CN101280179B - Surfactant composition and use thereof - Google Patents
Surfactant composition and use thereof Download PDFInfo
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- CN101280179B CN101280179B CN2007100390568A CN200710039056A CN101280179B CN 101280179 B CN101280179 B CN 101280179B CN 2007100390568 A CN2007100390568 A CN 2007100390568A CN 200710039056 A CN200710039056 A CN 200710039056A CN 101280179 B CN101280179 B CN 101280179B
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Abstract
The invention relates to surface active agent combination and the application of the combination which solve the disadvantages of bad displacement efficiency under the condition of high temperature and high salt, bringing harm to the strata due to the containing of alkali, equipment and channel corrosion and high production cost found in the oil displacement agent which contains surface active agent in the prior art. The surface active agent combination and the application of the combination solves the problem through the technical proposal of the surface active agent combination which contains fatty alcohol-polyoxyethylene ether sulfonates, polymers and water; the surface active agent combination is applicable to the tertiary oil recovery production of the oil field.
Description
Technical field
The present invention relates to a kind of surfactant composition and uses thereof.
Background technology
From containing and the exploitation situation of China's oil resource, large-scale oil fields such as China's grand celebration, triumph, Central Plains, North China, huge port all have been in the exploitation middle and later periods, extraction oil water ratio is up to 90%, enter the tertiary phase that adopts intensified oil reduction (EOR) technology, improved the grand strategy measure that recovery ratio has become China Petroleum.And wherein chemical flooding is one of main method of tertiary oil recovery.
In the tertiary oil recovery chemical flooding technology, no matter be used surfactant flooding (micella drives, microemulsion drive), still be considered to the most promising combination flooding (alkali+tensio-active agent+polymkeric substance) at present, all be unable to do without and select suitable tensio-active agent, reduce oil water interfacial tension to reach the purpose that improves oil recovery factor.
And the dominant mechanism of using tensio-active agent can improve oil recovery factor is: after the oil field enters high water-cut stage, surplus oil with discontinuous oil film by trap in the hole of reservoir rocks, two main power that act on the oil droplet are viscaps, if select suitable surfactant system for use, reduce the interfacial tension between profit, make the interfacial tension between the oil bearing reservoir profit reduce to lower or ultralow value (10 from 20～30mN/m
-3～10
-4MN/m), just can reduce the resistance that the oil droplet distortion was brought when surplus oil was moved, thereby significantly improve oil displacement efficiency.
Surfactant flooding improves oil recovery factor and depends mainly on sweep efficiency and the oil displacement efficiency of tensio-active agent in oil reservoir.Promptly
E?r＝Eυ·E?d
In the formula: E r represents recovery ratio, %; E υ represents sweep efficiency, %; E d represents oil displacement efficiency, %.Therefore, improving E r must start with from improving E v and E d.Promoting agent (comprising tensio-active agent and alkali) has effects such as the oil water interfacial tension of reduction, can improve E d (oil displacement efficiency).This effect can be described by combined effect parameter hollow billet number (N):
E?d∝N
N=motivating force/viscous force ∝ μ υ/Y
Ow
In the formula: μ represents to inject phase viscosity; υ represents to inject the phase flow stream velocity; Y
OwInterfacial tension between the expression profit.Practice proves: reduce residual oil saturation effectively, the hollow billet number must be improved 3～4 orders of magnitude.Because oil reservoir injection rate and pressure are limited, it is not enough therefore depending merely on raising μ and υ, but can be with oil water interfacial tension Y
OwReduce by 3 or the higher order of magnitude, thereby improve the hollow billet number greatly and E d (oil displacement efficiency) is significantly improved, this also is the main oil-displacement mechanism of promoting agent.And to improve sweep efficiency, and main way is the mobility that reduces displacing fluid, this point can realize by adding polymkeric substance increase displacing fluid viscosity.Adopt in the operation three, utilization A S P ternary composite driving (tensio-active agent/alkali/polymkeric substance) flooding system, can make the ultra low interfacial tension between profit that the displacement of reservoir oil (E d) rate of imitating is increased by adding tensio-active agent, (E v) injects alkali to reduce the absorption of tensio-active agent to increase injection fluid viscosity raising sweep efficiency by injection of polymer.Make full use of the useful synergistic combination effect of A S P, improve oil recovery factor (E r).
