CN103540303A - Composite surfactant composition as well as preparation method thereof - Google Patents
Composite surfactant composition as well as preparation method thereof Download PDFInfo
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- CN103540303A CN103540303A CN201210239959.1A CN201210239959A CN103540303A CN 103540303 A CN103540303 A CN 103540303A CN 201210239959 A CN201210239959 A CN 201210239959A CN 103540303 A CN103540303 A CN 103540303A
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- 239000004094 surface-active agent Substances 0.000 title claims description 72
- 239000000203 mixture Substances 0.000 title claims description 50
- 238000002360 preparation method Methods 0.000 title claims description 9
- 239000002131 composite material Substances 0.000 title description 2
- -1 ammonium radical ion Chemical class 0.000 claims description 51
- 239000013543 active substance Substances 0.000 claims description 48
- 150000001875 compounds Chemical class 0.000 claims description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 34
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 33
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 239000003153 chemical reaction reagent Substances 0.000 claims description 20
- 241000282326 Felis catus Species 0.000 claims description 17
- 239000003513 alkali Substances 0.000 claims description 15
- 230000021523 carboxylation Effects 0.000 claims description 10
- 238000006473 carboxylation reaction Methods 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 150000001412 amines Chemical group 0.000 claims description 2
- 229910052728 basic metal Inorganic materials 0.000 claims description 2
- 150000003818 basic metals Chemical class 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000002736 nonionic surfactant Substances 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- 125000006850 spacer group Chemical group 0.000 claims description 2
- 125000005207 tetraalkylammonium group Chemical group 0.000 claims description 2
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 239000003921 oil Substances 0.000 description 92
- 239000007864 aqueous solution Substances 0.000 description 19
- 239000010779 crude oil Substances 0.000 description 16
- 238000011084 recovery Methods 0.000 description 16
- 230000000694 effects Effects 0.000 description 13
- 239000000126 substance Substances 0.000 description 12
- 239000003208 petroleum Substances 0.000 description 11
- 239000003945 anionic surfactant Substances 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 238000006073 displacement reaction Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 6
- 125000002091 cationic group Chemical group 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 239000011435 rock Substances 0.000 description 6
- 208000027418 Wounds and injury Diseases 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 150000007942 carboxylates Chemical class 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 5
- 239000003093 cationic surfactant Substances 0.000 description 5
- 230000006378 damage Effects 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- 208000014674 injury Diseases 0.000 description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 description 5
- 239000011707 mineral Substances 0.000 description 5
- 239000003129 oil well Substances 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 4
- 239000004141 Sodium laurylsulphate Substances 0.000 description 4
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 4
- 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 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000003027 oil sand Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- GAWAYYRQGQZKCR-REOHCLBHSA-N (S)-2-chloropropanoic acid Chemical compound C[C@H](Cl)C(O)=O GAWAYYRQGQZKCR-REOHCLBHSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 238000010795 Steam Flooding Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000002547 anomalous effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- HMPHJJBZKIZRHG-UHFFFAOYSA-N chloromethanesulfonic acid Chemical compound OS(=O)(=O)CCl HMPHJJBZKIZRHG-UHFFFAOYSA-N 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- GQFZYTXZJHSSEA-UHFFFAOYSA-M decyl(triethyl)azanium;hydroxide Chemical compound [OH-].CCCCCCCCCC[N+](CC)(CC)CC GQFZYTXZJHSSEA-UHFFFAOYSA-M 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- REZZEXDLIUJMMS-UHFFFAOYSA-M dimethyldioctadecylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC REZZEXDLIUJMMS-UHFFFAOYSA-M 0.000 description 1
- 239000004664 distearyldimethylammonium chloride (DHTDMAC) Substances 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000008398 formation water Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000015784 hyperosmotic salinity response Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 230000015227 regulation of liquid surface tension Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 229940045998 sodium isethionate Drugs 0.000 description 1
- LADXKQRVAFSPTR-UHFFFAOYSA-M sodium;2-hydroxyethanesulfonate Chemical compound [Na+].OCCS([O-])(=O)=O LADXKQRVAFSPTR-UHFFFAOYSA-M 0.000 description 1
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- SFVFIFLLYFPGHH-UHFFFAOYSA-M stearalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SFVFIFLLYFPGHH-UHFFFAOYSA-M 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 239000012747 synergistic agent Substances 0.000 description 1
- MQAYPFVXSPHGJM-UHFFFAOYSA-M trimethyl(phenyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)C1=CC=CC=C1 MQAYPFVXSPHGJM-UHFFFAOYSA-M 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
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)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a composite surfactant composition as well as a preparation method thereof, and mainly solves the problems that an existing surfactant is poor in oil driving efficiency during three times of oil extraction processes, meanwhile, an oil driving system contains inorganic alkaline, hurts the ground layer and an oil well, and corrodes equipment and pipelines, and demulsification is difficult. According to the composition and the preparation method, the surfactant composition comprises a cation surfactant and an anion-non-ion surfactant, wherein the cation surfactant is selected from any one of quaternary ammonium salt and quaternary amine alkali, the anion-non-ion surfactant is a surfactant containing ethoxy nonionic groups and carboxyl or sulfo anionic groups, and the mole ratio of the cation surfactant to the anion-non-ion surfactant is (1:0.01)-(1:100); by using the composition and the preparation method, the problems are solved well, and the composite surfactant composition as well as the preparation method thereof can be used in the process of three times of oil extraction in an oil field.
