CN113684013B - Oil displacement cleanup additive and preparation method and application thereof - Google Patents
Oil displacement cleanup additive and preparation method and application thereof Download PDFInfo
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- 238000006073 displacement reaction Methods 0.000 title claims abstract description 67
- 239000000654 additive Substances 0.000 title claims abstract description 55
- 230000000996 additive effect Effects 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000004094 surface-active agent Substances 0.000 claims abstract description 55
- -1 sulfonate compound Chemical class 0.000 claims abstract description 47
- JMFRWRFFLBVWSI-NSCUHMNNSA-N coniferol Chemical compound COC1=CC(\C=C\CO)=CC=C1O JMFRWRFFLBVWSI-NSCUHMNNSA-N 0.000 claims abstract description 46
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 34
- 150000001875 compounds Chemical class 0.000 claims abstract description 33
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229940119526 coniferyl alcohol Drugs 0.000 claims abstract description 23
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 20
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 20
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 18
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000001768 cations Chemical class 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 5
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 3
- 239000011149 active material Substances 0.000 claims description 2
- 230000000638 stimulation Effects 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 45
- 238000003306 harvesting Methods 0.000 abstract description 4
- 239000003921 oil Substances 0.000 description 73
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 238000011084 recovery Methods 0.000 description 17
- 239000011734 sodium Substances 0.000 description 14
- 229910052708 sodium Inorganic materials 0.000 description 12
- 150000003839 salts Chemical class 0.000 description 10
- 239000010779 crude oil Substances 0.000 description 9
- 239000003513 alkali Substances 0.000 description 8
- 239000006260 foam Substances 0.000 description 8
- 230000008901 benefit Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000010793 Steam injection (oil industry) Methods 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 230000002195 synergetic effect Effects 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000003945 anionic surfactant Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000007853 buffer solution Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000005187 foaming Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- YQGOJNYOYNNSMM-UHFFFAOYSA-N eosin Chemical compound [Na+].OC(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C(O)=C(Br)C=C21 YQGOJNYOYNNSMM-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 description 1
- 230000000930 thermomechanical effect Effects 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/04—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups
- C07C303/06—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups by reaction with sulfuric acid or sulfur trioxide
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/24—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfuric acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/02—Preparation of ethers from oxiranes
- C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/26—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of hydroxy or O-metal groups
-
- 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
-
- 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
- E21B43/24—Enhanced recovery methods for obtaining hydrocarbons using heat, e.g. steam injection
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Mining & Mineral Resources (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Environmental & Geological Engineering (AREA)
- Geochemistry & Mineralogy (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides an oil displacement cleanup additive, a preparation method and an application thereof. The preparation method comprises the step S1 of carrying out ring opening reaction on coniferyl alcohol, ethylene oxide and a first solvent under alkaline conditions to obtain a product system containing a ring opening compound; step S2, adding the product system containing the ring-opening compound, SO 3 And a second solvent to carry out sulfonation reaction to obtain a sulfonate compound; and step S3, mixing the sulfonate compound and the surface active substance to obtain the oil displacement cleanup additive; wherein the surface active substance is a mixture of a fluorocarbon surfactant and ammonium bicarbonate, and the ring-opening compound and the sulfonate compound respectively have the following structural formulas:
M + is a monovalent cation. The method is simple and low in cost, and the effect of solving the problem that the multi-cycle steam huff and puff harvesting effect is poor is obvious.
Description
Technical Field
The invention relates to the technical field of petroleum development, and relates to an oil displacement cleanup additive, and a preparation method and application thereof.
Background
The steam huff and puff technology is one of the important technologies for developing the heavy oil reservoir, and has the advantages of less investment, relatively simple process technology, fast yield increase and good economic benefit. However, after the heavy oil reservoir is subjected to multi-cycle steam huff-puff oil extraction, the formation pressure is greatly reduced, the underground water storage amount is large, the thermal efficiency of injected steam is deteriorated, the recovery period is long, the oil-steam ratio is reduced, and the extraction effect is increasingly poor, so that how to further improve the multi-cycle steam huff-puff development effect of the heavy oil reservoir and improve the recovery efficiency in the huff-puff stage is an urgent problem to be solved.
