CN114456788A - Super-amphiphobic composition and preparation method and application thereof - Google Patents
Super-amphiphobic composition and preparation method and application thereof Download PDFInfo
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- 239000000203 mixture Substances 0.000 title claims abstract description 115
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 181
- 239000000843 powder Substances 0.000 claims abstract description 43
- 238000003756 stirring Methods 0.000 claims abstract description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 21
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 20
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 20
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 20
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 20
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000002347 injection Methods 0.000 claims description 154
- 239000007924 injection Substances 0.000 claims description 154
- 239000007788 liquid Substances 0.000 claims description 33
- 238000006073 displacement reaction Methods 0.000 claims description 24
- 238000010276 construction Methods 0.000 claims description 14
- 239000012756 surface treatment agent Substances 0.000 claims description 13
- 238000012544 monitoring process Methods 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 239000003921 oil Substances 0.000 description 60
- 238000011084 recovery Methods 0.000 description 20
- 230000035699 permeability Effects 0.000 description 16
- -1 tert-hexyl Chemical group 0.000 description 15
- 150000002500 ions Chemical class 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
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- 238000005096 rolling process Methods 0.000 description 7
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- 238000011161 development Methods 0.000 description 6
- 230000018109 developmental process Effects 0.000 description 6
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- 238000012360 testing method Methods 0.000 description 6
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- 239000003129 oil well Substances 0.000 description 4
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- 238000009412 basement excavation Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000002120 nanofilm Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 238000009738 saturating Methods 0.000 description 2
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- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- LPZOCVVDSHQFST-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-3-ethylpyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)CC LPZOCVVDSHQFST-UHFFFAOYSA-N 0.000 description 1
- APLNAFMUEHKRLM-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(3,4,6,7-tetrahydroimidazo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)N=CN2 APLNAFMUEHKRLM-UHFFFAOYSA-N 0.000 description 1
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- WTFUTSCZYYCBAY-SXBRIOAWSA-N 6-[(E)-C-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-N-hydroxycarbonimidoyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C/C(=N/O)/C1=CC2=C(NC(O2)=O)C=C1 WTFUTSCZYYCBAY-SXBRIOAWSA-N 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000036772 blood pressure Effects 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
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- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000015784 hyperosmotic salinity response Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005244 neohexyl group Chemical group [H]C([H])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000005325 percolation Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
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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
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/10—Nanoparticle-containing well treatment fluids
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- Engineering & Computer Science (AREA)
- Mining & Mineral Resources (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Environmental & Geological Engineering (AREA)
- Fluid Mechanics (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Geochemistry & Mineralogy (AREA)
- Cosmetics (AREA)
Abstract
The invention discloses a super-amphiphobic composition, which comprises the following components: 100 parts of an alcohol; 20-80 parts of water; 18-59 parts of nano TiO2Powder; 1.8-47 parts of nano SiO2Powder; 0.6-3.7 parts of a surface treating agent. The invention also discloses a preparation method of the super-amphiphobic composition, which comprises the following steps: (1) mixing alcohol and water according to the formula amount, and uniformly stirring to obtain an alcohol-water mixed solution; (2) mixing the nano TiO according to the formula amount2Powder and nano SiO2Uniformly mixing the powder to obtain a mixture A; (3) and (2) adding the surface treating agent in the formula amount into the alcohol-water mixed solution obtained in the step (1) under the condition of stirring at the temperature of 35-45 ℃, stirring for 5-20 minutes, adding the mixture A obtained in the step (2), and continuously stirring for 20-40 minutes to obtain the super-amphiphobic composition. The invention also discloses the application of the super-amphiphobic composition as a pressure-reducing oil-displacing agent.
Description
Technical Field
The invention belongs to the field of material science and engineering, and particularly relates to a super-amphiphobic composition and a preparation method and application thereof.
Background
In the crude oil geological reserves which are proved by China, the proportion of the medium-low permeability reserves is large, the development effect of the used medium-low permeability reserves is not ideal, and the defects of low reserve utilization degree, low single-well yield and high comprehensive water content generally exist. Under the background that the demand of China for petroleum is getting larger and larger, how to develop the medium and low permeability reservoir efficiently becomes a problem which needs to be solved urgently.
The efficient development of the medium-low permeability reservoir is mainly realized by increasing recoverable reserves and potential excavation of residual oil, and the main measures of the two aspects are to improve the water drive development effect. More and more petroleum workers carry out analytical research on evaluation of oil field development effect, residual oil distribution and potential excavation.
