CN103421481A - Glycine betaine surfactant composition system and purpose thereof - Google Patents
Glycine betaine surfactant composition system and purpose thereof Download PDFInfo
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- CN103421481A CN103421481A CN2013103973431A CN201310397343A CN103421481A CN 103421481 A CN103421481 A CN 103421481A CN 2013103973431 A CN2013103973431 A CN 2013103973431A CN 201310397343 A CN201310397343 A CN 201310397343A CN 103421481 A CN103421481 A CN 103421481A
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Abstract
The invention discloses a glycine betaine surfactant composition system and a purpose thereof. The glycine betaine surfactant composition system comprises one or more mixtures of a glycine betaine surfactant and an anionic surfactant. The glycine betaine surfactant comprises alkyl dimethyl betaine, alkyl amide propyl dimethyl betaine, alkyl sulphobetaine and alkyl hydroxy sulphobetaine. The use concentration ratio of the glycine betaine surfactant and the anionic surfactant, by 100% pure activity, is 1:0.1-10. The glycine betaine surfactant composition system is used for chemical displacement of reservoir oil, and enables the oil deposit of an oil well in which secondary oil-production efficiency in the later period is decreased seriously to be developed by 10-15%, and the economic efficiency is very obvious. Moreover, the use concentration is low, and cost is lowered greatly. Due to the fact that other conventional alkalis are of no need, the select face of polymers is made to be wider, and the significance for protecting natural resources is great.
Description
Technical field
The invention belongs to the oil-field development field, relate to the chemical displacement of reservoir oil additive for oil-field development, particularly, relate to a kind of beet alkali surface activator composition system and for the purposes of the chemical displacement of reservoir oil, be applicable to low surfactant concentration, the change drive system that alkali-free adds.
Background technology
In the typical oilfield exploitation, reoovery method at first is to utilize the energy exploitation of oil reservoir own, namely primary oil recovery.In this stage, crude oil goes out with the well casing eruption by self-energy.Usually the oil reservoir of 15-20% left and right leans on (being primary oil recovery) like this to develop.Along with going deep into of exploitation, when natural energy can't be satisfied the demand due to decay, water or gas need to be injected into output or the recovery ratio that oil reservoir maintains oil well, and this is secondary phase of oil production.The former oil stock of 15-20% is gathered in the crops by secondary development in addition.Along with the efficiency of secondary oil recovery constantly descends, to oil reservoir injecting fluid or energy, utilize the physics produced, chemistry is biological action even, with this, improves output or recovery ratio-tertiary phase.Thisly inject the whole bag of tricks that fluid or energy improve crude oil yield or recovery ratio to stratum, be commonly referred to as intensified oil reduction (Enhanced Oil Recovery or EOR), i.e. tertiary oil recovery.
The reason of secondary oil recovery decrease in efficiency is, due to capillary force, remaining crude oil is bound in the space of the rock sand of reservoir layer with interrupted form, causes the crude oil can't be with the unrestricted flow of injected water system.Common water flood can't effectively overcome this capillary force, causes that to be injected into the crude oil that water carries fewer and feweri, the produce oil decrease in efficiency.This capillary force can mean its size by a capillary number in theory.Only have when the capillary number of crude oil is overcome, bound crude oil just likely is released.Following formula can be used for estimating the capillary number had of injected water system:
Nc = V * μ/IFT
Wherein, Nc is the capillary number of injected water system, and V is the flow velocity of injected water system, and μ is the viscosity of injected water system, and IFT is oil water interfacial tension.Only have when the capillary number of injected water system is greater than a critical numerical value (critical capillary number), the capillary number of crude oil can be overcome.From this formula, the method that improves capillary number has following several: 1) improve flow velocity; 2) improve viscosity; 3) reduce oil water interfacial tension.
Due to the restriction that is subject to injection device and formation condition, the space of improving flow velocity is very limited.Raising system viscosity (generally realizing by adding polymkeric substance) can improve order of magnitude of capillary number.And effective means is to reduce oil water interfacial tension, if the 10-30 dyn/cm(dynes per centimeter of interfacial tension from usually containing tensio-active agent the time) drop to ~ 10
-3The ultralow scope of dyn/cm, the capillary number of system promotes 4 orders of magnitude at this point.The attenuating of this interfacial tension is normally by adding tensio-active agent to realize.
