CN102504790A - Method for reversing gas humidity on surface of rock core by using cationic fluorocarbon surfactant - Google Patents
Method for reversing gas humidity on surface of rock core by using cationic fluorocarbon surfactant Download PDFInfo
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- CN102504790A CN102504790A CN2011103533644A CN201110353364A CN102504790A CN 102504790 A CN102504790 A CN 102504790A CN 2011103533644 A CN2011103533644 A CN 2011103533644A CN 201110353364 A CN201110353364 A CN 201110353364A CN 102504790 A CN102504790 A CN 102504790A
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Abstract
The invention relates to a method for reversing gas humidity on the surface of a rock core by using cationic fluorocarbon surfactant. The humidity reserving treatment agent used by the method contains the cationic fluorocarbon surfactant, a quaternary ammonium salt surfactant and a polar fluid, preferably FC911, hexadecyl trimethyl ammonium bromide and water. The invention also provides a method for reversing the humidity on the surface of sandstone into gas humidity, which comprises: pumping a humidity reversing treatment agent which contains 0.1 to 1 weight percent of cationic fluorocarbon surfactant into a rock stratum of a gas oil well till the entire surface of the sandstone in the rock stratum is immersed in the humidity reversing treatment agent; and thus, realizing the reversion into the gas humidity on the surface of the rock core. The method can effectively reserve the liquid humidity on the surface of the sandstone into gas humidity. The method is simple, convenient and easy.
Description
Technical field
The present invention relates to a kind of method that improves gas condensate reservoir output and protection hydrocarbon zone, be specifically related to a kind of cation fluorine carbon surface active agent that utilizes the formation rock surface wettability is wet or the wet method that changes middle air humidity property into of water from oil.
Background technology
China's hydrocarbon resources becomes the bottleneck of restriction Chinese society Economic development just day by day.The wettability of hydrocarbon zone rock surface is not only the key factor that control hydrocarbon zone fluid flows and distributes in pore media, and oil, gas, water in the hydrocarbon zone are also had very big influence to rate of permeation and RF.In the hypotonic gas reservoir of densification, usually because the obstruction of water and the gathering of white oil significantly reduce gas permeability.Water slug is because the water that waterfrac treatment is injected causes.Along with being reduced to the following white oil of DPP, can assemble pressure.The principal element that liquid is detained in rock is that strong wetted makes the liquid migration velocity very slow.Thereby rock wettability is become the migration rate raising gas yield that neutral air humidity can improve liquid from strong wetted.
2008; Yao Tongyu etc. have delivered the article of " air humidity is to the influence of gas condensate reservoir penetration signature " by name at " oilfield chemistry " the 25th volume the 2nd phase 101-104 page or leaf; Reported chemical agents such as X 2073, cetyl trimethylammonium bromide, octyl phenol Soxylat A 25-7 OP-15, dimethyl silicone oil GB-2201, dichlorodimethylsilane can be effectively with sandstone surface from the moist air humidity property that changes into of strong liquid; But they use inconvenience, and have certain danger.
CN102076809A (CN200980123817.5) provides a kind of method that is used to change the lithostratigraphy wettability; This method comprises: the wettability treatment agent is pumped in the lithostratigraphy; Wherein said wettability agent composition is selected from microemulsion, nanoemulsions, emulsion and miniemulsion, and the microemulsion that the Monophase microemulsion in the wettability treatment agent (SPME) and original position form can be used to reverse before the wettability of the subsurface rock that drills through with oil-base mud or synthetic basic mud before the agent of leak-off extrusion process or crosslinking Treatment agent or other water base treatment agent fall in the pumping height.When wettability treatment agent contact apolar substance through apolar substance is dissolved in this wettability reverse takes place in the microemulsion.Form the original position microemulsion in the time of can contacting reservoir formation in the organic phase of one or more tensio-active agents and polar phase (for example water or salt solution) and final some amounts and reverse the wettability of finding in the porous medium.Said microemulsion is effective to reverse the wettability that is produced by apolar substance.
Employed tensio-active agent fails to change core surface into the preferential air humidity of ideal surface in the above method, and wherein organosilicon and polymkeric substance use inconvenient operation, cause the infringement on stratum.