The addition of the oil displacement and discharge aiding agent while steam huff and puff is an effective method for solving the problems. The oil displacement and drainage assistant can reduce the viscosity of crude oil, reduce the pressure of steam injection and reduce the lifting resistance, thereby achieving the purpose of improving the recovery ratio in the later period of multiple rounds of steam huff and puff. At present, the main component of the oil displacement cleanup additive is a hydrocarbon surfactant, but the oil displacement cleanup additive has the problems of insufficient surface activity, difficult application in high temperature and acidic environment and the like, and has limited capability of solving the problem of poor development effect after multi-cycle steam huff and puff oil recovery.
Disclosure of Invention
The invention mainly aims to provide an oil displacement cleanup additive, and a preparation method and application thereof, so as to solve the problem that the oil displacement cleanup additive in the prior art has limited capability of deteriorating development effect after multi-cycle steam huff-puff oil recovery.
In order to achieve the above objects, according to one aspect of the present invention, there is provided a method for preparing an oil displacement assistant, the method comprising: step S1, carrying out ring-opening reaction on coniferyl alcohol, ethylene oxide and a first solvent under an alkaline condition to obtain a product system containing a ring-opening compound; step S2, adding a product system containing a ring-opening compound, SO 3 And a second solvent to carry out sulfonation reaction to obtainTo sulfonate compounds; and step S3, mixing the sulfonate compound and the surface active substance to obtain the oil displacement cleanup additive; wherein the surface active substance is a mixture of a fluorocarbon surfactant and ammonium bicarbonate, and the ring-opening compound and the sulfonate compound respectively have the following structural formulas:
M + is a monovalent cation.
Further, the mass ratio of the coniferyl alcohol to the ethylene oxide is 1: 2-1: 1.
Further, the coniferyl alcohol and SO 3 The mass ratio of (A) to (B) is 1: 0.5-1: 1.
Furthermore, the mass ratio of the fluorocarbon surfactant to the ammonium bicarbonate in the surface active substance is 0.1: 1.5-2.5.
Further, the mass ratio of the sulfonate compound to the surface active substance is 1:1 to 2: 1.
Further, the ring-opening reaction is carried out at 80-90 ℃.
Further, an alkaline substance is adopted to form an alkaline condition, the alkaline substance is preferably selected from one or more of sodium hydroxide, potassium hydroxide and lithium hydroxide, and the molar ratio of coniferyl alcohol to the alkaline substance is preferably 1: 3-2: 3.
Further, the first solvent and the second solvent are respectively and independently selected from one or more of dichloroethane, acetonitrile, toluene and dioxane.
According to another aspect of the invention, an oil displacement cleanup additive is provided, and is prepared by any one of the preparation methods.
According to another aspect of the invention, the application of the oil displacement cleanup additive is provided, the oil displacement cleanup additive is used in cooperation with steam huff and puff, and the oil displacement cleanup additive is any one of the oil displacement cleanup additives.
