CN114790384A - Micromolecule imbibition agent and preparation method and application thereof - Google Patents
Micromolecule imbibition agent and preparation method and application thereof Download PDFInfo
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- CN114790384A CN114790384A CN202210609585.1A CN202210609585A CN114790384A CN 114790384 A CN114790384 A CN 114790384A CN 202210609585 A CN202210609585 A CN 202210609585A CN 114790384 A CN114790384 A CN 114790384A
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- imbibition
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- polyoxyethylene ether
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- 238000005213 imbibition Methods 0.000 title claims abstract description 103
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 71
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 21
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 21
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 15
- 239000010452 phosphate Substances 0.000 claims abstract description 15
- ZEIKCEMXRDTCPG-UHFFFAOYSA-N 2-ethylhexyl benzenesulfonate Chemical compound CCCCC(CC)COS(=O)(=O)C1=CC=CC=C1 ZEIKCEMXRDTCPG-UHFFFAOYSA-N 0.000 claims abstract description 12
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 150000003384 small molecules Chemical class 0.000 claims description 42
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 13
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims description 6
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000012074 organic phase Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- -1 isoamylene alcohol Chemical compound 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 230000003472 neutralizing effect Effects 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 230000002269 spontaneous effect Effects 0.000 abstract description 26
- 239000011148 porous material Substances 0.000 abstract description 25
- 238000011084 recovery Methods 0.000 abstract description 24
- 230000000694 effects Effects 0.000 abstract description 13
- 230000035699 permeability Effects 0.000 abstract description 8
- 239000003945 anionic surfactant Substances 0.000 abstract description 7
- 239000012188 paraffin wax Substances 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 49
- 239000000243 solution Substances 0.000 description 37
- 239000004094 surface-active agent Substances 0.000 description 15
- 239000010779 crude oil Substances 0.000 description 12
- 239000002245 particle Substances 0.000 description 11
- 239000012530 fluid Substances 0.000 description 9
- 239000011435 rock Substances 0.000 description 9
- 230000033558 biomineral tissue development Effects 0.000 description 8
- 238000002347 injection Methods 0.000 description 8
- 239000007924 injection Substances 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 6
- 238000006073 displacement reaction Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000000149 penetrating effect Effects 0.000 description 5
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- 230000008859 change Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
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- 238000010438 heat treatment Methods 0.000 description 4
- 230000015784 hyperosmotic salinity response Effects 0.000 description 4
- 239000003350 kerosene Substances 0.000 description 4
- 239000002736 nonionic surfactant Substances 0.000 description 4
- 239000012466 permeate Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002357 osmotic agent Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 230000007480 spreading Effects 0.000 description 3
- 238000003892 spreading Methods 0.000 description 3
- 239000013589 supplement Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 2
- 229940077388 benzenesulfonate Drugs 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical group OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000005465 channeling Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000008398 formation water Substances 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- QVDTXNVYSHVCGW-ONEGZZNKSA-N isopentenol Chemical compound CC(C)\C=C\O QVDTXNVYSHVCGW-ONEGZZNKSA-N 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000012795 verification 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
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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
- C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
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- 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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- 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
- E21B43/25—Methods for stimulating production
- E21B43/26—Methods for stimulating production by forming crevices or fractures
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- Geochemistry & Mineralogy (AREA)
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Abstract
The invention discloses a micromolecule imbibition agent and a preparation method and application thereof, and belongs to the technical field of tight oil reservoir exploitation. The micromolecular imbibition agent comprises the following raw material components in percentage by mass: 20% of isopropanolamide, 15% of isopentene polyoxyethylene ether phosphate, 15% of 2-ethylhexanol benzene sulfonate and 50% of water. The micromolecule penetrant is a micromolecule system compounded by a nonionic-anionic surfactant composed of short paraffin as a main component, has the characteristics of small molecular size and small molecular weight, has extremely strong permeability and excellent spontaneous imbibition effect, can obviously improve the sweep coefficient and the oil washing efficiency of a compact oil reservoir in a micro-nano pore throat, and improves the spontaneous imbibition recovery ratio in the micro-nano pore throat, thereby improving the spontaneous imbibition recovery ratio of the compact oil reservoir.
