CN105441043B - Temporary plugging microsphere and preparation method thereof - Google Patents
Temporary plugging microsphere and preparation method thereof Download PDFInfo
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- CN105441043B CN105441043B CN201410392694.8A CN201410392694A CN105441043B CN 105441043 B CN105441043 B CN 105441043B CN 201410392694 A CN201410392694 A CN 201410392694A CN 105441043 B CN105441043 B CN 105441043B
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- 238000002360 preparation method Methods 0.000 title claims description 11
- 239000004005 microsphere Substances 0.000 title abstract description 13
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 37
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 37
- 229920000159 gelatin Polymers 0.000 claims abstract description 33
- 235000019322 gelatine Nutrition 0.000 claims abstract description 33
- 108010010803 Gelatin Proteins 0.000 claims abstract description 30
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 30
- 239000008273 gelatin Substances 0.000 claims abstract description 30
- 235000011852 gelatine desserts Nutrition 0.000 claims abstract description 30
- 229920001817 Agar Polymers 0.000 claims abstract description 29
- 239000008272 agar Substances 0.000 claims abstract description 29
- 229910021538 borax Inorganic materials 0.000 claims abstract description 26
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000004328 sodium tetraborate Substances 0.000 claims abstract description 26
- 235000010339 sodium tetraborate Nutrition 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000011259 mixed solution Substances 0.000 claims description 48
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical group [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 34
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical group O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 27
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 23
- 239000000654 additive Substances 0.000 claims description 22
- 230000000996 additive effect Effects 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 20
- 150000001299 aldehydes Chemical class 0.000 claims description 19
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- NWGKJDSIEKMTRX-MDZDMXLPSA-N Sorbitan oleate Chemical compound CCCCCCCC\C=C\CCCCCCCC(=O)OCC(O)C1OCC(O)C1O NWGKJDSIEKMTRX-MDZDMXLPSA-N 0.000 claims description 10
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 8
- 239000008346 aqueous phase Substances 0.000 claims description 8
- 239000003995 emulsifying agent Substances 0.000 claims description 7
- 239000012071 phase Substances 0.000 claims description 7
- 238000013517 stratification Methods 0.000 claims description 4
- 239000011806 microball Substances 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims description 2
- 230000015556 catabolic process Effects 0.000 abstract description 7
- 238000006731 degradation reaction Methods 0.000 abstract description 7
- 239000011148 porous material Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 1
- 230000000717 retained effect Effects 0.000 abstract 1
- 230000002195 synergetic effect Effects 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 10
- 208000010392 Bone Fractures Diseases 0.000 description 7
- 206010017076 Fracture Diseases 0.000 description 7
- 230000000903 blocking effect Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- 239000012530 fluid Substances 0.000 description 5
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 238000006073 displacement reaction Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- 238000012956 testing procedure Methods 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 239000001828 Gelatine Substances 0.000 description 2
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001739 density measurement Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000005213 imbibition Methods 0.000 description 1
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- 239000007924 injection Substances 0.000 description 1
- 239000010977 jade Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 229920005615 natural polymer Polymers 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
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- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- Manufacturing Of Micro-Capsules (AREA)
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Abstract
The invention discloses a temporary plugging microsphere, and belongs to the technical field of fracture acidizing. The diameter of the temporary plugging microsphere is 50-700 microns, and the temporary plugging microsphere comprises the following components in percentage by weight: 23-26% of polyvinyl alcohol, 32-36% of gelatin, 4-6% of agar, 25-32% of weighting agent, 0.01-1% of sodium tetraborate and 3-4% of aldehyde curing agent. The temporary plugging microspheres provided by the invention enable the formed temporary plugging agent to be in a microsphere shape with the diameter of 50-700 microns through the synergistic effect among the components, the strength of the temporary plugging agent is favorably improved, the temporary plugging microspheres absorb water to expand, the expansion ratio of the temporary plugging microspheres can reach 3.5, pores of a reservoir can be effectively plugged, after plugging is finished, the temperature is increased to 100-plus-material temperature of 120 ℃, the temporary plugging microspheres are degraded, the degradation rate reaches 100% within 4-7 hours, the temporary plugging microspheres are prevented from being retained in the reservoir, and the temporary plugging microspheres are safe and harmless to the reservoir.
Description
Technical field
The present invention relates to fracture acidizing technical field, more particularly to a kind of temporarily stifled microballoon and preparation method thereof.
Background technology
Fracture acidizing is the important measures of oil well production increasing, intensified injection of wells, by being enough to press off stratum formation crack or opening
Acid is squeezed under the pressure of layer primary fracture of turning up the soil to stratum to implement.During fracture acidizing, thing is needed to Thief zone reservoir
First blocked using diverting agent, to carry out pressure break to low permeability reservoir.