By applying the technical scheme of the invention, coniferyl alcohol and ethylene oxide are utilized under alkaline condition (M) + Is a cation from alkaline conditions) to obtain a ring-opened compound, and then the ring-opened compound and SO are utilized 3 The sulfonate compound is used as a novel aralkyloxyalkyl sulfonate, and the structure of the sulfonate compound has a high-temperature-resistant phenol-like structure, so that the sulfonate compound has high-temperature-resistant performance as a novel anionic surfactant, and has the advantages of strong interfacial activity, high salt resistance, complex formulation, high temperature resistance, foamability and good compatibility with crude oil. Although the fluorocarbon surfactant has high surface activity, high thermomechanics and high chemical stability (acid resistance, alkali resistance and oxidation resistance), the price is expensive, so that the sulfonate compound, the ammonium bicarbonate and the fluorocarbon surfactant are matched for use, on one hand, the two can further strengthen the performances of each other by synergistic action, so that the oil displacement cleanup additive comprising the two has the performances of strong surface activity, foamability, high salt resistance, high temperature resistance, high chemical stability and the like, on the other hand, the cost can be reduced, and simultaneously, the ammonium bicarbonate is decomposed to generate CO 2 And NH 3 Gas of CO 2 Has the functions of increasing energy and reducing viscosity, NH 3 The alkaline buffer solution formed after being dissolved in water has stronger oil washing capacity. Therefore, the oil displacement cleanup additive is matched with steam huff and puff to displace oil, so that the oil displacement cleanup additive can collect steam, surfactant, alkali and CO 2 、NH 3 The foam is integrated with the oil-water interface tension, the water lock is removed, flowback is facilitated, the viscosity of crude oil and the steam injection pressure are reduced, the lifting resistance is reduced, the low-permeability layer is started by utilizing the foam profile control effect, the steam swept volume is enlarged, the steam huff and puff effect is improved, the actual problem that the multi-cycle steam huff and puff recovery effect is poor is solved, and the recovery yield in the huff and puff stage is effectively improved. The method is simple and low in cost, and the effect of solving the problem that the multi-cycle steam huff and puff harvesting effect is poor is obvious.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As analyzed by the background technology, the oil displacement cleanup additive in the prior art has the problem of limited capability of solving the problem of poor development effect after multi-cycle steam huff and puff oil recovery, and in order to solve the problem, the invention provides the oil displacement cleanup additive and the preparation method and the application thereof.
In an exemplary embodiment of the present application, a method for preparing an oil displacement and drainage aid is provided, the method comprising: step S1, carrying out ring-opening reaction on coniferyl alcohol, ethylene oxide and a first solvent under alkaline conditions to obtain a ring-opening compound; step S2, adding ring-opening compound and SO 3 And a second solvent to carry out sulfonation reaction to obtain a sulfonate compound; step S3, mixing a sulfonate compound and a surface active substance to obtain an oil displacement cleanup additive; wherein the surface active substance is a mixture of a fluorocarbon surfactant and ammonium bicarbonate, and the ring-opening compound and the sulfonate compound respectively have the following structural formulas:
M + is a monovalent cation.
The application utilizes coniferyl alcohol and ethylene oxide under alkaline conditions (M) + Is a cation from alkaline conditions) to obtain a ring-opened compound, and then the ring-opened compound and SO are utilized 3 The sulfonate compound is used as a novel aralkyloxyalkyl sulfonate, and the structure of the sulfonate compound has a high-temperature-resistant phenol-like structure, so that the sulfonate compound has high-temperature-resistant performance as a novel anionic surfactant, and has the advantages of strong interfacial activity, high salt resistance, complex formulation, high temperature resistance, foamability and good compatibility with crude oil. The fluorocarbon surfactant hasHigh surface activity, high thermomechanical and high chemical stability (acidproof, alkali-proof, anti-oxidation), but its price is more expensive, therefore this application uses sulfonate compound and ammonium bicarbonate, fluorocarbon surfactant cooperation, on the one hand the two carry out synergistic action and can further strengthen performance each other for displacement of reservoir oil cleanup additive including the two possesses extremely strong surface activity, foamability, high salt resistance, high temperature resistance, high chemical stability's performance, on the other hand can reduce cost, ammonium bicarbonate decomposes simultaneously and produces CO 2 And NH 3 Gas of CO 2 Has the functions of increasing energy and reducing viscosity, NH 3 The alkaline buffer solution formed after dissolving in water has stronger oil washing capacity. Therefore, the oil displacement cleanup additive is matched with steam huff and puff to displace oil, so that the oil displacement cleanup additive can collect steam, surfactant, alkali and CO 2 、NH 3 The foam is integrated with the oil-water interface tension, the water lock is removed, flowback is facilitated, the viscosity of crude oil and the steam injection pressure are reduced, the lifting resistance is reduced, the low-permeability layer is started by utilizing the foam profile control effect, the steam swept volume is enlarged, the steam huff and puff effect is improved, the actual problem that the multi-cycle steam huff and puff recovery effect is poor is solved, and the recovery yield in the huff and puff stage is effectively improved. The method is simple and low in cost, and the effect of solving the problem that the multi-cycle steam huff and puff harvesting effect is poor is obvious.