Oil water interfacial tension is the mutually exclusive results of two kinds of different liqs (You Heshui).Because tensio-active agent has oleophylic and hydrophilic function simultaneously, they are gathered in water-oil interface and form single or multiple lift absorption.Their lipophilic groups are towards oil reservoir, and hydrophilic radical is towards water.The reduction degree of oil water interfacial tension depends on the balanced degree of their oleophilic function and hydrophilic interaction.More close when these two kinds of effects, the numerical value of interfacial tension is less.When these two kinds effect convergence balances, oil water interfacial tension just may enter ultra low interfacial tension zone (~ 10
-3Dyn/cm).
Traditional tensio-active agent is that basic tertiary oil recovery adopts the ternary built technology: by tensio-active agent, polymkeric substance and alkali ternary built, formed.Wherein, tensio-active agent is that a class chemical substance has lipophilic group and hydrophilic radical simultaneously.Polymkeric substance is a family macromolecule chemical substance, in the time of in they are dissolved in water, can form full-bodied solution.Alkali is referring to the mineral-type chemical substance, they can produce hydroxide ion in the aqueous solution, alkalimetal oxide (as sodium oxide), the salt (sodium carbonate) that alkali metal hydroxide (sodium hydroxide) and strong base weak acid form etc. is the representative of the alkali of indication here.Traditional ternary built technology is for the tertiary oil recovery of oil-field development, and subject matter has: 1) use of long-term alkali can cause the destruction on stratum, and oil recovery and environment are caused to negative impact; 2) use of alkali causes the unstable of some tensio-active agents and polymkeric substance and decomposes, and has limited the selection of Surfactant and polymkeric substance.
The tensio-active agent of traditional tertiary oil recovery is cationic, and modal is petroleum sulfonate surfactant.Their common and polymkeric substance, alkali is used simultaneously, forms " ternary built system ".Due to the side effect of alkali to stratum and environment, the use of alkali more and more is restricted.The independent use of the tensio-active agent of alkali-free or surfactant and polymer " binary built system " are just becoming new developing direction.
In conventional ternary built system, alkali is the acidic substance in saponification crude oil at the Main Function of tertiary oil recovery, make them become the tensio-active agent of saponification, utilize this tensio-active agent produced on the spot, increase the total concentration (reduce the actual surfactant concentration added, lower the cost recovered the oil) of tensio-active agent.Due to the negative impact of aforesaid alkali, the direction of newly filling a prescription is to find the surfactant system of cost-effective alkali-free.But usually do not add in the situation of alkali, prior art is generally that the concentration by improving tensio-active agent realizes.Under the condition of high surface agent concentration (effective working concentration of tensio-active agent is more than 3%), due to the ability of the dissolving oil of the formed micella of tensio-active agent, this injected water cording that contains tensio-active agent has and highlyer than simple injection water system carries oily ability.But this dissolves by micella, the raising of oil-producing capacity is limited.And, due to the cost reason of tensio-active agent, the application limitations of this high density is very large.
But the formula of lower concentration system, particularly in the condition of alkali-free, lack corresponding laboratory study and theoretical direction, the experience of practical application lacks, and a little less than causing thus the ability of systematicness formula and optimization of C/C composites, while finding formula, blindness is large.At present, relevant report is not also arranged.
Summary of the invention
The objective of the invention is above deficiency, improve traditional ternary built system, provide a kind of under the condition of alkali-free, use the beet alkali surface activator composition system of lower concentration, for the chemical displacement of reservoir oil, especially the chemical displacement of reservoir oil of tertiary oil recovery, by the tertiary oil recovery of this mode, the oil well in a secondary oil recovery later stage can be developed the oil reservoir of 10-15% more.