CN1597837A discloses a kind of water-solubility acidity temporary plugging agent for press cracking, including：Gelatine, sulfonated gilsonite and guanidine glue, its
Weight ratio between middle three is：Gelatine：Sulfonated gilsonite:Guanidine glue is 5.5-6.5:1.5-3.5:1-2.
Inventor has found that prior art at least has problems with：
The intensity for the diverting agent that prior art provides is relatively low, and is easily trapped in reservoir, and reservoir is damaged.
The content of the invention
Technical problem to be solved of the embodiment of the present invention is, there is provided a kind of high intensity, it is safe and harmless to reservoir
Temporarily stifled microballoon and preparation method thereof.Concrete technical scheme is as follows：
In a first aspect, the embodiments of the invention provide a kind of temporarily stifled microballoon, a diameter of 50-700 of the temporarily stifled microballoon are micro-
Rice, the temporarily stifled microballoon include the composition of following percentage by weight：Polyvinyl alcohol 23-26%, gelatin 32-36%, agar 4-
6%th, heavy weight additive 25-32%, sodium tetraborate 0.01-1%, aldehydes curing agent 3-4%.
Specifically, preferably, the heavy weight additive is sodium bromide and/or KBr.
Specifically, preferably, the aldehydes curing agent is formaldehyde and/or glutaraldehyde.
Preferably, the temporarily stifled microballoon includes the composition of following weight percent：Polyvinyl alcohol 25%, gelatin 35%, fine jade
Fat 5%, sodium bromide 31%, sodium tetraborate 1%, formaldehyde 3%.
Specifically, preferably, the polyvinyl alcohol is polyvinyl alcohol 1799.
Specifically, preferably, the density of the temporarily stifled microballoon is 1.2-1.4g/cm3.
Second aspect, microballoon Zan Du microballoons group, including multiple temporarily stifled microballoons are temporarily blocked up the embodiments of the invention provide a kind of,
Temporarily the diameter range of stifled microballoon is 50-700 microns in the Zan Du microballoons group, and the temporarily stifled microballoon includes following weight percent
The composition of ratio：Polyvinyl alcohol 23-26%, gelatin 32-36%, agar 4-6%, heavy weight additive 25-32%, sodium tetraborate 0.01-
1%th, aldehydes curing agent 3-4%,
The intermediate value of the diameter of temporarily stifled microballoon in the Zan Du microballoons group is 400-420 microns.
Specifically, preferably, the number for temporarily blocking up microballoon of a diameter of 500-600 microns in the Zan Du microballoons group
Account for more than the 40% of the number of total temporarily stifled microballoon.
The third aspect, the embodiments of the invention provide a kind of preparation method of temporarily stifled microballoon, including：
Step a, according to the part by weight between each composition in the embodiment of first aspect offer, polyethylene is added into water
Alcohol, gelatin, agar and heavy weight additive, it is well mixed, obtains the first mixed solution；
Step b, first mixed solution is added in 75-80 DEG C of the oil solution containing emulsifying agent, obtains the second mixing
Solution, after second mixed solution is stirred into 8-15 minutes by 400-600rpm mixing speed, it is cooled to 15-20 DEG C；
Step c, sodium tetraborate is added into second mixed solution, obtains the 3rd mixed solution, stir 25-35 minutes
Afterwards, stratification, phase of fetching water；
Step d, the aqueous phase is added in the aqueous isopropanol of aldehyde-containing type curing agent, stirs 55-65 minutes, temporarily blocked up
Microballoon.
Specifically, preferably, in the step a, the concentration of first mixed solution is 21-38%.
Specifically, preferably, in the step a, the heavy weight additive is sodium bromide and/or KBr.
Specifically, preferably, in the step b, the oil solution containing emulsifying agent is the white oil containing sorbester p17 and/liquid
Body paraffin solution.
Specifically, preferably, the concentration of the aqueous isopropanol of the aldehyde-containing type curing agent is 80.0%.
Specifically, preferably, methods described also includes step e：It is temporary using being obtained in the petroleum ether cleaning step d
Stifled microballoon.