At present, in tertiary oil recovery, the tensio-active agent that generally uses contains the tensio-active agent of phenyl ring as sulfonated petro-leum, alkylbenzene sulfonate or other.Document CN1458219A discloses the pure binary ultra low interfacial tension of the surfactant polymer combination flooding prescription that a kind of tertiary oil recovery is used, use therein tensio-active agent is sulfonated petro-leum or is the complexed surfactant that host adds thinner and other surfactant compound with the sulfonated petro-leum, the weight percent of its component is a sulfonated petro-leum 50～100%, alkylsulfonate 0～50%, carboxylate salt 0～50%, alkylaryl sulphonate 0～35%, low-carbon alcohol 0～20%.These tensio-active agents have the source extensively, and no matter quantity advantage big, that price is low for common oil reservoir, is combination flooding or single surfactant flooding, all has the mass-producing product, are also obtaining ideal effect aspect the raising recovery ratio.But deep day by day along with the oilfield exploitation degree, the oil recovery stratum is more and more darker, and the use temperature of tensio-active agent is more and more higher, the water-mineralizing degree is also more and more higher.The surfactant system of the above successful Application in common oil reservoir (one, two class oil reservoirs), under the high salt of high temperature (formation temperature is greater than 80 ℃) (more than salinity 20000 mg/litre) condition (three class oil reservoirs), because chemical structure malleable, compound system poor stability produce serious chromatographic separation in oil displacement process, cause the oil displacement efficiency variation.In order to reduce oil/water termination tension force to a greater extent, often add the alkali of high density, as sodium hydroxide, yellow soda ash etc.Alkali can generate new tensio-active agent on the spot with the reaction of acidic substance in the crude oil, and adds tensio-active agent and plays synergistic effect.Document CN1439689A discloses a kind of ternary composite oil-displacing system and application thereof of alkali, mixed surfactant and polymer, and the alkali of wherein selecting for use is Na
2CO
3But in use, alkali not only brings huge injury to stratum and oil well etc., and equipment and corrosive pipeline are serious, spends substantial contribution in maintenance, maintenance; And, have to improve greatly the working concentration of polymkeric substance for reaching required viscosity because alkali can seriously reduce the viscosity and the visco-elasticity of polymkeric substance, the oil recovery comprehensive cost is improved.
Summary of the invention
One of technical problem to be solved by this invention is that the composition that contains tensio-active agent in the prior art exists under the high temperature and high salt condition oil displacement efficiency poor, simultaneously owing to contain alkali, injury is brought on stratum and oil well, etching apparatus and pipeline, the problem that production cost is high provides a kind of new surfactant composition.This surfactant composition still can form 10 with crude oil under alkali-free, high temperature and high salt condition
-3～10
-4Milli ox/rice ultra low interfacial tension.Two of technical problem to be solved by this invention provides a kind of purposes of this surfactant composition.This surfactant composition is applied in the tertiary oil recovery, has the advantages that to improve the high temperature and high salt oil deposit recovery ratio.
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 surfactant composition comprises following component by weight percentage:
1) 0.01～5.0% aliphatic acid polyethenoxy ether sulphonate;
2) 0.01～3.0% polymkeric substance;
3) water of surplus;
Wherein said polymkeric substance is at least a in polyacrylamide, modified polyacrylamide or the xanthan gum; The aliphatic acid polyethenoxy ether sulphonate general molecular formula is:
C
nH
2n+1CO(CH
2CH
2O)
mCH
2CH
2SO
3M
Wherein M is a basic metal, and n is any one integer in 10～24, and m is any one integer in 1～10.
