CN1814692A - Carboxyl-betaine and sulfosalt surfactant formula system and use in the third oil-production - Google Patents
Carboxyl-betaine and sulfosalt surfactant formula system and use in the third oil-production Download PDFInfo
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Abstract
This invention relates to a carboxy beet alkali and sulfosalt surface active agent formula system and its application in the tertiary oil recovery, in which, the formula system can be added with some aids, alkali, salt, polymer and water to be mixed uniformly and the oil driven system prepared by said formula system or the surface active agent-polymer duality compound oil driven system and underground crude oil can get the low interfacial tension of 10<SUP>-2</SUP>mN/m to drive the residual oil in the oil layer and increase the collection rate by over 20%, the surface active agent-polymer-alkali tribasic compound oil driven system and the underground crude oil can get a super low interfacial tension of 10<SUP>-3</SUP>-10<SUP>-4</SUP>mN/m and increase the collection rate by over 25%.
Description
Technical field
The present invention relates to a kind of carboxybetaine and sulfosalt surfactant formula system, and the application in tertiary oil recovery.
Background technology
The application surface promoting agent recovers the oil to study and originates in earlier 1930s in oil exploitation technology, and the history in more than 70 year is arranged so far.Seven during the last ten years, all obtained very big development in the theory and practice, at present, formed following several injection systems basically.(1) active water drive, (2) micellar solution flooding, the displacement of reservoir oil of (3) low interfacial tension system, (4) ternary composite driving.Wherein ternary composite driving (alkali-polymkeric substance-tensio-active agent) is a kind of novel method that improves oil recovery factor that just grows up the 1980s, because this method still can obtain higher oil displacement efficiency under the situation of low surfactant consumption, therefore, it has become the new technology at economic and technical all very successful raising oil recovery factor.
After the oil field enters high water-cut stage, surplus oil with discontinuous oil droplet by trap in the hole of reservoir rocks, two main power that act on the oil droplet are viscaps.If use suitable surfactant system, reduce the interfacial tension between profit, just reduced the resistance that the oil droplet distortion was brought when irreducible oil was moved, thus oil recovery factor improved.
The research contents of relevant ternary composite oil-displacing system aspect, existing both at home and abroad a large amount of bibliographical information has all been done detailed introduction as the surface active agent composition that, US4216097 etc. uses in the oil-displacing agent prescription to rig-site utilization.Wherein tensio-active agent mainly uses the application of anticalcium magnesium ion in water drive separately with carboxybetaine and sultaine, and it is of the present invention mainly with carboxybetaine and sulfonate compounded surfactant formula system, and the application in tertiary oil recovery, thereby improve oil recovery factor.
Summary of the invention
The object of the present invention is to provide a kind of carboxybetaine and sulfosalt surfactant formula system of containing, under the alkali-free condition, form 10 with crude oil
-2The low interfacial tension of mN/m.Containing under the alkali condition, forming 10 with crude oil
-3～10
-4The ultra low interfacial tension of mN/m.
Another object of the present invention provides the application of above-mentioned surfactant formula system in tertiary oil recovery.
Through a large amount of experiments, a kind of carboxybetaine and sulfosalt surfactant formula system of containing, this formula system comprises following several composition:
(1) carboxybetaine and sulfonate compounded surfactant are 0.001%～0.5% (weight);
(2) polymkeric substance is 0～0.5% (weight);
(3) alkali is 0.1～2.0% (weight);
(4) surplus is that clear water or sewage are injected in the oil field;
The molecular formula of this carboxyl betaine surfactant is:
Wherein: R is C
14～C
22In any one alkyl;
N is any one in 1～3;
This sulfosalt surfactant is any one in alkylaryl sulphonate, sulfonated petro-leum, the heavy alkylbenzene sulfonate; The molecular formula of alkylaryl sulphonate is: R-SO
3M
Wherein: R is any one in alkyl, phenyl, alkyl phenyl, dialkyl phenyl organic, naphthyl, alkyl naphthyl, dialkyl group naphthyl, alkylnaphthalene methylene radical, the alkylbenzene methylene radical; M is any one in basic metal, Monoethanolamine MEA BASF, diethanolamine, the trolamine;
The composite ratio of carboxybetaine and sulfonate is 1: 9～9: 1.
