CN104745168A - High-temperature-resistant low-tension foam oil-displacing agent and application thereof - Google Patents
High-temperature-resistant low-tension foam oil-displacing agent and application thereof Download PDFInfo
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- CN104745168A CN104745168A CN201510018194.2A CN201510018194A CN104745168A CN 104745168 A CN104745168 A CN 104745168A CN 201510018194 A CN201510018194 A CN 201510018194A CN 104745168 A CN104745168 A CN 104745168A
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- elevated temperatures
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Abstract
A high-temperature-resistant low-tension foam oil-displacing agent comprises an anionic surfactant and a zwitterionic surfactant, wherein the mass concentration ratio of the anionic surfactant to the zwitterionic surfactant is (1-50):1. The invention further discloses an application of the high-temperature-resistant low-tension foam oil-displacing agent to tertiary oil recovery to increase the recovery efficiency of crude oil in a high-temperature oil reservoir with the formation temperature of 80-200 DEG C. The high-temperature-resistant low-tension foam oil-displacing agent provided by the invention has the characteristics of ultralow interfacial tension, high foaming capacity, good foam stabilizing effect, good high-temperature resistance and the like, cannot be decomposed at the high temperature of 300DEG C. Ultralow interfacial tension less than 10<-2>mN/m can be achieved between an aqueous solution of the high-temperature-resistant low-tension foam oil-displacing agent and crude oil, wherein the concentration of the aqueous solution of the high-temperature-resistant low-tension foam oil-displacing agent is 0.1-0.5wt%.
Description
Technical field
The present invention relates to the foam flooding finish improving oil deposil erude petroleum recovery ratio.More specifically, a kind of the low-tension foam flooding finish with resistance to elevated temperatures and the application thereof that improve oil deposil erude petroleum recovery ratio is related to.
Background technology
Along with the intensification of petroleum exploration and development degree, the whole world has entered High water cut even super-high water-cut stage more than the oil field of 30 maximum-norms, people more and more pay close attention to and pay attention to improving the oil recovery factor of these maturing fields, increase the workable reserve of crude oil in the urgent need to new tertiary oil recovery technology.Wherein, low-tension foam flooding technology attracts most attention under current condition and the most potential oil recovery new technology, it fully can excavate the displacement of reservoir oil potentiality of tensio-active agent, the selective control of foam can be utilized again to improve swept volume, thus oil recovery factor is greatly enhanced.Low-tension foam flooding technology is at expansion swept volume or is all better than the technology of reservoir sweep such as polymer flooding, binary combination flooding and ternary composite driving on displacement efficiency, oil reservoir etc. for the oil reservoir of the oil reservoir after long-period water drive, postpolymer flood, the oil reservoir of high temperature and high salt and serious heterogeneity all can increase substantially the recovery ratio of crude oil, has a good application prospect.The key problem of low-tension foam flooding technology is exactly that low-tension foaming agent will possess ultra low interfacial tension, foaming power is strong, stability is strong, good with local water compatibleness, high temperature resistant resistance to high salinity.
Foam flooding finish in the market does not generally possess ultra low interfacial tension, mainly contains anionic foaming agent and the large class of non-ionic type foaming agent two.For high-temperature oil reservoir, because non-ionic type foaming agent exists cloud point, resistance to elevated temperatures is poor, limits its application separately in tertiary oil recovery; For anionic alkylsurfuric acid ester sodium salt, due to the existence of sulfuric acid ester bond in molecule, have hydrolysis to a certain degree in the basic conditions, and a non-refractory, an Applicable temperature is lower than the oil reservoir of 100 DEG C.
Summary of the invention
An object of the present invention is not there is ultra low interfacial tension to solve above-mentioned foaming agent, poor stability can not meet the needs of high-temperature oil reservoir foam flooding, thus provide that one has ultra low interfacial tension, foaming power is strong, froth stability good and resistance to elevated temperatures is good, the low-tension foam flooding finish with resistance to elevated temperatures of oil deposil erude petroleum recovery ratio can be improved.
Another object of the present invention is to provide a kind of application with the low-tension foam flooding finish of resistance to elevated temperatures that can improve oil deposil erude petroleum recovery ratio.