In order to convert coniferyl alcohol and the ring-opened compound into a ring-opened compound as much as possible, it is preferable that the amount of ethylene oxide is excessive, and in order to keep costs down, it is more preferable that the mass ratio of coniferyl alcohol to ethylene oxide is 1:2 to 1:1.
In order to convert the ring-opened compound into a sulfonate compound as much as possible, SO is preferred 3 In order to achieve both an excess and cost reduction, coniferyl alcohol and SO are more preferably used 3 The mass ratio of (A) to (B) is 1: 0.5-1: 1.
In an embodiment of the present application, a mass ratio of the fluorocarbon surfactant to the ammonium bicarbonate in the surfactant is 0.1: 1.5-2.5.
The fluorocarbon surfactant and the ammonium bicarbonate in the proportion can effectively exert the surface activity of the fluorocarbonThe high surface activity, high thermodynamic and chemical stability of the agent are realized, the cost is controlled, and the CO is controlled 2 And NH 3 The amount of the gas further controls the recovery effect of the oil displacement by matching the oil displacement and displacement assistant with the steam throughput.
As stated above, the sulfonate compound and the surface active substance respectively have some excellent performances, and in order to improve the synergistic effect of the sulfonate compound and the surface active substance and obtain the oil displacement cleanup additive with excellent performances, the mass ratio of the sulfonate compound to the surface active substance is preferably 1: 1-2: 1.
In order to improve the ring-opening reaction efficiency of coniferyl alcohol and ethylene oxide, the ring-opening reaction is preferably carried out at 80-90 ℃.
In order to promote the ring-opening reaction of coniferyl alcohol and ethylene oxide and obtain the ring-opened compound with high efficiency, the alkaline condition is preferably formed by using an alkaline substance, the alkaline substance is preferably selected from one or more of sodium hydroxide, potassium hydroxide and lithium hydroxide, and the molar ratio of the coniferyl alcohol to the alkaline substance is preferably 1: 3-2: 3. M + From cations in alkaline substances, e.g. Na + ，K + ，Cs + ，NH 4 + M is preferred in this application + Is Na + 、K + 、Cs + One or more of (a).
In one embodiment of the present application, the first solvent and the second solvent are each independently selected from one or more of dichloroethane, acetonitrile, toluene, dioxane.
The ring-opening reaction and sulfonation reaction of the present application are carried out in the above organic solvent with higher efficiency.
In another exemplary embodiment of the application, an oil displacement cleanup additive is provided, and the oil displacement cleanup additive is prepared by the preparation method.