At present, the extraction degree of primary oil recovery and secondary oil recovery in China is about 35%, a large amount of residual oil remains in a reservoir, and a considerable part of movable oil is not affected by injected water due to the serious heterogeneity of the reservoir, so that the movable oil cannot be extracted under the existing technical and economic conditions.
In order to improve the recovery efficiency and increase the recoverable reserves, most of the prior methods are to inject an aqueous solution containing a depressurization oil displacement agent into a water injection well. However, the existing pressure-reducing oil displacement agent aqueous solution has the following defects: 1. the effective period of pressure reduction and oil displacement is short; 2. the effect of reducing blood pressure is not obvious; 3. the price is relatively expensive and the dosage is large.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the defects of the prior art, the invention discloses a super-amphiphobic composition and a preparation method and application thereof.
The technical scheme is as follows: a super-amphiphobic composition comprises the following components in parts by mass:
100 parts of an alcohol;
20-80 parts of water;
18-59 parts of nano TiO2Powder;
1.8-47 parts of nano SiO2Powder;
0.6-3.7 parts of a surface treatment agent having the structure of formula:
wherein: n is more than or equal to 20 and more than or equal to 2, m is more than or equal to 100 and more than or equal to 2, R is C1-C10Alkyl group of (1).
Further, the structure of the surface treatment agent is that: n is more than or equal to 15 and more than or equal to 3, and m is more than or equal to 80 and more than or equal to 10.
Further, the surface treatment agent has a structure in which: n is more than or equal to 10 and more than or equal to 4, and m is more than or equal to 30 and more than or equal to 15.
Further, R is C1-C5Alkyl group of (1).
Further, nano SiO2The using amount of the powder is 9-29.5 parts.
Further, nano TiO2The median diameter of the powder is 50-150 nm.
Further, nano SiO2The median diameter of the powder is 50-150 nm.
Further, the amount of water is 25-35 parts.
Further, the alcohol is one or more of methanol, ethanol, propanol, ethylene glycol, glycerol and isopropanol.
The preparation method of the super-amphiphobic composition comprises the following steps:
(1) mixing alcohol and water according to the formula amount, and uniformly stirring to obtain an alcohol-water mixed solution;
(2) mixing the nano TiO according to the formula amount2Powder and nano SiO2Uniformly mixing the powder to obtain a mixture A;
(3) and (2) adding the surface treating agent in the formula amount into the alcohol-water mixed solution obtained in the step (1) under the condition of stirring at the temperature of 35-45 ℃, stirring for 5-20 minutes, adding the mixture A obtained in the step (2), and continuously stirring for 20-40 minutes to obtain the super-amphiphobic composition.
The super-amphiphobic composition is used as a pressure-reducing oil displacement agent.
Further, the above use comprises the steps of:
s1, firstly recording the water injection pressure A of a water injection well to be injected with the super-amphiphobic composition, and recording the daily dose Q1 of the water injection pressure A lower than the dry pressure of 1-2 MPa on the day;
s2, injecting injection liquid containing the super-amphiphobic composition into the water injection well according to the daily injection quantity of Q1, simultaneously monitoring the injection pressure of the water injection well, recording the water injection pressure B until the injection pressure is reduced by 1-3 MPa compared with the water injection pressure A, wherein:
the injection liquid comprises a super-amphiphobic composition and water, and the mass ratio of the super-amphiphobic composition to the water is (0.1-0.6): (99.4 to 99.9);
s3, continuously injecting clear water into the water injection well, wherein the daily dose Q2 of the clear water is n multiplied by Q1, wherein n is the number of days of water injection, and the water injection pressure C and the daily dose Q2 at the moment are recorded until the water injection pressure is 0.5-1 MPa higher than the water injection pressure B;
s4, preparing injection liquid containing the super-amphiphobic composition according to the daily injection quantity of Q2, then injecting the prepared injection liquid into a water injection well, monitoring the injection pressure of the water injection well at the same time, and ending construction until the water injection pressure is reduced by 1-3 MPa compared with the water injection pressure C, wherein:
the injection liquid comprises a super-amphiphobic composition and water, and the mass ratio of the super-amphiphobic composition to the water is (0.1-0.6): (99.4-99.9).