Summary of the invention
To the method for existing air humidity counter-rotating and the shortcoming and defect of used chemical agent; The present invention provides a kind of wettability reversal treatment agent; The present invention also provides the method that sandstone surface is changed into the gas wettability; Realizing the counter-rotating of core surface air humidity with the wettability reversal treatment agent that contains the cation fluorine carbon surface active agent, can be gas wettability and simple and easy to do with sandstone surface from the wetted sex reversal effectively.
Technical scheme of the present invention is following:
A kind of wettability reversal treatment agent comprises at least a cation fluorine carbon surface active agent; At least a quaternary surfactant; With at least a polar fluid; Described cation fluorine carbon surface active agent is perfluorinated octyl sulfuryl amine quaternary ammonium salt compounded of iodine or fluorine-containing alkylamide quaternary ammonium salt compounded of iodine.
Further preferred, said cation fluorine carbon surface active agent is selected from FC911 or C
7F
15CONH (CH
2)
3N (CH
3) I.
Described quaternary surfactant is selected from cetyl trimethylammonium bromide (CTAB), Trimethyllaurylammonium bromide or dodecyl benzyl dimethyl ammonium chloride (1227), Trimethyllaurylammonium bromide or cetyl trimethylammonium bromide.
Said polar fluid comprises water or salt solution.
The mass ratio of described quaternary surfactant and described cation fluorine carbon surface active agent is 1: 98~99.
The mass concentration of described cation fluorine carbon surface active agent in the wettability reversal treatment agent is 0.1%-1%.Further preferred, the mass concentration of positively charged ion fluorocarbon surfactant is 0.2%-0.3% in the said wettability reversal treatment agent solution.
The term explanation:
The FC911 molecular formula is: C
8F
17SO
2NH (CH
2)
3(CH
3)
3I.
Said FC911 and C
7F
15CONH (CH
2)
3N (CH
3) I is the cation fluorine carbon surface active agent, is known raw material, and is commercially available.
According to the present invention; Preferably; Said wettability reversal treatment agent is made up of FC911, cetyl trimethylammonium bromide and water, and cetyl trimethylammonium bromide (CTAB) is 1: 98~99 with the mass ratio of FC911, and the mass concentration of FC911 is 0.1%-1% in the said wettability reversal treatment agent.Further preferred, the mass concentration of FC911 is 0.2%-0.3% in the said wettability reversal treatment agent solution.
Wettability reversal treatment agent according to the invention is used to realize core surface air humidity counter-rotating processing.Concrete grammar is following:
A kind ofly change sandstone surface the method for gas wettability into, this method comprises:
The wettability reversal treatment agent is pumped in the lithostratigraphy, and wherein said wettability reversal treatment agent comprises as stated:
At least a cation fluorine carbon surface active agent; At least a quaternary surfactant; With at least a polar fluid;
The sandstone surface of lithostratigraphy all is dipped in the said wettability reversal treatment agent, and making the part sandstone surface is the gas wettability from the wetted sex reversal, reaches tangible middle air humidity, and the solid three-phase contact angle θ of oil gas changes 50-80 ° into from 0 °.
Further preferred, said sandstone surface immersion treatment time in the wettability reversal treatment agent is 10-12 hour.
Further preferred, said wettability reversal treatment agent contacts the temperature condition of handling with sandstone surface be 20~60 ℃.
According to the present invention; A kind of preferred scheme is: the method that sandstone surface is changed into the gas wettability; Form reverse wetting agent by cetyl trimethylammonium bromide and cation fluorine carbon surface active agent FC911 by 1: 98~99 mass ratio; Add water be made into FC911 concentration be the diluting soln of 0.1-1wt% as the wettability reversal treatment agent, this wettability reversal treatment agent is pumped in the gas and oil well lithostratigraphy, the sandstone surface of lithostratigraphy all is soaked in the said wettability reversal treatment agent; 25~60 ℃ of subsurface temperatures, the treatment time is 10-12 hour.Preferably, FC911 concentration is 0.2-0.3wt% in the wettability reversal treatment agent.