For reaching above-mentioned first object, the present invention adopts following technical proposals:
A kind of low-tension foam flooding finish with resistance to elevated temperatures, mainly carry out mixing composite obtaining by anion surfactant and zwitterionics, in the low-tension foam flooding finish with resistance to elevated temperatures, the mass concentration ratio of described anion surfactant and zwitterionics is 1 ~ 50:1.
Preferably, described anion surfactant is selected from one or both in the tensio-active agent of following structure type:
A) saturated or unsaturated fatty acids base salt
R-YM
In formula, R is C
8~ C
24saturated or unsaturated fatty acids base; Y is carboxylate radical or sulfonate radical; M is the Na in alkalimetal ion
+or K
+, or be the Ca in alkaline-earth metal ions
2+or Mg
2+, or more the mixture of described ion;
B) alkylbenzene salt
In formula, R is C
8~ C
24saturated or unsaturated fatty acids base; Y is sulfonate radical; M is the Na in alkalimetal ion
+or K
+, or be the Ca in alkaline-earth metal ions
2+or Mg
2+, or more the mixture of described ion.
Tensio-active agent alkylsulphonic acid (or carboxylic acid) salt or alkylbenzene sulfonate have good foam performance; And the existence of carboxylate radical or sulfonate radical, make it have very strong resistance to elevated temperatures, effectively can improve foam performance and the high-temperature behavior of foam flooding finish of the present invention.
Described zwitterionics molecular formula is:
In formula, R is C
6~ C
30alkyl; Y is CH
2cOO
-or CH
2cHOHCH
2sO
3 -.
Beet alkali ampholytic ionic surface active agent has soluble in water, that foam stability energy is good advantage; Adding of it, add the described foam stability energy with the low-tension foam flooding finish of resistance to elevated temperatures and solubility property, be conducive to industrial application.
Preferably, the present invention has in the low-tension foam flooding finish of resistance to elevated temperatures and can add a small amount of additive further.
Preferably, described additive is selected from C
2~ C
24fatty alcohol and inorganic salt in one or more.
Preferably, described inorganic salt are selected from one or more in sodium-chlor, Repone K, calcium chloride, magnesium chloride, sodium carbonate, salt of wormwood, sodium bicarbonate, saleratus, Magnesium hydrogen carbonate, Calcium hydrogen carbonate.
For reaching above-mentioned second object, the low-tension foam flooding finish with resistance to elevated temperatures of the present invention is applied in tertiary oil recovery, for improving the oil recovery factor that formation temperature is the high-temperature oil reservoir of 80 ~ 200 DEG C.
Preferably, described application by not containing the low-tension foam flooding finish with resistance to elevated temperatures described in additive and water carry out composite after the aqueous liquid that obtains tie up in tertiary oil recovery and apply; Wherein, in water solution system, the mass concentration of described anion surfactant and the mass concentration ratio of zwitterionics are 1 ~ 50:1, and the mass concentration of described anion surfactant is 0.1 ~ 100 ‰.
Preferably, described application by carry out containing the low-tension foam flooding finish with resistance to elevated temperatures described in additive and water composite after the aqueous liquid that obtains tie up in tertiary oil recovery and apply; Wherein, in water solution system, the mass concentration of described anion surfactant and the mass concentration concentration ratio of zwitterionics are 1 ~ 50:1, and the mass concentration of described anion surfactant is 0.01 ~ 100 ‰, and the mass concentration of described additive is 0.001 ~ 50 ‰.
Preferably, the low-tension foam flooding finish with resistance to elevated temperatures of the present invention, does not decompose under the high temperature of 300 DEG C.
Preferably, of the present invention there is resistance to elevated temperatures low-tension foam flooding finish and water composite after the concentration applied in tertiary oil recovery of the aqueous solution be 1 ~ 5wt ‰, can <10 be reached between itself and crude oil
-2the ultra low interfacial tension of mN/m.