In the technique scheme, the basic metal preferred version is sodium or potassium; The n preferred version is any one integer in 12～18; The m preferred version is any one integer in 3～7.The water preferred version is that clear water or sewage are injected in the oil field.By weight percentage, the consumption preferable range of aliphatic acid polyethenoxy ether sulphonate is 0.1～1.0%, and more preferably scope is 0.1～0.3%.By weight percentage, the consumption preferable range of polymkeric substance is 0.05～0.5%, and more preferably scope is 0.1～0.2%.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: the application of a kind of surfactant composition in tertiary oil recovery.
The preparation method of aliphatic acid polyethenoxy ether sulphonate among the present invention may further comprise the steps:
A) lipid acid and oxyethane are 85～160 ℃ in temperature of reaction, and pressure is under 0～0.40MPa gauge pressure condition, under catalyst action, react aliphatic acid polyethenoxy alkene ether; Wherein said fatty acid carbons atomicity is any one integer in 10～24, and the mol ratio of fatty acid carbons atomicity and oxyethane is 3～4: 1; Described catalyzer is the basic cpd of calcium, and consumption is 0.3～3% of a fatty acid wt;
B) step (a) synthetic aliphatic acid polyethenoxy ether and thionyl chloride are to react under 60～80 ℃ of conditions to get the chlorinated fatty acid Soxylat A 25-7 in 2～10 hours in temperature of reaction under catalyst action; The mol ratio of thionyl chloride and aliphatic acid polyethenoxy ether is 1.5～3: 1; Described catalyzer is a pyridine, with the mol ratio of aliphatic acid polyethenoxy ether be 1.5～4: 1;
C) step (b) synthetic chlorinated fatty acid Soxylat A 25-7 and sulphonating agent are to react under 120～200 ℃ of conditions to get aliphatic acid polyethenoxy ether sulphonate in 1～10 hour in temperature of reaction; Described sulphonating agent is selected from sulphite, hydrosulphite or its mixture, and the mol ratio of sulphonating agent and chlorinated fatty acid Soxylat A 25-7 is 1～5: 1.
Wherein a) in the step temperature of reaction preferable range be 140～160 ℃, the pressure preferable range is 0.20～0.40MPa gauge pressure, the catalyst levels preferable range is 0.8～2% of a fatty acid wt; B) the temperature of reaction preferable range is 60～70 ℃ in the step, and the reaction times preferable range is 2～5 hours.C) the temperature of reaction preferable range is 160～170 ℃ in the step, and the reaction times preferable range is 5～8 hours.Fatty acid carbons atomicity preferable range is any one integer in 12～18.
Aliphatic acid polyethenoxy ether sulphonate of the present invention can pass through the infrared analysis spectral characterization, and sweep limit is 4000～400cm
-1In wave number is 1739.5cm
-1The place is 1351cm for the characteristic peak of the POE affixture of lipid acid in wave number
-1The place is be lower than wave number 1200cm by the charateristic avsorption band of polyethylene oxide
-11177cm
-1The place is the charateristic avsorption band of sulfonate groups.
Not only introduced the oxygen ethylene unit but also introduced the azochlorosulfonate acid anion structure in the aliphatic acid polyethenoxy ether sulphonate molecular structure among the present invention, so both strengthened the heat resistance of tensio-active agent, the low again micelle-forming concentration value of tensio-active agent, reduced usage quantity, can make this tensio-active agent can be when lower working concentration and crude oil form ultra low interfacial tension, and it is easier to degraded, and this tensio-active agent is the alkyl polyoxyethylene ether compound, do not possess aromatic hydrocarbons, therefore less to the harm of human body and environment.