In the surfactant formula system, be preferably that R is C in the molecular formula of this carboxyl betaine surfactant
16～C
20In any one alkyl, n be 1; This sulfosalt surfactant is any one in alkylaryl sulphonate, sulfonated petro-leum, the heavy alkylbenzene sulfonate; R is any one in alkyl, phenyl, alkyl phenyl, dialkyl phenyl organic, naphthyl, alkyl naphthyl, dialkyl group naphthyl, alkylnaphthalene methylene radical, the alkylbenzene methylene radical in the molecular formula of alkylaryl sulphonate; Wherein, the alkyl in the alkyl is C
14～C
28In any one, the alkyl in the dialkyl phenyl organic is C
6～C
24In any one, the alkyl in the alkyl phenyl is C
9～C
20In any one, alkyl is C in the dialkyl group naphthyl
6～C
24In any one, the alkyl in the alkylnaphthalene methylene radical is C
3～C
20In any one, the alkyl in the alkylbenzene methylene radical is C
9～C
20In any one; M is any one in the basic metal; The composite ratio of carboxybetaine and sulfonate is 1: 5～5: 1.
In the surfactant formula system, more preferably R is C in the molecular formula of this carboxyl betaine surfactant
16～C
20In any one alkyl, n be 1; This sulfosalt surfactant is any one in alkylaryl sulphonate, sulfonated petro-leum, the heavy alkylbenzene sulfonate; R is that the alkyl in alkyl phenyl, the alkyl phenyl is C in the molecular formula of alkylaryl sulphonate
9～C
20In any one, M is in sodium, potassium, the lithium any one; The composite ratio of carboxybetaine and sulfonate is 1: 3～3: 1.
In the surfactant formula system, more more preferably in the molecular formula of this carboxyl betaine surfactant R be C
16～C
20In any one alkyl, n be 1; This sulfosalt surfactant is any one in alkylaryl sulphonate, sulfonated petro-leum, the heavy alkylbenzene sulfonate; R is that the alkyl in alkyl phenyl, the alkyl phenyl is C in the molecular formula of alkylaryl sulphonate
9～C
18In any one, M is sodium; The composite ratio of carboxybetaine and sulfonate is 1: 2～3: 1.
In the surfactant formula system, more more preferably in the molecular formula of this carboxyl betaine surfactant R be C
16～C
18In any one alkyl, n be 1; This sulfosalt surfactant is any one in sulfonated petro-leum, the heavy alkylbenzene sulfonate; The composite ratio of carboxybetaine and sulfonate is 1: 1～3: 1.
Most preferably be that R is C in the molecular formula of this carboxyl betaine surfactant
18Alkyl, n are 1; This sulfosalt surfactant is a sulfonated petro-leum; The composite ratio of carboxybetaine and sulfonated petro-leum is 2: 1.
Displacing surfactant system that this surfactant formula system is mixed with or tensio-active agent---polymkeric substance binary combination flooding oil body system can reach 10 with underground crude oil
-2The low interfacial tension of mN/m, the surplus oil in the displacement oil reservoir improves oil recovery factor more than 20% effectively.Tensio-active agent---polymkeric substance---alkali ternary composite oil-displacing system and underground crude oil can reach 10
-3～10
-4The ultra low interfacial tension of mN/m, the surplus oil in the displacement oil reservoir improves oil recovery factor more than 25% effectively.
The application of formula system of the present invention in tertiary oil recovery can add polymkeric substance in formula system, polymkeric substance is a water-soluble polyacrylamide, molecular weight 300～50,000,000.It has the effect of control viscosity.A kind of used for tertiary oil recovery surfactant formula system that is used for of the present invention when the oil field is uniform formation or low permeability oil field, does not just need to add polymkeric substance in practical application, can use tensio-active agent separately, can also be with salt or alkali; For the saturating oil field of middle and high infiltration, can use tensio-active agent separately, can also be with salt or alkali, further the addition polymerization compound can both reach best oil displacement efficiency.
The application of formula system of the present invention in tertiary oil recovery can add alkali in formula system, alkali is any one in sodium hydroxide, potassium hydroxide, sodium bicarbonate, yellow soda ash, the water glass.
