CN102373042A - Foaming agent composition used for high temperature and high salt oil reservoir - Google Patents
Foaming agent composition used for high temperature and high salt oil reservoir Download PDFInfo
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Abstract
The invention relates to a foaming agent composition used for a high temperature and high salt oil reservoir, which mainly solves the problems existed in a foam flooding reinforcement oil extraction technology that the foaming agent has poor thermal stability, deposition is generated when meeting with divalent ion, the requirements of the foam flooding in a high temperature and high salinity stratum are not satisfied. According to the invention, the technical scheme of the foaming agent composition which is composed of polyoxyethylene alkyl ether benzene sulfonate, alkybenzene sulfonate and water is used for better solving the problems, and can be used for oil extraction by reinforcing the foam flooding.
Description
Technical field
The present invention relates to a kind of foaming agent combination that is used for high temperature and high salt oil deposit.
Background technology
How China's main oilfield improves oil recovery factor through once with behind the secondary recovery having got into high water-cut stage, develops remaining reserves to greatest extent, and tertiary oil recovery technology is guaranteeing to have brought into play important effect aspect the oilfield stable production high yield.In the TOR new technology, chemical combined flooding remains one of very promising method of tool.Its oil-displacement mechanism is mainly the viscosity of polymkeric substance or glue increase displacement water, reduces the profit mobility ratio, alleviates the channelling phenomenon, improves sweep efficiency; Tensio-active agent and alkali reduce oil/water termination tension force, increase the hollow billet number, impel crude oil desorption and effectively dispersion on rock, realize the effective driving to irreducible oil, thereby improve RF.Yet the polymkeric substance in the chemical combined flooding is dry powder, offset plate mostly, so its solvability is very bad, and the temperature resistant antisalt property of polymkeric substance is the difficult problem that puzzlement high temperature and high salinity oil reservoir is used always.
In order to improve the ability of shutoff most permeable zone, people are through a large amount of discovering, foam has than polymkeric substance or glue better gets into and the infiltrative ability of reduction most permeable zone.Mix through adding foaming agent and gas, carry out displacement with the form of aerated fluid, selectively the shutoff high permeability zone; The adjustment fluid entry profile increases sweep efficiency, again because foaming agent itself is a tensio-active agent; Have interfacial activity, reduce oil/water termination tension force, increase the hollow billet number; Can bring into play better effect, increase substantially RF.
Foaming agent in the market mainly contains two big types: anionic foaming agent and non-ionic type foaming agent.Yet, for high temperature, the high salinity oil reservoir because independent negatively charged ion foaming agent is relatively poor with the compatibleness of local water, easily with local water in calcium, the formation of high valence ions such as magnesium precipitates, and works as Ca
2+, Mg
2+Just lose oil displacement efficiency when surpassing 300 μ g/g; And there is cloud point in the nonionic foaming agent, and heat resistance is poor, and FT is higher than cloud point, and tensio-active agent promptly begins from water, to separate out, and has limited its application in TOR.And foam is a kind of thermodynamic unstable system, when adopting foam flooding, needs foam to keep the long as far as possible time on the stratum again.Therefore, the key problem of foam flooding is that the development foaming power is strong, and good stability is good with the local water compatibility, the foaming agent system of temperature resistance salt tolerant.
Document CN1648199A discloses a kind of foam formulation that is used for the raising RF of conventional oil reservoir; Wherein said whipping agent host is dodecyl polyethenoxy ether sodium sulfovinate salt, but since in the host existence of sulfuric acid ester bond make this system to be applicable to be lower than 100 ℃ oil reservoir.
Summary of the invention
One of technical problem to be solved by this invention is the foaming agent poor heat stability that exists in the prior art, meets the divalent ion deposition, can not satisfy the problem of high temperature and high salinity stratum foam flooding needs, and a kind of new foaming agent combination is provided.Said composition has at salinity 200000mg/L, clear under the local water condition of calcium ions and magnesium ions concentration 8000mg/L, 200 ℃ of wear out foam foaming and unconverted basically advantages of transformation period after 10 days.Two of technical problem to be solved by this invention provides a kind of purposes of this foaming agent combination.