In order to achieve the above object, the invention provides a kind of beet alkali surface activator composition system, this beet alkali surface activator composition system comprises:
The mixture of one or more of beet alkali surface activator, this beet alkali surface activator comprises: alkyl dimethyl betaine, alkylamidoalkyl propyl-dimethyl trimethyl-glycine, alkyl sulfo betaines, alkyl hydroxy sultaine;
Anion surfactant;
Wherein, the working concentration ratio of described beet alkali surface activator and anion surfactant is 1:0.1-10, with 100% pure activity meter.
Above-mentioned beet alkali surface activator composition system, wherein, more than any one in the ester of described anion surfactant selection vitriol, sulfonate, sulfonation, the acid amides of sulfonation, carbonate, phosphate surfactant active.
Above-mentioned beet alkali surface activator composition system, wherein, described sulphate anion surface active agent comprises alkyl-sulphate, polyoxyethylene alkyl ether sulfate salt, alkyl phenol ether sulfuric acid, alkylol amide sulfuric acid, glycoside sulfuric acid; Described sulfonate anionic surfactant comprises alkylbenzene sulfonate, alkylsulfonate, alkenyl sulphonate; The esters surface active agent of described sulfonation comprises sulfosuccinic acid alkyl ester, acyl-hydroxyethyl sulfonate, sulfonated fatty ester; The amide anion tensio-active agent of described sulfonation comprises acyl methyl taurine salt, alkyl sulfo-succinic acid list acyl ester amine; Described carbonate surface promoting agent comprises the alkyl carboxylate, Alkyl ethoxy carboxylate acid salt, acyl sarcosinate; Described phosphate surfactant active comprises alkylphosphonic, alkyl ether phosphate.
Above-mentioned beet alkali surface activator composition system, wherein, when this system is used, the water in advance dilution, then inject the crude oil mineral reserve, with the chemical displacement of reservoir oil for oil recovery process.Wherein, the water of dilution use can be from re-injection water (namely during field produces crude oil from the underground water that comes taken out, after treatment, again with tensio-active agent, annotates back that underground, such water is common contains higher mineralizer, sometimes be called as " sewage "); The water of dilution use also can be used fresh water (i.e. " clear water "), and " clear water " can not add mineral substance here, also can selectively add mineral substance and reach the best mineralization degree of system.
Above-mentioned beet alkali surface activator composition system, wherein, in use, the total size of all tensio-active agent working concentrations is 0.005%-1% to this system, and this working concentration refers to the concentration of tensio-active agent after this system injected water dilution in 100% pure activity.
Above-mentioned beet alkali surface activator composition system, wherein, in use, the total size of all tensio-active agent working concentrations is 0.05%-0.4% to this system.
Above-mentioned beet alkali surface activator composition system, wherein, described beet alkali surface activator composition system also comprises polymkeric substance, this polymkeric substance select in guar gum, Mierocrystalline cellulose and polyacrylamide any one or more than one; The concentration range of described polymkeric substance when the dilution of system injected water is used is 100ppm – 2000ppm.
Above-mentioned beet alkali surface activator composition system, wherein, when this system is used in the injected water dilution, pH is at 6.0 – 9.0, and preferably, this pH is at 7.0 – 8.0.
The present invention also provides a kind of purposes of above-mentioned beet alkali surface activator composition system, this system can be for the chemical displacement of reservoir oil of oil-field development, the working concentration of tensio-active agent is lower than 1%, and do not need to add alkali, this alkali to refer to while using in water, to produce the alkali of hydroxide ion.
Below by explaining that principle of the present invention illustrates technical superiority of the present invention further.
Structure due to the uniqueness of beet alkali surface activator:
Make them in the situation that alkali-free has the effect of efficient attenuating interfacial tension.In tensio-active agent working concentration 0.005% left and right, oil water interfacial tension just can reach ultra low interfacial tension.Can be from oil composition or plant constituent due to the lipophilic group of beet alkali surface activator, make the range of choice of the carbon chain lengths of lipophilic group and structure large, can more easily find the lipophilic group with the oil coupling than the tensio-active agent of other type.Simultaneously their hydrophilic radical has negatively charged ion and cationic function (so they are called zwitter-ion) simultaneously, so not only strengthens the effect of tensio-active agent and water, also increases the effect with the synergy of polymkeric substance and other tensio-active agent simultaneously.The effect of this synergy is that the tensio-active agent of other traditional tertiary recovery lacks.