Description
Technical field
The present invention relates to a kind of compound surfactant composition and method of making the same.
Background technology
Along with the increase of world energy sources demand, the rational exploitation and utilization of oil has caused people's very big attention, also more and more higher to the requirement of the produced quantity of oil and production efficiency.Realize the high-efficiency mining of hydrocarbon resources, for improving crude production rate, not only there is realistic meaning, have more important strategic importance.1/3 of the conventional general only extraction oil in-place of oil production method (once with secondary method), 2/3 the crude oil of also having an appointment is failed extraction, the in the situation that of being therefore becoming tight in energy day, improves the key subjects that tar productivity has become oil production research.Tertiary oil recovery technology is a kind of method of effective raising tar productivity, can be divided into four large classes: the one, and heating power drives, and comprises steam flood, combustion in situ etc.; The 2nd, mixed phase drives, and comprises CO
2mixed phase, hydrocarbon mixed phase and other rare gas element mixed phases drive; The 3rd, chemical flooding; The 4th, microbe oil production, comprises that biological polymer, MICROBIAL SURFACTANT drive.Chemical flooding is the technology of extremely important in intensified oil reduction and extensive enforcement, comprises the multiple combination technology of polymer flooding, surfactant flooding, caustic waterflooding etc. and polymkeric substance, alkali, tensio-active agent.The effect of chemical flooding is the result of physical action and chemical action, and physical action refers to the effect that involves of displacing fluid, and chemical action refers to the microcosmic oil drive effect of displacing fluid.The core of chemical action is to reduce the interfacial tension of displacing fluid and crude oil.Tensio-active agent is owing to having oleophylic (hydrophobic) and hydrophilic (oleophobic) character concurrently, and when tensio-active agent is water-soluble, molecule is mainly distributed on water-oil interface, can significantly reduce oil water interfacial tension.The reduction of oil water interfacial tension means that surfactant system can overcome the force of cohesion between crude oil, and larger oil droplet is dispersed into little oil droplet, thereby improves the percent of pass of crude stream when pore throat.The oil displacement efficiency of tensio-active agent also shows the effects such as wettability of rock surface reversion, emulsification of crude oil, raising surface charge density and oil droplet coalescence that make oleophylic, and this is the reason that tensio-active agent plays very important effect in chemical flooding technology.
Surface active agent for tertiary oil recovery adopts Recompounded multielement system mostly at present, comprises nonionic surface active agent and ionogenic surfactant simultaneously, in part formula, also adds the auxiliary agents such as alkali and alcohol.As the tensio-active agent that patent CN101024764A provides a kind of oil-field thick-oil well to use, this promoting agent is comprised of water, sheet alkali, ethanol, oleic acid, alkylphenol polyoxyethylene, Sodium dodecylbenzene sulfonate.For another example patent CN1458219A discloses a kind of pure binary ultra low interfacial tension of surfactant polymer combination flooding formula of tertiary oil recovery application, use therein tensio-active agent is that sulfonated petro-leum or the sulfonated petro-leum of take add the complexed surfactant of thinner and other surfactant compound as host, the weight percent of its component is sulfonated petro-leum 50～100%, alkylsulfonate 0～50%, carboxylate salt 0～50%, alkylaryl sulphonate 0～35%, low-carbon alcohol 0～20%.And for example patent CN1394935 has invented a kind of chemical oil displacement agent, and it mainly comprises octyl group benzene sulfonic acid sodium salt anion surfactant, surfactant adjuvant, tensio-active agent synergistic agent, surface active agent solubilization agent.This oil-displacing agent can reduce the structural viscosity of viscous crude significantly, can reduce oil water interfacial tension simultaneously, thereby improves oil recovery factor.