The tensio-active agent of fatty acids polyethenoxy ether sulphonate of the present invention is used for tertiary oil recovery, has the following advantages:
(1) can alkali-free in the composition.The surfactant composition of fatty acids polyethenoxy ether sulphonate still can form 10 with underground crude oil under the alkali-free condition
-3～10
-4The ultra low interfacial tension of milli ox/rice has not only overcome when using at the scene high concentration alkali to the huge injury of stratum and oil well, and has met environmental protection requirement, and equipment is not had injury, can reach the oil displacement efficiency of the best;
(2) heatproof, salt tolerant.The surfactant composition of fatty acids polyethenoxy ether sulphonate in formation temperature greater than 90 ℃, salinity greater than 30000 mg/litre, Ca
2+, Mg
2+Concentration is still can form 10 with underground crude oil under the condition of 0～1000 mg/litre
-3～10
-4The ultra low interfacial tension of milli ox/rice improves oil recovery factor 17.4%, has obtained better technical effect.
The present invention is further elaborated below by embodiment.
Figure of description
Fig. 1 is the infrared analysis spectrum of aliphatic acid polyethenoxy ether sulphonate.
Wherein, wave number is 1739.5cm
-1The place is the characteristic peak of the POE affixture of lipid acid, and wave number is 1351cm
-1The place is the charateristic avsorption band of polyethylene oxide, is lower than wave number 1200cm
-11177cm
-1The place is the charateristic avsorption band of sulfonate groups.
Embodiment
[embodiment 1]
Synthesizing of stearic acid polyoxyethylene (6) ether sulfonic acid sodium
(1) in the reactor that condensing works, whipping appts and gas distributor are housed, adds 142 stearic acids and 1.5 that restrain (about 0.5 mole) and restrain calcium oxide, when logical nitrogen limit, limit is heated to 135 ℃, add the water of stearic acid 14 weight %, stirring reaction 1 hour.First then normal pressure steams water, and the back decompression vacuumizes steaming in 20 minutes in 140 ℃ and removes moisture under 20 mmhg vacuum, and this solution is cooled to 80 ℃, slowly drips the vitriol oil of catalyst neutralisation theoretical acid amount 20 weight %.System temperature is heated to 85～90 ℃, open vacuum system, dehydration is 1 hour under high vacuum, then with nitrogen purging 3～4 times with the air in the system of removing, then the system temperature of reaction is transferred to 150 ℃ and slowly feed 135 gram oxyethane, control pressure≤0.40MPa carries out alkoxylation; Reaction is used the nitrogen purging system after finishing, and removes unreacted oxyethane, and cooling post neutralization, decolouring, filtration, dehydration get stearic acid polyoxyethylene (6) ether.
(2) step (1) synthetic stearic acid polyoxyethylene (6) ether 270 gram (0.5 mole) and 72 gram pyridines are placed backflow is housed, stir, in the reactor of gas absorbing device, under agitation slowly add 108 gram chlorination reagent thionyl chloride, reaction is 10 hours under 70 ℃ of temperature, reaction finishes the excessive thionyl chloride of back pressure reducing and steaming, the residuum cooling, standing demix, lower floor is the solid pyridine hydrochloride, the upper strata organic layer is neutralized to neutrality with the sodium hydroxide solution of 15 weight %, tell inorganic salt, organic layer washes with water 5～6 times again, dry again chloro stearic acid polyoxyethylene (5) ether, the yield 83% of getting.
(3) step (2) synthetic chloro 18 carbonic acid polyoxyethylene (5) ethers 290 grams are placed 500 milliliters of autoclaves, add solvent 60 gram n-hexyl alcohols and 60 gram water, 110 gram S-WATs and 7 gram sodium bisulfites, reaction is 8 hours under 160 ℃ of temperature, reaction finishes the back underpressure distillation and boils off most of moisture, add an amount of Virahol standing over night in the mixture, the inorganic salt that filtering is precipitated out add the further filtering of an amount of methylene dichloride inorganic salt wherein again.Dry 18 carbonic acid polyoxyethylene (5) the ether sulfonic acid sodium that get of evaporating solvent, product purity is 85%.
