liquid, cooling processing is carried out, it is mixed to obtain solid phase
Close object；
(c) solid-phase mixture is subjected to grinding and makes powder, obtain the gel particle sealing agent.
8. according to the method described in claim 7, wherein, the mass ratio of the gel particle and thermoplastic resin is 1:(0.5-
2), preferably 1:(1-1.5)；
Preferably, the softening point of the thermoplastic resin is 90-240 DEG C；
It is highly preferred that the thermoplastic resin be C5 Petropols, C9 Petropols, polyurethane resin, in terpene resin extremely
Few one kind；
Preferably, the partial size of the gel particle is 200-400 μm, preferably 250-350 μm；
Preferably, the partial size of the gel particle sealing agent is 300-800 μm, preferably 400-600 μm.
9. method according to claim 7 or 8, wherein in step (b), the mixing time being stirred is no more than
0.5h, preferably 0.2-0.4h；
The rate of temperature fall of the cooling processing is not less than 10 DEG C/min；Preferably 15-20 DEG C/min.
10. gel particle sealing agent described in a kind of any one of claim 1-6 or by any one of claim 7-9
The application of gel particle sealing agent made from the method, wherein the application is drilling fluid leak stopping.
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