Yet still there is more problem in above-mentioned surface active agent for tertiary oil recovery, be mainly that surfactant activity is poor, oil displacement efficiency is low, simultaneously because surfactant system is too complicated, thereby Produced Liquid breakdown of emulsion difficulty, sewage disposal difficulty is large; In addition because flooding system is containing mineral alkali, injury is brought in stratum and oil well, cause the problems such as etching apparatus and pipeline, and because mineral alkali can seriously reduce the viscosity of polymkeric substance, for reaching required viscosity, have to greatly improve the working concentration of polymkeric substance, the comprehensive cost that makes to recover the oil improves; The high temperature resistance of tensio-active agent, high salt tolerance, anti-high salinity limited in one's ability.
As everyone knows, anion surfactant, as sulfonated petro-leum, petroleum carboxylate, alkylbenzene sulfonate etc. are widely used in tertiary oil recovery process at present, and cats product is easily adsorbed by stratum or produces precipitation because of it, therefore reduce the ability of oil water interfacial tension, be generally not used in tertiary oil recovery.While approaching equal proportion mixing due to cationic and anionic surfactant, its aqueous solution easily forms precipitation, thereby causes cationic and anionic surfactant mixed system not only in application, to become incompatibility, and correlation theory research also relatively lags behind.Research is in recent years found, the cationic and anionic surfactant mixed system aqueous solution has a lot of anomalous properties, as existed the interaction between strong electrostatic interaction and hydrophobicity carbochain in the aqueous solution due to cationic and anionic surfactant, promoted two kinds to be with the interionic association of different charged surface promoting agents, in solution, be easy to form micella, produce the surfactivity higher than single tensio-active agent.In addition, cationic and anionic surfactant mixed system can obviously reduce the absorption loss of cats product on rock core, thereby can significantly reduce the inherent defect of cats product.
Gong Yujun etc. (seeing volume the 1st phase Northwest University's journal (natural science edition) February the 30th in 2000,28～31) research thinks that cetyl trimethylammonium bromide (CTAB) and sodium lauryl sulphate (SDS) mixed system have solublization.In oil production process, utilize the solublization can " displacement of reservoir oil ", by under the oil wash sticking on the sandstone of rock stratum, thereby improve oil recovery.Huang Hongdu etc. (seeing oil and gas journal the 29th the 4th phase of volume of August in 2007,101～104) have studied the interfacial tension of the anion surfactants such as sulfonated petro-leum, petroleum carboxylate, alkylbenzene sulfonate and cetyl trimethylammonium bromide, alkali compound system and have drawn to draw a conclusion: adding of cats product improves the interfacial activity of petroleum carboxylate, alkylbenzene sulfonate, sulfonated petro-leum.
Above-mentioned result of study shows that yin, yang ionic surface active agent compound system has certain effect for reduction oil water interfacial tension, raising oil displacement efficiency.But the former result of study shows its interface performance and still have much room for improvement, the latter has still adopted alkali in system, thereby cannot avoid alkali to bring injury to stratum and oil well, the problems such as etching apparatus and pipeline and breakdown of emulsion difficulty.Above-mentioned system ratio is easier to generate precipitation in addition, is unfavorable for practical application.
For this reason, one aspect of the present invention absorbs has used for reference forefathers about yin, yang ionic surface active agent mixed system result of study, adopt on the other hand Anionic-nonionic tensio-active agent to replace traditional anion surfactant, the easy shortcoming such as precipitation while having overcome cationic anionic surfactant combination, has invented cats product and the Anionic-nonionic tensio-active agent compound surfactant composition for improving oil recovery factor, used.
