CN116970380B - Carboxylic acid type carbon quantum dot foam system and preparation method and application thereof - Google Patents
Carboxylic acid type carbon quantum dot foam system and preparation method and application thereof Download PDFInfo
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- CN116970380B CN116970380B CN202311235241.XA CN202311235241A CN116970380B CN 116970380 B CN116970380 B CN 116970380B CN 202311235241 A CN202311235241 A CN 202311235241A CN 116970380 B CN116970380 B CN 116970380B
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 138
- 239000006260 foam Substances 0.000 title claims abstract description 120
- 150000001732 carboxylic acid derivatives Chemical class 0.000 title claims abstract description 97
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 230000033558 biomineral tissue development Effects 0.000 claims abstract description 34
- 239000003921 oil Substances 0.000 claims abstract description 27
- 239000007788 liquid Substances 0.000 claims abstract description 23
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 18
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 14
- 239000012071 phase Substances 0.000 claims abstract description 14
- 239000007791 liquid phase Substances 0.000 claims abstract description 12
- 239000007790 solid phase Substances 0.000 claims abstract description 11
- 125000000524 functional group Chemical group 0.000 claims abstract description 5
- 125000002843 carboxylic acid group Chemical group 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 62
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 27
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 23
- 229910017604 nitric acid Inorganic materials 0.000 claims description 23
- -1 carboxylic acid compound Chemical class 0.000 claims description 21
- 238000005187 foaming Methods 0.000 claims description 21
- 239000008398 formation water Substances 0.000 claims description 18
- 239000004094 surface-active agent Substances 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 14
- 238000000120 microwave digestion Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000002270 dispersing agent Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000003963 antioxidant agent Substances 0.000 claims description 7
- 230000003078 antioxidant effect Effects 0.000 claims description 7
- 235000006708 antioxidants Nutrition 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000012265 solid product Substances 0.000 claims description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- 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 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- 239000003570 air Substances 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 4
- 230000021523 carboxylation Effects 0.000 claims description 4
- 238000006473 carboxylation reaction Methods 0.000 claims description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 4
- 239000005457 ice water Substances 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000003345 natural gas Substances 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 229960005070 ascorbic acid Drugs 0.000 claims description 3
- 235000010323 ascorbic acid Nutrition 0.000 claims description 3
- 239000011668 ascorbic acid Substances 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- AOMUHOFOVNGZAN-UHFFFAOYSA-N N,N-bis(2-hydroxyethyl)dodecanamide Chemical compound CCCCCCCCCCCC(=O)N(CCO)CCO AOMUHOFOVNGZAN-UHFFFAOYSA-N 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- HDMXIELEUKTYFR-UHFFFAOYSA-N bis(2-ethylhexyl) butanedioate;sodium Chemical compound [Na].CCCCC(CC)COC(=O)CCC(=O)OCC(CC)CCCC HDMXIELEUKTYFR-UHFFFAOYSA-N 0.000 claims description 2
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
- 229940031957 lauric acid diethanolamide Drugs 0.000 claims description 2
- 229920000609 methyl cellulose Polymers 0.000 claims description 2
- 239000001923 methylcellulose Substances 0.000 claims description 2
- 235000010981 methylcellulose Nutrition 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims 2
- 238000011161 development Methods 0.000 abstract description 4
- 230000018109 developmental process Effects 0.000 abstract description 4
- 239000010779 crude oil Substances 0.000 abstract description 3
- 238000000605 extraction Methods 0.000 abstract description 2
- 150000001768 cations Chemical class 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 230000001965 increasing effect Effects 0.000 description 8
- 239000011575 calcium Substances 0.000 description 7
- 229910001424 calcium ion Inorganic materials 0.000 description 7
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000015784 hyperosmotic salinity response Effects 0.000 description 6
- 229910001425 magnesium ion Inorganic materials 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000006073 displacement reaction Methods 0.000 description 4
- 239000002096 quantum dot Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000004088 foaming agent Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 229940072056 alginate Drugs 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000004872 foam stabilizing agent Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000004715 keto acids Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
-
- 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
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to the technical field of development engineering of oil and gas fields, in particular to a carboxylic acid type carbon quantum dot foam system, a preparation method and application thereof, wherein the foam system comprises a gas phase, a liquid phase and a solid phase, the liquid phase is an anionic surfactant solution, the solid phase is carboxylic acid type carbon quantum dots, the density of carboxyl functional groups in the carboxylic acid type carbon quantum dots is 70% -80%, and the mineralization resistance range of the carboxylic acid type carbon quantum dot foam system is 15 multiplied by 10 4 mg/L‑25×10 4 mg/L; the half-life of the separating liquid of the carboxylic acid type carbon quantum dot foam system is 60 min-129 min. By adding the carboxylic acid type carbon quantum dots (CQDs- (COOH)), the foam system can realize good mineralization resistance, and the stability of the foam system is effectively improved, so that the foam system can be applied to the crude oil extraction of high-mineralization and high-water-content oil field areas.