Description
Technical Field
The invention relates to the technical field of tight oil reservoir exploitation, in particular to a micromolecule imbibition agent and a preparation method and application thereof.
Background
Because conventional oil reservoirs are continuously explored, developed and exploited in a large scale, the reserves of conventional oil and gas contained in the earth are greatly reduced, the energy requirements cannot be met, and the research and development of unconventional oil and gas resources such as compact oil and gas and the like gradually become hot spots of the petroleum industry and become important replacement resources for the future sustainable development of various oil fields. For the development of compact oil, the key is to solve two problems, namely how to furthest reform a reservoir, taking the reformation of the matrix permeability and the volume of the reservoir as targets, fully utilizing hydraulic fracturing to improve the controlled reserves of fractures, enabling more reserves to become movable fluids to participate in seepage and improving the yield after the fracturing; and secondly, the problem of energy effective supplement is solved, and in view of the fact that the energy supplement by water injection is difficult to be effective, the functions of the fracturing fluid must be expanded, so that the fracturing fluid has double functions of energy supplement and crude oil displacement while the fracturing task is perfected. The research on the compact oil fracturing production increasing technology is developed to form a matched fracturing production increasing technology, which is the primary problem to be solved at present.
The low-porosity and low-permeability basic characteristics of a compact oil reservoir make the seepage rule of the compact oil reservoir fundamentally different from that of a conventional oil reservoir, the movement of fluid is described by using a traditional seepage theory under the structural characteristics of a nanoscale pore throat, the exchange of the fluid is expressed as an imbibition effect to a greater extent, the capillary force of the reservoir plays a dominant role, and the capillary force is a key index for influencing the recovery ratio. At present, a compact oil reservoir is generally reformed by large-scale volume fracturing, fracturing fluid can penetrate into small pores of the reservoir under a large-scale fracture network structure, oil gas in the pores can be displaced by imbibition as wetting phase fluid under the action of pore capillary force, and the oil gas enters an artificial fracture system to complete the imbibition process, so that the research on imbibition is a basic work in the development of compact oil. The dynamic characteristics of production after the compact oil fracturing are high yield at the initial stage, fast yield decreasing, large decreasing amplitude, and urgent need of the technology of attack, fracture and energy increasing integration and fracture and later energy increasing and stable production.
The conventional oil reservoir enhanced oil recovery technology cannot be completely copied in a compact oil reservoir, for example, polymer flooding, ternary combination flooding and other injection systems contain macromolecules, cannot be injected into a compact oil reservoir mainly comprising nano pores, and has poor porosity and permeability.
From the injection fluid, the feasible methods for increasing the recovery ratio of the compact oil comprise three methods, namely miscible (immiscible) gas flooding, surfactant (active water) and low-salinity water flooding, and from the injection mode, the feasible methods comprise two modes, namely interwell displacement and single-well throughput. Gas injection (CO) 2 And natural gas) is the mainstream development mode at present, most of the prior experiments are successful, the crude oil recovery rate can be improved by 3-30%, but the laboratory model is too ideal, the energy sweep is unbalanced due to field crack interference and channeling, and the effect difference is larger and even contradictory to the field experiment; the permeability of compact oil reservoir is very low and is less than 0.1 multiplied by 10 -3 μm 2 The method has the advantages that the injectivity of fluid is greatly challenged, the effectiveness of water injection is generally considered to be low, the wettability of a compact oil reservoir belongs to oleophylic to medium wetting, the capillary force is resistance during water injection, the injectivity of the compact oil reservoir is greatly reduced, a surfactant solution (active water) can change the wettability, the potential of improving the recovery ratio of compact oil is realized, but the effect of adding the surfactant is influenced by the temperature of an oil layer, the salinity of formation water, the type and the concentration of the surfactant, and the temperature resistance and the salt tolerance are poor; meanwhile, the surfactant can be adsorbed by huge rock surfaces, particularly for the stratum with higher clay content, the surfactant is quickly adsorbed to change the modified water into clear water, and the effect of improving the recovery ratio is greatly reduced; on the other hand, the viscosity of the surfactant-added water does not vary much, and therefore, the modified water hardly has a significant influence on the oil-water fluidity ratio, and the sweep efficiency is highStill not high.