Further, the mass ratio of the super-amphiphobic composition to the water in the step S2 is 0.3: 99.7.
further, the mass ratio of the super-amphiphobic composition to the water in the step S4 is 0.3: 99.7.
the super-amphiphobic composition can weaken the acting force of oil and the rock surface, drop the oil from the rock surface, and form a molecular film on the solid surface, wherein the molecular film also has the lotus leaf effect function, and can achieve the effects of water resistance and oil resistance (namely amphiphobic) so as to avoid secondary adsorption. Due to the super-strong temperature resistance and salt tolerance, the oil displacement agent is not sensitive to water quality, is expected to play a role in the development of ultra-low permeability reservoirs, and has important significance for the oil displacement technical reserve of the ultra-low permeability reservoirs.
The super-amphiphobic composition, the preparation method and the application thereof disclosed by the invention have the following beneficial effects:
1. the super-amphiphobic composition is nontoxic and harmless, does not pollute the environment, has the salt resistance of 50000mg/L, the divalent ion resistance of more than or equal to 2000mg/L and the temperature resistance of 140 ℃;
2. good hydrophobic and oleophobic effect, namely the contact angle of the oil and water is more than or equal to 150 degrees, and the rolling angle is less than or equal to 5 degrees;
3. the oil displacement agent has obvious effect of improving the recovery ratio, can improve the recovery ratio by at least 20% through an indoor physical model test, can play a role in the development of an ultra-low permeability reservoir, and has important significance on the oil displacement technology of the ultra-low permeability reservoir;
4. the preparation method is simple.
Description of the drawings:
fig. 1 is a schematic view of an apparatus for indoor object molding.
1-advection pump
2-first joint
3-first intermediate Container
4-second intermediate container
5-third intermediate Container
6-pressure gauge
7-core tube
8-measuring cylinder
The specific implementation mode is as follows:
the technical solutions of the present invention are further described below with reference to examples, but the examples of the present invention are only illustrative and the present invention is not limited to the embodiments in any way.
In the present invention, all proportions, parts and percentages are by mass unless otherwise indicated.
In the present invention, the substances used are all known substances, and are commercially available or synthesized by known methods.
In the present invention, C1-C10The alkyl group of (b) includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, isohexyl, neohexyl, tert-hexyl, n-heptyl, isoheptyl, neoheptyl, tert-heptyl, n-octyl, isooctyl, neooctyl, tert-octyl, n-nonyl, isononyl, neononyl, tert-nonyl, n-decyl, isodecyl, neodecyl, tert-decyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl.
In the present invention, the apparatus or equipment used is conventional apparatus or equipment known in the art, and is commercially available.
In the invention, the divalent ion resistance test of the super-amphiphobic material adopts a titration method in water quality detection; the contact angle and the rolling angle were measured by using a contact angle measuring instrument (SDC-100S, Guangdong Danit) and a rolling angle measuring instrument (LAUDA Scientific, LSA200-T), respectively.
The experiment for increasing the recovery ratio of the indoor physical model is carried out as follows:
1. test method
1) Measurement of permeability
The oil-gas-water seepage in most formations conforms to Darcy's law, i.e.
Q-seepage through the sand bed, cm3/s
K-permeability of sand layer, Darcy
A-cross sectional area of seepage cm2Here isInternal cross-sectional area of core barrel
DeltaL-the distance between two percolation sections, cm, here the length of the core barrel
Viscosity of mu-liquid, centipoise
Delta P is the converted pressure difference between the cross sections of two seepage flows, MPa, and when the heights of all points are the same, the converted pressure is equal to the actually measured pressure difference.
The permeability is then
Since the permeability is independent of the nature of the liquid, the permeability of the filled core barrel can be measured by water injection. The viscosity of water is known, Δ P is read by a pressure gauge, Q is calculated from the amount of discharged liquid and the discharge time, and the sum of A is a known value, the value of K can be obtained.
2. The test process comprises the following steps:
(1) measuring permeability of the cemented rock core through saturated water;
(2) cementing the core saturated crude oil;
(3) water is driven to 98 percent of water content;
(4) injecting a super-amphiphobic composition system of 0.5PV, and injecting water for replacement of 0.1 PV;
(5) and finishing the subsequent water flooding to 98 percent of water content.
3. Principle of experiment
The test is carried out indoor simulation according to the actual condition of the oil field, the test device diagram is shown in figure 1, and the saturated water permeability measurement is carried out on a cemented rock core with a certain permeability at first; then saturating the core with crude oil; in order to enable the simulation test to be closer to the field, crude oil aging needs to be carried out on the core tube, and the core tube with saturated oil is placed in a 70 ℃ oven to be aged for about 48 hours; and (3) driving water to reach the water content of 98%, injecting a super-amphiphobic composition system to drive 0.5PV, injecting water to replace by 0.1PV, and stopping driving water when the water content reaches 98%.