Description
Technical Field
The invention relates to the technical field of oil and gas field development engineering, in particular to a carboxylic acid type carbon quantum dot foam system and a preparation method and application thereof.
Background
Petroleum is a strategic resource that is particularly important for its exploitation and utilization. Since petroleum is a non-renewable resource, and as the demand for petroleum increases, the probability of finding larger reserves of the field decreases, and how to increase the recovery efficiency of existing fields is a current research hotspot. Foam is popular in oilfield development due to its excellent characteristics of large and small plugging and water and oil plugging. Foam flooding is widely applied as a technical means for improving the recovery ratio of crude oil, and has been applied for nearly 60 years.
There is a current face of unconventional reservoir production requirements that require the application of foam flooding to such reservoirs. Formation mineralization is also a problem that must be considered during foam flooding. In unconventional oil reservoir development processes, highly mineralized environments such as marine sedimentary oil reservoirs place higher demands on the performance of the foam. For an oil reservoir with high mineralization degree caused by perennial phase deposition, sodium ions and calcium ions in a stratum neutralize the charge of a system, so that the adsorption charge concentration of a foam liquid film is reduced, repulsive force on two sides is weakened, the structure of a double-electron layer is damaged, the thickness of the liquid film is thinned, the liquid discharge speed is increased, and the foam stability is greatly reduced; in addition, salt ions of the stratum and molecules of the foaming agent are subjected to chemical reaction to generate insoluble or indissolvable salt, so that the molecular structure of the foaming agent is destroyed, the activity is deteriorated or even deactivated to different degrees, and the performance of a foam system is further influenced.
Chinese patent CN 114381253A (application No. 202210291895.3) provides a thixotropic reinforced foam system and its preparation method, wherein sodium alginate component in the foam system contacts with formation water and then contacts with Ca naturally contained in formation water 2+ 、Mg 2+ An insoluble alginate gel is formed, and the foam system is separated from the water layer by the foam injected later to realize salt tolerance. The foam system is suitable for heterogeneous oil reservoirs and can resist formation water with mineralization degree of 4000 mg/L. However, the reservoir conditions were severe due to the sea-phase sedimentary (total degree of mineralization 22×10) 4 mg/L) limits its application in this field of oilfield.
The nano material oil displacement is a new oil displacement mode at present, and the characteristics of grafting functional side chains and the like are receiving more and more attention due to the smaller particle size. However, conventional nanoparticles have poor dispersion stability in aqueous solutions due to high cost, are easy to agglomerate, and are required to be used together with surfactants. Chinese patent CN 109401742A (application No. 201811298872.5) provides a temperature-resistant salt-tolerant foam flooding system prepared from hypersalinity formation water. Partially Hydrolyzed Polyacrylamide (HPAM) and nano SiO by salt tolerant surfactant THSB, polymer 2 The particles can be matched with each other to mineralize 22×10 4 mg/L, wherein Ca 2+ With Mg 2+ The foam which exists stably is generated under the condition that the ion concentration is 2000 mg/L. The foam system chelates calcium and magnesium ions by citrate to prevent nano SiO 2 The particles further react with calcium and magnesium ions to form a precipitate, and meanwhile, nano SiO 2 The granules and the salt-tolerant surfactant THSB cooperate to enable SiO to be formed 2 The interfacial activity is enhanced, and the surfactant is uniformly and stably dispersed in the system, so that the salt tolerance of the system is improved. The system is mainly aimed at fracture-cavity oil reservoirs, foam stability is improved by adding modified polymers so as to improve salt tolerance, but HPAM contained in components of the system has an average molecular weight of 400-800 ten thousand, high-molecular polymers have poor shearing resistance, are easy to shear failure when injected near a shaft, are easy to adsorb in stratum to cause pollution, and meanwhile, the system contains more components and has complex formula, so that the foam system is difficult to popularize and apply in oil fields on a large scale.
Chinese patent CN 115287052A (202211001209.0) provides a compound oil displacement system of carbon point, surfactant and polymer in 12×10 4 The mg/L mineralized water has good salt tolerance, the interfacial activity of the system is greatly improved through the synergistic effect of carbon points and surfactants, and the viscosity of the system is improved by the polymer so as to improve the salt tolerance of the system. However, the system does not consider that the carbon point nano fluid is easy to generate finger-in phenomenon after being injected into the stratum, is easy to see water for oil displacement of the hypertonic stratum, has an unobvious recovery ratio improving effect, only improves an oil-water interface, does not consider the implementation effect of an oil-gas-water three-phase interface, and does not consider the modification of the carbon point to improve the mineralization resistance of the carbon point.