Disclosure of Invention
The invention aims to provide a small-molecule osmotic agent, a preparation method and application thereof, which are used for solving the problems in the prior art and enabling the small-molecule osmotic agent to have an excellent spontaneous imbibition effect so as to permeate into micro-nano pore throats of a tight oil reservoir and improve the spontaneous imbibition recovery ratio of the tight oil reservoir.
In order to achieve the purpose, the invention provides the following scheme:
one purpose of the invention is to provide a micromolecule imbibition agent, which comprises the following raw material components in percentage by mass: 20% of isopropanolamide, 15% of isopentene polyoxyethylene ether phosphate, 15% of 2-ethylhexanol benzene sulfonate and 50% of water;
the preparation method of the isopentene polyoxyethylene ether phosphate comprises the following steps:
a. under the nitrogen atmosphere, with sodium hydroxide as a catalyst, reacting isoamylene alcohol and ethylene oxide at 90 ℃ until the pressure of a reaction system is not changed;
b. cooling the reaction system to 60 ℃, and neutralizing until the pH value is 7 to obtain isoamylene polyoxyethylene ether;
c. mixing isoamylene polyoxyethylene ether with P 2 O 5 Reacting to obtain isopentene polyoxyethylene ether phosphate;
the preparation method of the 2-ethyl hexanol benzene sulfonate comprises the following steps:
d. under the condition of existence of HCl gas, using anhydrous aluminum trichloride as a catalyst, reacting ethylbenzene and 2-ethylhexanol at 60 ℃, filtering after the reaction is finished, and washing a product to be neutral;
e. d, reacting the product obtained in the step d with sulfuric acid, standing, extracting and collecting an organic phase;
f. and (3) mixing the organic phase with a sodium hydroxide solution, adjusting the pH value of the system to 7, and filtering to obtain the 2-ethylhexanol benzene sulfonate.
Further, the mole ratio of isoamylene alcohol and ethylene oxide in the step a is 1: 3.
further, in step c isoamylene is polymerizedOxyethylene ethers with P 2 O 5 In a molar ratio of 5: 2.
furthermore, the reaction temperature in the step e is 25-30 ℃, and the reaction time is 3 h.
The second purpose of the invention is to provide a preparation method of the micromolecule imbibition agent, which comprises the following steps:
mixing the raw material components according to the mass fraction ratio, and performing ultrasonic treatment to obtain the micromolecule imbibition agent.
Wherein: the temperature of mixing ultrasonic treatment is 50 deg.C, and the time is 5-10 min.
The invention also aims to provide a micromolecule imbibition agent solution which takes water as a solvent and comprises the micromolecule imbibition agent.
Further, the content of the small molecule imbibition agent in the small molecule imbibition agent solution is 0.3 wt%.
The fourth purpose of the invention is to provide the application of the micromolecule imbibition agent and the micromolecule imbibition agent solution in the exploitation of compact oil reservoirs.
The invention overcomes the defect of long chain of the prior polyoxyethylene ether, utilizes short chain olefin and ethylene oxide to synthesize the polyoxyethylene ether, prepares phosphate with the highest esterification rate by controlling variables and changing conditions, enhances the permeability of small molecular chains, replaces nano pore throat crude oil, and further improves the spontaneous imbibition effect.
According to the characteristics of a carbon chain, a lipophilic group and a hydrophilic group of the surfactant and the HLB value, the invention prepares the anionic surfactant SEBS (2-ethylhexanol benzene sulfonate), the HLB value ranges from 12 to 14, the optimal penetrating ability is kept, and the penetration performance of the surfactant is greatly improved by introducing a branched chain of the carbon chain and a benzene sulfonic acid group.
According to the invention, the small molecule imbibition agent system is injected for soaking, the fracturing is carried out through energizing, spontaneous imbibition oil displacement is initiated in the later period to improve the recovery ratio of a compact oil reservoir, and the integrated goal of fracturing and energizing is realized through the integration of injection, soaking, pressing and extraction, so that the energizing and stable production can be realized in the later period of fracturing.