4) Test procedure
(1) And accurately measuring the permeability K of the rock core by using clear water under the pump displacement of 200mL/h and 300mL/h in sequence: three values are measured under each displacement, and the measurement is carried out under the condition that the displacements are sequentially increased, because the larger the system displacement is, the larger the pressure difference at two ends of the core is, and thus, a large pore channel is easily formed in the core.
(2) Saturated crude oil: and (3) saturating the oil under the pump displacement of 200mL/h until the discharged crude oil does not contain water, and reading the saturated oil quantity through the volume of the discharged clear water.
(3) Aging of crude oil: the core tube was placed in a 70 ℃ oven and aged for about 48 h.
(4) Taking out the core tube, placing the core tube in a 70 ℃ constant-temperature water bath, connecting a pipeline, and performing water drive (paying attention to the uniform setting of the water drive, the discharge capacity is 200 mL/h): and (3) receiving the discharged liquid at the outlet end of the rock core by using a 10mL measuring cylinder during water flooding, recording the pressure when the scale is full, placing the measuring cylinder in a water bath, and respectively reading the oil quantity and the water quantity when an oil-water interface is clear. The water was driven to about 98% moisture content in the core barrel exit effluent (10 mL graduated cylinder was used to receive the core exit effluent) and the water injection was stopped.
(5) The oil displacement agent of the super-amphiphobic system comprises: after a 0.5PV system (with the concentration of 5000mg/L) oil displacement agent is filled into a clean and dry intermediate container, the oil displacement agent enters an oil displacement stage, the pump displacement is uniformly set to be 200mL/h at the stage, and the pressure, the oil quantity and the water quantity of the discharged liquid are recorded every 10mL as in the water displacement.
(6) And (3) subsequent water flooding: the method is similar to the earlier stage water drive, and the water drive is stopped when 2-3 PV is reached.
(7) And calculating the recovery ratio, and dividing the oil quantity produced from the beginning of the injection system to the end of the subsequent water flooding by the saturated oil quantity to obtain the enhanced recovery ratio value.
Example 1
A super-amphiphobic composition comprises the following components in parts by mass:
100 parts of an alcohol;
30 parts of water;
40 parts of nano TiO2Powder;
20 parts of nano SiO2Powder;
2 parts of a surface treatment agent having the formula:
wherein: n is 9, m is 20 and R is ethyl.
Further, nano TiO2The median diameter of the powder is 100 nanometers.
Further, nano SiO2The median diameter of the powder is 100 nanometers.
Further, the alcohol is methanol.
The preparation method of the super-amphiphobic composition comprises the following steps:
(1) mixing alcohol and water according to the formula amount, and uniformly stirring to obtain an alcohol-water mixed solution;
(2) mixing the nano TiO according to the formula amount2Powder and nano SiO2Uniformly mixing the powder to obtain a mixture A;
(3) and (2) adding the surface treating agent with the formula amount into the alcohol-water mixed solution obtained in the step (1) under the condition of stirring at 40 ℃, stirring for 10 minutes, adding the mixture A obtained in the step (2), and continuously stirring for 30 minutes to obtain the super-amphiphobic composition.
The superamphiphobic compositions prepared in this example were tested for their resistance to divalent ions (mainly Ca) by the methods described above2+、Mg2+Ion) is 2200mg/L, can resist the temperature up to 135 ℃, has a contact angle of 155 degrees to oil and water and a rolling angle of 5 degrees; the indoor physical model improves the recovery ratio by 24.5 percent.
The super-amphiphobic composition disclosed by the invention is temperature resistant and salt tolerant, and is suitable for improving the recovery ratio of a low-permeability oil reservoir.
The super-amphiphobic composition is used as a pressure-reducing oil displacement agent.
Injection rate of 20m for day A of water injection well3The actual daily dose is 10m310m of short note3The dry pressure is 32MPa, the water injection pressure (oil pressure) is 30.9MPa, the corresponding oil well contains 58.9 percent of water, the daily oil yield is 5.2t, the oil deposit temperature is 125 ℃, the injected water is clear water, the mineralization degree is 36540mg/L, the pressure reduction and the injection increase are urgently needed, and the recovery ratio is improved.