To synthetic 18 carbonic acid polyoxyethylene (5) ether sulfonic acid sodium, use U.S. Nicolet-5700 infrared spectrometer, adopt liquid-film method to carry out Infrared spectroscopy (sweep limit 4000～400cm
-1), have characteristic peak shown in Figure 1.
With above synthetic 18 carbonic acid polyoxyethylene (5) ether sulfonic acid sodium nonionic-negatively charged ion amphotericses, actual reservoir temperature is 90.2 ℃ on the stratum, formation water salinity 33000 mg/litre, Ca
2+, Mg
2+Under the condition of concentration 1000 mg/litre, measured the tensio-active agent mineralized water solution of 0.1 weight %～0.3 weight % and the dynamic interface tension value between the Shengli Oil Field victory Tuo Er district crude oil, the interfacial tension value between tensio-active agent and the crude oil is 10
-3The mN/m order of magnitude, reach ultra low interfacial tension, at consumption be under the condition of 0.3 weight % with the composite formation of the polymkeric substance of 0.15 weight % PS combination flooding after, can on the water drive basis, improve oil recovery factor 17.4% through the evaluation of physical simulation displacement test at this oil-displacing agent on high temperature, the high salinity reservoir.
[embodiment 2]
(1) in the reactor that condensing works, whipping appts and gas distributor are housed, adds 228 gram (1.0 moles) TETRADECONIC ACID and 2.5 gram calcium oxide, when logical nitrogen limit, limit is heated to 135 ℃, add 25 water, stirring reaction 1 hour.First then normal pressure steams water, and the back decompression vacuumizes steaming in 20 minutes in 140 ℃ and removes moisture under 20 mmhg vacuum, and this solution is cooled to 80 ℃, slowly drips the vitriol oil of 0.8 gram.System temperature is heated to 85～90 ℃, open vacuum system, dehydration is 1 hour under high vacuum, then with nitrogen purging 3～4 times with the air in the system of removing, then the system temperature of reaction is transferred to 150 ℃ and slowly feed 180 gram oxyethane, control pressure≤0.40MPa carries out alkoxylation; Reaction is used the nitrogen purging system after finishing, and removes unreacted oxyethane, and cooling post neutralization, decolouring, filtration, dehydration get TETRADECONIC ACID polyoxyethylene (4) ether.
(2) step (1) synthetic TETRADECONIC ACID polyoxyethylene (4) ether 192 gram and 71 gram pyridines are placed backflow is housed, stir, in the reactor of gas absorbing device, under agitation slowly add chlorination reagent thionyl chloride 108 grams, reaction is 10 hours under 70 ℃ of temperature, reaction finishes the excessive thionyl chloride of back pressure reducing and steaming, the residuum cooling, standing demix, lower floor is the solid pyridine hydrochloride, the upper strata organic layer is neutralized to neutrality with the sodium hydroxide solution of 15 weight %, tell inorganic salt, organic layer washes with water 5～6 times again, dry again chloro TETRADECONIC ACID polyoxyethylene (3) ether, the yield 88% of getting.
(3) step (2) synthetic chloro TETRADECONIC ACID polyoxyethylene (3) ether 202 grams are placed autoclave, add solvent 40 gram n-hexyl alcohols and 40 gram water, 95 gram S-WATs, reaction is 6 hours under 160 ℃ of temperature, reaction finishes the back underpressure distillation and boils off most of moisture, add an amount of Virahol standing over night in the mixture, the inorganic salt that filtering is precipitated out add the further filtering of an amount of methylene dichloride inorganic salt wherein again.Dry TETRADECONIC ACID polyoxyethylene (3) the ether sulfonic acid sodium that gets of evaporating solvent, product purity is 86%.