Beneficial effect of the present invention is as follows:
1, tensio-active agent alkylsulphonic acid (or carboxylic acid) salt or alkylbenzene sulfonate have good foam performance; And the existence of carboxylate radical or sulfonate radical, make it have very strong resistance to elevated temperatures.Beet alkali ampholytic ionic surface active agent has soluble in water, that foam stability energy is good advantage; Adding of it, add the described foam stability energy with the low-tension foam flooding finish of resistance to elevated temperatures and solubility property, be conducive to industrial application.
2, low by cost, performance good, be easy to extensive alkylsulphonic acid (or carboxylic acid) salt that uses or alkylbenzene sulfonate and beet alkali ampholytic ionic surface active agent as host, the low-tension foam flooding finish with resistance to elevated temperatures of the present invention obtained as auxiliary combination with fatty alcohol and inorganic salt, and can <10 be reached between crude oil
-2the ultra low interfacial tension of mN/m is (as reached 10 with the crude oil interfacial tension of NW Hebei
-3mN/m, use of the present invention there is resistance to elevated temperatures low-tension foam flooding finish and water prepares is the described aqueous solution with the low-tension foam flooding finish of resistance to elevated temperatures of 1 ~ 5wt ‰ containing concentration).
3, foaming properties test is carried out to the low-tension foam flooding finish with resistance to elevated temperatures of the present invention, adopt " method for evaluating foam property and factors affecting stability summary " (Wang Qi practises Hai Ling etc. chemical industry and engineering .2007) in air-flow method Latherometer measure:
Mensuration process is:
Step 1: be connected with thermostat with water outlet by the water-in of air-flow method Latherometer, starts thermostat and carries out 50 DEG C of constant temperature water baths more than 30 minutes;
Step 2: use of the present invention there is resistance to elevated temperatures low-tension foam flooding finish and water prepares is the described aqueous solution with the low-tension foam flooding finish of resistance to elevated temperatures of 1 ~ 5wt ‰ containing concentration, get the 50mL low-tension foam flooding agent solution with resistance to elevated temperatures of the present invention to pour in air-flow method Latherometer, then carry out 50 DEG C of constant temperature 30 minutes;
Step 3: with the bottom blowing air (or nitrogen) 20 second of peristaltic pump constant speed (10mL/s) from air-flow method Latherometer, record the lather volume V after 20 seconds
0(mL) measuring as foamable composition ability;
Step 4: record lather volume decays to original half (1/2V
0) time required time, be the transformation period t of foam
1/2.
Below by embodiment, the low-tension foam flooding finish with resistance to elevated temperatures of the present invention is further detailed.
Embodiment
In order to be illustrated more clearly in the present invention, below in conjunction with preferred embodiment, the present invention is described further.It will be appreciated by those skilled in the art that specifically described content is illustrative and nonrestrictive, should not limit the scope of the invention with this below.
Embodiment 1
Preparation has the aqueous solution of the low-tension foam flooding finish of resistance to elevated temperatures, wherein, the mass concentration of the tetradecyl alpha-olefin sodium sulfonate in the aqueous solution is 1.0 ‰, the mass concentration of tetradecyl benzene sulfonic acid sodium salt is 1.0 ‰, the mass concentration of cetyl betaine is 2.0 ‰ (mass concentrations of anion surfactant: the mass concentration=1:1 of zwitterionics), the mass concentration of sodium-chlor is 0.1 ‰, and the mass concentration of lauryl alcohol is 0.1 ‰.
The above-mentioned low-tension foam flooding finish with resistance to elevated temperatures, does not decompose under the high temperature of 300 DEG C.
Getting the above-mentioned aqueous solution 50mL with the low-tension foam flooding finish of resistance to elevated temperatures pours in air-flow method Latherometer, 50 DEG C of constant temperature 30 minutes; With the bottom blowing air 20 second of peristaltic pump constant speed (10mL/s) from air-flow method Latherometer, test foam volume and transformation period.Foam volume 265mL, the transformation period is 360 minutes, reaches 2.8 × 10 with NW Hebei crude oil interfacial tension
-3(oil density is 0.8316g/m to mN/m
3).