According to the invention, through analyzing the carbon chain composition, hydrophilic group and hydrophilic oil group structure and characteristics and HLB value of the surfactant, the polyoxyethylene ether phosphate nonionic surfactant and the benzene sulfonate anionic surfactant are automatically synthesized, the polyoxyethylene ether phosphate nonionic surfactant and the benzene sulfonate anionic surfactant are small molecular surfactants only having 8-10 carbon atoms, the molecular weight and the molecular size are small, the added organic solvent also has extremely strong carrying and penetrating effects, and the small molecular imbibition agent compounded by the anionic surfactant and the nonionic surfactant can greatly reduce the adsorption loss in the imbibition process, thereby realizing anion-nonionic synergistic effect and obviously improving the spontaneous imbibition recovery rate.
The short-chain alkane group of the micromolecule imbibition agent reduces the molecular weight, and the micromolecule size ensures that the micromolecule imbibition agent has strong permeability, promotes the micromolecule osmotic agent to enter the tiny pore throats of the compact oil reservoir, obviously enlarges the swept range of the compact oil reservoir, improves the swept degree, and further improves the spontaneous imbibition recovery ratio.
The micromolecule penetrant has good temperature resistance (130 ℃) and salt resistance (100000ppm mineralization degree), simultaneously has moderate wetting reversal and interfacial tension reducing capability, so that the micromolecule penetrant has moderate rock spreadability, and can strip crude oil from the rock wall surface and continuously displace the crude oil to achieve the purpose of increasing the yield.
The invention discloses the following technical effects:
aiming at the defects of the prior art, the invention provides a micromolecule penetrant which has the advantages of temperature resistance (130 ℃), excellent salt resistance (100000ppm), low use concentration, wide application range, small molecular size (0.5-1 angstrom), small adsorption loss, large spread degree and good spontaneous imbibition effect. The main component of the micromolecule penetrant is a micromolecule system compounded by nonionic-anionic surfactant consisting of short paraffin, the micromolecule penetrant has the characteristics of small molecular size and small molecular weight, the penetrating power is extremely strong, the micromolecule penetrant has excellent spontaneous imbibition effect due to the synergistic effect of the micromolecule surfactants, the micromolecule penetrant permeates into the micro-nano pore throat of the compact oil reservoir and plays a role in stripping crude oil due to the spreading effect on the surface of rocks, so that the sweep coefficient and the oil washing efficiency of the compact oil reservoir in the micro-nano pore throat are obviously improved, the spontaneous imbibition recovery ratio in the micro-nano pore throat is improved, and the spontaneous imbibition recovery ratio of the compact oil reservoir is further improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required in the embodiments will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is an appearance diagram of a 0.3 wt% small molecule imbibition agent solution according to the invention;
FIG. 2 is a graph of the particle size distribution of a 0.3 wt% small molecule imbibition agent solution of the invention;
FIG. 3 is a graph of the interfacial tension of the small molecule imbibition agent solution of the invention;
figure 4 is a graph of spontaneous imbibition recovery in tight reservoirs for different systems of example 6 of the present invention.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but rather as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in the present disclosure, it is understood that each intervening value, to the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated herein by reference to disclose and describe the methods and/or materials in connection with which the documents are cited. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
Example 1
Preparation of nonionic surfactant YEO-1 (isoamylene polyoxyethylene ether phosphate):
(1) adding 2.4g of sodium hydroxide catalyst into a reaction kettle at normal temperature, then adding 5mol of isopentenol, replacing the air in the kettle with nitrogen, maintaining a vacuum environment, then heating to 90 ℃, continuously adding 15mol of ethylene oxide, and ensuring that the molar ratio is 1: the mixture is added at a constant speed within 3, 5 hours, stirred and kept warm until the pressure is not changed any more;
(2) after the reaction process is finished, cooling, adding 0.1% HCl for neutralization until the pH value is 7 when the temperature is reduced to 60 ℃, and filtering and purifying to obtain a reaction product isoamylene polyoxyethylene ether;
(3) 5mol of isoamylene polyoxyethylene ether is put into a three-neck flask, the temperature is kept at 45 ℃, and 2mol of P is slowly added under the condition of high-speed stirring 2 O 5 And adding the mixture at a constant speed within 2 hours, slowly heating to 80 ℃ after the addition, keeping the temperature and continuously reacting for 5 hours, adding 200g of water every 1.5 hours in the esterification reaction until the reaction is finished, and continuously adding 50g of water at 70 ℃ for reacting for 1 hour to ensure that reactants are completely esterified, thereby finishing the synthesis work of the phosphate and detecting the acid value. Cooling to below 50 ℃, neutralizing phosphate with 1% sodium hydroxide solution at 70 ℃ according to the measured acid value result until the pH value is 7, and carrying out heat preservation reaction for 3h to obtain the product, wherein the content of the monoester is measured to be as high as 96%.