To synthetic TETRADECONIC ACID polyoxyethylene (3) ether sulfonic acid sodium, use U.S. Nicolet-5700 infrared spectrometer, adopt liquid-film method to carry out Infrared spectroscopy (sweep limit 4000～400cm
-1), have characteristic peak shown in Figure 1.
With above synthetic TETRADECONIC ACID polyoxyethylene (3) ether sulfonic acid sodium nonionic-negatively charged ion amphoterics, actual reservoir temperature is 90.2 ℃ on the stratum, formation water salinity 33000 mg/litre, Ca
2+, Mg
2+Under the condition of concentration 1000 mg/litre, measured the tensio-active agent mineralized water solution of 0.1 weight %～0.3 weight % and the dynamic interface tension value between the Shengli Oil Field victory Tuo Er district crude oil, the interfacial tension value between tensio-active agent and the crude oil is 10
-3The mN/m order of magnitude, reach ultra low interfacial tension, at consumption be under the condition of 0.3 weight % with the composite formation of the polymkeric substance of 0.15 weight % PS combination flooding after, can on the water drive basis, improve oil recovery factor 16.4% through the evaluation of physical simulation displacement test at this oil-displacing agent on high temperature, the high salinity reservoir.
[embodiment 3]
(1) in the reactor that condensing works, whipping appts and gas distributor are housed, adds 100 gram (0.5 mole) laurostearic acids and 1.0 gram calcium oxide, when logical nitrogen limit, limit is heated to 135 ℃, add 10 gram water, stirring reaction 1 hour.First then normal pressure steams water, and the back decompression vacuumizes steaming in 20 minutes in 140 ℃ and removes moisture under 20 mmhg vacuum, and this solution is cooled to 80 ℃, slowly drips the vitriol oil of catalyst neutralisation theoretical acid amount 20 weight %.System temperature is heated to 85～90 ℃, open vacuum system, dehydration is 1 hour under high vacuum, then with nitrogen purging 3～4 times with the air in the system of removing, then the system temperature of reaction is transferred to 150 ℃ and slowly feed 68 gram oxyethane, control pressure≤0.40MPa carries out alkoxylation; Reaction is used the nitrogen purging system after finishing, and removes unreacted oxyethane, and cooling post neutralization, decolouring, filtration, dehydration get laurostearic acid polyoxyethylene (3) ether.
(2) step (1) synthetic laurostearic acid polyoxyethylene (3) ether 166 gram and 70 gram pyridines are placed backflow is housed, stir, in the reactor of gas absorbing device, under agitation slowly add chlorination reagent thionyl chloride 108 grams, reaction is 10 hours under 70 ℃ of temperature, reaction finishes the excessive thionyl chloride of back pressure reducing and steaming, the residuum cooling, standing demix, lower floor is the solid pyridine hydrochloride, the upper strata organic layer is neutralized to neutrality with the sodium hydroxide solution of 15 weight %, tell inorganic salt, organic layer washes with water 5～6 times again, dry again chloro laurostearic acid polyoxyethylene (2) ether, the yield 87% of getting.
(3) step (2) synthetic chloro tetradecanoic acid polyoxyethylene (2) ether 175 grams are placed autoclave, add solvent 35 gram n-hexyl alcohols and 40 gram water, 110 gram S-WATs and 7 gram sodium bisulfites, reaction is 6 hours under 155 ℃ of temperature, reaction finishes the back underpressure distillation and boils off most of moisture, add an amount of Virahol standing over night in the mixture, the inorganic salt that filtering is precipitated out add the further filtering of an amount of methylene dichloride inorganic salt wherein again.Dry laurostearic acid polyoxyethylene (2) the ether sulfonic acid sodium that gets of evaporating solvent, product purity is 89%.