Summary of the invention
One of technical problem to be solved by this invention is that existing tensio-active agent oil displacement efficiency in tertiary oil recovery process is poor, simultaneously because flooding system contains mineral alkali, injury is brought in stratum and oil well, the problem of etching apparatus and pipeline and breakdown of emulsion difficulty, a kind of new compound surfactant composition is provided, said composition has that interfacial activity is high, washing oil ability is strong, system is simple, can not bring injury to stratum and oil well, can etching apparatus and pipeline and can not cause the advantage of breakdown of emulsion difficulty.
Two of technical problem to be solved by this invention is to provide a kind of preparation method of the surfactant composition corresponding with technical solution problem one.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of compound surfactant composition and method of making the same, comprise cats product and Anionic-nonionic tensio-active agent, the mol ratio of described cats product and Anionic-nonionic tensio-active agent is 1: 0.01～1: 100, wherein cats product is selected from least one in quaternary ammonium salt or quaternary amine alkali, and Anionic-nonionic surfactant molecule general formula is:
Wherein M is any one in basic metal, alkaline-earth metal or ammonium radical ion, and R is H, C
1～C
20alkyl, aryl, COOM or SO
3any one in M, oxyethyl group polymerization degree n is any one integer or the decimal in 1～40, spacer R ' is C
1～C
5alkyl.
In technique scheme, described cats product preferred version is selected from least one in tetra-alkyl ammonium chloride or tetra-alkyl ammonium hydroxide; In described Anionic-nonionic tensio-active agent, positively charged ion M preferred version is selected from Na, K, Mg, Ca or NH
4 +in any one; Described substituent R preferred version is H, C
5～C
15alkyl, aryl, COOM or SO
3any one in M; Described oxyethyl group polymerization degree n preferable range is any one integer or the decimal in 1～20; The mol ratio preferable range of described cats product and Anionic-nonionic tensio-active agent is 1: 0.1～1: 10.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: a kind of preparation method of compound surfactant composition, comprises the following steps:
A) alkylphenol polyoxyethylene, catalyzer are added to reactor according to mol ratio 1:1～5, in room temperature～100
oc alkalization 1～10 hour, then adds sulfonated reagent or carboxylation reagent, wherein alkylphenol polyoxyethylene: the mol ratio of sulfonated reagent or carboxylation reagent is 1:1～4, is warming up to 50～100
oc continues reaction 1～20 hour, then adds hydrochloric acid to be neutralized to pH<3, and carries out oily water separation, and oil phase adds alkali lye to neutralize, and finally obtains alkylphenol polyoxyethylene sulfonate or alkylphenol polyoxyethylene carboxylate salt;
B) cats product and the Anionic-nonionic tensio-active agent that a) obtains according to step are dissolved in the water respectively, then according to mol ratio, within 1: 0.1～1: 10, mix and obtain required composition.
In technique scheme, described catalyzer is selected from least one in NaOH or KOH; Described sulfonated reagent is hydroxyl sulfoacid and salt or halogenosulfonic acid and salt thereof; Described carboxylation reagent is halogenated carboxylic acid and salt thereof.
Compound surfactant composition of the present invention is on the one hand due to strong electrostatic attraction effect between yin, yang ionic surface active agent opposite charges polar group, surfactant molecule adsorptive capacity on interface is increased, micelle-forming concentration significantly reduces, thereby has the incomparable high surface of single tensio-active agent; Due to the interfacial activity of compound surfactant superelevation, its aqueous solution can form ultra low interfacial tension with crude oil, thereby effectively overcomes the force of cohesion between crude oil, is conducive to former oil-out, and then significantly improves oil displacement efficiency simultaneously.Compound surfactant composition can change oil reservoir wettability of the surface on the other hand, if the cats product in composition is by the electronegative Interaction of substituents with being adsorbed on solid surface, its desorption is got off, making glossy wet surface modification is intermediate wet or water-wet surface, reduce crude oil at the work of adhesion of solid surface, thereby be conducive to peeling off of crude oil.Yin, yang ionic surface active agent mixing solutions has solublization to crude oil simultaneously, can, further by under the former oil wash sticking on the sandstone of rock stratum, improve oil recovery factor.