The application of formula system of the present invention in tertiary oil recovery, in surfactant formula system, can also add auxiliary agent, be used for improving the flowability and the solubleness of surfactant formula system, described auxiliary agent is any one or the multiple auxiliary agent that mixes in alcohols, ethers, the salt.Here that usefulness is C
1～C
12Monohydroxy-alcohol, ethylene glycol, glycerol, glycol ether, propylene glycol, sodium-chlor, any one in Repone K, the urea or the multiple auxiliary agent that mixes.
In sum, in actual applications, because the difference of oil field block, reservoir condition is inconsistent, the composition difference of crude oil, underground water, clay mineral, therefore---polymkeric substance binary combination flooding oil body system or tensio-active agent---polymkeric substance---alkali ternary composite oil-displacing system are to reach best oil displacement efficiency at different reservoir conditions, just can to select various combination, different ratios to make displacing surfactant system or tensio-active agent.
The present invention has the following advantages:
(1) has good acidproof, heatproof, alkaline-resisting and ionogen performance and be easy to biodegradable characteristic;
(2) can improve more than the oil recovery factor 25% (OOIP), and cost is very low, can brings huge economic benefit for the oil field.
The present invention is elaborated with the following examples, and these embodiment only are used for description effect, rather than limit the scope of the invention.
If no special instructions, reagent that uses among the embodiment and testing tool are as follows:
One, uses reagent
N, N-dimethyl 18 carboxybetaines are newly synthetic
Water-soluble polyacrylamide Daqing oil field auxiliary reagent factory produces (salt-resistant polymer)
Experiment water Daqing oil field recover the oil four factory's clear water, four factory's sewage
Crude oil Daqing oil field dewatered oil
Two, testing tool
The production of interfacial tensimeter Texas ,Usa university is dripped in the rotation of 500 types
45 ℃ of experimental temperatures
Embodiment
Embodiment one: N, N-dimethyl 18 carboxybetaines synthetic
Sodium chloroacetate, 200ml water and the 300ml Virahol of 269g 18 tertiary amines, 130g are joined in the 1000ml there-necked flask that has condenser and agitator, be warmed up to 70 ℃ of reactions 10 hours behind the thorough mixing, static heat extraction water and the Virahol of adding, with n-propyl alcohol extraction product and unreacted raw material, remove n-propyl alcohol again and use the unreacted raw material of petroleum ether extraction, remove sherwood oil then and obtain pure product.
Synthesizing of 21 kinds of surfactant formula systems of embodiment
Get N, N-dimethyl 18 carboxybetaine 0.06g, N, N-dimethyl 18 sultaine 0.04g polyacrylamide 0.25g, sodium hydroxide 0.4g water 99.25g stirred 30 minutes, obtained a kind of surfactant formula system.
Embodiment three
N, the displacing surfactant system that N-dimethyl 18 carboxybetaines are mixed with when being 0.001～0.1% (weight) and the interfacial tension of underground crude oil are 10
-2The low interfacial tension of mN/m, can make the displacing surfactant system that is mixed with and the interfacial tension of underground crude oil in sodium hydroxide 0.1～0.5% (weight) is 10
-2～10
-3The ultra low interfacial tension of mN/m, experiment water is the Daqing oil field four factory's sewage that recover the oil, crude oil is the Daqing oil field dewatered oil.What emphasize here is that when oil property changed, interfacial tension can change.
Embodiment four
N, the composite ratio of N-dimethyl 18 carboxybetaines and hexadecyl benzene sulfonic acid sodium salt is 2: 1, the displacing surfactant system that concentration is mixed with when being 0.001～0.1% (weight) and the interfacial tension of underground crude oil are 10
-2The low interfacial tension of mN/m, can make the displacing surfactant system that is mixed with and the interfacial tension of underground crude oil in sodium hydroxide 0.1～0.5% (weight) is 10
-3～10
-4The ultra low interfacial tension of mN/m, experiment water is the Daqing oil field four factory's sewage that recover the oil, crude oil is the Daqing oil field dewatered oil.What emphasize here is that when oil property changed, interfacial tension can change.