The beneficial effect that technical scheme provided in an embodiment of the present invention is brought is：
Temporarily stifled microballoon provided in an embodiment of the present invention, passes through 23-26% polyvinyl alcohol (percentage by weight), 32-36%
Gelatin, 4-6% agar, 25-32% heavy weight additive, 0.01-1% sodium tetraborate and 3-4% aldehydes curing agent association
Same-action, make the microspheroidal that formed diverting agent is diametrically 50-700 microns, beneficial to its intensity is improved, this temporarily blocks up microballoon and inhaled
Water is expanded, and its expansion ratio can be blocked effectively to reservoir pore space up to 3.5, and after closure, improve temperature extremely
100-120 DEG C, then this temporarily stifled microballoon will degrade, its degradation rate avoids being trapped in reservoir up to 100% within 4-7 hour
In, it is safe and harmless to reservoir.
Brief description of the drawings
Technical scheme in order to illustrate the embodiments of the present invention more clearly, make required in being described below to embodiment
Accompanying drawing is briefly described, it should be apparent that, drawings in the following description are only some embodiments of the present invention, for
For those of ordinary skill in the art, on the premise of not paying creative work, other can also be obtained according to these accompanying drawings
Accompanying drawing.
Fig. 1 is the scanning electron microscope (SEM) photograph for the temporarily stifled microballoon that the embodiment of the present invention 1 provides.
Embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with accompanying drawing to embodiment party of the present invention
Formula is described in further detail.
In a first aspect, the embodiments of the invention provide a kind of temporarily stifled microballoon, a diameter of 50-700 of the temporarily stifled microballoon are micro-
Rice, the temporarily stifled microballoon include the composition of following percentage by weight：Polyvinyl alcohol 23-26%, gelatin 32-36%, agar 4-
6%th, heavy weight additive 25-32%, sodium tetraborate 0.01-1%, aldehydes curing agent 3-4%.
By the synergy between above-mentioned each composition, make formed diverting agent into the microballoon of a diameter of 50-700 microns
Shape, beneficial to its intensity is improved, this temporarily blocks up microballoon water swelling, and its expansion ratio can be sealed effectively up to 3.5 to reservoir pore space
It is stifled, and after closure, improve temperature to 100-120 DEG C, then this temporarily stifled microballoon will degrade, within 4-7 hour its
Degradation rate avoids being trapped in reservoir up to 100%, safe and harmless to reservoir.
Specifically, because the aqueous solution of gelatin and agar is at normal temperatures solid gel, degrade at high temperature.So pass through
Using gelatin and agar, in the presence of aldehydes curing agent, it is not only easy to make formed diverting agent into the stabilization of high intensity
Microspheroidal, and beneficial to the temporarily stifled microballoon water swelling, so as to be blocked to reservoir pore space.Further, gelatin and agar are equal
For natural polymer, it is not only easy to degrade, and reservoir will not be damaged.Above-mentioned aldehydes curing agent is preferably first
Aldehyde and/or glutaraldehyde, more preferably formaldehyde.
By using the polyvinyl alcohol of good thermal stability, in the presence of sodium tetraborate, the polyvinyl alcohol is set to form three
Network structure is tieed up, not only further increases the intensity of temporarily stifled microballoon, and effectively increases the resistance to elevated temperatures of temporarily stifled microballoon, should
Temporarily stifled microballoon is at 100-120 DEG C and can degraded, and chain rupture turns into soluble small molecular material, within 4-7 hours its
Degradation rate will effectively reduce its residual in reservoir up to 100%.
By using heavy weight additive, the density of prepared temporarily stifled microballoon is improved, is easy to make it be suspended in fracturing fluid, smoothly
It is pumped in stratum, realizes the temporary stall of convection body to improving the efficiency of fracture acidizing.Above-mentioned heavy weight additive is preferably sodium bromide
And/or KBr.Because sodium bromide and KBr are water soluble salt, be easy to the fracturing fluid together row of returning, be not detained in storage
It is safe and harmless to reservoir in layer.
The a diameter of 50-700 microns for the temporarily stifled microballoon being made up of above-mentioned each composition, in order to improve plugging effect, this is temporary
The preferred 100-300 microns of diameter of stifled microballoon, 300-550 microns, 250 microns, 350 microns, 400 microns, 450 microns etc..
Second aspect, the embodiments of the invention provide a kind of preferable composition for temporarily blocking up microballoon, including following weight percent：
Polyvinyl alcohol 25%, gelatin 35%, agar 5%, sodium bromide 31%, sodium tetraborate 1%, formaldehyde 3%.By between above-mentioned each composition
Synergy, this temporarily block up microballoon have good resistance to elevated temperatures, intensity, degradability and temporarily block up performance.
In order to further improve the resistance to elevated temperatures that this temporarily blocks up microballoon, polyvinyl alcohol used is polyvinyl alcohol 1799.Its
In, polyvinyl alcohol 1799 is state of the art, is a kind of common commercially available product.