In tertiary oil recovery process, adopt compound surfactant composition of the present invention, there is interfacial activity high: compound surfactant composition consumption is still can form 10 with underground crude oil under 0.01～0.05% condition
-3～10
-4mN/m ultra low interfacial tension; Washing oil ability is strong: compound surfactant composition surpasses 40% to the washing oil rate of crude oil; Surfactant composition system is simple.Because system is containing mineral alkali, thereby the problem of mineral alkali causes stratum while having avoided rig-site utilization injury, the corrosion that equipment is caused and the breakdown of emulsion difficulty that causes thus, good technique effect obtained.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
Alkylphenol polyoxyethylene, NaOH are added to reactor according to mol ratio 1:5, in 100
oc alkalization 1 hour, then according to alkylphenol polyoxyethylene: chloromethyl sulfonic acid mol ratio 1:4 adds sulfonated reagent, is cooled to 50
oc continues reaction 20 hours, then adds hydrochloric acid to be neutralized to pH<3, stratification, and oil phase adds the 30%NaOH aqueous solution to neutralize, and obtains alkylphenol polyoxyethylene sodium sulfonate.
Alkylphenol polyoxyethylene sodium sulfonate tensio-active agent prepared by palmityl trimethyl ammonium chloride and the present invention is dissolved in the water respectively, stir 30 minutes, be mixed with 0.3% aqueous solution, then by above-mentioned tensio-active agent according to positively charged ion: Anionic-nonionic tensio-active agent mol ratio mixes at 1: 0.3, obtain compound surfactant composition 1, its composition, structure are in Table 1.
[embodiment 2]
Alkylphenol polyoxyethylene, KOH are added to reactor according to mol ratio 1:1, in room temperature alkalization 10 hours, then according to alkylphenol polyoxyethylene: sodium isethionate mol ratio 1:3 adds sulfonated reagent, is warming up to 70
oc continues 10 hours, then adds hydrochloric acid to be neutralized to pH<3, and carries out oily water separation, and oil phase adds ammoniacal liquor to neutralize, and obtains alkylphenol polyoxyethylene ammonium sulphonate.
Alkylphenol polyoxyethylene ammonium sulphonate tensio-active agent prepared by benzyltriethylammoinium chloride and the present invention is dissolved in the water respectively, stir 30 minutes, be mixed with 0.3% aqueous solution, then by above-mentioned tensio-active agent according to positively charged ion: Anionic-nonionic tensio-active agent mol ratio mixes at 1: 0.1, obtain compound surfactant composition 2, its composition, structure are in Table 1.
[embodiment 3]
Alkylphenol polyoxyethylene, KOH are added to reactor according to mol ratio 1:1.5, in 30
oc alkalization 8 hours, then according to alkylphenol polyoxyethylene: chlorine amyl group sodium sulfonate mol ratio 1:2 adds sulfonated reagent, is warming up to 60
oc continues 15 hours, then adds hydrochloric acid to be neutralized to pH<3, and carries out oily water separation, and oil phase adds 10%Ca (HCO
3)
2the aqueous solution neutralizes, and obtains alkylphenol polyoxyethylene calcium sulphonate.
Phenyl trimethyl ammonium chloride and the alkylphenol polyoxyethylene calcium sulphonate tensio-active agent prepared according to the present invention are dissolved in the water respectively, stir 30 minutes, be mixed with 0.3% aqueous solution, then by above-mentioned tensio-active agent according to positively charged ion: Anionic-nonionic tensio-active agent mol ratio mixes at 1: 1.2, obtain compound surfactant 3, its composition, structure are in Table 1.
[embodiment 4]
Alkylphenol polyoxyethylene, NaOH are added to reactor according to mol ratio 1:2, in 50
oc alkalization 6 hours, then according to alkylphenol polyoxyethylene: 3-chlorine-2-hydroxyl propanesulfonate mol ratio 1:2 adds sulfonated reagent, is warming up to 80
oc continues 8 hours, then adds hydrochloric acid to be neutralized to pH<3, and carries out oily water separation, and oil phase adds the unsaturated carbonate hydrogen magnesium aqueous solution to neutralize, and obtains alkylphenol polyoxyethylene sulfonic acid magnesium.
Stearyl dimethyl benzyl ammonium chloride and the alkylphenol polyoxyethylene sulfonic acid magnesium tensio-active agent prepared according to the present invention are dissolved in the water respectively, stir 30 minutes, be mixed with 0.3% aqueous solution, then by above-mentioned tensio-active agent according to positively charged ion: Anionic-nonionic tensio-active agent mol ratio mixes at 1: 2.0, obtain compound surfactant 4, its composition, structure are in Table 1.