The existing foam system has poor stability under the severe environment of high mineralization, and the complex formula or preparation method limits the application of the foam system in oil fields, so that a foam system with high salt resistance, strong stability and shearing resistance is needed.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a carboxylic acid type carbon quantum dot foam system, a preparation method and application thereof, wherein the carboxylic acid type carbon quantum dot (CQDs- (COOH)) is added to enable the foam system to achieve good mineralization resistance, the stability of the foam system is effectively improved, and the foam system can be applied to crude oil extraction in high mineralization and high water content oil field areas.
In order to achieve the technical effects, the invention adopts the following technical scheme:
a carboxylic acid type carbon quantum dot foam system comprises a gas phase, a liquid phase and a solid phase, wherein the liquid phase is an anionic surfactant solution, the solid phase is carboxylic acid type carbon quantum dots,
the density of carboxyl functional groups in the carboxylic acid type carbon quantum dots is 70% -80%,
the mineralization resistant range of the carboxylic acid type carbon quantum dot foam system is 15 multiplied by 10 4 mg/L-25×10 4 mg/L；
The half-life period of the solution of the carboxylic acid type carbon quantum dot foam system is 60-129 min.
The invention provides a solid-liquid-gas three-phase foam system, wherein a solid phase is carboxylic acid type carbon quantum dots with negatively charged surfaces, and the solid phase is adsorbed with an anionic surfactant in a liquid phase through hydrophobic association, so that aggregation and sedimentation of the carbon quantum dots are prevented, further, carbon quantum dots stacked on the upper layer are peeled off from carbon quantum dots on the lower layer, the dispersibility of the carbon quantum dots is improved, meanwhile, the dispersed carbon quantum dots and metal cation nano-particles in stratum water are ensured to generate good association, so that metal cations in a local free state are consumed, the influence of the surfactant by the metal cations is avoided, a crosslinked skeleton network is formed, a stable armor layer is formed at a gas-liquid interface between the carbon quantum dots and the metal cations in the foam system, the mechanical strength of a foam liquid film is remarkably improved, and the liquid separation half life of foam is prolonged. The density of carboxyl functional groups in the carboxylic acid type carbon quantum dots is 70% -80%, so that the foam system can withstand higher mineralization conditions.
Preferably, in the carboxylic acid type carbon quantum dot foam system, the gas phase is one of nitrogen, carbon dioxide, natural gas or air; the anionic surfactant in the liquid phase is at least one of sodium bis (2-ethylhexyl) succinate, sodium dodecyl sulfate, sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate, sodium alpha-alkenyl sulfonate, lauric acid diethanolamide, fatty alcohol polyoxyethylene ether sulfate or sodium methylcellulose.
Further preferably, the solid phase and the liquid phase form a foam system solution, wherein in the foam system solution, the mass fraction of the carboxylic acid type carbon quantum dots is 0.1-1.5 wt%, the mass fraction of the anionic surfactant is 0.1-1.0 wt%, and the balance is stratum water; more preferably, the mass fraction of carboxylic acid type carbon quantum dots in the foam system solution is 1.2wt%, the mass fraction of anionic surfactant is 0.3wt%, and the balance is formation water.
The invention provides a preparation method of the carboxylic acid type carbon quantum dot foam system, which comprises the following steps:
s1, adding an anionic surfactant into stratum water, and stirring to obtain a surfactant solution;
s2, adding the carboxylic acid type carbon quantum dots into the surfactant solution obtained in the step S1, and performing ultrasonic dispersion to obtain a foam system solution;
s3, foaming the foaming liquid prepared in the step S2 with gas to obtain foam, and obtaining the carboxylic acid type carbon quantum dot foam system.
Preferably, in the step S1, the mineralization degree of the formation water is 15×10 4 mg/L-25×10 4 mg/L; further preferably, the formation water has a mineralization of 20-25X 10 4 mg/L。
Preferably, in the step S2, the mass concentration of the anionic surfactant in the foam system solution is 0.1wt% to 1.0wt%, and the mass fraction of the carboxylic acid type carbon quantum dots is 0.1wt% to 1.5wt%; more preferably, the mass concentration of the anionic surfactant is 0.3wt%, and the mass fraction of the carboxylic acid type carbon quantum dots is 1.2wt%.
Preferably, in the step S1, the stirring speed is 1000rpm, and the stirring time is 0.5h-1h; in the step S2, the ultrasonic dispersion condition is that the time is 1-3h; the ultrasonic power is 500-1000W, in order to avoid overheating and foaming, an interval of 30s is set every 10s of ultrasound, and the temperature is kept at 25 ℃ by a water bath; the air source in the step S3 is any one of nitrogen, carbon dioxide, natural gas or air.