Further, the density for temporarily blocking up microballoon is 1.2-1.4g/cm3.
By between 1.2-1.4g/cm3, making it be slightly larger than pressure break commonly used in the art the density limitations of temporary stifled microballoon
The density of liquid, to meet in work progress at the scene, this temporarily blocks up microballoon and can be uniformly suspended within fracturing fluid, makes its smooth pump
Stratum, or even deeper stratum are delivered to, so as to realize effective closure to the hole in stratum at diverse location.
The third aspect, the embodiment of the present invention additionally provide a kind of temporarily stifled microballoon Zan Du microballoons group, including multiple temporarily stifled micro-
Ball, temporarily the diameter range of stifled microballoon be 50-700 microns in the Zan Du microballoons group, wherein, temporarily stifled microballoon includes following weight for this
The composition of percentage：Polyvinyl alcohol 23-26%, gelatin 32-36%, agar 4-6%, heavy weight additive 25-32%, sodium tetraborate
0.01-1%, aldehydes curing agent 3-4%,
Preferably, the intermediate value of the diameter for temporarily blocking up microballoon in Zan Du microballoons group is 400-420 microns.
Above-mentioned " the temporarily intermediate value of the diameter of stifled microballoon " refers to that the accumulative diameter percentile of temporarily stifled microballoon reaches 50%
When corresponding particle diameter.Its physical significance is that the diameter of microballoon accounts for 50% more than its particle, is also accounted for less than its particle
50%.
There is the value of the diameter of the temporarily stifled microballoon of 50% or so amount in whole temporarily stifled microballoons.
Specifically, preferably, the number for temporarily blocking up microballoon of a diameter of 500-600 microns in the Zan Du microballoons group
Account for more than the 40% of the number of total temporarily stifled microballoon.For example, between 40%-50%, or between 45%-60%.
Fourth aspect, the embodiment of the present invention additionally provide a kind of preparation method of temporarily stifled microballoon, including：
Ratio in step 101, the embodiment provided according to first aspect between composition, added into water polyvinyl alcohol,
Gelatin, agar and heavy weight additive, it is well mixed, obtains the first mixed solution.
In step 101, because prepared temporarily stifled microballoon includes the composition of following percentage by weight：Polyvinyl alcohol 23-
26%th, gelatin 32-36%, agar 4-6%, heavy weight additive 25-32%, sodium tetraborate 0.01-1%, aldehydes curing agent 3-4%.Institute
So that according to the proportioning between above-mentioned each composition, polyvinyl alcohol, gelatin, agar and heavy weight additive to be added to the water, formed well mixed
First mixed solution.Wherein, above-mentioned heavy weight additive is preferably sodium bromide and/or KBr；The concentration of first mixed solution is preferably
21-38%.
Step 102, the first mixed solution for obtaining step 101 are added in 75-80 DEG C of the oil solution containing emulsifying agent, are obtained
To the second mixed solution, after second mixed solution is stirred into 8-15 minutes by 400-600rpm mixing speed, 15- is cooled to
20℃。
In step 102, by the way that the first mixed solution is added in the oil solution containing emulsifying agent, to enter to the first mixed solution
Row emulsion dispersion, the uniformity that raising polyvinyl alcohol, gelatin, agar and heavy weight additive disperse in aqueous.Specifically, this contains breast
The temperature of the oil solution of agent is preferably 80 DEG C, and the oil solution for containing emulsifying agent is preferably white oil and/liquid stone containing sorbester p17
Wax solution, wherein, in white oil and/atoleine solution containing sorbester p17, the mass fraction of sorbester p17 is 2-5%.
Sodium tetraborate is added in step 103, the second mixed solution obtained into step 102, obtains the 3rd mixed solution,
After stirring 25-35 minutes, stratification, phase of fetching water.
By adding sodium tetraborate into the second mixed solution, it is crosslinked polyvinyl alcohol, to form three-dimensional network knot
Structure, improve its heat-resisting property.
By being stirred 25-35 minutes to the 3rd mixed solution, after preferably 30 minutes, polyvinyl alcohol therein will be complete
Crosslinking, now, by stratification, makes the 3rd mixed solution be divided into water layer and oil reservoir, and after oil reservoir is toppled over, water intaking is mutually
Can.
Step 104, by the aqueous phase obtained in step 103 add aldehyde-containing type curing agent aqueous isopropanol in, stir 55-65
Minute, obtain temporarily blocking up microballoon.
By the way that above-mentioned aqueous phase is added in the aqueous isopropanol of aldehyde-containing type curing agent, stir 55-65 minutes, preferably 60 points
Clock, gelatin therein, agar is carried out solidification dehydration, so as to form the temporarily stifled microballoon with regular shape, and make each microballoon it
Between adhesion.It is understood that the temporarily stifled microballoon being initially formed is present in aqueous isopropanol, it need to be separated.