For one of solving the problems of the technologies described above, the technical scheme that the present invention adopts is following: a kind of foaming agent combination comprises following component in parts by weight:
(1) 0.1～1 part AEO benzene sulfonate;
(2) 0.1～1 parts sulfonated alkylbenzene;
(3) 90～100 parts water;
AEO benzene sulfonate wherein has following general molecular formula:
In the formula, M is basic metal, earth alkali metal or ammonium, and R is C
8～C
24Alkyl, n is the arbitrary integer in 3～20.
In the technique scheme, alkali-metal preferred version is sodium or potassium, and more preferably scheme is a sodium; The R preferred version is C
8～C
18Alkyl, more preferably scheme is C
12～C
18Alkyl; The preferred version of n is any integer in 3～15.By weight percentage, aliphatic alcohol polyoxyethylene sulfonate consumption preferable range is 0.1～1.0%, and the consumption preferable range of sulfonated alkylbenzene is 0.1～1.0%.
In the technique scheme, foaming agent combination can also include the alcamines suds-stabilizing agent, is preferably diethylolamine.The consumption preferable range of suds-stabilizing agent is 0.1～0.3%.
For solve the problems of the technologies described above two, the technical scheme that the present invention adopts is following: a kind of foaming agent combination is applied in the foam flooding intensified oil reduction.
The preparation method of the AEO benzene sulfonate among the present invention may further comprise the steps:
A) Fatty Alcohol(C12-C14 and C12-C18) and oxyethane are 85～160 ℃ in temperature of reaction, and pressure is under 0～0.80MPa gauge pressure condition, under catalyst action, react AEO; Wherein said Fatty Alcohol(C12-C14 and C12-C18) is the alkyl that contains 8～24 carbon atoms; The mol ratio of oxyethane and Fatty Alcohol(C12-C14 and C12-C18) is 3～20: 1; Described catalyzer is the basic cpd of calcium, and consumption is 0.3～3% of a Fatty Alcohol(C12-C14 and C12-C18) weight;
B) step a) synthetic AEO and Benzyl Chloride are under 50～80 ℃ of conditions in temperature of reaction, react to get AEO benzene in 2～10 hours; Wherein the mol ratio of AEO and Benzyl Chloride is 1: 1～2;
C) the synthetic AEO benzene and the vitriol oil are under 40～60 ℃ of conditions in temperature of reaction in the step b), react to get the AEO Phenylsulfonic acid in 0.5～10 hour; Wherein the mol ratio of the vitriol oil and AEO is 2～10: 1.
In the technique scheme a) the temperature of reaction preferable range in the step be 140～160 ℃, the pressure preferable range is 0.20～0.60MPa gauge pressure; B) the step preferred version be alkyl polyoxyethylene ether earlier 50 ℃ of alkalization 0.5～2 hour down, and then with the Benzyl Chloride reaction in, the temperature of reaction preferable range is 70～80 ℃, the reaction times preferable range is 2～5 hours; C) the temperature of reaction preferable range in the step is 40～45 ℃, and the reaction times preferable range is 2～5 hours.The alkyl preferred version of said Fatty Alcohol(C12-C14 and C12-C18) is the alkyl that contains 12～18 carbon atoms.
The AEO benzene sulfonate designs anionic group and nonionic fragment in a surfactant molecule structure simultaneously among the present invention, has formed one type of novel the moon-non-amphoterics.This molecule has the heat resistance of ionic surface active agent and the anti-salt advantage of nonionogenic tenside concurrently, and produces synergistic effect with the composite use of sulfonated alkylbenzene, can improve the anti-salt property of whole composition system.Foaming agent combination of the present invention is not higher than 250 ℃ applicable to reservoir temperature, and salinity is lower than 200000mg/L, and calcium ions and magnesium ions concentration is lower than the oil reservoir of 10000mg/L.This foaming agent combination and nitrogen; Air; Carbonic acid gas and Sweet natural gas mix and form stable foam, are applied to Central Plains five factories of recovering the oil and 12 inject bubble foam system shop experiments recklessly, and the Luo Shi foaming process is measured its foam volume greater than 400mL in the time of 90 ℃; Its transformation period of foam sweep measurement, 110 ℃ of resistance factors were greater than 25 greater than 5min.