Preferably, in the step S2, the preparation method of the carboxylic acid type carbon quantum dot is to increase the carboxyl group of the existing carbon quantum dot by using cyclic carboxylation, and the preparation steps are as follows:
a. adding the carbon quantum dots and the carboxylic acid compound into an aromatic hydrocarbon solvent, and stirring for 20-40 min to obtain a mixed solution;
b. adjusting the pH value of the mixed solution to be alkaline, and reacting under stirring to obtain an intermediate solution;
c. adjusting the pH value of the intermediate solution to be acidic, centrifuging to retain a solid product after stirring,
d. and mixing the solid product with ethanol, performing ultrasonic treatment, washing with deionized water until the washing liquid is colorless, and drying to obtain the carboxylic acid type carbon quantum dots.
Preferably, in step a, the carboxylic acid compound is any one of carboxylic acid anhydride or organic acid, and the organic acid includes oxalic acid, citric acid, malonic acid and the like.
Preferably, in the step a, the input mass ratio of the carbon quantum dots to the carboxylic acid compound is 1 (1-5).
Preferably, in the step b, the pH is adjusted to 8-10, and the reaction time is 4-10 hours; in the step c, the pH is adjusted to 6-7.
Further preferably, in the step a, the preparation method of the carbon quantum dots comprises the following steps: adding residual oil into concentrated nitric acid for microwave digestion, cooling to room temperature after reaction, centrifuging, washing and drying to obtain carbon quantum dots; more preferably, the preparation method of the carbon quantum dot comprises the following steps:
1) Placing part of concentrated nitric acid into ice water bath, and stirring until the temperature is reduced to 2-6 ℃;
2) Adding the hydrotreated residual oil, adding the residual concentrated nitric acid, uniformly mixing, and stirring for 30min from timing to obtain an intermediate solution;
3) And (3) carrying out microwave digestion on the intermediate solution, cooling to room temperature, centrifuging, washing with water until nitrate ions are absent in the solution, and drying at 40-50 ℃ to obtain the carbon quantum dots.
Further preferably, the mass concentration of the concentrated nitric acid is 65%, and the mass ratio of the residual oil to the total concentrated nitric acid is 1 (5-30); the concentrated nitric acid used in step 1) accounts for 85% -95% of the total concentrated nitric acid mass.
Further preferably, in the step 3), the power of microwave digestion is 600W, and the duration of microwave digestion is 10min-30min; more preferably, the microwave digestion period is 25 minutes.
Preferably, in the step S2, the preparation method of the carboxylic acid type carbon quantum dot is to add a carboxylic acid group in the process of preparing the carbon quantum dot, and the preparation steps are as follows:
(1) Placing part of concentrated nitric acid into ice water bath, and stirring until the temperature is reduced to 2-6 ℃;
(2) Adding the hydrotreated residual oil, adding concentrated sulfuric acid and residual concentrated nitric acid, and stirring for 30min from timing to obtain an intermediate solution;
(3) Cooling the intermediate solution to room temperature after microwave digestion, centrifuging, and washing with water until nitrate ions and sulfate ions are absent in the solution to obtain a carbon quantum dot intermediate solution;
(4) Adding an additive, a dispersing agent and a carboxyl compound into the carbon quantum dot intermediate solution, stirring for 1h, adding an antioxidant, and heating to 100-200 ℃;
(5) And (3) cooling the solution prepared in the step (4) to room temperature, centrifuging, washing with water, and drying at 40-50 ℃ to obtain the required carboxylic acid type carbon quantum dot.
Further preferably, the mass ratio of the concentrated sulfuric acid to the total concentrated nitric acid is 1:3, the mass concentration of the concentrated nitric acid is 65%, the mass ratio of the residual oil to the total concentrated nitric acid is 1 (5-30), and the concentrated nitric acid used in the step (1) accounts for 85% -95% of the total concentrated nitric acid.
Further preferably, in the step (3), the microwave digestion power is 600W, and the microwave digestion duration is 10-20 min; more preferably, the microwave digestion period is 15 minutes.
Further preferably, in the step (4), the additive is Sodium Dodecyl Sulfate (SDS) or sodium dodecyl benzene sulfonate (LAS), and the input mass of the additive is 0.1% -0.5% of the total mass of the intermediate solution. The additive is added in the preparation process, so that the reaction rate of the carbon quantum dots and the carboxyl compound can be effectively improved, and the uniform distribution of carboxyl groups on the surfaces of the carbon quantum dots is facilitated.
Further preferably, in the step (4), the dispersing agent is polyethylene glycol (PEG) or polypropylene glycol (PPG), and the added mass of the dispersing agent is 0.1% -0.3% of the total mass of the intermediate solution. The dispersing agent can improve the dispersibility of the carbon quantum dots in the intermediate solution, and is beneficial to improving the reaction rate and increasing the product quality.
Further preferably, in the step (4), the carboxylic compound is carboxylic acid or keto acid, and the charged mass of the carboxylic compound is 1 to 5% of the total mass of the intermediate solution. The carboxyl compound reacts with hydrogen atoms in the intermediate of the carbon quantum dots, so that the number of carboxyl groups on the carbon quantum dots is increased.