Mechanism with the wettability reversal treatment agent acquisition air humidity rock core that contains fluorocarbon surfactant among the present invention is following:
Fluorocarbon surfactant has the property of not only hydrophobic but also oleophobic, is because special physics and the chemical property of fluorine atom.The fluorine atom volume ratio is less; Van der Waals radius is big by about 10% than Wasserstoffatoms only, can wrap carbon skeleton is tight, so fluorine carbon molecule can be taked " Z " font row portion; And then make the atom of outside be difficult to get in the fluorine carbon molecule; Again because the strong negative of fluorine makes the share electron pair of C-F key be partial to fluorine atom, at a kind of negative electricity resist of the peripheral formation of carbon skeleton; Other electronegativity nucleophilic reagent since the repulsion of same sex electric charge be difficult near carbon atom, thereby make fluorocarbon surfactant have shielding effect.Fluorine is that atomic electronegativity is maximum in all elements, is 4.0, so compare with hydrocarbon molecules, fluorine carbon molecule is extremely difficult oxidized; The bond energy of C-F is 484kJmol
-1, all bigger than other singly-bound bond energys, can big 69kJmol than c h bond
-1, and polarizability is smaller, so the C-F key is very firm, and the homolysis mode with covalent linkage of being difficult to decompositions of rupturing, the heterolytic fission mode that also is difficult to covalent linkage is decomposed, thereby makes fluorocarbon surfactant have the thermostability of excellence, and has good chemicalstability.The polarizability of carbon-fluorine bond is also little, and the intermolecular cohesive force of compound that therefore contains a large amount of C-F keys is little, and the result also reduces surface free energy, has formed various liquid are difficult to ins and outs wetting, that be difficult to adhere to.
The present invention has following technical characterstic and excellent results:
(1) because the good hydrophobic oleophobic performance of fluorocarbon surfactant can make sandstone surface reach tangible middle air humidity after the processing, can be used for improving the stratum wettability, help improving gas-condensate well gas RF and improve the reservoir choke phenomenon.
(2) fluorocarbon surfactant good water solubility used in the present invention, nontoxicity, therefore safe and convenient to use.
(3) use fluorocarbon surfactant, can avoid that organosilicon and polymkeric substance bring to the pollution on stratum and the various troublesome operation in the construction.
Description of drawings
Fig. 1 is shape and the contact angle θ of water droplet at untreated sandstone core surface, θ=0;
The solid three-phase contact angle size of the shape of Fig. 2-the 6th, water droplet sandstone core surface after the processing of embodiment 1-5 and aqueous vapor θ, θ=65 °, 72 °, 80 °, 40 °, 40 °;
Fig. 7 is shape and the contact angle θ of oil droplet at untreated sandstone core surface, θ=0;
The solid three-phase contact angle θ size of the shape of Fig. 8-the 12nd, oil droplet sandstone core surface after the processing of embodiment of the invention 1-5 and oil gas, θ=64 °, 68 °, 74 °, 52 °, 76 °;
Wherein, water is 0.2% NaCl, and oil phase is a n-decane.The wettability reversal treatment agent formula is the aqueous solution of cetyl trimethylammonium bromide and cation fluorine carbon surface active agent FC911; Treatment process such as embodiment 1, treatment agent concentration is respectively 0,0.1%FC911,0.2%FC911,0.3%FC911,0.5%FC911,1.0%FC911.
Embodiment
Below in conjunction with embodiment the present invention is further specified, but do not limit the present invention.Except that specifying, all per-cents are mass percent among the embodiment, raw materials used this area common used material that is.Employed fluorocarbon surfactant FC911, C
7F
15CONH (CH
2)
3N (CH
3) I provides by Shanghai Organic Chemistry Institute, Chinese Academy of Sciences.
Embodiment 1:
The aqueous solution that the wettability reversal treatment agent is made up of cetyl trimethylammonium bromide and cation fluorine carbon surface active agent FC911, the FC911 mass percent is 0.1%, cetyl trimethylammonium bromide and FC911 mass ratio are 1: 99.
Sandstone surface wettability reversal experimental technique: earlier with the sandstone slabbed core, process diameter 2.5cm, thickness is approximately the core wafer of 1cm, and its surface finish is smooth.Then that the rock core sheet is clean with ethanol, acetone.The rock core sheet is immersed in the described wettability reversal treatment agent, under 25 ℃ of temperature, handled 10 hours, then the rock core sheet is taken out and at room temperature dry or dry.