Embodiment
In actual design with in implementing; The present invention is these characteristics of salt tolerance that the good AEO benzene sulfonate that utilizes salt resistant character can improve sulfonated alkylbenzene; Select a kind of AEO benzene sulfonate and sulfonated alkylbenzene to carry out composite; Through regulating the salt resistant character of compound proportion adjustment mix-froth flooding system, to be fit to the reservoir formation of different salinities.Through embodiment the present invention is done further elaboration below.
[embodiment 1]
(1) in the reactor drum that condensing works, whipping appts and gas distributor are housed, adds the calcium oxide catalyst of 93g (0.5 mole) lauryl alcohol and pure weight 1%, when logical nitrogen limit, limit is heated to 135 ℃, add 8g water, stirring reaction 1 hour.First then normal pressure steams water, and the back decompression was steamed except that moisture in 140 ℃ of vacuum under 20 mmhg vacuum in 20 minutes, and this solution is cooled to 80 ℃, slowly dripped the vitriol oil of catalyst neutralisation theoretical acid amount 20 weight %.System temperature is heated to 80～90 ℃; The 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 feeds 155 gram oxyethane, control pressure＜0.60MPa carries out alkoxylation; Reaction is used the nitrogen purging system after finishing, and removes unreacted oxyethane, and cooling post neutralization, decolouring, filtration, dehydration get lauryl alcohol T 46155 (7) ether.
(2) step (1) institute's synthetic lauryl alcohol T 46155 (7) the ether 240g (0.5 mole) and the sodium hydroxide powder of 40g porphyrize are placed reactor drum; Start under whipping appts≤50 ℃; Alkalized 2 hours, and be warming up to 80 ℃ and slowly drip the Benzyl Chloride benzole soln that contains 216 grams, 35 weight %, after adding; Under reflux state, continue reaction 5 hours, get product lauryl alcohol T 46155 (7) ether benzene through aftertreatment.
(3) step (2) institute's synthetic lauryl alcohol T 46155 (7) ether benzene 290 gram (0.5 mole) is added in the reactor drum that TM, whisking appliance are housed be warming up to 45 ℃; Stir the vitriol oil that slowly drips 200 grams, 98 weight % down; 1.5 add in hour; Insulation reaction is 2 hours again, finishes reaction, gets lauryl alcohol T 46155 (7) ether Supragil GN thick liquid through aftertreatment.
(4) get synthetic lauryl alcohol T 46155 (7) ether Supragil GN X (weight) %, X 2073 Y (weight) %, water recklessly 12 inject in Zhongyuan Oil Field five factories of recovering the oil, and stir 20 minutes, must a foaming agent combination.The Zhongyuan Oil Field recover the oil five factories recklessly 12 injection water quality analytical resultss see table 1.Under 90 ℃ of water bath condition, the Luo Shi method measures the said composition latherability and foam scanner measurement its transformation period result sees table 2.
Table 1
| Water sample | K ++Na + | Mg 2+ | Ca 2+ | Cl - | SO 4 - | HCO 3 - | Total mineralization mg/L |
| 12 recklessly in five factories | 52560 | 746 | 6435 | 94022 | 566 | 213 | 154542 |
Table 2
| X (weight) % | 0.3 | 0.5 | 0.5 |
| Y (weight) % | 0.1 | 0.1 | 0.2 |
| Foam number (mL) | 400 | 430 | 460 |
| Transformation period (min) | 5 | 5.5 | 6 |
[embodiment 2]
Get foaming agent combination in [embodiment 1] pressure of packing into and hold in the bullet, put into baking oven and took out in aging 10 days at 200 ℃, under 90 ℃ of water bath condition, the Luo Shi method is measured aging back said composition latherability and is seen table 3 with foam scanner measurement its transformation period result.
Table 3
| X (weight) % | 0.3 | 0.5 |
| Y (weight) % | 0.1 | 0.1 |
| Foam number (mL) | 390 | 410 |
| Transformation period (min) | 4.8 | 5.4 |
[embodiment 3]
Get foaming agent combination lauryl alcohol T 46155 (7) ether Supragil GN 0.5 (weight) % in [embodiment 1]; X 2073 0.1 (weight) % carries out the sealing characteristics evaluation experimental, and silica sand is filled and presented basket rate of permeation 4D; Inject the foaming agent combination aqueous solution with 2mL/min speed to sandpipe; Speed with 9mL/min is pressed into nitrogen simultaneously, and 110 ℃ are measured shutoff pressure reduction is 1.07MPa, and calculating resistance factor is 25.5.The foam flooding mining site requires resistance factor greater than 4.