Example 2
Preparation of anionic surfactant SEBS (2-ethylhexanol benzenesulfonate):
(1) adding 5mol of ethylbenzene and anhydrous aluminum trichloride as a catalyst into a reactor, stirring and heating to 60 ℃, then introducing dry HCl gas, adding 5mol of 2-ethylhexanol at a constant speed, heating to 60 ℃ after dropwise adding, continuously reacting for 5 hours, then performing suction filtration and separation, and washing a product to be neutral by using hot water;
(2) dropwise adding 98 wt% sulfuric acid under stirring, controlling the time to be 1h, keeping the temperature at 25 ℃, reacting for 3h, stopping stirring after the reaction is finished, standing for 1h, then cooling to 40 ℃, slowly adding 10mL of water at a constant speed, pouring into a separating funnel, standing for layering, and separating an upper organic phase for later use;
(3) adding 50mL of 10 wt% sodium hydroxide solution into a four-mouth bottle to neutralize the residual sulfuric acid, slowly adding the organic phase after stirring, keeping the temperature at 50 ℃, finally adjusting the pH value to 7 by using 10 wt% sodium hydroxide solution, finally adding a small amount of sodium chloride, and filtering to obtain a white pasty product.
Example 3
A micromolecule imbibition agent comprises the following raw material components in percentage by mass: 20% isopropanolamide; 15% of isoamylene polyoxyethylene ether phosphate; 15% 2-ethylhexanol benzenesulphonate; 50% clear water.
Wherein isopentenyl polyoxyethylene ether phosphate and 2-ethylhexanol benzenesulfonate were prepared from examples 1 and 2, respectively.
The preparation method of the micromolecule imbibition agent comprises the following steps:
the raw material components are placed in a beaker according to the mass fraction ratio, and the beaker is placed in an ultrasonic cleaning instrument, the temperature is kept at 50 ℃, and the ultrasonic treatment is carried out for 5min, so as to prepare the micromolecule imbibition agent.
And (3) performing performance verification on the prepared micromolecule imbibition agent:
the small molecule imbibition agent in example 3 was diluted with clear water to prepare a 0.3 wt% small molecule imbibition agent solution.
Example 4 particle size of Small molecule imbibition agent solution
The micromolecule imbibition agent prepared in embodiment 3 of the invention is prepared by compounding short-chain alkane group surfactants, the molecular weight is small, the molecular size is 0.5-1 angstrom, the sub-nanoscale surfactant size is beneficial to forming nanoscale solution, the particle size of the formed solution is 10-20nm, the solution can enter the tiny complex pore throat of a compact rock core, and crude oil in the tiny pore throat of a compact oil reservoir is replaced, so that the swept degree of the compact oil reservoir is improved, and the spontaneous imbibition effect is improved.
Wherein, the appearance of the 0.3 wt% micromolecule imbibition agent solution is shown in figure 1, and the particle size distribution is shown in figure 2.