What last mensuration core wafer surface wettability was used is the method for dripping of stopping, and concrete measuring method is following:
Rock core sheet after handling is placed on the instrument Stage microscope, sucks water and oil with microsyringe then, respectively at core surface drip size approximately water droplet and the oil droplet of 0.3cm.Instrument is taken pictures and is charged to computer then, adopts goniometry to calculate the size of contact angle according to photo, and every block of rock core repeats this operation three times, reads the MV of contact angle.
Oil is n-decane (n-C10), and specific density is 0.73, viscosity 0.92cp, air/n-decane surface tension 23.4mN/m.Water is 0.2% NaCl, density 1.012, and viscosity 1.0cp, air/salt water surface tension is 72.8mN/m.Measuring temperature is 25 ℃ of room temperatures.
Rock core sheet surface contact angle after the measurement processing in the present embodiment, salt solution air sandstone system contact angle be 65 ° (as shown in Figure 2), n-decane air sandstone system contact angle be 64 ° (as shown in Figure 8).
Embodiment 2:
Of embodiment 1, different is that the FC911 mass concentration is 0.2% in the wettability reversal treatment agent solution.
Core surface contact angle after the present embodiment measurement processing, salt solution air sandstone system contact angle be 72 ° (as shown in Figure 3), n-decane air sandstone system contact angle be 68 ° (as shown in Figure 9).
Embodiment 3:
Of embodiment 1, different is that the FC911 mass concentration is 0.3% in the wettability reversal treatment agent solution.Present embodiment is handled the back and is measured the core surface contact angle, salt solution air sandstone system contact angle be 80 ° (as shown in Figure 4), n-decane air sandstone system contact angle be 74 ° (shown in figure 10).
Embodiment 4:
Of embodiment 1, different is that the FC911 mass concentration is 0.5% in the wettability reversal treatment agent solution.Core surface contact angle after the present embodiment measurement processing, salt solution air sandstone system contact angle be 40 ° (as shown in Figure 5), n-decane air sandstone system contact angle be 52 ° (shown in figure 11).
Embodiment 5:
Of embodiment 1, different is that the FC911 mass concentration is 1.0% in the wettability reversal treatment agent solution.Core surface contact angle after the present embodiment measurement processing, salt solution air sandstone system contact angle be 40 ° (as shown in Figure 6), n-decane air sandstone system contact angle be 76 ° (shown in figure 12).
Embodiment 6:
The aqueous solution that the wettability reversal treatment agent is made up of cetyl trimethylammonium bromide and cation fluorine carbon surface active agent FC911, the FC911 mass percent is 0.3% in the solution, cetyl trimethylammonium bromide and FC911 mass ratio are 1: 98.
Sandstone surface wettability reversal experimental technique such as embodiment 1 are said, and different is that the rock core sheet is immersed in the described wettability reversal treatment agent, under 50 ℃ of following temperature, handle 10 hours, then the rock core sheet are taken out and at room temperature dry or dry.Rock core sheet surface wettability measuring method is with embodiment 1.Present embodiment is handled back core surface contact angle, salt solution air sandstone system contact angle be 75 °, n-decane air sandstone system contact angle be 75 °.
Embodiment 7:
The wettability reversal treatment agent is by cetyl trimethylammonium bromide and cation fluorine carbon surface active agent C
7F
15CONH (CH
2)
3N (CH
3) aqueous solution formed of I, C in the solution
7F
15CONH (CH
2)
3N (CH
3) the I mass percent is 0.3%, cetyl trimethylammonium bromide and C
7F
15CONH (CH
2)
3N (CH
3) the I mass ratio is 1: 99.
Sandstone surface wettability reversal experimental technique such as embodiment 1 are said, and different is that the rock core sheet is immersed in the described wettability reversal treatment agent, under 40 ℃ of following temperature, handle 12 hours, then the rock core sheet are taken out and at room temperature dry or dry.Rock core sheet surface wettability measuring method is with embodiment 1.Present embodiment is handled back core surface contact angle, salt solution air sandstone system contact angle be 55 °, n-decane air sandstone system contact angle be 70 °.
Embodiment 8: application examples, Gudao area of Shengli Oilfield oil recovery factory 3# gas-condensate well
The aqueous solution that the wettability reversal treatment agent is made up of cetyl trimethylammonium bromide and cation fluorine carbon surface active agent FC911, the FC911 mass percent is 0.35% in the solution, cetyl trimethylammonium bromide and FC911 mass ratio are 1: 99.