In order to further remove the isopropanol and other impurities of temporarily stifled microsphere surface, method provided in an embodiment of the present invention is also
Including step 105, obtained temporarily stifled microballoon is cleaned in the step 104 using petroleum ether.
The present invention will be further described through by specific embodiment below.
The specification difference of raw material used is as follows in following examples：
Polyvinyl alcohol is purchased from Shanghai Petrochemial Co Ltd, China Petrochemical Corp, polyvinyl alcohol 1799；
Gelatin is purchased from Hengshui Zhong Yujiao industry Co., Ltd, 2-3 degree industrial gelatines；
Agar is purchased from Yunnan Su Fu Science and Technology Ltd.s, technical grade；
Sodium bromide is purchased from Wujiang Nuo Pu Chemical Co., Ltd.s, technical grade；
KBr is purchased from Wujiang Nuo Pu Chemical Co., Ltd.s, technical grade；
Sodium tetraborate is purchased from Jinan De Wang Chemical Co., Ltd.s, technical grade；
Formaldehyde is purchased from Chemical Co., Ltd. of Jinan Xin Yuan Longhai City, technical grade；
Glutaraldehyde is purchased from Chemical Co., Ltd. of Jinan Xin Yuan Longhai City, technical grade；
Sorbester p17 is purchased from Jinzhou of CNPC, technical grade.
Embodiment 1
A kind of temporarily stifled microballoon is present embodiments provided, this temporarily blocks up microballoon and temporarily stifled microballoon is prepared using following preparation methods
Include the composition of following percentage by weight：Polyvinyl alcohol 23%, gelatin 36%, agar 4%, sodium bromide 30.5%, sodium tetraborate
0.5%th, formaldehyde 4%.
Temporarily stifled microballoon is prepared via a method which to obtain for this：
According to the proportioning of above-mentioned each composition in temporary stifled microballoon, polyvinyl alcohol, gelatin, agar and sodium bromide are added into water,
It is well mixed, obtain the first mixed solution；
First mixed solution of gained is added in 75 DEG C of the white oil solution containing sorbester p17, obtains the second mixed solution,
After second mixed solution is stirred 15 minutes by 400rpm mixing speed, 15 DEG C are cooled to；
Sodium tetraborate is added into the second mixed solution of gained, obtains the 3rd mixed solution, after stirring 25 minutes, is stood
Layering, phase of fetching water.
Gained aqueous phase is added in the aqueous isopropanol containing formaldehyde, stirred 55 minutes, isolated temporarily stifled microballoon, and use
The temporarily stifled microballoon is cleaned multiple times in petroleum ether, dries.
Using the structure of the temporarily stifled microballoon prepared by scanning electron microscopic observation, accompanying drawing 1 is the temporarily stifled microballoon that the present embodiment provides
Scanning electron microscope (SEM) photograph.As shown in Figure 1, the temporarily stifled microballoon prepared by the present embodiment is in uniform chondritic, and prepared is temporary
For the diameter of stifled microballoon about between 50-700 microns, its median diameter is about 411 microns.
Embodiment 2
A kind of temporarily stifled microballoon is present embodiments provided, this temporarily blocks up microballoon and temporarily stifled microballoon is prepared using following preparation methods
Include the composition of following percentage by weight：Polyvinyl alcohol 25%, gelatin 35%, agar 5%, sodium bromide 31%, sodium tetraborate
1%th, formaldehyde 3%.
Temporarily stifled microballoon is prepared via a method which to obtain for this：
According to the proportioning of above-mentioned each composition in temporary stifled microballoon, polyvinyl alcohol, gelatin, agar and sodium bromide are added into water,
It is well mixed, obtain the first mixed solution；
First mixed solution of gained is added in 80 DEG C of the white oil solution containing sorbester p17, obtains the second mixed solution,
After second mixed solution is stirred 10 minutes by 500rpm mixing speed, 18 DEG C are cooled to；
Sodium tetraborate is added into the second mixed solution of gained, obtains the 3rd mixed solution, after stirring 30 minutes, is stood
Layering, phase of fetching water.
Gained aqueous phase is added in the aqueous isopropanol containing formaldehyde, stirred 60 minutes, isolated temporarily stifled microballoon, and use
The temporarily stifled microballoon is cleaned multiple times in petroleum ether, dries.