The application utilizes coniferyl alcohol and ethylene oxide under alkaline conditions (M) + Is a cation from alkaline conditions) to obtain a ring-opened compound, and then the ring-opened compound and SO are utilized 3 Carrying out sulfonation reaction, introducing sulfonic group into the structure of ring-opening compound, and obtaining the product under alkaline conditionThe sulfonate compound is used as a novel aralkyloxy alkyl sulfonate, and the structure of the sulfonate compound has a high-temperature-resistant phenol-like structure, so that the sulfonate compound has high-temperature resistance as a novel anionic surfactant, and has the advantages of strong interfacial activity, high salt resistance, high compounding property, high temperature resistance, foaming property and good compatibility with crude oil. When the sulfonate compound is matched with the fluorocarbon surfactant for use, the fluorocarbon surfactant has high surface activity, high thermomechanics and high chemical stability (acid resistance, alkali resistance and oxidation resistance), but the price is expensive, so the sulfonate compound and the fluorocarbon surfactant are matched for use, on one hand, the two are subjected to synergistic action to further strengthen the performances of each other, so that the oil displacement cleanup additive comprising the two has extremely strong surface activity, foamability, high salt resistance, high temperature resistance, high chemical stability and other performances, on the other hand, the cost can be reduced, and simultaneously, the ammonium bicarbonate is decomposed to generate CO 2 And NH 3 Gas of CO 2 Has the functions of increasing energy and reducing viscosity, NH 3 The alkaline buffer solution formed after dissolving in water has stronger oil washing capacity. Therefore, the oil displacement cleanup additive is matched with steam huff and puff to displace oil, so that the oil displacement cleanup additive can collect steam, surfactant, alkali and CO 2 、NH 3 The foam is integrated with the oil-water interface tension, the water lock is removed, flowback is facilitated, the viscosity of crude oil and the steam injection pressure are reduced, the lifting resistance is reduced, the low-permeability layer is started by utilizing the foam profile control effect, the steam swept volume is enlarged, the steam huff and puff effect is improved, the actual problem that the multi-cycle steam huff and puff recovery effect is poor is solved, and the recovery yield in the huff and puff stage is effectively improved. Therefore, the oil displacement cleanup additive obtained by the method has the advantages of strong surface activity, high temperature resistance, acid resistance and alkali resistance, low cost and wider applicability.
In another exemplary embodiment of the present application, an application of the displacement aid is provided, where the displacement aid is used in combination with steam stimulation, and the displacement aid is any one of the displacement aids.
The oil displacement cleanup additive is used for thick oil development by matching with steam huff and puff, can be used in various environments such as high temperature of 300 ℃, acidity, alkalinity and the like, and has excellent performance, so that the actual problem of poor multi-cycle steam huff and puff recovery effect can be effectively solved, and the recovery yield of the huff and puff stage is improved.
The advantageous effects of the present application will be described below with reference to specific examples and comparative examples.
Example 1
Taking 1g of coniferyl alcohol, 2g of ethylene oxide and 0.1g of sodium hydroxide in a 25mL three-neck flask, adding 10mL of dioxane solvent, carrying out ring-opening reaction at 80 ℃ for 5h, cooling the system to room temperature, adding water, and washing the system for 3 times to obtain a product system containing a ring-opening compound; the product system comprising the ring-opening compound is brought into contact with 0.5g of SO 3 Carrying out sulfonation reaction for 6h in 10mL of dioxane solvent at normal temperature, and then carrying out extraction treatment to obtain a sodium sulfonate compound; 0.1g of fluorocarbon surfactant and 2g of ammonium bicarbonate are uniformly mixed to obtain a surface active substance, and then 0.3g of sodium sulfonate compound and 0.2g of the surface active substance are uniformly mixed to obtain the oil displacement cleanup additive 1.
Example 2
Carrying out ring-opening reaction on 1g of coniferyl alcohol and 1g of ethylene oxide at 85 ℃ for 4h, cooling the system to room temperature, and adding water to wash the system for 3 times to obtain a product system containing a ring-opening compound; obtaining a product system containing a ring-opening compound; the resulting product system comprising the ring-opening compound is reacted with 1gSO 3 Carrying out sulfonation reaction for 4h in 10mL of dioxane solvent at normal temperature, and then carrying out extraction treatment to obtain a sodium sulfonate compound; 0.1g of fluorocarbon surfactant and 2g of ammonium bicarbonate are uniformly mixed to obtain a surface active substance, and then 0.3g of sodium sulfonate compound and 0.2g of the surface active substance are uniformly mixed to obtain an oil displacement cleanup additive 2.