Sandstone surface is changed into the method for gas wettability; Described wettability reversal treatment agent is pumped in the gas and oil well lithostratigraphy, the sandstone surface of lithostratigraphy all is soaked in wherein, 60 ℃ of subsurface temperatures; Treatment time 10-12 hour; Making sandstone surface is the gas wettability from the wetted sex reversal, reaches tangible middle air humidity, and the solid three-phase contact angle of oil gas becomes about 75 ° from 0 °.In the actual production, handle once half a year at interval, finally can make the condensate gas well flow index improve 2-3 doubly.
Claims (10)
1. a wettability reversal treatment agent comprises at least a cation fluorine carbon surface active agent; At least a quaternary surfactant; With at least a polar fluid; Described cation fluorine carbon surface active agent is perfluorinated octyl sulfuryl amine quaternary ammonium salt compounded of iodine or fluorine-containing alkylamide quaternary ammonium salt compounded of iodine.
2. wettability reversal treatment agent as claimed in claim 1 is characterized in that it is C that described cation fluorine carbon surface active agent is selected from molecular formula
8F
17SO
2NH (CH
2)
3(CH
3)
3The FC911 of I or C
7F
15CONH (CH
2)
3N (CH
3) I.
3. wettability reversal treatment agent as claimed in claim 1 is characterized in that described quaternary surfactant is selected from cetyl trimethylammonium bromide, Trimethyllaurylammonium bromide, dodecyl benzyl dimethyl ammonium chloride, Trimethyllaurylammonium bromide or cetyl trimethylammonium bromide.
4. wettability reversal treatment agent as claimed in claim 1 is characterized in that said polar fluid comprises water or salt solution.
5. wettability reversal treatment agent as claimed in claim 1 is characterized in that the mass ratio of described quaternary surfactant and described perfluoro octyl sulfonic acid quaternary amine iodide is 1: 98~99.
6. wettability reversal treatment agent as claimed in claim 1 is characterized in that the mass concentration of described cation fluorine carbon surface active agent in the wettability reversal treatment agent is 0.1%-1%; Preferably, this mass concentration is 0.2%-0.3%.
7. wettability reversal treatment agent as claimed in claim 1; It is characterized in that said wettability reversal treatment agent is made up of FC911, cetyl trimethylammonium bromide and water; The mass ratio of cetyl trimethylammonium bromide and FC911 is 1: 98~99, and the mass concentration of FC911 is 0.1%-1% in the said wettability reversal treatment agent; Preferably, the mass concentration of FC911 is 0.2%-0.3% in the said wettability reversal treatment agent solution.
8. one kind changes sandstone surface the method for gas wettability into, and this method comprises:
Each described wettability reversal treatment agent of claim 1~7 is pumped in the lithostratigraphy; The sandstone surface of lithostratigraphy all is dipped in the said wettability reversal treatment agent; Making the part sandstone surface is the gas wettability from the wetted sex reversal; Reach tangible middle air humidity, the solid three-phase contact angle θ of oil gas changes 50~80 ° into from 0 °.
9. as claimed in claim 8ly change sandstone surface the method for gas wettability into, it is characterized in that said sandstone surface immersion treatment time in the wettability reversal treatment agent is 10~12 hours; Preferably, contact the temperature condition of handling with sandstone surface be 20~60 ℃ to said wettability reversal treatment agent.
10. the method that sandstone surface is changed into the gas wettability as claimed in claim 8; It is characterized in that forming reverse wetting agent by 1: 98~99 mass ratio by cetyl trimethylammonium bromide and cation fluorine carbon surface active agent FC911; Adding water, to be made into FC911 concentration be that the diluting soln of 0.1-1wt% is as the wettability reversal treatment agent; This wettability reversal treatment agent is pumped in the gas and oil well lithostratigraphy; The sandstone surface of lithostratigraphy all is soaked in the said wettability reversal treatment agent, 25~60 ℃ of subsurface temperatures, the treatment time is 10~12 hours; Preferably, FC911 concentration is 0.2-0.3wt% in the wettability reversal treatment agent.
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