Embodiment five
N, the composite ratio of N-dimethyl 18 carboxybetaines and petroleum sodium sulfonate is 2: 1, the displacing surfactant system that concentration is mixed with when being 0.001～0.1% (weight) and the interfacial tension of underground crude oil are 10
-2The low interfacial tension of mN/m, can make the displacing surfactant system that is mixed with and the interfacial tension of underground crude oil in sodium hydroxide 0.1～0.5% (weight) is 10
-3～10
-4The ultra low interfacial tension of mN/m, experiment water is the Daqing oil field four factory's sewage that recover the oil, crude oil is the Daqing oil field dewatered oil.What emphasize here is that when oil property changed, interfacial tension can change.
Embodiment six
N, the composite ratio of N-dimethyl 18 carboxybetaines and heavy alkylbenzene sulfonic acid sodium is 1.5: 1, the displacing surfactant system that concentration is mixed with when being 0.001～0.1% (weight) and the interfacial tension of underground crude oil are 10
-2The low interfacial tension of mN/m, can make the displacing surfactant system that is mixed with and the interfacial tension of underground crude oil in sodium hydroxide 0.1～0.5% (weight) is 10
-3～10
-4The ultra low interfacial tension of mN/m, experiment water is the Daqing oil field four factory's sewage that recover the oil, crude oil is the Daqing oil field dewatered oil.What emphasize here is that when oil property changed, interfacial tension can change.
Embodiment seven
In perm-plug method is 1000md, inject the binary slug in the core earlier, it consists of above-mentioned tensio-active agent (N, the composite ratio of N-dimethyl 18 carboxybetaines and hexadecyl benzene sulfonic acid sodium salt is 2: 1, in sodium hydroxide 0.5% (weight)) tensio-active agent---polymkeric substance---the alkali ternary composite oil-displacing system 0.38PV (volume of voids) that is mixed with, follow-up slug 0.1PV (volume of voids) polymkeric substance that reinjects can improve more than the recovery ratio 25% (OOIP) of crude oil.
Embodiment eight
In perm-plug method is 1000md, inject the binary slug in the core earlier, it consists of above-mentioned tensio-active agent (N, the composite ratio of N-dimethyl 18 carboxybetaines and heavy alkylbenzene sulfonic acid sodium is 1.5: 1, in sodium hydroxide 0.5% (weight)) tensio-active agent---polymkeric substance---the alkali ternary composite oil-displacing system 0.38PV (volume of voids) that is mixed with, follow-up slug 0.1PV (volume of voids) polymkeric substance that reinjects can improve more than the recovery ratio 25% (OOIP) of crude oil.
Embodiment nine
In perm-plug method is 1000md, inject the binary slug in the core earlier, it consists of above-mentioned tensio-active agent (N, the composite ratio of N-dimethyl 18 carboxybetaines and petroleum sodium sulfonate is 2: 1, in yellow soda ash 0.5% (weight)) tensio-active agent---polymkeric substance---the alkali ternary composite oil-displacing system 0.38PV (volume of voids) that is mixed with, follow-up slug 0.1PV (volume of voids) polymkeric substance that reinjects can improve more than the recovery ratio 25% (OOIP) of crude oil.
Embodiment ten
In perm-plug method is 200md, inject above-mentioned surfactant formula system (N in the core earlier, the composite ratio of N-dimethyl 18 carboxybetaines and petroleum sodium sulfonate is 2: 1, in yellow soda ash 0.5% (weight)) tensio-active agent---polymkeric substance---the alkali ternary composite oil-displacing system 0.38PV (volume of voids) that is mixed with, can improve more than the recovery ratio 15% (OOIP) of crude oil.
Claims (10)
1, a kind of carboxybetaine and sulfosalt surfactant formula system, this formula system comprise following several composition:
(1) carboxybetaine and sulfonate compounded surfactant are 0.001%～0.5% (weight);
(2) polymkeric substance is 0～0.5% (weight);
(3) alkali is 0.1～2.0% (weight);
(4) surplus is that clear water or sewage are injected in the oil field;
The molecular formula of this carboxyl betaine surfactant is:
Wherein: R is C
14～C
22In any one alkyl;
N is any one in 1～3;
This sulfosalt surfactant is any one in alkylaryl sulphonate, sulfonated petro-leum, the heavy alkylbenzene sulfonate; Wherein the molecular formula of alkylaryl sulphonate is: R-SO
3M
Wherein: R is any one in alkyl, phenyl, alkyl phenyl, dialkyl phenyl organic, naphthyl, alkyl naphthyl, dialkyl group naphthyl, alkylnaphthalene methylene radical, the alkylbenzene methylene radical; M is any one in basic metal, Monoethanolamine MEA BASF, diethanolamine, the trolamine;
The composite ratio of carboxybetaine and sulfonate is 1: 9～9: 1.