Yet, due to the various and complicated component of oil property, add that the composition of re-injection water is different because of each place.Single beet alkali surface activator or their mixture can't adapt to the diversity of crude oil and re-injection water.Add, to any structural improvement of trimethyl-glycine (as changed the character of 3 alkyl being connected with nitrogen-atoms, comprise the introducing of the length, structure or other functional group that change their carbochains etc.), can only come from the variation of starting raw material and the reactant of trimethyl-glycine.Improvement not only is confined to the limitation of raw material type like this, the restriction of raw materials market, and the restriction of chemical reaction mechanism and working condition, and waste time and energy, because each is changed, mean a new multistage chemosynthesis process.
Therefore further improve the effect of beet alkali surface activator by surfactant compound, just have very large realistic meaning and economic benefit, such compound prescription can not only bring more handiness, and can save time and the investment of experiment.Anion surfactant and beet alkali surface activator have synergistic effect, and this synergy is more notable under the pH neutrallty condition.Because beet alkali surface activator has negatively charged ion and cationic character simultaneously, they and anion surfactant have adelphotaxy.But be different from the sucking action between anion surfactant and cats product, the sucking action between beet alkali surface activator and anion surfactant, under the pH neutrallty condition, can not produce the side effect such as precipitation.Along with different beet alkali surface activators and the concentration ratio between anion surfactant, the effect between them also changes thereupon.The reactive force that also has whole surfactant system and water thereupon simultaneously changed.By the concentration ratio between this change beet alkali surface activator and anion surfactant, can reach the scanning of the reactive force of a surfactant system and water, in the hope of the surfactant system of finding a best and the reactive force of water, carry out the reactive force of balance sheet surfactant system and oil phase with the reactive force of this surfactant system and water.When the reactive force of the reactive force of surfactant system and water and surfactant system and oil phase reaches balance, ultralow oil water interfacial tension also just can be realized.
Lower concentration beet alkali surface activator composition system provided by the invention, synergy by beet alkali surface activator and anion surfactant, can under the condition of non-polymer, use separately, also can match with polymkeric substance, form two Yuans composite systems and use, to realize the ultra low interfacial tension under the alkali-free condition.By beet alkali surface activator composition system provided by the invention, in the situation that alkali-free, add the surfactant system of the tertiary oil recovery chemical displacement of reservoir oil that prior art used to use, can significantly improve oil displacement efficiency, can be by the oil well of a secondary oil recovery later stage oil-production efficiency degradation through tertiary oil recovery, the oil reservoir of many exploitation 10-15%, the economic benefit highly significant.And, beet alkali surface activator system of the present invention, for the chemical displacement of reservoir oil, working concentration very low (lower than 1%), cost declines to a great extent; Further, because this system does not need to add other conventional alkali, not only make the selection face of polymkeric substance wider, also very great for the meaning of protecting national resource.
Embodiment
Below in conjunction with embodiment, technical scheme of the present invention is described further.
Embodiment 1
Tensio-active agent preparation: get the oil base dimethyl betaine (from (the Western Surfactants Research and Development Center of U.S. west tensio-active agent research and development centre, USA, there is 30% activity, pH 6.0-7.0) 70 grams, heavy alkylbenzene sulfonic acid sodium is (from Liaoning Panjin sea billows chemical industry, effective content 30%, molecular-weight average 390) 6.25 grams, deionized water 23.75 grams; Below add respectively a beaker, then at room temperature stir with magnetic stirrer.With sodium hydroxide and vinegar acid for adjusting pH to 7-8.Formed surfactant system is homogeneous transparent liquid.
Crude oil: from the oil field, Northeast China, crude oil presents peracid, high aromatic hydrocarbon composition.