Embodiment 2
Preparation has the aqueous solution of the low-tension foam flooding finish of resistance to elevated temperatures, wherein, the mass concentration of the dodecyl alpha-olefin sodium sulfonate in the aqueous solution is 50 ‰, the mass concentration of Sodium dodecylbenzene sulfonate is 50 ‰, the mass concentration of empgen BB is 2.0 ‰ (mass concentrations of anion surfactant: the mass concentration=50:1 of zwitterionics), the mass concentration of sodium-chlor is 15 ‰, the mass concentration of calcium chloride is 1 ‰, and the mass concentration of tetradecyl alcohol is 3 ‰.
The above-mentioned low-tension foam flooding finish with resistance to elevated temperatures, does not decompose under the high temperature of 300 DEG C.
Getting the above-mentioned aqueous solution 50mL with the low-tension foam flooding finish of resistance to elevated temperatures pours in air-flow method Latherometer, 50 DEG C of constant temperature 30 minutes; With the bottom blowing air 20 second of peristaltic pump constant speed (10mL/s) from air-flow method Latherometer, test foam volume and transformation period.Foam volume 260mL, the transformation period is 380 minutes, reaches 1.9 × 10 with NW Hebei crude oil interfacial tension
-3(oil density is 0.8316g/m to mN/m
3).
Embodiment 3
Preparation has the aqueous solution of the low-tension foam flooding finish of resistance to elevated temperatures, wherein, the mass concentration of the sodium cetanesulfonate in the aqueous solution is 1.7 ‰, the mass concentration of octadecyl benzenesulfonic acid sodium is 1.7 ‰, the mass concentration of octadecyl betaine is 2.0 ‰ (mass concentrations of anion surfactant: the mass concentration=1.7:1 of zwitterionics), the mass concentration of sodium-chlor is 5 ‰, the mass concentration of calcium chloride is 1.5 ‰, and the mass concentration of stearyl alcohol is 0.5 ‰.
The above-mentioned low-tension foam flooding finish with resistance to elevated temperatures, does not decompose under the high temperature of 300 DEG C.
Getting the above-mentioned aqueous solution 50mL with the low-tension foam flooding finish of resistance to elevated temperatures pours in air-flow method Latherometer, 50 DEG C of constant temperature 30 minutes; With the bottom blowing air 20 second of peristaltic pump constant speed (10mL/s) from air-flow method Latherometer, test foam volume and transformation period.Foam volume 270mL, the transformation period is 390 minutes, reaches 3.1 × 10 with NW Hebei crude oil interfacial tension
-3(oil density is 0.8316g/m to mN/m
3).
Embodiment 4
Preparation has the aqueous solution of the low-tension foam flooding finish of resistance to elevated temperatures, wherein, the mass concentration of the Sodium dodecylbenzene sulfonate in the aqueous solution is 3 ‰, the mass concentration of empgen BB is 0.6 ‰ (mass concentrations of anion surfactant: the mass concentration=5:1 of zwitterionics), the mass concentration of sodium-chlor is 20 ‰, the mass concentration of calcium chloride is 1.5 ‰, and the mass concentration of hexadecanol is 0.5 ‰.
The above-mentioned low-tension foam flooding finish with resistance to elevated temperatures, does not decompose under the high temperature of 300 DEG C.
Getting the above-mentioned aqueous solution 50mL with the low-tension foam flooding finish of resistance to elevated temperatures pours in air-flow method Latherometer, 50 DEG C of constant temperature 30 minutes; With the bottom blowing air 20 second of peristaltic pump constant speed (10mL/s) from air-flow method Latherometer, test foam volume and transformation period.Foam volume 272mL, the transformation period is 410 minutes, reaches 2.5 × 10 with NW Hebei crude oil interfacial tension
-3(oil density is 0.8316g/m to mN/m
3).
Embodiment 5
Preparation has the aqueous solution of the low-tension foam flooding finish of resistance to elevated temperatures, wherein, the mass concentration of the cetyl benzenesulfonic acid sodium in the aqueous solution is 3 ‰, the mass concentration of cetyl hydroxy azochlorosulfonate propyl lycine is 0.2 ‰ (mass concentrations of anion surfactant: the mass concentration=15:1 of zwitterionics), the mass concentration of sodium-chlor is 15 ‰, the mass concentration of calcium chloride is 1.5 ‰, and the mass concentration of lauryl alcohol is 0.5 ‰.