Further preferably, in the step (4), the antioxidant is benzophenone tetrazole (DPT) or Ascorbic Acid (AA), and the input mass of the antioxidant is 0.1% -0.3% of the total mass of the intermediate solution.
The invention also provides an application of the carboxylic acid type carbon quantum dot foam system or the carboxylic acid type carbon quantum dot foam system prepared by the preparation method, and the carboxylic acid type carbon quantum dot foam system is particularly used for foam flooding in oil reservoirs with high mineralization degree caused by sea phase deposition.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention provides a gas, liquid and solid three-phase foam system, wherein an anionic surfactant in the three-phase foam system and negatively charged carboxylic acid type carbon quantum dots are subjected to interaction of hydrophobic association, and surfactant molecules are used for effectively adsorbing the carboxylic acid type carbon quantum dots so as to prevent agglomeration and sedimentation of the carboxylic acid type carbon quantum dots and nano association of metal cations in formation water, so that a cross-linked skeleton network and the surface activity of the carboxylic acid type carbon quantum dots can generate synergistic effect, and the stability and salt tolerance of the foam system are effectively improved.
2. The foam system solution is simple to prepare, a polymer with high molecular weight is not needed, carboxylic acid type carbon quantum dots are used as foam stabilizers, metal cations in formation water are used as crosslinking materials, no additional metal cations are needed, and the production cost can be effectively reduced by utilizing the metal cations in the formation water. The carboxylic acid type carbon quantum dots serve as foam system foam stabilizer, not only play a role in stabilizing foam by nano particles, but also play a role in associating calcium and magnesium ions in formation water, and are crosslinked at a gas-liquid interface to form a stable armor layer and a complex skeleton crosslinked network, so that the mechanical strength of a foam liquid film can be remarkably improved, meanwhile, the effect of protecting a surfactant by using local free calcium and magnesium ions is consumed, the half life of the foam is prolonged, and the stability of the foam system is greatly improved.
3. The carboxylic acid type carbon quantum dot prepared by the invention has higher carboxyl group density than the conventional carbon quantum dot, and a cross-linked network formed based on nano association is more complex, so that the mechanical strength of a liquid film is obviously improved after the reinforced foam contacts formation water, and the foam system still has better performance under the condition of high mineralization.
4. The foam system is directly prepared by high-mineralization water, is suitable for sea-phase sedimentary high-mineralization oil reservoirs, has good stability in high-mineralization stratum water and has mineralization degree of 22 multiplied by 10 4 The half-life under the condition of mg/L can reach 136min.
5. The invention also provides a method for preparing the carboxylic acid type carbon quantum dot, which not only can be prepared based on the existing carbon quantum dot, but also can be subjected to simultaneous carboxylation treatment in the process of preparing the carbon quantum dot, so that the prepared carboxylic acid type carbon quantum dot has the carboxyl functional group density of 70-80%.
Drawings
FIG. 1 is a TEM scan image of carboxylic acid type carbon quantum dots prepared in example 1;
FIG. 2 is a TEM scan image of carboxylic acid type carbon quantum dots prepared in example 2;
FIG. 3 is FITR spectra of carboxylic acid type carbon quantum dots prepared in example 1 and example 2;
FIG. 4 is a graph showing the foaming volume and half-life of the carboxylic acid type carbon quantum dot reinforced foam system prepared in example 3 and comparative examples 1 to 3 at different concentrations of carboxylic acid type carbon quantum dots.
FIG. 5 is a graph showing the foaming volume and half-life of the carboxylic acid type carbon quantum dot reinforced foam systems prepared in example 3 and comparative examples 4 to 7 at different mineralization degrees.
FIG. 6 is a graph of the foam volume and half-life of carboxylic acid type carbon quantum dot reinforced foam systems prepared in comparative examples 8-12 at different concentrations of carboxylic acid type carbon quantum dots.
Detailed Description
The invention will be further described with reference to the drawings and examples.
Example 1:
a method for preparing carboxylic acid type carbon quantum dots by modifying carbon quantum dots comprises the following steps:
a. mixing 1g of carbon quantum dots and 4g of carboxylic acid compound, putting into an aromatic hydrocarbon solvent, stirring for 20-40 min, and uniformly mixing;
b. dropwise adding NaOH solution under stirring, adjusting the pH value to 9.0, keeping the alkaline environment of the solution, stirring and reacting to obtain an intermediate solution, and reacting the carbon quantum dots with the carboxylic acid compound for 4 hours, wherein the reaction temperature is kept within the range from room temperature to the boiling point of the reaction solvent;
c. after the reaction is completed, adding concentrated sulfuric acid dropwise, stirring for 30min to adjust the pH to 6.5, and centrifuging the reaction mixture to separate a solid product and a liquid part;
d. mixing the separated solid product with ethanol solvent, and performing ultrasonic treatment for 30min. After washing for one time, separating the washing solution from the solid product, and repeating the washing steps to ensure that the washing is clean and remove the residual solvent and unreacted materials, repeating the washing for a plurality of times until the washing solution is basically colorless, and drying at 40-50 ℃ to obtain the pure carboxylic acid type carbon quantum dots.