To synthetic laurostearic acid polyoxyethylene (2) ether sulfonic acid sodium, use U.S. Nicolet-5700 infrared spectrometer, adopt liquid-film method to carry out Infrared spectroscopy (sweep limit 4000～400cm
-1), have characteristic peak shown in Figure 1.
With above synthetic laurostearic acid polyoxyethylene (2) ether sulfonic acid sodium new non-ionic-negatively charged ion amphoterics, actual reservoir temperature is 90.2 ℃ on the stratum, formation water salinity 33000 mg/litre, Ca
2+, Mg
2+Under the condition of concentration 1000 mg/litre, measured the tensio-active agent mineralized water solution of 0.1 weight %～1.0 weight % and the dynamic interface tension value between the Shengli Oil Field victory Tuo Er district crude oil, the interfacial tension value between tensio-active agent and the crude oil is 10
-3The mN/m order of magnitude, reach ultra low interfacial tension, at consumption be under the condition of 0.3 weight % with the composite formation of the polymkeric substance of 0.15 weight % PS combination flooding after, can on the water drive basis, improve oil recovery factor 16.4% through the evaluation of physical simulation displacement test at this oil-displacing agent on high temperature, the high salinity reservoir.
[embodiment 4]
(1) adding 0.5 mole of 128 gram palmitinic acid and 1.5 gram calcium oxide catalysts in the reactor that condensing works, whipping appts and gas distributor are housed when logical nitrogen limit, limit is heated to 135 ℃, adds 12 and restrain water, stirring reaction 1 hour.First then normal pressure steams water, and the back decompression vacuumizes steaming in 20 minutes in 140 ℃ and removes moisture under 20 millimeters vacuum, and this solution is cooled to 80 ℃, slowly drips the vitriol oil of catalyst neutralisation theoretical acid amount 20 weight %.System temperature is heated to 85～90 ℃, open vacuum system, dehydration is 1 hour under high vacuum, then with nitrogen purging 3～4 times with the air in the system of removing, then the system temperature of reaction is transferred to 150 ℃ and slowly feed 112 gram oxyethane, control pressure≤0.40MPa carries out alkoxylation; Reaction is used the nitrogen purging system after finishing, and removes unreacted oxyethane, and cooling post neutralization, decolouring, filtration, dehydration get palmitic acid polyoxyethylene (5) ether.
(2) step (1) synthetic palmitic acid polyoxyethylene (5) ether 238 gram and 70 gram pyridines are placed backflow is housed, stir, in the reactor of gas absorbing device, under agitation slowly add chlorination reagent thionyl chloride 108 grams, reaction is 10 hours under 70 ℃ of temperature, reaction finishes the excessive thionyl chloride of back pressure reducing and steaming, the residuum cooling, standing demix, lower floor is the solid pyridine hydrochloride, the upper strata organic layer is neutralized to neutrality with the sodium hydroxide solution of 15 weight %, tell inorganic salt, organic layer washes with water 5～6 times again, dry again chloro palmitic acid polyoxyethylene (4) ether, the yield 85% of getting.
(3) step (2) synthetic chloro palmitic acid polyoxyethylene (4) ether 242 grams are placed autoclave, the mixing sulphonating agent that adds solvent 50 gram n-hexyl alcohols, 50 gram water, 110 gram S-WATs and 7 gram sodium bisulfites, reaction is 6 hours under 160 ℃ of temperature, reaction finishes the back underpressure distillation and boils off most of moisture, add an amount of Virahol standing over night in the mixture, the inorganic salt that filtering is precipitated out add the further filtering of an amount of methylene dichloride inorganic salt wherein again.Dry palmitic acid polyoxyethylene (4) the ether sulfonic acid sodium that gets of evaporating solvent, product purity is 86%.
To synthetic palmitic acid polyoxyethylene (4) ether sulfonic acid sodium, use U.S. Nicolet-5700 infrared spectrometer, adopt liquid-film method to carry out Infrared spectroscopy (sweep limit 4000～400cm
-1), have characteristic peak shown in Figure 1.