The application comprises the following steps:
s1, recording the water injection pressure A at 30.9MPa, and recording the daily dose at 10m when the water injection pressure A is lower than the dry pressure of 1.1MPa3；
S2, according to 10m3Daily injection amount, injecting injection liquid containing super-amphiphobic composition into the water injection well, and monitoring injection pressure when 120m is injected3At that time (i.e. by day 12), the injection pressure B was reduced to 28MPa (the injection pressure B was reduced by 2.9 compared to the injection pressure a), the injection of the injection liquid containing the superamphiphobic composition was stopped, and the injection pressure B at that time was recorded, wherein:
the injection liquid comprises a super-amphiphobic composition and water, and the mass ratio of the super-amphiphobic composition to the water is 0.3: 99.7;
s3, then injecting clear water, wherein the daily dose is 10m in the first day3The next day 20m3And 30m on the third day3At this time, the injection pressure increased to 29MPa, and the daily injection amount was recorded at 30m3；
Fourthly, according to the length of 30m3Daily injection amount, injecting injection liquid containing super-amphiphobic composition into water injection well, monitoring injection pressure, and injecting into 200m3Reducing the pressure to 27.5MPa, and finishing construction, wherein:
the injection liquid comprises a super-amphiphobic composition and water, and the mass ratio of the super-amphiphobic composition to the water is 0.3: 99.7.
after the construction is finished, the water injection pressure is reduced by 3.4MPa compared with that before the construction, the validity period is 1 year, and oil is accumulated for 9800 t. And better economic benefit is obtained.
Example 2
A super-amphiphobic composition comprises the following components in parts by mass:
100 parts of an alcohol;
20 parts of water;
18 parts of nano TiO2Powder;
1.8 parts of nano SiO2Powder;
0.6 parts of a surface treatment agent having the structure of the formula:
wherein: n is 2, m is 100 and R is methyl.
Further, nano TiO2The median diameter of the powder is 50 nanometers.
Further, nano SiO2The median diameter of the powder is 50 nanometers.
Further, the alcohol is ethanol.
The preparation method of the super-amphiphobic composition comprises the following steps:
(1) mixing alcohol and water according to the formula amount, and uniformly stirring to obtain an alcohol-water mixed solution;
(2) mixing the nano TiO according to the formula amount2Powder and nano SiO2Uniformly mixing the powder to obtain a mixture A;
(3) and (2) adding the surface treating agent with the formula amount into the alcohol-water mixed solution obtained in the step (1) under the condition of stirring at the temperature of 35 ℃, stirring for 20 minutes, adding the mixture A obtained in the step (2), and continuously stirring for 20 minutes to obtain the super-amphiphobic composition.
The superamphiphobic compositions prepared in this example were tested by the methods described above and were resistant to divalent ions (mainly Ca)2+、Mg2+Ion) 2000mg/L, can resist temperature up to 135 ℃, has a contact angle of 152 degrees to oil and water and a rolling angle of 4.5 degrees; the indoor physical model improves the recovery ratio by 23.1 percent.
Therefore, the super-amphiphobic composition disclosed by the embodiment is temperature-resistant and salt-tolerant, and is suitable for improving the recovery efficiency of low-permeability oil reservoirs.
The super-amphiphobic composition is used as a pressure-reducing oil displacement agent.
Injection well B day injection amount 21m3The actual daily dose is 12m39m of short notes3The dry pressure is 30MPa, the water injection pressure (oil pressure) is 28.5MPa, the water content of a corresponding oil well is 60 percent, the daily oil yield is 5.5t, the oil deposit temperature is 130 ℃, the injected water is clear water, the mineralization degree is 34840mg/L, the pressure reduction and the injection increase are urgently needed, and the recovery ratio is improved.
The application comprises the following steps:
s1, recording water injection firstThe pressure A is 28.5MPa, and the daily dose is 12m when the water injection pressure A is lower than the dry pressure of 1.5MPa3；
S2, according to 12m3Daily injection amount, injecting injection liquid containing super-amphiphobic composition into the water injection well, and simultaneously monitoring injection pressure when 108m is injected3At that time (i.e. by day 9), the injection pressure B was reduced to 27MPa (the injection pressure B was reduced by 1.5 compared to the injection pressure a), the injection of the injection liquid containing the superamphiphobic composition was stopped, and the injection pressure B at that time was recorded, wherein:
the injection liquid comprises a super-amphiphobic composition and water, and the mass ratio of the super-amphiphobic composition to the water is 0.1: 99.9;
s3, then injecting clear water, wherein the daily dose is 12m in the first day324m the next day3At this time, the injection pressure increased to 28MPa, and the daily injection amount was recorded at 24m3；
Fourthly, according to 24m3Daily injection amount, injecting injection liquid containing super-amphiphobic composition into water injection well, monitoring injection pressure, and injecting for 180m3Reducing the pressure to 25.5MPa, and finishing construction, wherein:
the injection liquid comprises a super-amphiphobic composition and water, and the mass ratio of the super-amphiphobic composition to the water is 0.6: 99.4.
after the construction is finished, the water injection pressure is reduced by 3.0MPa compared with that before the construction, the effective period is 11 months, and 9000t of oil is accumulated. And better economic benefit is obtained.