Example 2:
increasing carboxylic acid groups during preparation of carbon quantum dots
(1) Firstly, 15ml of concentrated nitric acid and 75ml of concentrated sulfuric acid are placed in an ice-water bath, and the temperature is reduced to 4 ℃;
(2) Adding 10g of hydrotreated residual oil, adding 10ml of concentrated nitric acid, completely leaching the residual oil stuck on the cup wall into the solution, uniformly mixing, and stirring for 30min from timing to obtain an intermediate solution;
(3) Carrying out microwave digestion on the intermediate solution for 15min under the power of 600W, cooling to room temperature, centrifuging for multiple times, and washing with water until nitrate ions and sulfate ions are not contained in the solution, thereby obtaining a carbon quantum dot intermediate solution;
(4) Adding 0.2g of additive Sodium Dodecyl Sulfate (SDS), 0.2g of dispersant polyethylene glycol (PEG) and 1g of carboxylic acid into the carbon quantum dot intermediate solution, stirring for 1h, adding an antioxidant and heating to 150 ℃;
(5) And cooling the obtained solution to room temperature, centrifuging, washing for multiple times, and drying at 45 ℃ to obtain the required carboxylic acid type carbon quantum dot.
Example 3:
a carboxylic acid type carbon quantum dot reinforced foam system comprises the following preparation steps:
s1 0.3g of surfactant was added to 98.5g of a mineral having a degree of mineralization of 22X 10 4 Stirring in the formation water of mg/L at 1000rpm for 1h to obtain a surfactant solution;
s2, adding 1.2g of carboxylic acid type carbon quantum dots into the surfactant solution obtained in the step S1, then performing ultrasonic dispersion for 2 hours by using 600W to avoid aggregation of particles, obtaining foaming liquid, and keeping the water bath temperature at 25 ℃;
s3: and (3) passing the foaming liquid obtained in the step (S2) and nitrogen through a foam generator together, and fully contacting to obtain foam, thus obtaining the required carboxylic acid type carbon quantum dot reinforced foam system.
Wherein, in the foaming liquid prepared in the step S2, the mass concentration of the anionic surfactant is 0.3wt percent, and the mass fraction of the carboxylic acid type carbon quantum dots is 1.2wt percent.
The foaming volume and the half-life of the carboxylic acid type carbon quantum dot reinforced foam system are measured.
To verify the influence of carboxylic acid type carbon quantum dots with different concentrations on a foam system, the foam system is prepared according to the mass ratio and the method, and the difference is that the mass concentration of the carboxylic acid type carbon quantum dots in foaming liquid is respectively 0.1wt%, 1.0wt% and 1.5wt% which are respectively used as comparative examples 1, 2 and 3.
The foaming volume and the half life of the carboxylic acid type carbon quantum dot reinforced foam system prepared in the above example 3 and comparative examples 1 to 3 were measured, as shown in fig. 4. The figure shows that the half life of the foam is obviously enhanced along with the increase of the concentration of the carboxylic acid type quantum dots, which indicates that the carboxylic acid type quantum dots play a role in enhancing the stability of the foam in high mineralization formation water. However, when the mass concentration of the carboxylic acid type carbon quantum dots is increased from 1.2wt% to 1.5wt%, both the foaming volume and the half-life are reduced slightly.
This is because, when the amount of the surfactant added is the same, the high mass concentration of carboxylic acid type carbon quantum dots have a high amount of surfactant molecules adsorbed on the surface thereof, which results in a decrease in the effective concentration of the foaming agent and thus affects the foaming volume, and thus it is known that the foam system has the best performance when the mass concentration of carboxylic acid type carbon quantum dots is 1.2wt%.
To verify the effect of different mineralizations on the foam system, foam systems were prepared according to the above-described mass ratios and methods, except that the formation water had mineralizations of 15, 18, 20, 25×10 4 mg/L as comparative examples 4, 5, 6, 7, respectively.
The foaming volume and the half-life of the carboxylic acid type carbon quantum dot reinforced foam system are measured as shown in figure 5. As can be seen, the half life of the foam increases with increasing mineralization, at 22X 10 4 The half-life period reaches the longest under the condition of mg/L mineralization, which indicates that the foam system is suitable for the sea-phase sediment reservoir under the condition of the mineralization. When the mineralization degree is 22 multiplied by 10 4 mg/L is increased to 25×10 4 At mg/L, there is a small decrease in both the foaming volume and half-life.