The above-mentioned low-tension foam flooding finish with resistance to elevated temperatures, does not decompose under the high temperature of 300 DEG C.
Getting the above-mentioned aqueous solution 50mL with the low-tension foam flooding finish of resistance to elevated temperatures pours in air-flow method Latherometer, 50 DEG C of constant temperature 30 minutes; With the bottom blowing air 20 second of peristaltic pump constant speed (10mL/s) from air-flow method Latherometer, test foam volume and transformation period.Foam volume 265mL, the transformation period is 430 minutes, reaches 3.3 × 10 with NW Hebei crude oil interfacial tension
-3(oil density is 0.8316g/m to mN/m
3).
Embodiment 6
Preparation has the aqueous solution of the low-tension foam flooding finish of resistance to elevated temperatures, wherein, the mass concentration of the octadecyl alpha-olefin sodium sulfonate in the aqueous solution is 5 ‰, the mass concentration of octadecyl hydroxyl azochlorosulfonate propyl lycine is 2.5 ‰ (mass concentrations of anion surfactant: the mass concentration=2:1 of zwitterionics), the mass concentration of sodium-chlor is 15 ‰, the mass concentration of calcium chloride is 1.5 ‰, and the mass concentration of magnesium chloride is 0.5 ‰.
The above-mentioned low-tension foam flooding finish with resistance to elevated temperatures, does not decompose under the high temperature of 300 DEG C.
Getting the above-mentioned aqueous solution 50mL with the low-tension foam flooding finish of resistance to elevated temperatures pours in air-flow method Latherometer, 50 DEG C of constant temperature 30 minutes; With the bottom blowing air 20 second of peristaltic pump constant speed (10mL/s) from air-flow method Latherometer, test foam volume and transformation period.Foam volume 250mL, the transformation period is 350 minutes, reaches 1.4 × 10 with NW Hebei crude oil interfacial tension
-3(oil density is 0.8316g/m to mN/m
3).
Embodiment 7
Preparation has the aqueous solution of the low-tension foam flooding finish of resistance to elevated temperatures, wherein, the mass concentration of the sodium laurate in the aqueous solution is 3 ‰, the mass concentration of empgen BB is 0.3 ‰ (mass concentrations of anion surfactant: the mass concentration=10:1 of zwitterionics), and the mass concentration of sodium-chlor is 100 ‰.
The above-mentioned low-tension foam flooding finish with resistance to elevated temperatures, does not decompose under the high temperature of 300 DEG C.
Getting the above-mentioned aqueous solution 50mL with the low-tension foam flooding finish of resistance to elevated temperatures pours in air-flow method Latherometer, 50 DEG C of constant temperature 30 minutes; With the bottom blowing air 20 second of peristaltic pump constant speed (10mL/s) from air-flow method Latherometer, test foam volume and transformation period.Foam volume 275mL, the transformation period is 450 minutes, reaches 4.9 × 10 with NW Hebei crude oil interfacial tension
-3(oil density is 0.8316g/m to mN/m
3).
Obviously; the above embodiment of the present invention is only for example of the present invention is clearly described; and be not the restriction to embodiments of the present invention; for those of ordinary skill in the field; can also make other changes in different forms on the basis of the above description; here cannot give exhaustive to all embodiments, every belong to technical scheme of the present invention the apparent change of extending out or variation be still in the row of protection scope of the present invention.
Claims (10)
1. there is a low-tension foam flooding finish for resistance to elevated temperatures, it is characterized in that: comprise anion surfactant and zwitterionics; Have in the low-tension foam flooding finish of resistance to elevated temperatures described, the mass concentration ratio of described anion surfactant and zwitterionics is 1 ~ 50:1.
2. a kind of low-tension foam flooding finish with resistance to elevated temperatures according to claim 1, is characterized in that: described anion surfactant be selected from the tensio-active agent of following structure type one or both:
A) saturated or unsaturated fatty acids base salt
R-YM
In formula, R is C
8~ C
24saturated or unsaturated fatty acids base; Y is carboxylate radical or sulfonate radical; M is Na
+, K
+, Ca
2+or Mg
2+, or more the mixture of described ion;
B) alkylbenzene salt
In formula, R is C
8~ C
24saturated or unsaturated fatty acids base; Y is sulfonate radical; M is Na
+, K
+, Ca
2+or Mg
2+, or more the mixture of described ion.