[embodiment 4]
(1) in the reactor drum that condensing works, whipping appts and gas distributor are housed, adds the calcium oxide catalyst of 135g (0.5 mole) stearyl alcohol and pure weight 1%, 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 was steamed except that moisture in 140 ℃ of vacuum under 20 mmhg vacuum in 20 minutes, and this solution is cooled to 80 ℃, slowly dripped the vitriol oil of catalyst neutralisation theoretical acid amount 20 weight %.System temperature is heated to 80～90 ℃; The 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 feeds 330 gram oxyethane, control pressure＜0.60MPa carries out alkoxylation; Reaction is used the nitrogen purging system after finishing, and removes unreacted oxyethane, and cooling post neutralization, decolouring, filtration, dehydration get octodecyl alcohol polyoxyethylene (15) ether.
(2) sodium hydroxide powder with step (1) institute's synthetic octodecyl alcohol polyoxyethylene (15) ether 465g (0.5 mole) and 40 gram porphyrizes places reactor drum; Start under 50 ℃ of the whipping apptss; Alkalized 2 hours, and be warming up to 85 ℃ and slowly drip the Benzyl Chloride benzole soln that contains 216 grams, 35 weight %, after adding; Under reflux state, continue reaction 5 hours, get product octodecyl alcohol polyoxyethylene (15) ether benzene through aftertreatment.
(3) step (2) institute's synthetic octodecyl alcohol polyoxyethylene (15) ether benzene 510 gram (0.5 mole) is added in the reactor drum that reflux condensate device, TM, whisking appliance are housed be warming up to 45 ℃; Stir the vitriol oil that slowly drips 150 grams, 98 weight % down; 1.5 add in hour; Insulation reaction is 2 hours again, finishes reaction, gets octodecyl alcohol polyoxyethylene (15) ether Supragil GN thick liquid through aftertreatment.
(4) get synthetic octodecyl alcohol polyoxyethylene (15) ether Supragil GN X (weight) %, X 2073 Y (weight) %, water recklessly 12 inject in Zhongyuan Oil Field five factories of recovering the oil, and stir 20 minutes, must a foaming agent combination.Under 90 ℃ of water bath condition, the Luo Shi method measures the said composition latherability and foam scanner measurement its transformation period result sees table 4.
Table 4
| X (weight) % | 0.3 | 0.5 |
| Y (weight) % | 0.15 | 0.2 |
| Foam number (mL) | 400 | 440 |
| Transformation period (min) | 6 | 6.5 |
[embodiment 5]
Get foaming agent combination in [embodiment 4] pressure of packing into and hold in the bullet, put into baking oven and took out in aging 10 days at 200 ℃, under 90 ℃ of water bath condition, the Luo Shi method is measured aging back said composition latherability and is seen table 5 with foam scanner measurement its transformation period result.
Table 5
| X (weight) % | 0.3 | 0.5 |
| Y (weight) % | 0.15 | 0.2 |
| Foam number (mL) | 400 | 430 |
| Transformation period (min) | 5.8 | 6.2 |
[embodiment 6]
Get octodecyl alcohol polyoxyethylene (15) ether Supragil GN 0.5 (weight) % in [embodiment 4]; X 2073 0.2 (weight) %; Zhongyuan Oil Field five factories of recovering the oil recklessly 12 inject the foaming agent combination that water form and carry out the sealing characteristics evaluation experimental according to the condition of [embodiment 3]; 110 ℃ are measured shutoff pressure reduction is 1.16MPa, and resistance factor is 29.0.
[embodiment 7]
(1) in the reactor drum that condensing works, whipping appts and gas distributor are housed, adds the calcium oxide catalyst of 135g (0.5 mole) stearyl alcohol and pure weight 1%, 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 was steamed except that moisture in 140 ℃ of vacuum under 20 mmhg vacuum in 20 minutes, and this solution is cooled to 80 ℃, slowly dripped the vitriol oil of catalyst neutralisation theoretical acid amount 20 weight %.System temperature is heated to 80～90 ℃; The 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 feeds 220 gram oxyethane, control pressure＜0.60MPa carries out alkoxylation; Reaction is used the nitrogen purging system after finishing, and removes unreacted oxyethane, and cooling post neutralization, decolouring, filtration, dehydration get octodecyl alcohol polyoxyethylene (10) ether.