Example 3
A super-amphiphobic composition comprises the following components in parts by mass:
100 parts of an alcohol;
80 parts of water;
59 parts of nano TiO2Powder;
47 parts of nano SiO2Powder;
3.7 parts of a surface treatment agent having the structure of the formula:
wherein: n is 20, m is 100 and R is n-propyl.
Further, nano TiO2The median diameter of the powder is 150 nm.
Further, nano SiO2The median diameter of the powder is 150 nm.
Further, the alcohol is propanol.
The preparation method of the super-amphiphobic composition comprises the following steps:
(1) mixing alcohol and water according to the formula amount, and uniformly stirring to obtain an alcohol-water mixed solution;
(2) mixing the nano TiO according to the formula amount2Powder and nano SiO2Uniformly mixing the powder to obtain a mixture A;
(3) and (2) adding the surface treating agent with the formula amount into the alcohol-water mixed solution obtained in the step (1) under the condition of stirring at 45 ℃, stirring for 5 minutes, adding the mixture A obtained in the step (2), and continuously stirring for 40 minutes to obtain the super-amphiphobic composition.
The superamphiphobic composition prepared in this example was tested against divalent ions (mainly Ca) by the method described above2+、Mg2+Ion) 2500mg/L, can resist temperature up to 135 ℃, has a contact angle of 160 degrees to oil and water and a rolling angle of 5 degrees; the indoor physical model improves the recovery efficiency by 24.7 percent.
Therefore, the super-amphiphobic composition disclosed by the embodiment is temperature resistant and salt tolerant, and is suitable for improving the recovery ratio of a low-permeability oil reservoir.
The super-amphiphobic composition is used as a pressure-reducing oil displacement agent.
Injection well C day injection quantity 19m3The actual daily dose is 9m310m of short note3The dry pressure is 33MPa, the water injection pressure (oil pressure) is 31.9MPa, the water content of a corresponding oil well is 60.9 percent, the daily oil yield is 5t, the oil deposit temperature is 115 ℃, the injected water is clear water, the mineralization degree is 37542mg/L, the pressure reduction and the injection increase are urgently needed, and the recovery ratio is improved.
The application comprises the following steps:
s1, recording the water injection pressure A at 31.9MPa, and recording the daily dose at 9m when the water injection pressure A is lower than the dry pressure of 1.1MPa3；
S2, according to 9m3Daily injection amount, injecting injection liquid containing super-amphiphobic composition into the water injection well, monitoring injection pressure, and when 90m is injected3At that time (i.e. by day 10), the injection pressure B was reduced to 29MPa (the injection pressure B was reduced by 2.9 from the injection pressure a), the injection of the injection fluid containing the superamphiphobic composition was stopped, and the injection pressure B at that time was recorded, wherein:
the injection liquid comprises a super-amphiphobic composition and water, and the mass ratio of the super-amphiphobic composition to the water is 0.6: 99.4 of the total weight of the mixture;
s3, then injecting clear water, wherein the daily dose is 9m in the first day3The next day, 18m3And 27m on day three3At this time, the injection pressure increased to 29.8MPa, and the daily dose was recorded as 27m3；
Fourthly, according to 27m3Daily injection amount, injecting injection liquid containing super-amphiphobic composition into water injection well, monitoring injection pressure, and injecting into 140m3And reducing the pressure to 26.8MPa, and finishing construction, wherein:
the injection liquid comprises a super-amphiphobic composition and water, and the mass ratio of the super-amphiphobic composition to the water is 0.1: 99.9.
after construction, the water injection pressure is reduced by 5.1MPa compared with that before construction, the validity period is 1 year and 3 months, and oil 12504t is accumulated. And better economic benefit is obtained.
Example 4
A super-amphiphobic composition comprises the following components in parts by mass:
100 parts of an alcohol;
35 parts of water;
30 parts of nano TiO2Powder;
40 parts of nano SiO2Powder;
3.5 parts of a surface treatment agent having the structure of the formula:
wherein: n is 3, m is 80 and R is n-butyl.
Further, nano TiO2The median diameter of the powder is 60 nanometers.
Further, nano SiO2The median diameter of the powder is 120 nanometers.