Testing tool: TX-500C interfacial tension
Test condition: 55 degrees centigrade of (1) temperature; (2) re-injection water is containing salinity 4000 mg/L; (3) non-polymer adds; (4) surfactant concentration: 1.0 g/L, the surfactant system (70% surfactant soln, the activity 30% of tensio-active agent) of the soon above-mentioned configuration of 1 gram, dilution is mixed with 1 liter of (1000 gram) aqueous solution and is tested; , in this test macro, this tensio-active agent is with 100% activity meter, and mass percent concentration is: 1 * 70% * 30%/1000=0.021%; In other following embodiment, the meaning of surfactant concentration is identical with the present embodiment.
Test result: oil water interfacial tension 2.3 * 10
-3Dyn/cm.
Experiment shows, need not add polymkeric substance, and the mixture be comprised of oil base dimethyl betaine tensio-active agent and anion surfactant heavy alkylbenzene sulfonic acid sodium is used in water filling, when tensio-active agent effective concentration is 1.0 g/L, oil water interfacial tension reaches ~ and 10
-3Ultralow state, can obtain the higher yields of tertiary oil recovery.
Embodiment 2
Tensio-active agent preparation: get oil base acid amides dimethyl propyl trimethyl-glycine (from (the Western Surfactants Research and Development Center of U.S. west tensio-active agent research and development centre, USA, there is 35% activity, pH 6.0-7.0) 50 grams, heavy alkylbenzene sulfonic acid sodium (with the source of embodiment 1) 20 grams, deionized water 30 grams; Below add respectively a beaker, then at room temperature stir with magnetic stirrer.With sodium hydroxide and vinegar acid for adjusting pH to 7-8.Formed surfactant system is homogeneous transparent liquid.
Crude oil: with embodiment 1.
Testing tool: TX-500C interfacial tension.
Test condition: 55 degrees centigrade of (1) temperature; (2) re-injection water is containing salinity 4000 mg/L; (3) non-polymer adds; (4) surfactant concentration: 1.0 g/L.
Test result: oil water interfacial tension 7.8 * 10
-3Dyn/cm.
Experiment shows, need not add polymkeric substance, the mixture be comprised of oil base acid amides dimethyl propyl beet alkali surface activator and anion surfactant heavy alkylbenzene sulfonic acid sodium, used in water filling, when tensio-active agent effective concentration is 1.0 g/L, oil water interfacial tension reaches ~ and 10
-3Ultralow state, can obtain the higher yields of tertiary oil recovery.
Embodiment 3
Tensio-active agent preparation: get the tetradecyl dimethyl betaine (from U.S. west tensio-active agent research and development centre, Western Surfactants Research and Development Center, USA, there is 30% activity, pH 6.0-7.0) 30 grams, oil base acid amides dimethyl propyl trimethyl-glycine (with the source of embodiment 2) 10 grams, Witco 1298 Soft Acid is (from the extra large billows chemical industry of Liaoning Panjin, 100%), propylene glycol, (analytical pure, from Fisher Scientific) 100 grams, propylene glycol is as water-soluble additive, help tensio-active agent to form homogeneous phase flowable solution, deionized water 106 grams.Below add respectively a beaker, then at room temperature stir with magnetic stirrer.With sodium hydroxide and vinegar acid for adjusting pH to 7-8.Formed surfactant system is homogeneous transparent liquid.
Crude oil: with the source of embodiment 1.
Testing tool: TX-500C interfacial tension.
Test condition: 55 degrees centigrade of (1) temperature; (2) re-injection water is containing salinity 4000 mg/L; (3) polymkeric substance: 1000 ppm polyacrylamides (from the extra large billows chemical industry of Liaoning Panjin molecular weight 2,500 ten thousand); (4) surfactant concentration: 1.0 g/L, 4.0g/L.
Test result: when (1) surfactant concentration is 1.0 g/L, oil water interfacial tension is 6.3 * 10
-3Dyn/cm; (2) when surfactant concentration is 4.0 g/L, oil water interfacial tension: 8.8 * 10
-3Dyn/cm.