Utilize the structure of the temporarily stifled microballoon prepared by scanning electron microscopic observation, it is known that, the temporarily stifled microballoon prepared by the present embodiment
In uniform chondritic, the diameter of prepared temporarily stifled microballoon is about between 50-700 microns.
Embodiment 3
A kind of temporarily stifled microballoon is present embodiments provided, this temporarily blocks up microballoon and temporarily stifled microballoon is prepared using following preparation methods
Include the composition of following percentage by weight：Polyvinyl alcohol 26%, gelatin 32%, agar 6%, KBr 32%, sodium tetraborate
0.01%th, glutaraldehyde 3.09%.
Temporarily stifled microballoon is prepared via a method which to obtain for this：
According to the proportioning of above-mentioned each composition in temporary stifled microballoon, polyvinyl alcohol, gelatin, agar and KBr are added into water,
It is well mixed, obtain the first mixed solution；
First mixed solution of gained is added in 77 DEG C of the atoleine solution containing sorbester p17, it is molten to obtain the second mixing
Liquid, after second mixed solution is stirred 15 minutes by 600pm mixing speed, it is cooled to 20 DEG C；
Sodium tetraborate is added into the second mixed solution of gained, obtains the 3rd mixed solution, after stirring 35 minutes, is stood
Layering, phase of fetching water.
Gained aqueous phase is added in the aqueous isopropanol containing glutaraldehyde, stirred 65 minutes, isolated temporarily stifled microballoon, and make
The temporarily stifled microballoon is cleaned multiple times with petroleum ether, dries.
Utilize the structure of the temporarily stifled microballoon prepared by scanning electron microscopic observation, it is known that, the temporarily stifled microballoon prepared by the present embodiment
In uniform chondritic, the diameter of prepared temporarily stifled microballoon is about between 50-700 microns.
Utilize the structure of the temporarily stifled microballoon prepared by scanning electron microscopic observation, it is known that, the temporarily stifled microballoon prepared by the present embodiment
In uniform chondritic, the diameter of prepared temporarily stifled microballoon is about between 50-700 microns.
Embodiment 4
A kind of temporarily stifled microballoon is present embodiments provided, this temporarily blocks up microballoon and temporarily stifled microballoon is prepared using following preparation methods
Include the composition of following percentage by weight：Polyvinyl alcohol 25%, gelatin 35%, agar 5%, KBr 31%, sodium tetraborate
0.5%th, glutaraldehyde 3.5%.
Temporarily stifled microballoon is prepared via a method which to obtain for this：
According to the proportioning of above-mentioned each composition in temporary stifled microballoon, polyvinyl alcohol, gelatin, agar and KBr are added into water,
It is well mixed, obtain the first mixed solution；
First mixed solution of gained is added in 79 DEG C of the atoleine solution containing sorbester p17, it is molten to obtain the second mixing
Liquid, after second mixed solution is stirred 13 minutes by 550pm mixing speed, it is cooled to 18 DEG C；
Sodium tetraborate is added into the second mixed solution of gained, obtains the 3rd mixed solution, after stirring 30 minutes, is stood
Layering, phase of fetching water.
Gained aqueous phase is added in the aqueous isopropanol containing glutaraldehyde, stirred 60 minutes, isolated temporarily stifled microballoon, and make
The temporarily stifled microballoon is cleaned multiple times with petroleum ether, dries.
Utilize the structure of the temporarily stifled microballoon prepared by scanning electron microscopic observation, it is known that, the temporarily stifled microballoon prepared by the present embodiment
In uniform chondritic, the diameter of prepared temporarily stifled microballoon is about between 50-700 microns.
Utilize the structure of the temporarily stifled microballoon prepared by scanning electron microscopic observation, it is known that, the temporarily stifled microballoon prepared by the present embodiment
In uniform chondritic, the diameter of prepared temporarily stifled microballoon is about between 50-700 microns.
Embodiment 5
The density for the temporarily stifled microballoon that the present embodiment is prepared to embodiment 1-4 is tested, and testing procedure is as follows：
The cyclohexane solution for taking certain volume is weighed, then weighs the above-mentioned temporarily stifled microballoon of certain mass, it is complete will temporarily to block up microballoon
Infiltrate entirely in cyclohexane solution, test the volume incrementss of hexamethylene, then the density of microballoon can be calculated by following formula
Go out：
ρ=m/ (v2-v1)
In formula：ρ-be microballoon density, g/cm3；
M-be microballoon quality, g；
v1, v2- it is respectively the volume for infiltrating the hexamethylene before and after temporarily stifled microballoon, cm3。
Test result is as shown in table 1：
Table 1 temporarily blocks up the density measurement table of microballoon
| Temporarily stifled microballoon | Density (g/cm3) |
| Embodiment 1 | 1.2 |
| Embodiment 2 | 1.3 |
| Embodiment 3 | 1.4 |
| Embodiment 4 | 1.3 |
As shown in table 1, the density of temporarily stifled microballoon provided in an embodiment of the present invention is in 1.2-1.3g/cm3Between, higher than routine
Density (the 1.0-1.1g/cm of fracturing fluid3), above-mentioned each temporarily stifled microballoon is suspended in fracturing fluid, be smoothly pumped to stratum,
Improve the efficiency of fracture acidizing.