Further, the alcohol is propanol.
The preparation method of the super-amphiphobic composition comprises the following steps:
(1) mixing alcohol and water according to the formula amount, and uniformly stirring to obtain an alcohol-water mixed solution;
(2) mixing the nano TiO according to the formula amount2Powder and nano SiO2Uniformly mixing the powder to obtain a mixture A;
(3) and (2) adding the surface treating agent with the formula amount into the alcohol-water mixed solution obtained in the step (1) under the condition of stirring at 38 ℃, stirring for 6 minutes, adding the mixture A obtained in the step (2), and continuously stirring for 35 minutes to obtain the super-amphiphobic composition.
The superamphiphobic compositions prepared in this example were tested by the methods described above and were resistant to divalent ions (mainly Ca)2+、Mg2+Ion) 2000mg/L, can resist temperature up to 135 ℃, has a contact angle of 150 degrees to oil and water and a rolling angle of 5 degrees; the indoor physical model improves the recovery ratio by 21.5 percent.
Therefore, the super-amphiphobic composition disclosed by the embodiment is temperature resistant and salt tolerant, and is suitable for improving the recovery ratio of a low-permeability oil reservoir.
The super-amphiphobic composition is used as a pressure-reducing oil displacement agent.
D day injection amount of water injection well is 18m3The actual daily dose is 10m38m under note3The dry pressure is 30MPa, the water injection pressure (oil pressure) is 28MPa, the water content of a corresponding oil well is 56.9 percent, the daily oil yield is 4.8t, the oil deposit temperature is 130 ℃, the injected water is clear water, the mineralization degree is 36576mg/L, the pressure reduction and injection increase are urgently needed, and the recovery ratio is improved.
The application comprises the following steps:
s1, recording the water injection pressure A at 28MPa, and recording the daily dose at 10m when the water injection pressure A is lower than the dry pressure by 2MPa3；
S2, according to 10m3Daily injection amount, injecting the composition containing super-amphiphobic into the water injection wellWhile monitoring the injection pressure when injecting 120m3At that time (i.e. by day 10), the injection pressure B was reduced to 26MPa (the injection pressure B was reduced by 2 compared to the injection pressure a), the injection of the injection liquid containing the superamphiphobic composition was stopped, and the injection pressure B at that time was recorded, wherein:
the injection liquid comprises a super-amphiphobic composition and water, and the mass ratio of the super-amphiphobic composition to the water is 0.2: 99.8 of the total weight of the powder;
s3, then injecting clear water, wherein the daily dose is 10m in the first day3The next day 20m3And 30m on the third day3At this time, the injection pressure increased to 27MPa, and the daily injection amount was recorded at 30m3；
Fourthly, according to the length of 30m3Daily injection amount, injecting injection liquid containing super-amphiphobic composition into water injection well, monitoring injection pressure, and injecting into 200m3Reducing the pressure to 25.5MPa, and finishing construction, wherein:
the injection liquid comprises a super-amphiphobic composition and water, and the mass ratio of the super-amphiphobic composition to the water is 0.3: 99.7.
after the construction is finished, the water injection pressure is reduced by 2.5MPa compared with that before the construction, the effective period is 10 months, and the oil is cumulatively increased by 7900 t. And better economic benefit is obtained.
Examples 5 to 11
Substantially the same as in example 1, except that the number of m and n in the structure of the surface treatment agent was different, as shown in the following table:
| n | m | |
| example 5 | 4 | 15 |
| Example 6 | 6 | 20 |
| Example 7 | 10 | 30 |
| Example 8 | 3 | 10 |
| Example 9 | 12 | 40 |
| Example 10 | 20 | 80 |
| Example 11 | 2 | 2 |
Examples 12 to 45
Substantially the same as in example 1, except that the kind of the substituent in the structure of the surface treatment agent is different:
examples 46 to 54
The same as example 2, differing only in the alcohol, is shown in the following table:
the embodiments of the present invention have been described in detail. However, the present invention is not limited to the above-described embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the spirit of the present invention.
Claims (14)
1. A super-amphiphobic composition is characterized by comprising the following components in parts by mass:
100 parts of an alcohol;
20-80 parts of water;
18-59 parts of nano TiO2Powder;
1.8-47 parts of nano SiO2Powder;
0.6-3.7 parts of a surface treatment agent having the structure of formula:
wherein: n is more than or equal to 20 and more than or equal to 2, m is more than or equal to 100 and more than or equal to 2, R is C1-C10The alkyl group of (1).