Experiment shows, add polymkeric substance, the mixture formed by tetradecyl dimethyl betaine, oil base acid amides dimethyl propyl beet alkali surface activator and anion surfactant Witco 1298 Soft Acid, in water filling, use, when tensio-active agent effective concentration is 1.0 g/L, oil water interfacial tension reaches ~ and 10
-3Ultralow state, can obtain the higher yields of tertiary oil recovery.The application of tensio-active agent ultra low interfacial tension has individual concentration " window ".Sometimes concentration raises, and interfacial tension deflects away from " window ", causes that interfacial tension raises on the contrary, as lifted in the present embodiment, and the test result while adopting higher concentration 4L/g.
Although content of the present invention has been done detailed introduction by above preferred embodiment, will be appreciated that above-mentioned description should not be considered to limitation of the present invention.After those skilled in the art have read foregoing, for multiple modification of the present invention with to substitute will be all apparent.Therefore, protection scope of the present invention should be limited to the appended claims.
Claims (10)
1. a beet alkali surface activator composition system, is characterized in that, this beet alkali surface activator composition system comprises:
The mixture of one or more of beet alkali surface activator, this beet alkali surface activator comprises: alkyl dimethyl betaine, alkylamidoalkyl propyl-dimethyl trimethyl-glycine, alkyl sulfo betaines, alkyl hydroxy sultaine;
Anion surfactant;
Wherein, the working concentration ratio of described beet alkali surface activator and anion surfactant is 1:0.1-10, with 100% pure activity meter.
2. beet alkali surface activator composition system as claimed in claim 1, it is characterized in that, more than any one in the ester of described anion surfactant selection vitriol, sulfonate, sulfonation, the acid amides of sulfonation, carbonate, phosphate surfactant active.
3. beet alkali surface activator composition system as claimed in claim 1, is characterized in that, described sulphate anion surface active agent comprises alkyl-sulphate, polyoxyethylene alkyl ether sulfate salt, the alkyl phenol ether sulfuric acid, alkylol amide sulfuric acid, glycoside sulfuric acid; Described sulfonate anionic surfactant comprises alkylbenzene sulfonate, alkylsulfonate, alkenyl sulphonate; The esters surface active agent of described sulfonation comprises sulfosuccinic acid alkyl ester, acyl-hydroxyethyl sulfonate, sulfonated fatty ester; The amide anion tensio-active agent of described sulfonation comprises acyl methyl taurine salt, alkyl sulfo-succinic acid list acyl ester amine; Described carbonate surface promoting agent comprises the alkyl carboxylate, Alkyl ethoxy carboxylate acid salt, acyl sarcosinate; Described phosphate surfactant active comprises alkylphosphonic, alkyl ether phosphate.
4. as the described beet alkali surface activator composition of any one in claim 1-3 system, it is characterized in that, when this system is used, the water in advance dilution, then inject the crude oil mineral reserve, with the chemical displacement of reservoir oil for oil recovery process; In use, the total size of all tensio-active agent working concentrations is 0.005%-1% to this system, and this working concentration refers to the concentration of tensio-active agent after this system injected water dilution in 100% pure activity.
5. beet alkali surface activator composition system as claimed in claim 4, is characterized in that, in use, the total size of all tensio-active agent working concentrations is 0.05%-0.4% to this system.
6. beet alkali surface activator composition system as claimed in claim 4, it is characterized in that, described beet alkali surface activator composition system also comprises polymkeric substance, this polymkeric substance select in guar gum, Mierocrystalline cellulose and polyacrylamide any one or more than one.
7. beet alkali surface activator composition system as claimed in claim 6, is characterized in that, the concentration range of described polymkeric substance when the dilution of system injected water is used is 100ppm – 2000ppm.
8. beet alkali surface activator composition system as claimed in claim 4, is characterized in that, when this system is used in the injected water dilution, pH is at 6.0 – 9.0.
9. beet alkali surface activator composition system as claimed in claim 8, is characterized in that, when this system is used in the injected water dilution, pH is at 7.0 – 8.0.
10. the purposes of a beet alkali surface activator composition system according to claim 1, it is characterized in that, this system can be for the chemical displacement of reservoir oil of oil-field development, the working concentration of tensio-active agent is lower than 1%, and while using, do not need to add alkali, this alkali to refer to and can in water, produce the alkali of hydroxide ion.
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