Example 5 Small molecule imbibition agent solution interfacial tension
The interfacial tension of the small molecule imbibition agent solution and kerosene was measured using an interfacial tension meter, as shown in fig. 3. The micromolecule imbibition agent solution and kerosene reach the equilibrium interfacial tension value in a short time, and the micromolecule imbibition agent solution and kerosene have the capability of properly reducing the interfacial tension (10) -1 mN/m), the oil-water interfacial tension determines the spreading capacity of the micromolecule penetrating and absorbing agent on the rock surface, and the proper low interfacial tension value is beneficial to the micromolecule penetrating agent system to strip crude oil on the rock surface and reduce the adsorption quantity of the crude oil on the shale, so that the spreading coefficient is improved by changing the oil-water interfacial tension, the stripping degree of the crude oil on the core surface is greatly improved, and the oil washing efficiency is improved.
FIG. 3 is a diagram of interfacial tension of a small molecule imbibition agent solution.
Example 6 spontaneous imbibition recovery ratio of Small molecule imbibition agent solution
And (3) carrying out spontaneous imbibition experiments on the prepared small molecule imbibition agent solution (0.3 wt%), conventional surfactant (0.3 wt% SDS) solution, single YEO-1 small molecule imbibition agent solution (0.3 wt%) and clean water in a 0.1md compact core, wherein the experiment temperature is normal temperature, the experimental oil is kerosene, and the spontaneous imbibition recovery ratio of the small molecule imbibition agent solution (0.3 wt%) is up to 40% and is far higher than that of the clean water, the conventional surfactant (0.3 wt% SDS) and the single YEO-1 small molecule imbibition agent solution (0.3 wt%) in the compact oil reservoir. The micromolecule imbibition agent is automatically adsorbed on an oil/water interface to form a micromolecule adsorption layer, so that the interfacial tension is reduced, oil drops are favorably dispersed and deformed, the migration resistance is reduced, and the oil washing efficiency is improved; secondly, the small-molecule penetrant has strong permeability to permeate into the micro-nano pore throats, quickly permeate into the oil phase from the water phase, effectively clean and strip crude oil, and improve sweep efficiency. Both effects make it possible to significantly increase the rate of imbibition recovery in both the large pore throat and the small pore throat.
Of these, the single YEO-1 small molecule imbibition agent solution differs from the small molecule imbibition agent solutions prepared herein only in that it does not contain the 2-ethylhexanol benzenesulfonate component.
Figure 4 is the spontaneous imbibition recovery in tight reservoirs for different systems.
Example 7 evaluation method of spontaneous imbibition recovery ratio of tight reservoir
The spontaneous imbibition experiment can show the imbibition performance of the micromolecule imbibition agent, but the extraction degree of the micromolecule imbibition agent to pore throats of compact rock cores with different scales cannot be judged. By observing saturated water and saturated oil of the rock core and performing Nuclear Magnetic Resonance (NMR) images after spontaneous imbibition and oil displacement by using a micromolecule imbibition agent solution, the recovery ratios of the micromolecule imbibition agent to pore throats with different sizes are obtained, and therefore the micromolecule imbibition agent with strong osmotic capacity and spontaneous imbibition capacity is selected preferably. The stronger the permeability is, the stronger the crude oil displacement ability of the micro-nano pore throat is, and the higher the spontaneous imbibition recovery rate is.
The spontaneous imbibition recovery ratio of the small molecule imbibition agent at different pore throats is shown in table 1.
TABLE 1
| Type of hole | Pore size (micron) | Spontaneous imbibition recovery |
| Nano-pores | 0～0.7 | 17％ |
| Micro-pores | 0.7～9 | 8％ |
| Macroscopic hole | 9～300 | 12％ |
Example 8 temperature and salt tolerance experiment of small molecule imbibition agent
(1) Temperature resistance test: and fifthly, dividing the prepared 100g of micromolecule imbibition agent solution into five equal parts, respectively placing the five equal parts into constant-temperature drying ovens at 20 ℃, 50 ℃, 80 ℃, 110 ℃ and 130 ℃, standing the five equal parts for one week, taking out the five equal parts, observing the appearance of the five equal parts, and measuring the change condition of the particle size at different temperatures. The results are shown in Table 2.