In water with higher mineralization degree, the concentration of carboxylic acid type carbon quantum dots is relatively low, so that the influence of metal cations such as calcium ions, magnesium ions and the like in formation water on an anion surfactant can not be completely shielded, the metal cations can compress an electric double layer to weaken the electrostatic repulsive force between foam liquid films, thinning the liquid films, accelerating the cracking of the foam and reducing the stability of the foam.
However, the foam volume and half-life at this time are still at a preferred level, indicating that the foam system provided herein is capable of tolerating 25X 10 4 mg/L or even higher mineralization.
Thus to verify that the mineral is not highly mineralizedThe foam system is prepared according to the mass ratio and the method, and the difference is that the mass concentration of the carboxylic acid type carbon quantum dots in the foaming liquid is 1.8wt%, 2.0wt%, 2.2wt%, 2.5wt%, 3.0wt% and the mineralization degree of stratum water is 25 multiplied by 10 4 mg/L was used as comparative examples 8, 9, 10, 11, 12, respectively.
The foaming volume and the half life of the carboxylic acid type carbon quantum dot reinforced foam system prepared in the comparative examples 8 to 12 were measured, and are shown in FIG. 6. The graph shows that the foaming volume of the foam is not changed greatly with the increase of the concentration of the carboxylic acid type quantum dots, and the half life of the foam is enhanced, which indicates that the carboxylic acid type quantum dots play a role in enhancing the stability of the foam in high mineralization degree stratum water. However, when the mass concentration of the carboxylic acid type carbon quantum dots is increased from 2.0wt% to 3.0wt%, the foaming volume and half-life are reduced to a certain extent, because the larger particle size solid particles formed by crosslinking the carboxylic acid type carbon quantum dots with calcium and magnesium ions in the water with high mineralization degree, which are formed by the higher concentration, have a destructive effect on the foam structure due to the self gravity effect, so that the initial foam volume is reduced.
Claims (7)
1. A carboxylic acid type carbon quantum dot foam system comprises a gas phase, a liquid phase and a solid phase, and is characterized in that the gas phase is one of nitrogen, carbon dioxide, natural gas or air; the liquid phase is an anionic surfactant solution, the solid phase is carboxylic acid type carbon quantum dots, and the anionic surfactant in the liquid phase is at least one of sodium bis (2-ethylhexyl) succinate sulfonate, sodium dodecyl sulfate, sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate, alpha-alkenyl sodium sulfonate, lauric acid diethanolamide, fatty alcohol polyoxyethylene ether sulfate or methyl cellulose sodium;
the preparation method of the carboxylic acid type carbon quantum dot is to increase the carboxyl group of the existing carbon quantum dot by cyclic carboxylation, or to increase the carboxyl group in the process of preparing the carbon quantum dot,
the density of carboxyl functional groups in the carboxylic acid type carbon quantum dots is 70% -80%;
the mineralization resistant range of the carboxylic acid type carbon quantum dot foam system is 15 multiplied by 10 4 mg/L-25×10 4 mg/L；
The half-life period of the solution of the carboxylic acid type carbon quantum dot foam system is 60-129 min;
in the carboxylic acid type carbon quantum dot foam system,
the solid phase and the liquid phase form a foam system solution, wherein the mass fraction of the carboxylic acid type carbon quantum dots in the foam system solution is 0.1-1.5 wt%, the mass fraction of the anionic surfactant is 0.1-1.0 wt%, and the balance is stratum water.
2. The carboxylic acid type carbon quantum dot foam system of claim 1, wherein the carboxylic acid type carbon quantum dot foam system comprises a plurality of carbon quantum dot foam layers,
the solid phase and the liquid phase form a foam system solution, wherein the mass fraction of carboxylic acid type carbon quantum dots in the foam system solution is 1.2wt%, the mass fraction of anionic surfactant is 0.3wt%, and the balance is formation water.
3. A method for preparing the carboxylic acid type carbon quantum dot foam system as claimed in any one of claims 1 to 2, comprising the following steps:
s1, adding an anionic surfactant into stratum water, and stirring to obtain a surfactant solution;
s2, adding the carboxylic acid type carbon quantum dots into the surfactant solution obtained in the step S1, and performing ultrasonic dispersion to obtain a foam system solution;
s3, foaming the foaming liquid prepared in the step S2 with gas to obtain foam, and obtaining a carboxylic acid type carbon quantum dot foam system;
in the step S1, the stirring rotation speeds are 1000rpm, and the stirring time is 0.5h-1h;
in the step S2, the mass concentration of the anionic surfactant in the foam system solution is 0.1-1.0 wt%, and the mass fraction of the carboxylic acid type carbon quantum dots is 0.1-1.5 wt%;
in the step S2, the ultrasonic dispersion condition is that the time is 1-3h; the ultrasonic power is 500-1000W, an interval of 30s is set for every 10s of ultrasonic, and the temperature is kept at 25 ℃ through a water bath;
the air source in the step S3 is any one of nitrogen, carbon dioxide, natural gas or air.