Example 3
Taking 1g coniferyl alcohol and 1.5g ethylene oxide, carrying out reaction at 90 ℃ in the presence of 0.07g sodium hydroxideAfter ring-opening reaction for 5h, when the temperature of the system is reduced to room temperature, adding water to wash the system for 3 times to obtain a product system containing a ring-opening compound; obtaining a product system containing a ring-opening compound; the resulting product system comprising the ring-opening compound was mixed with 0.75gSO 3 Carrying out sulfonation reaction for 5h in 10mL of dioxane solvent at normal temperature, and then carrying out extraction treatment to obtain a sodium sulfonate compound; 0.1g of fluorocarbon surfactant and 2g of ammonium bicarbonate are uniformly mixed to obtain a surface active substance, and then 0.3g of sodium sulfonate compound and 0.2g of the surface active substance are uniformly mixed to obtain an oil displacement cleanup additive 3.
Example 4
Example 4 differs from example 1 in that 0.1g of fluorocarbon surfactant was mixed well with 1.5g of ammonium bicarbonate to give the oil displacing cleanup additive 4.
Example 5
Example 5 differs from example 1 in that 0.1g of fluorocarbon surfactant was mixed well with 2.5g of ammonium bicarbonate to give the oil displacing cleanup additive 5.
Example 6
Example 6 differs from example 1 in that 0.075g of fluorocarbon surfactant was mixed well with 2g of ammonium bicarbonate to give the oil displacing cleanup additive 6.
Example 7
The difference between the embodiment 7 and the embodiment 1 is that 0.25g of sodium sulfonate compound and 0.25g of surface active substance are mixed evenly to obtain the oil displacement cleanup additive 7.
Example 8
The difference between the example 8 and the example 1 is that 0.33g of sodium sulfonate compound and 0.17g of surface active substance are mixed evenly to obtain the oil displacement and drainage aid 8.
Example 9
The difference between the example 9 and the example 1 is that 0.15g of sodium sulfonate compound and 0.35g of surface active substance are mixed evenly to obtain the oil displacement cleanup additive 9.
Comparative example 1
The difference between the comparative example 1 and the example 1 is that 0.4g of fluorocarbon surfactant is added into the comparative example 1, and sodium sulfonate compound is not added, so that the oil displacement cleanup additive 10 is obtained.
Comparative example 2
The difference between the comparative example 2 and the example 1 is that 0.4g of sodium sulfonate compound is added in the comparative example 2, and the fluorocarbon surfactant is not added, so that the oil displacement cleanup additive 11 is obtained.
The properties of the oil displacing and cleanup additives 1 to 11, such as surface tension, interfacial tension, active material content, foaming volume, salt resistance, etc., were tested and listed in table 1, specifically,
preparing the oil displacement cleanup additive 1 to 11 into aqueous solutions with the volume fraction of 0.3 percent respectively, and testing the surface tension and the interfacial tension of the aqueous solutions;
after the mixture is placed at 300 ℃ for 48 hours, the content of active substances after temperature resistance is measured;
preparing the oil displacement cleanup additive 1 to 11 into 200mL of aqueous solution with the volume fraction of 1 percent respectively, and testing the foaming volume of the aqueous solution respectively;
preparing 100mL of water solution with the volume fraction of 1% from 1 to 11 oil displacement cleanup additives respectively, mixing the water solution with 100mL of NaCl solution with the mass fraction of 0.5%, and testing the salt resistance of the mixture.
TABLE 1
Respectively evaluating the performances of the oil displacement cleanup additive 1 to 11:
in an oil well of an eosin oil production plant in a Liaohe oil field, 500L of preparation liquid is firstly injected for 6 hours, then 20L of oil displacement cleanup additive is respectively injected for 1 to 11 hours, after 1 hour, steam is injected for 1000L, after 3 hours, the oil is stewed and then blown out, a pump is put down for production, the production rate of the oil displacement cleanup additive after 6 cycles of steam huff-and-puff oil production is tested, and the results are listed in Table 2.