With above synthetic palmitic acid polyoxyethylene (4) ether sulfonic acid sodium new non-ionic-negatively charged ion amphoterics, actual reservoir temperature is 90.2 ℃ on the stratum, formation water salinity 33000 mg/litre, Ca
2+, Mg
2+Under the condition of concentration 1000 mg/litre, measured the tensio-active agent mineralized water solution of 0.1 weight %～0.3 weight % and the dynamic interface tension value between the Shengli Oil Field victory Tuo Er district crude oil, the interfacial tension value between tensio-active agent and the crude oil is 10
-3The mN/m order of magnitude, reach ultra low interfacial tension, at consumption be under the condition of 0.3 weight % with the composite formation of the polymkeric substance of 0.15 weight % PS combination flooding after, can on the water drive basis, improve oil recovery factor 16.9% through the evaluation of physical simulation displacement test at this oil-displacing agent on high temperature, the high salinity reservoir.
Claims (8)
1. surfactant composition comprises following component by weight percentage:
1) 0.01～5.0% aliphatic acid polyethenoxy ether sulphonate;
2) 0.01～3.0% polymkeric substance;
3) water of surplus;
Wherein said polymkeric substance is at least a in polyacrylamide, modified polyacrylamide or the xanthan gum; Described aliphatic acid polyethenoxy ether sulphonate general molecular formula is:
C
nH
2n+1COO(CH
2CH
2O)
mCH
2CH
2SO
3M
Wherein M is a basic metal, and n is any one integer in 10～24, and m is any one integer in 1～10.
2. surfactant composition according to claim 1 is characterized in that described basic metal is sodium or potassium; N is any one integer in 12～18, and m is any one integer in 3～7.
3. surfactant composition according to claim 1 is characterized in that described water is that clear water or sewage are injected in the oil field.
4. surfactant composition according to claim 1 is characterized in that by weight percentage, and the consumption of aliphatic acid polyethenoxy ether sulphonate is 0.1～1.0%.
5. surfactant composition according to claim 4 is characterized in that by weight percentage, and the consumption of aliphatic acid polyethenoxy ether sulphonate is 0.1～0.3%.
6. surfactant composition according to claim 1 is characterized in that by weight percentage, and the consumption of polymkeric substance is 0.05～0.5%.
7. surfactant composition according to claim 6 is characterized in that by weight percentage, and the consumption of polymkeric substance is 0.1～0.2%.
8. the application of the described surfactant composition of claim 1 in tertiary oil recovery.
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| CN102029124B (en) * | 2009-09-25 | 2012-10-24 | 中国石油化工股份有限公司 | Polyacrylamide surfactant and preparation method thereof |
| CN102030851B (en) * | 2009-09-25 | 2012-07-25 | 中国石油化工股份有限公司 | Modified polyacrylamide and preparation method thereof |
| CN101864286B (en) * | 2010-06-04 | 2014-09-10 | 中国海洋石油总公司 | Mother liquor of oil displacement agent and preparation method thereof |
| CN102373053B (en) * | 2010-08-23 | 2015-08-12 | 中国石油化工股份有限公司 | Foaming agent combination and uses thereof |
| CN103215019B (en) * | 2012-12-17 | 2016-06-08 | 江南大学 | The preparation of the compound alkali-free surfactant oil displacement of a kind of alkylolamides-sulfate and application |
| CN104277809B (en) * | 2013-07-09 | 2017-06-20 | 中国石油化工股份有限公司 | Displacement composition and preparation method thereof |
| CN104277813B (en) * | 2013-07-09 | 2017-06-20 | 中国石油化工股份有限公司 | Oil extraction in oil field composition and preparation method thereof |
| CN105001380B (en) * | 2015-07-27 | 2017-08-22 | 长江大学 | Hydrophobic association sulfonate type surface-active polymer and preparation method thereof |
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