4. The method of claim 3, wherein in step S1, the mineralization degree of the formation water is 15X 10 4 mg/L-25×10 4 mg/L。
5. The method of claim 3, wherein in the step S2, the carboxylic acid type carbon quantum dot is prepared by adding a carboxyl group of an existing carbon quantum dot by cyclic carboxylation, and the preparation steps are as follows:
a. adding the carbon quantum dots and the carboxylic acid compound into an aromatic hydrocarbon solvent, and stirring for 20-40 min to obtain a mixed solution;
b. adjusting the pH value of the mixed solution to be alkaline, and reacting under stirring to obtain an intermediate solution;
c. adjusting the pH value of the intermediate solution to be acidic, centrifuging to retain a solid product after stirring,
d. mixing the solid product with ethanol, performing ultrasonic treatment, washing with deionized water until the washing liquid is colorless, and drying to obtain carboxylic acid type carbon quantum dots;
in the step a, the carboxylic acid compound is any one of carboxylic anhydride or organic acid, and the organic acid comprises oxalic acid, citric acid or malonic acid;
in the step a, the input mass ratio of the carbon quantum dots to the carboxylic acid compound is 1 (1-5);
in the step b, the pH is adjusted to 8-10, and the reaction time is 4-10 h; in the step c, the pH is adjusted to 6-7.
6. The method according to claim 3, wherein in the step S2, the carboxylic acid type carbon quantum dots are prepared by adding carboxylic acid groups during the preparation of the carbon quantum dots, and the preparation steps are as follows:
(1) Placing part of concentrated nitric acid into ice water bath, and stirring until the temperature is reduced to 2-6 ℃;
(2) Adding the hydrotreated residual oil, adding concentrated sulfuric acid and residual concentrated nitric acid, and stirring for 30min from timing to obtain an intermediate solution;
(3) Cooling the intermediate solution to room temperature after microwave digestion, centrifuging, and washing with water until nitrate ions and sulfate ions are absent in the solution to obtain a carbon quantum dot intermediate solution;
(4) Adding an additive, a dispersing agent and a carboxyl compound into the carbon quantum dot intermediate solution, stirring for 1h, adding an antioxidant, and heating to 100-200 ℃;
(5) Cooling the solution prepared in the step (4) to room temperature, centrifuging, washing with water, and drying at 40-50 ℃ to obtain the required carboxylic acid type carbon quantum dots;
the mass ratio of the concentrated sulfuric acid to the total concentrated nitric acid is 1:3, the mass concentration of the concentrated nitric acid is 65%, the mass ratio of the residual oil to the total concentrated nitric acid is 1 (5-30), and the concentrated nitric acid used in the step (1) accounts for 85% -95% of the total concentrated nitric acid;
in the step (3), the microwave digestion power is 600W, and the microwave digestion time is 10-20 min;
in the step (4), the additive is sodium dodecyl sulfonate or sodium dodecyl benzene sulfonate, and the input mass of the additive is 0.1-0.5% of the total mass of the intermediate solution;
in the step (4), the dispersing agent is polyethylene glycol or polypropylene glycol, and the input mass of the dispersing agent is 0.1-0.3% of the total mass of the intermediate solution;
in the step (4), the carboxyl compound is carboxylic acid, and the input mass of the carboxyl compound is 1% -5% of the total mass of the intermediate solution;
in the step (4), the antioxidant is benzophenone tetrazole or ascorbic acid, and the input mass of the antioxidant is 0.1% -0.3% of the total mass of the intermediate solution.
7. Use of a carboxylic acid type carbon quantum dot foam system according to any one of claims 1-2 or a carboxylic acid type carbon quantum dot foam system produced by a method according to any one of claims 3-6, in particular for foam flooding in reservoirs with high mineralization due to sea deposition.
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| CN112920074A (en) * | 2021-02-05 | 2021-06-08 | 西南石油大学 | Amphiphilic carbon quantum dot foam stabilizer and preparation method thereof |
| CN116676078A (en) * | 2023-08-03 | 2023-09-01 | 中国石油大学(华东) | Amide type carbon quantum dot reinforced foam system and preparation method and application thereof |
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| CN107626258A (en) * | 2017-10-23 | 2018-01-26 | 安徽工业大学 | A kind of synthetic method of carbon quantum dot quaternary cationics |
| CN112920074A (en) * | 2021-02-05 | 2021-06-08 | 西南石油大学 | Amphiphilic carbon quantum dot foam stabilizer and preparation method thereof |
| CN116676078A (en) * | 2023-08-03 | 2023-09-01 | 中国石油大学(华东) | Amide type carbon quantum dot reinforced foam system and preparation method and application thereof |
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