[embodiment 5]
Alkylphenol polyoxyethylene, NaOH are added to reactor according to mol ratio 1:3, in 60
oc alkalization 5 hours, then according to alkylphenol polyoxyethylene: Mono Chloro Acetic Acid mol ratio 1:1 adds carboxylation reagent, is warming up to 100
oc continues 1 hour, then adds hydrochloric acid to be neutralized to pH<3, and carries out oily water separation, and oil phase adds the 30%NaOH aqueous solution to neutralize, and obtains alkylphenol polyoxyethylene carboxylic acid sodium.
Decyl triethyl ammonium hydroxide and the alkylphenol polyoxyethylene carboxyl acid natrium surfactant prepared according to the present invention are dissolved in the water respectively, stir 30 minutes, be mixed with 0.3% aqueous solution, then by above-mentioned tensio-active agent according to positively charged ion: Anionic-nonionic tensio-active agent mol ratio mixes at 1: 10, obtain compound surfactant 5, its composition, structure are in Table 1.
[embodiment 6]
Alkylphenol polyoxyethylene, NaOH are added to reactor according to mol ratio 1:4, in 80
oc alkalization 2 hours, then according to alkylphenol polyoxyethylene: chloropropionic acid mol ratio 1:1.5 adds carboxylation reagent, is cooled to 50
oc continues 18 hours, then adds hydrochloric acid to be neutralized to pH<3, and carries out oily water separation, and oil phase adds 10%Ca (HCO
3)
2neutralize, obtain alkylphenol polyoxyethylene calcium carboxylates.
Dodecyl trimethyl ammonium chloride and the alkylphenol polyoxyethylene calcium carboxylates tensio-active agent prepared according to the present invention are dissolved in the water respectively, stir 30 minutes, be mixed with 0.3% aqueous solution, then by above-mentioned tensio-active agent according to positively charged ion: Anionic-nonionic tensio-active agent mol ratio mixes at 1: 0.9, obtain compound surfactant 6, its composition, structure are in Table 1.
[embodiment 7]
Alkylphenol polyoxyethylene, KOH are added to reactor according to mol ratio 1:1, in room temperature alkalization 10 hours, then according to alkylphenol polyoxyethylene: sodium chloroacetate mol ratio 1:3 adds carboxylation reagent, is warming up to 80
oc continues 8 hours, then adds hydrochloric acid to be neutralized to pH<3, and carries out oily water separation, and oil phase adds the 30%KOH aqueous solution to neutralize, and obtains alkylphenol polyoxyethylene carboxylic acid potassium.
Distearyl dimethyl ammonium chloride and the alkylphenol polyoxyethylene carboxylic acid potassium tensio-active agent prepared according to the present invention are dissolved in the water respectively, stir 30 minutes, be mixed with 0.3% aqueous solution, then by above-mentioned tensio-active agent according to positively charged ion: Anionic-nonionic tensio-active agent mol ratio mixes at 1: 4, obtain compound surfactant 7, its composition, structure are in Table 1.
[embodiment 8]
Alkylphenol polyoxyethylene, NaOH are added to reactor according to mol ratio 1:3, in 65
oc alkalization 2 hours, then according to alkylphenol polyoxyethylene: chloropropionic acid mol ratio 1:2 adds carboxylation reagent, is warming up to 75
oc continues 9 hours, then adds hydrochloric acid to be neutralized to pH<3, and carries out oily water separation, and oil phase adds the 30%NaOH aqueous solution to neutralize, and obtains alkylphenol polyoxyethylene carboxylic acid sodium.
Four octyl group ammonium chlorides and the alkylphenol polyoxyethylene carboxyl acid natrium surfactant prepared according to the present invention are dissolved in the water respectively, stir 30 minutes, be mixed with 0.3% aqueous solution, then by above-mentioned tensio-active agent according to positively charged ion: Anionic-nonionic tensio-active agent mol ratio mixes at 1: 6, obtain compound surfactant 8, its composition, structure are in Table 1.