Embodiment 6
The sealing characteristics for the temporarily stifled microballoon that the present embodiment is prepared by the evaluation test of back-up sand reservoir core plugging to embodiment 1-4 enters
Row test, specifically include this temporarily expansion ratio of stifled microballoon and its when to form the thickness of filter cake be 0.9cm, 8.1 MPa's
Breakthrough pressure gradient when being broken through under pressure to the filter cake.
Specific testing procedure is as follows：
The temporarily stifled microballoon of unit mass is put into liquid to be absorbed, according to the front and rear Mass Calculation of temporary stifled microsphere sample swelling
Expansion ratio (q)：
Q=(m1-m0)/m0
In formula：m0、m1The weight respectively temporarily blocked up before and after microballoon imbibition, g.
Breakthrough pressure gradient is evaluated using back-up sand reservoir core plugging, and certain thickness microballoon is laid in the end face of back-up sand rock core,
Then small displacement displacement clear water, treat that temporarily block up microballoon expands completely, form filter cake, increase displacement pressure, until filter cake is broken through, break through
The ratio for the thickness that pressure is laid with microballoon is to break through fracture gradient.
Test result is as shown in table 2：
Table 2 temporarily blocks up the sealing characteristics test table of microballoon
| Temporarily stifled microballoon | Expansion ratio | Breakthrough pressure gradient (MPa/cm) |
| Embodiment 1 | 3.5 | 9 |
| Embodiment 2 | 3.2 | 9.3 |
| Embodiment 3 | 2.7 | 9.5 |
| Embodiment 4 | 2.9 | 9.1 |
As shown in table 2, the expansion ratio of temporarily stifled microballoon provided in an embodiment of the present invention is high, has good sealing characteristics, and
And its breakthrough pressure gradient is in the range of 9-9.5 MPa/cm, it is seen then that temporarily stifled microballoon intensity prepared by the embodiment of the present invention is higher,
Further increase its sealing characteristics.
Embodiment 7
The degradation property for the temporarily stifled microballoon that the present embodiment is prepared to embodiment 1-4 is tested, and specific testing procedure is as follows：
Take the temporarily stifled microballoon of certain mass to be mixed with as clear water, pour into ageing can, aging, drop in 120 DEG C of baking ovens
The regular hour is solved, filters, weigh afterwards, test its residual content.Test result is as shown in table 3：
Table 3 temporarily blocks up the degradation property test table of microballoon
| Temporarily stifled microballoon | Testing time (h) | Degradation rate (%) |
| Embodiment 1 | 7 | 100 |
| Embodiment 2 | 4 | 100 |
| Embodiment 3 | 5 | 100 |
| Embodiment 4 | 4 | 100 |
As shown in table 3, temporarily stifled microballoon provided in an embodiment of the present invention is degradable within 4-7 hour, and it will not be remained
In reservoir, avoid and reservoir damaged, be one kind to safely and effectively diverting agent.
Presently preferred embodiments of the present invention is the foregoing is only, the protection domain being not intended to limit the invention is all in this hair
Within bright spirit and principle, any modification, equivalent substitution and improvements made etc., protection scope of the present invention should be included in
Within.
Claims (13)
1. a kind of temporarily stifled microballoon, a diameter of 50-700 microns of the temporarily stifled microballoon, the temporarily stifled microballoon include following weight hundred
Divide the composition of ratio：Polyvinyl alcohol 23-26%, gelatin 32-36%, agar 4-6%, heavy weight additive 25-32%, sodium tetraborate 0.01-
1%th, aldehydes curing agent 3-4%；
The heavy weight additive is sodium bromide and/or KBr.
2. temporarily stifled microballoon according to claim 1, it is characterised in that the aldehydes curing agent is formaldehyde and/or glutaraldehyde.
3. temporarily stifled microballoon according to claim 2, it is characterised in that the temporarily stifled microballoon include following weight percent into
Point：Polyvinyl alcohol 25%, gelatin 35%, agar 5%, sodium bromide 31%, sodium tetraborate 1%, formaldehyde 3%.