3. a kind of low-tension foam flooding finish with resistance to elevated temperatures according to claim 1, is characterized in that: described zwitterionics molecular formula is:
In formula, R is C
6~ C
30alkyl; Y is CH
2cOO
-or CH
2cHOHCH
2sO
3 -.
4. a kind of low-tension foam flooding finish with resistance to elevated temperatures according to claim 1, is characterized in that: described in there is resistance to elevated temperatures low-tension foam flooding finish also comprise additive.
5. a kind of low-tension foam flooding finish with resistance to elevated temperatures according to claim 4, is characterized in that: described additive is selected from C
2~ C
24fatty alcohol and inorganic salt in one or more.
6. a kind of low-tension foam flooding finish with resistance to elevated temperatures according to claim 5, is characterized in that: described inorganic salt are selected from one or more in sodium-chlor, Repone K, calcium chloride, magnesium chloride, sodium carbonate, salt of wormwood, sodium bicarbonate, saleratus, Magnesium hydrogen carbonate and Calcium hydrogen carbonate.
7. the application of low-tension foam flooding finish in tertiary oil recovery with resistance to elevated temperatures as described in as arbitrary in claim 1-6.
8. application according to claim 7, is characterized in that: described application by not containing the low-tension foam flooding finish and water described in additive with resistance to elevated temperatures carry out composite after the aqueous liquid that obtains tie up in tertiary oil recovery and apply; In described water solution system, the mass concentration ratio of described anion surfactant and zwitterionics is 1 ~ 50:1, and the mass concentration of described anion surfactant is 0.1 ~ 100 ‰.
9. application according to claim 7, is characterized in that: described application by carry out containing the low-tension foam flooding finish and water described in additive with resistance to elevated temperatures composite after the aqueous liquid that obtains tie up in tertiary oil recovery and apply; In described water solution system, the mass concentration ratio of described anion surfactant and zwitterionics is 1 ~ 50:1, the mass concentration of described anion surfactant is 0.01 ~ 100 ‰, and the mass concentration of described additive is 0.001 ~ 50 ‰.
10. application according to claim 7, is characterized in that: described in have the low-tension foam flooding finish of resistance to elevated temperatures and water composite after the concentration applied in tertiary oil recovery of the aqueous solution that obtains be 1 ~ 5wt ‰.
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|---|---|---|---|
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|---|---|---|---|
| CN201510018194.2A CN104745168A (en) | 2015-01-14 | 2015-01-14 | High-temperature-resistant low-tension foam oil-displacing agent and application thereof |
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| CN105670589A (en) * | 2015-12-28 | 2016-06-15 | 工合聚能(天津)石油精化科技发展有限公司 | Foamer for enhancing crude oil recovery and preparation method thereof |
| CN106318358A (en) * | 2016-07-28 | 2017-01-11 | 山东大学 | Green and environmentally friendly foam oil displacement system based on alkyl glycoside and preparation method and application thereof |
| CN111334276A (en) * | 2020-03-10 | 2020-06-26 | 青岛金智瑞油气田开发技术发展有限公司 | Oil displacement agent and oil displacement method suitable for high-temperature low-salt oil reservoir |
| CN112266776A (en) * | 2020-10-29 | 2021-01-26 | 大庆轩隆化工有限公司 | Surfactant for oil displacement and preparation method thereof |
| CN113292982A (en) * | 2021-06-02 | 2021-08-24 | 中国石油大学(华东) | Viscoelastic surfactant foam system and preparation method and application thereof |
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| CN105670589A (en) * | 2015-12-28 | 2016-06-15 | 工合聚能(天津)石油精化科技发展有限公司 | Foamer for enhancing crude oil recovery and preparation method thereof |
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| CN113292982B (en) * | 2021-06-02 | 2023-02-17 | 中国石油大学(华东) | Viscoelastic surfactant foam system and preparation method and application thereof |
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