[embodiment 9]
0.30wt% compound surfactant and 0.15wt% polyacrylamide (the molecular weight 2,600 ten thousand) aqueous solution of embodiment 3 preparations is even, obtain a kind of Polymer Used For Oil Displacement-surfactant complex.
Table 1 compound surfactant composition forms and structure
The test of [embodiment 10] compound surfactant composition interface performance
With TX-500C rotation, drip interfacial tensimeter and measure compound surfactant composition and Shuanghe Oil Field
5-11 series of strata oil water interfacial tension.Measuring temperature is 81
oc, local water is NaHCO
3type, salinity is 7947mg/L, chloride ion content 2002 mg/L, Ca
2+content 20 mg/L, Mg
2+content 12.2 mg/L, compound surfactant composition consumption is 0.3%.
Table 2 compound surfactant composition and Shuan He oil field
5-11 series of strata oil water interfacial tension
| Embodiment | Interfacial tension (mN/m) |
| 1 | 0.0080 |
| 2 | 0.0096 |
| 3 | 0.0004 |
| 4 | 0.0006 |
| 5 | 0.0068 |
| 6 | 0.0075 |
| 7 | 0.0011 |
| 8 | 0.0075 |
| 9 | 0.0062 |
As shown in Table 2, the compound surfactant of embodiment 1～8 preparation has good interface performance for Henan Oil Field.Embodiment 9 shows, after tensio-active agent prepared by the present invention and polymkeric substance are composite, its interface performance is still good.
The compound surfactant of embodiment 3 preparations is mixed with to different concns, respectively test and Shuanghe Oil Field
5-11 series of strata oil water interfacial tension, the results are shown in Table 3.
Table 3 different concns surfactant composition 3 and Shuanghe Oil Field
5-11 series of strata oil water interfacial tension
| Dosage of surfactant (%) | 0.01 | 0.02 | 0.05 | 0.1 | 0.2 | 0.3 |
| Interfacial tension (MN/m) | 0.009 | 0.007 | 0.004 | 0.002 | 0.0007 | 0.0004 |
The above results shows, compound surfactant composition of the present invention has very high interfacial activity for Henan Oil Field crude oil.
With TX-500C rotation, drip interfacial tensimeter and again measure the compound surfactant of embodiment 4 preparations and the Zhongyuan Oil Field three factory's oil water interfacial tensions that recover the oil.Measuring temperature is 80
oc, formation water salinity is 79439mg/L, Ca
2+content 592 mg/L, Mg
2+content 2871mg/L, dosage of surfactant is 0.3%.Oil water interfacial tension is 0.003mN/m, shows that tensio-active agent of the present invention is not only for low mineralization oil reservoir, still has good interface performance for high temperature and high salt oil deposit simultaneously, has advantages of that the scope of application is wide.
The aptitude tests of [embodiment 11] compound surfactant composition washing oil
Get Shuanghe Oil Field
5-11 series of strata oil-sand, according to oil: sand=1:4 (weight ratio) 81
oaging 7 days of C, stirs 5 minutes for every 2 hours; Then take out above-mentioned oil-sand 5g after aging, with 0.3% surfactant soln by oil-sand: solution=1:10 mixes, under reservoir temperature after aging 48 hours, with the crude oil in petroleum ether extraction solution, with 50ml colorimetric cylinder constant volume, spectrophotometer is in wavelength 430nm place's colorimetric analysis.Utilize typical curve gauging surface activator solution Crude Oil concentration.
Table 4 compound surfactant composition washing oil result
| Embodiment | Washing oil rate % |
| 1 | 62.5 |
| 2 | 60.1 |
| 3 | 44.3 |
| 4 | 58.1 |
| 5 | 40.8 |
| 6 | 52.4 |
| 7 | 57.6 |
| 8 | 45.5 |
The research of [embodiment 12] compound surfactant composition Oil Displacing Capacity
In length, be 30 centimetres, diameter is 2.5 centimetres, and rate of permeation is 1.5 microns
2rock core on carry out oil displacement test.First use Shuanghe Oil Field
5-11 series of strata local water is driven to moisture 92 %, and after the compound surfactant composition of metaideophone 0.3pv (rock pore volume), water drive, to moisture 100%, improve oil recovery factor and the results are shown in Table 5.