TABLE 2
| Temperature/. |
20 | 50 | 80 | 110 | 130 |
| Particle size/nm | 16 | 18 | 18 | 17 | 20 |
As can be seen from Table 2, the particle size at different temperatures is not greatly different, and the small molecule imbibition agent has high temperature stability.
(2) Salt tolerance test: mineralized water with the degree of mineralization of 0ppm, 10000ppm, 50000ppm and 10000ppm is prepared respectively, the small molecule imbibition agent prepared in the embodiment 3 is diluted by water with different degrees of mineralization, and 0.3 wt% small molecule imbibition agent solution is prepared, and the degree of mineralization is different. Standing for one week, taking out, observing the appearance, and determining the particle size change of the small molecule imbibition agent under different mineralization degrees. The results are shown in Table 3.
TABLE 3
| Degree of mineralization/ppm | 0 | 10000 | 50000 | 100000 |
| Particle size/nm | 16 | 13 | 10 | 18 |
As can be seen from Table 3, the particle size of the small molecule imbibition agent solution decreases with increasing degree of mineralization, but when the degree of mineralization is higher than 50000ppm, the particle size of the small molecule imbibition agent solution slightly increases and the small molecule imbibition agent has strong salt tolerance.
The above-described embodiments are only intended to illustrate the preferred embodiments of the present invention, and not to limit the scope of the present invention, and various modifications and improvements made to the technical solution of the present invention by those skilled in the art without departing from the spirit of the present invention should fall within the protection scope defined by the claims of the present invention.
Claims (8)
1. The micromolecule imbibition agent is characterized by comprising the following raw material components in percentage by mass: 20% of isopropanolamide, 15% of isopentene polyoxyethylene ether phosphate, 15% of 2-ethylhexanol benzene sulfonate and 50% of water;
the preparation method of the isopentene polyoxyethylene ether phosphate comprises the following steps:
a. under the atmosphere of nitrogen, sodium hydroxide is used as a catalyst, isoamylene alcohol and ethylene oxide are reacted at the temperature of 90 ℃ until the pressure of a reaction system is not changed;
b. cooling the reaction system to 60 ℃, and neutralizing until the pH value is 7 to obtain isoamylene polyoxyethylene ether;
c. mixing isoamylene polyoxyethylene ether with P 2 O 5 Reacting to obtain isopentene polyoxyethylene ether phosphate;
the preparation method of the 2-ethyl hexanol benzene sulfonate comprises the following steps:
d. under the condition of existence of HCl gas, using anhydrous aluminum trichloride as a catalyst, reacting ethylbenzene and 2-ethylhexanol at 60 ℃, filtering after the reaction is finished, and washing a product to be neutral;
e. d, reacting the product obtained in the step d with sulfuric acid, standing, extracting and collecting an organic phase;
f. and (3) mixing the organic phase with a sodium hydroxide solution, then adjusting the pH value of the system to 7, and filtering to obtain the 2-ethylhexanol benzene sulfonate.
2. The small molecule imbibition agent of claim 1, wherein the molar ratio of isoamylene alcohol to ethylene oxide in step a is 1: 3.
3. the small molecule imbibing agent of claim 1, wherein said isoamylene polyoxyethylene ether is mixed with P in step c 2 O 5 In a molar ratio of 5: 2.
4. the small molecule imbibition agent of claim 1, wherein the reaction temperature in step e is 25-30 ℃ and the reaction time is 3 h.
5. The method of preparing a small molecule imbibition agent of any of claims 1-4, comprising the steps of:
mixing the raw material components according to the mass fraction ratio, and performing ultrasonic treatment to obtain the micromolecule imbibition agent.
6. A small molecule imbibition agent solution, which is characterized in that water is used as a solvent, and the composition comprises the small molecule imbibition agent of any one of claims 1-4.
7. The small molecule imbibition agent solution of claim 6, wherein the small molecule imbibition agent is present in the small molecule imbibition agent solution at a level of 0.3 wt%.
8. Use of a small molecule imbibition agent according to any of claims 1-4 or a small molecule imbibition agent solution according to any of claims 6-7 in tight reservoir exploitation.
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