4. temporarily stifled microballoon according to claim 3, it is characterised in that the polyvinyl alcohol is polyvinyl alcohol 1799.
5. the temporarily stifled microballoon according to claim any one of 1-4, it is characterised in that the density of the temporarily stifled microballoon is 1.2-
1.4g/cm3。
6. a kind of Zan Du microballoons group, it is characterised in that including multiple temporarily stifled microballoons, microballoon is temporarily blocked up in the Zan Du microballoons group
Diameter range be 50-700 microns, the temporarily stifled microballoon includes the composition of following percentage by weight：Polyvinyl alcohol 23-26%,
Gelatin 32-36%, agar 4-6%, heavy weight additive 25-32%, sodium tetraborate 0.01-1%, aldehydes curing agent 3-4%；
The intermediate value of the diameter of temporarily stifled microballoon in the Zan Du microballoons group is 400-420 microns；
The heavy weight additive is sodium bromide and/or KBr.
7. Zan Du microballoons group according to claim 6, it is characterised in that a diameter of in the Zan Du microballoons group
The number of the temporarily stifled microballoon of 500-600 microns accounts for more than the 40% of the number of total temporarily stifled microballoon.
8. a kind of preparation method of the temporarily stifled microballoon described in claim 1, including：
Step a, according to the part by weight in claim 1, polyvinyl alcohol, gelatin, agar and heavy weight additive, mixing are added into water
Uniformly, the first mixed solution is obtained；
Step b, first mixed solution is added in 75-80 DEG C of the oil solution containing emulsifying agent, obtains the second mixed solution,
After second mixed solution is stirred into 8-15 minutes by 400-600rpm mixing speed, 15-20 DEG C is cooled to；
Step c, sodium tetraborate is added into second mixed solution, obtains the 3rd mixed solution, after stirring 25-35 minutes,
Stratification, phase of fetching water；
Step d, the aqueous phase is added in the aqueous isopropanol of aldehyde-containing type curing agent, stirs 55-65 minutes, temporarily blocked up micro-
Ball；
The heavy weight additive is sodium bromide and/or KBr.
9. according to the method for claim 8, it is characterised in that in the step a, the concentration of first mixed solution is
21-38%.
10. according to the method for claim 8, it is characterised in that in the step a, the heavy weight additive be sodium bromide and/or
KBr.
11. according to the method for claim 8, it is characterised in that in the step b, the oil solution containing emulsifying agent is
White oil and/atoleine solution containing sorbester p17.
12. according to the method for claim 8, it is characterised in that the concentration of the aqueous isopropanol of the aldehyde-containing type curing agent
For 80.0%.
13. according to the method described in claim any one of 8-12, it is characterised in that methods described also includes step e：Utilize stone
Oily ether cleans in the step d obtained temporarily stifled microballoon.
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| CN106047323B (en) * | 2016-05-26 | 2019-02-15 | 中国石油集团渤海钻探工程有限公司 | A kind of water solubility diverting agent and preparation method thereof |
| WO2019031613A1 (en) * | 2017-08-10 | 2019-02-14 | 日本合成化学工業株式会社 | Diverting agent and method using same for filling crack of winze |
| CN108822817A (en) * | 2018-05-29 | 2018-11-16 | 北京大德广源石油技术服务有限公司 | Refracturing diverting agent and preparation method thereof |
| CN108952623B (en) * | 2018-08-12 | 2020-09-11 | 张馨月 | Equal-density plugging ball delivery device and method |
| EP3995556A4 (en) * | 2019-07-03 | 2022-08-17 | Mitsubishi Chemical Corporation | Diverting agent and method for blocking fractures in well using same |
| CN111892917B (en) * | 2020-10-09 | 2020-12-11 | 山东科兴化工有限责任公司 | Preparation method of calcium chloride-based water-soluble temporary plugging material for oil field |
| CN112851834B (en) * | 2021-01-08 | 2022-03-18 | 西南石油大学 | Preparation method and application of temperature-resistant agar |
| CN115572589B (en) * | 2022-10-28 | 2024-01-19 | 中国石油天然气集团有限公司 | Formula of gas well water shutoff agent and preparation method thereof |
| CN116120913A (en) * | 2023-04-17 | 2023-05-16 | 成都理工大学 | Self-degrading solid particle type sinking agent and preparation method thereof |
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| CN101848704A (en) * | 2007-07-24 | 2010-09-29 | 耐百生物制药有限公司 | Technology for the preparation of microparticles |
| CN102746837A (en) * | 2012-01-13 | 2012-10-24 | 宫立武 | Microsphere temporary plugging agent for leakage oil well |
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