Table 5 compound surfactant composition oil displacement test result
| Tensio-active agent sequence number | Improve recovery ratio % |
| 1 | 5.5 |
| 2 | 5.1 |
| 3 | 5.2 |
| 4 | 5.9 |
| 5 | 4.4 |
| 6 | 4.7 |
| 7 | 6.1 |
| 8 | 4.5 |
[comparative example 1]
According to Northwest University's journal (natural science edition) the 30th the 1st phase of volume of February in 2000, the methods such as 28～31Gong Yu armies are mixed with mixed system (mol ratio 1:1.5) by cetyl trimethylammonium bromide (CTAB) and sodium lauryl sulphate (SDS), test respectively it when 0.3% consumption and Shuanghe Oil Field
5-11 series of strata crude oil oil water interfacial tension, washing oil rate and Oil Displacing Capacity, result is as follows:
Table 6 reference oil-displacing agent performance
| Interfacial tension (MN/m) | Washing oil rate % | Improve recovery ratio % |
| 0.03 | 45.6 | 2.8 |
[comparative example 2]
According to oil and gas journal the 29th the 4th phase of volume of August in 2007, Huang Hongdu etc. (101～104) method etc. are by 0.01% cetyl trimethylammonium bromide and 0.02% anion surfactant sulfonated petro-leum and 1.8%Na
2cO
3be mixed with mixed system, test respectively it when 0.3% consumption and Shuanghe Oil Field
5-11 series of strata crude oil oil water interfacial tension, washing oil rate and Oil Displacing Capacity, result is as follows:
Table 7 reference oil-displacing agent performance
| Interfacial tension (MN/m) | Washing oil rate % | Improve recovery ratio % |
| 0.008 | 56.3 | 4.2 |
Claims (8)
1. a compound surfactant composition, comprise cats product and Anionic-nonionic tensio-active agent, the mol ratio of described cats product and Anionic-nonionic tensio-active agent is 1: 0.01～1: 100, wherein cats product is selected from least one in quaternary ammonium salt or quaternary amine alkali, and Anionic-nonionic surfactant molecule general formula is:
Wherein M is any one in basic metal, alkaline-earth metal or ammonium radical ion, and R is H, C
1～C
20alkyl, aryl, COOM or SO
3any one in M, R ' is C
1～C
10alkyl, n is any one integer or the decimal in 1～40.
2. compound surfactant composition according to claim 1, is characterized in that described cats product is selected from least one in tetra-alkyl ammonium chloride or tetra-alkyl ammonium hydroxide.
3. compound surfactant composition according to claim 1, is characterized in that in described Anionic-nonionic tensio-active agent, positively charged ion M is selected from Na, K, Mg, Ca or NH
4 +in any one.
4. compound surfactant composition according to claim 1, is characterized in that described substituent R is H, C
5～C
15alkyl, aryl, COOM or SO
3m.
5. compound surfactant composition according to claim 1, is characterized in that described spacer R ' is C
1～C
5alkyl.
6. compound surfactant composition according to claim 1, is characterized in that described oxyethyl group polymerization degree n is any one integer or the decimal in 1～20.
7. the preparation method of compound surfactant composition described in claim 1, comprises the following steps:
A) alkylphenol polyoxyethylene, catalyzer are added to reactor according to mol ratio 1:1～5, in room temperature～100
oc alkalization 1～10 hour, then adds sulfonated reagent or carboxylation reagent, wherein alkylphenol polyoxyethylene: the mol ratio of sulfonated reagent or carboxylation reagent is 1:1～4, is warming up to 50～100
oc continues reaction 1～20 hour, then adds hydrochloric acid to be neutralized to pH<3, and carries out oily water separation, and oil phase adds alkali lye to neutralize, and finally obtains alkylphenol polyoxyethylene sulfonate or alkylphenol polyoxyethylene carboxylate salt;
B) cats product and the Anionic-nonionic tensio-active agent that a) obtains according to step are dissolved in the water respectively, then according to mol ratio, within 1: 0.1～1: 10, mix, obtain required composition.
8. the preparation method of compound surfactant composition according to claim 7, is characterized in that described catalyzer is selected from least one in NaOH or KOH; Described sulfonated reagent is hydroxyl sulfoacid and salt or halogenosulfonic acid and salt thereof; Described carboxylation reagent is halogenated carboxylic acid and salt thereof.
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