TABLE 2
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
the application utilizes coniferyl alcohol and ethylene oxide under alkaline conditions (M) + Is a cation from alkaline conditions) to obtain a ring-opened compound, and then the ring-opened compound and SO are utilized 3 The sulfonate compound is used as a novel aralkyloxyalkyl sulfonate, and the structure of the sulfonate compound has a high-temperature-resistant phenol-like structure, so that the sulfonate compound has high-temperature-resistant performance as a novel anionic surfactant, and has the advantages of strong interfacial activity, high salt resistance, complex formulation, high temperature resistance, foamability and good compatibility with crude oil. When the sulfonate compound is matched with the fluorocarbon surfactant for use, the fluorocarbon surfactant has high surface activity, high thermomechanics and high chemical stability (acid resistance, alkali resistance and oxidation resistance), but the price is expensive, so the sulfonate compound and the fluorocarbon surfactant are matched for use, on one hand, the two are subjected to synergistic action to further strengthen the performances of each other, so that the oil displacement cleanup additive comprising the two has extremely strong surface activity, foamability, high salt resistance, high temperature resistance, high chemical stability and other performances, on the other hand, the cost can be reduced, and simultaneously, the ammonium bicarbonate is decomposed to generate CO 2 And NH 3 Gas of CO 2 Has the functions of increasing energy and reducing viscosity, NH 3 The alkaline buffer solution formed after dissolving in water has stronger oil washing capacity. Therefore, the oil displacement cleanup additive is matched with steam huff and puff to displace oil, so that the oil displacement cleanup additive can collect steam, surfactant, alkali and CO 2 、NH 3 The foam is integrated with the oil-water interface tension, the water lock is removed, the flowback is facilitated, the crude oil viscosity and the steam injection pressure are reduced, the lifting resistance is reduced, the low-permeability layer is started by utilizing the foam profile control effect, the steam swept volume is enlarged, and the steam huff and puff effect is improvedAnd the actual problem that the multi-period steam huff-puff recovery effect is poor is solved, and the recovery yield of the huff-puff stage is effectively improved. The method is simple and low in cost, and the effect of solving the problem that the multi-cycle steam huff and puff harvesting effect is poor is obvious.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (12)
1. A preparation method of an oil displacement cleanup additive is characterized by comprising the following steps:
step S1, carrying out ring-opening reaction on coniferyl alcohol, ethylene oxide and a first solvent under an alkaline condition to obtain a product system containing a ring-opening compound;
step S2, adding the product system containing the ring-opening compound and SO 3 And a second solvent to carry out sulfonation reaction to obtain a sulfonate compound; and
step S3, mixing the sulfonate compound and the surface active substance to obtain an oil displacement cleanup additive;
wherein the surface active substance is a mixture of a fluorocarbon surfactant and ammonium bicarbonate, and the ring-opening compound and the sulfonate compound respectively have the following structural formulas:
M + is a monovalent cation.
2. The preparation method according to claim 1, wherein the mass ratio of coniferyl alcohol to ethylene oxide is 1:2 to 1:1.
3. The method of claim 1, wherein the method comprisesSaid coniferyl alcohol and said SO 3 The mass ratio of (A) to (B) is 1: 0.5-1: 1.
4. The preparation method according to claim 1, wherein the mass ratio of the fluorocarbon surfactant to the ammonium bicarbonate in the surfactant is 0.1: 1.5-2.5.
5. The method according to claim 1, wherein the mass ratio of the sulfonate compound to the surface active material is 1:1 to 2: 1.
6. The method according to claim 1, wherein the ring-opening reaction is carried out at 80 to 90 ℃.
7. The production method according to claim 1, wherein the alkaline condition is formed using an alkaline substance.
8. The method according to claim 7, wherein the alkaline substance is selected from one or more of sodium hydroxide, potassium hydroxide, and lithium hydroxide.
9. The method according to claim 7, wherein the molar ratio of coniferyl alcohol to the basic substance is 1:3 to 2: 3.
10. The method of claim 1, wherein the first solvent and the second solvent are each independently selected from one or more of dichloroethane, acetonitrile, toluene, dioxane.
11. An oil displacement cleanup additive, which is prepared by the preparation method of any one of claims 1 to 10.
12. An application of a displacement aid, wherein the displacement aid is used in combination with steam stimulation, and is characterized in that the displacement aid is the displacement aid according to claim 11.
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