(2) sodium hydroxide powder with step (1) institute's synthetic octodecyl alcohol polyoxyethylene (10) ether 355g (0.5 mole) and 40 gram porphyrizes places reactor drum; Start under 50 ℃ of the whipping apptss; Alkalized 2 hours, and be warming up to 85 ℃ and slowly drip the Benzyl Chloride benzole soln that contains 216 grams, 35 weight %, after adding; Under reflux state, continue reaction 5 hours, get product octodecyl alcohol polyoxyethylene (10) ether benzene through aftertreatment.
(3) step (2) institute's synthetic octodecyl alcohol polyoxyethylene (10) ether benzene 400 gram (0.5 mole) is added in the reactor drum that reflux condensate device, TM, whisking appliance are housed be warming up to 45 ℃; Stir the vitriol oil that slowly drips 200 grams, 98 weight % down; 1.5 add in hour; Insulation reaction is 2 hours again, finishes reaction, gets octodecyl alcohol polyoxyethylene (10) ether Supragil GN thick liquid through aftertreatment.
(4) get synthetic octodecyl alcohol polyoxyethylene (10) ether Supragil GN X (weight) %, X 2073 Y (weight) %, diethylolamine Z (weight) %, water recklessly 12 inject in Zhongyuan Oil Field five factories of recovering the oil, and stir 20 minutes.Under 90 ℃ of water bath condition, the Luo Shi method measures this solution foaming ability and foam scanner measurement its transformation period result sees table 6.
Table 6
| X (weight) % | 0.3 | 0.3 | 0.3 |
| Y (weight) % | 0.15 | 0.15 | 0.15 |
| Z (weight) % | 0 | 0.1 | 0.2 |
| Foam number (mL) | 390 | 410 | 420 |
| Transformation period (min) | 5.8 | 6.1 | 6.2 |
[embodiment 8]
Get foaming agent combination in [embodiment 7] pressure of packing into and hold in the bullet, put into baking oven and took out in aging 10 days at 200 ℃, under 90 ℃ of water bath condition, the Luo Shi method is measured aging back said composition latherability and is seen table 7 with foam scanner measurement its transformation period result.
Table 7
| X (weight) % | 0.3 | 0.3 |
| Y (weight) % | 0.15 | 0.15 |
| Z (weight) % | 0 | 0.1 |
| Foam number (mL) | 380 | 390 |
| Transformation period (min) | 5.6 | 6 |
[embodiment 9]
Get octodecyl alcohol polyoxyethylene (10) ether Supragil GN 0.3% in [embodiment 7]; X 2073 0.15%; The foaming agent combination that water are formed recklessly 12 injects in diethylolamine 0.1%, Zhongyuan Oil Field five factories of recovering the oil, and under [embodiment 3] experiment condition, carries out the sealing characteristics evaluation experimental; 110 ℃ are measured shutoff pressure reduction is 1.15MPa, and calculating resistance factor is 28.8.
Claims (5)
1. foaming agent combination comprises following component in parts by weight:
(1) 0.1～1 part AEO benzene sulfonate;
(2) 0.1～1 parts sulfonated alkylbenzene;
(3) 90～100 parts water;
AEO benzene sulfonate wherein has following general molecular formula:
In the formula, M is basic metal, earth alkali metal or ammonium, and R is C
8～C
24Alkyl, n is the arbitrary integer in 3～20.
2. foaming agent combination according to claim 1 is characterized in that described basic metal is sodium; R is C
12～C
18Alkyl; N is the arbitrary integer in 3～15.
3. foaming agent combination according to claim 1 is characterized in that by weight percentage, and AEO benzene sulfonate consumption is 0.1～1.0%.
4. foaming agent combination according to claim 1 is characterized in that by weight percentage, and the consumption of sulfonated alkylbenzene is 0.1～1.0%.
5. the described foaming agent combination of claim 1 is applied in the foam flooding intensified oil reduction.
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