2. The super-amphiphobic composition of claim 1, wherein the surface treatment agent has the structure: n is more than or equal to 15 and more than or equal to 3, and m is more than or equal to 80 and more than or equal to 10.
3. The super-amphiphobic composition of claim 2, wherein the surface treatment agent has the structure: n is more than or equal to 10 and more than or equal to 4, and m is more than or equal to 30 and more than or equal to 15.
4. The super-amphiphobic composition of claim 1, wherein the substituent R in the structure of the surface treatment agent is C1-C5Alkyl group of (1).
5. The super-amphiphobic composition of claim 1, wherein the nano-SiO is2The using amount of the powder is 9-29.5 parts.
6. The super-amphiphobic composition of claim 1, wherein the nano-TiO is2The median diameter of the powder is 50-150 nm.
7. The super-amphiphobic composition of claim 1, wherein the nano-SiO is2The median diameter of the powder is 50-150 nm.
8. The super-amphiphobic composition of claim 1, wherein the amount of water is 25 to 35 parts.
9. A superamphiphobic composition according to claim 1, wherein the alcohol is one or more of methanol, ethanol, propanol, ethylene glycol, glycerol, isopropanol.
10. A process for the preparation of a super-amphiphobic composition according to any of claims 1 to 9, comprising the steps of:
(1) mixing alcohol and water according to the formula amount, and uniformly stirring to obtain an alcohol-water mixed solution;
(2) mixing the nano TiO according to the formula amount2Powder and nano SiO2Uniformly mixing the powder to obtain a mixture A;
(3) and (2) adding the surface treating agent in the formula amount into the alcohol-water mixed solution obtained in the step (1) under the condition of stirring at the temperature of 35-45 ℃, stirring for 5-20 minutes, adding the mixture A obtained in the step (2), and continuously stirring for 20-40 minutes to obtain the super-amphiphobic composition.
11. Use of the super-amphiphobic composition of any of claims 1 to 9 as a pressure reducing oil displacing agent.
12. The use according to claim 11, wherein the use of a super-amphiphobic composition for a pressure reducing oil displacement agent comprises the steps of:
s1, firstly recording the water injection pressure A of a water injection well to be injected with the super-amphiphobic composition, and recording the daily dose Q1 of the water injection pressure A lower than the dry pressure of 1-2 MPa on the day;
s2, injecting injection liquid containing the super-amphiphobic composition into the water injection well according to the daily injection quantity of Q1, simultaneously monitoring the injection pressure of the water injection well, recording the water injection pressure B until the injection pressure is reduced by 1-3 MPa compared with the water injection pressure A, wherein:
the injection liquid comprises a super-amphiphobic composition and water, and the mass ratio of the super-amphiphobic composition to the water is (0.1-0.6): (99.4 to 99.9);
s3, continuously injecting clear water into the water injection well, wherein the daily dose Q2 of the clear water is n multiplied by Q1, wherein n is the number of days of water injection, and the water injection pressure C and the daily dose Q2 at the moment are recorded until the water injection pressure is 0.5-1 MPa higher than the water injection pressure B;
s4, preparing injection liquid containing the super-amphiphobic composition according to the daily injection quantity of Q2, then injecting the prepared injection liquid into a water injection well, monitoring the injection pressure of the water injection well at the same time, and ending construction until the water injection pressure is reduced by 1-3 MPa compared with the water injection pressure C, wherein:
the injection liquid comprises a super-amphiphobic composition and water, and the mass ratio of the super-amphiphobic composition to the water is (0.1-0.6): (99.4-99.9).
13. The use according to claim 12, wherein the weight ratio of the super-amphiphobic composition to water in step S2 is 0.3: 99.7.
14. the use according to claim 12, wherein the weight ratio of the super-amphiphobic composition to water in step S4 is 0.3: 99.7.
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| US10308857B1 (en) * | 2018-02-28 | 2019-06-04 | China University Of Petroleum (Beijing) | Super-amphiphobic composite material and use of the same as inhibitor, lubricant, reservoir protectant, and accelerator in water-based drilling fluids |
| CN110724511A (en) * | 2019-10-30 | 2020-01-24 | 中国石油化工股份有限公司 | Super-amphiphobic oil displacement material and preparation method thereof |
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| CN1188502A (en) * | 1995-05-23 | 1998-07-22 | 联合胶体有限公司 | Polymers for drilling and reservoir fluids and their use |
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| CN109196074A (en) * | 2016-05-25 | 2019-01-11 | 罗地亚经营管理公司 | The shear restoration of thickening surfactant in stimulation fluid |
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