2, surfactant formula system according to claim 1, R is C in the molecular formula of this carboxyl betaine surfactant
16～C
20In any one alkyl, n be 1; This sulfosalt surfactant is any one in alkylaryl sulphonate, sulfonated petro-leum, the heavy alkylbenzene sulfonate; R is any one in alkyl, phenyl, alkyl phenyl, dialkyl phenyl organic, naphthyl, alkyl naphthyl, dialkyl group naphthyl, alkylnaphthalene methylene radical, the alkylbenzene methylene radical in the molecular formula of alkylaryl sulphonate; Wherein, the alkyl in the alkyl is C
14～C
28In any one, the alkyl in the dialkyl phenyl organic is C
6～C
24In any one, the alkyl in the alkyl phenyl is C
9～C
20In any one, alkyl is C in the dialkyl group naphthyl
6～C
24In any one, the alkyl in the alkylnaphthalene methylene radical is C
3～C
20In any one, the alkyl in the alkylbenzene methylene radical is C
9～C
20In any one; M is any one in the basic metal; The composite ratio of carboxybetaine and sulfonate is 1: 5～5: 1.
3, surfactant formula system according to claim 1 and 2, R is C in the molecular formula of this carboxyl betaine surfactant
16～C
20In any one alkyl, n be 1; This sulfosalt surfactant is any one in alkylaryl sulphonate, sulfonated petro-leum, the heavy alkylbenzene sulfonate; R is that the alkyl in alkyl phenyl, the alkyl phenyl is C in the molecular formula of alkylaryl sulphonate
9～C
20In any one, M is in sodium, potassium, the lithium any one; The composite ratio of carboxybetaine and sulfonate is 1: 3～3: 1.
4, according to the described surfactant formula system of one of claim 1～3, R is C in the molecular formula of this carboxyl betaine surfactant
16～C
20In any one alkyl, n be 1; This sulfosalt surfactant is any one in alkylaryl sulphonate, sulfonated petro-leum, the heavy alkylbenzene sulfonate; R is that the alkyl in alkyl phenyl, the alkyl phenyl is C in the molecular formula of alkylaryl sulphonate
9～C
18In any one, M is sodium; The composite ratio of carboxybetaine and sulfonate is 1: 2～3: 1.
5, according to the described surfactant formula system of one of claim 1～4, R is C in the molecular formula of this carboxyl betaine surfactant
16～C
18In any one alkyl, n be 1; This sulfosalt surfactant is any one in sulfonated petro-leum, the heavy alkylbenzene sulfonate; The composite ratio of carboxybetaine and sulfonate is 1: 1～3: 1.
6, according to the described surfactant formula system of one of claim 1～5, R is C in the molecular formula of this carboxyl betaine surfactant
18Alkyl, n are 1; This sulfosalt surfactant is a sulfonated petro-leum; The composite ratio of carboxybetaine and sulfonated petro-leum is 2: 1.
7, surfactant formula system according to claim 1 is characterized in that, can add polymkeric substance, and polymkeric substance is a water-soluble polyacrylamide, molecular weight 300～5,000 ten thousand.
According to the described surfactant formula system of one of claim 1～7, it is characterized in that 8, alkali is any one in sodium hydroxide, potassium hydroxide, sodium bicarbonate, yellow soda ash, the water glass.
9, according to the described surfactant formula system of one of claim 1～8, it is characterized in that, can also add auxiliary agent in surfactant formula system, described auxiliary agent is any one or the multiple auxiliary agent that mixes in alcohols, ethers, the salt.
10, according to the application of the described surfactant formula system of one of claim 1～9 in tertiary oil recovery, it is characterized in that,, can use tensio-active agent separately, can also can reach 10 with salt or alkali and underground crude oil for low permeability oil field
-2～10
-4The ultra low interfacial tension of mN/m improves oil recovery factor; For the saturating oil field of middle and high infiltration, can use tensio-active agent separately, can also be with salt or alkali, further addition polymerization compound and underground crude oil can reach 10
-2～10
-4The ultra low interfacial tension of mN/m improves oil recovery factor.
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