CN102020981A - Temperature-resistant, salt-resistant and low-tension foam flooding agent and preparation method thereof - Google Patents
Temperature-resistant, salt-resistant and low-tension foam flooding agent and preparation method thereof Download PDFInfo
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- CN102020981A CN102020981A CN2010105219534A CN201010521953A CN102020981A CN 102020981 A CN102020981 A CN 102020981A CN 2010105219534 A CN2010105219534 A CN 2010105219534A CN 201010521953 A CN201010521953 A CN 201010521953A CN 102020981 A CN102020981 A CN 102020981A
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Abstract
The invention relates to a temperature-resistant, salt-resistant and low-tension foam flooding agent and a preparation method thereof. The temperature-resistant, salt-resistant and low-tension foam flooding agent is prepared by continuously stirring alkanolamide, bipolar surfactant and water at 40-60DEG C until the alkanolamide, the bipolar surfactant and the water are completely dissolved. The temperature-resistant, salt-resistant and low-tension foam flooding agent provided by the invention is suitable for tertiary recovery under the conditions that the temperature is 50-120DEG C and the mineralization is 0-100000ppm. Compared with other common foam agents in the prior art, the oil-water interfacial tension is reduced from 10<-2>mN.m<-1> to 10<-3>mN.m<-1>; and compared with common interfacial active agents in the prior art, the half foam life period at 50DEG C is increased from 15 minutes to more than 40minutes, and the recovery ratio of an indoor model is increased by more than 15%.
Description
Technical field
The invention belongs to the oilfield chemistry field, relate to the used for tertiary oil recovery chemical oil displacement agent, be specifically related to can be used for the disposable tertiary oil recovery system that increases substantially recovery ratio of conventional oil reservoir high water-cut development later stage and high temperature and high salt oil deposit.
Background of invention
The whole world has all entered the exploitation later stage above the oil field of 30 maximum-norms at present, adopts technique means further to improve recovery ratio, i.e. tertiary oil recovery has been the technical measures that will carry out by generally acknowledging.
Existing studies show that, restriction crude oil is capillary effect and reservoir heterogeneity with the low principal contradiction of secondary oil recovery process recovery ratio once.Capillary effect is detained crude oil and is difficult to effectively be driven in sidewalk for visually impaired people and fine porosity, reservoir heterogeneity then causes displacement system sweep efficiency low, and the crude oil of hyposmosis band can't be driven.
Gas drive is development in recent years one of tertiary oil recovery technology the most rapidly, and alkane, carbonic acid gas, nitrogen even air all can be used as the displacing agent of gas drive.But because low density, low viscosity and the high workability of gas are compared with water drive, be subjected to the influence of reservoir heterogeneity bigger, be very easy to the fingering phenomenon takes place, can't involve the hyposmosis zone, raising recovery ratio effect is restricted.
By adding tensio-active agent, make the form displacement of gas with aerated fluid, be reduced in the velocity of flow in the most permeable zone by the increase of aerated fluid apparent viscosity, improve sweep efficiency, can improve recovery ratio.Because foaming agent itself is a tensio-active agent, have interfacial activity again,, enlarge markedly the hollow billet number, can bring into play better effect, increase substantially recovery ratio once if can reduce oil/water termination tension force to ultralow.
The characteristic of aerated fluid has determined optionally shutoff high permeability path of foam, can reduce height oozes the current capacity in district and does not destroy hypotonic district, and has oil/water selectivity, shutoff current and not shutoff oil stream, the realization because the optimization of the heatproof of foaming agent, anti-salt property also is not difficult in addition, therefore under the situation that the development of temperature resistant antisalt polymkeric substance can not get breaking through, foam has unrivaled application potential undoubtedly aspect the shutoff profile control.Particularly, have more the meaning of particularly important for the exploitation of high temperature and high salt oil deposit.
Tensio-active agent is in the enrichment behavior of gas/water, oil/water termination, determine by molecular structure, but structure activity relationship and mechanism are different, and be subjected to environmental factors, comprise the influence of factors such as gas phase composition, oil phase composition, temperature, salinity, additive, therefore to be optimized simultaneously be a difficult problem for froth stability and water-oil interface activity, not only had good foam stability but also had the active low-tension foam system of high water-oil interface extremely to lack.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of temperature resistant antisalt low-tension foam flooding finish and preparation method thereof.
The present invention is the froth stability excellence not only, and shutoff profile control ability is strong, and interfacial activity is strong, the crude oil/water interfacial tension can be reduced to ultralowly, and it is remarkable to improve the recovery ratio effect.
Technical scheme of the present invention is as follows:
A kind of temperature resistant antisalt low-tension foam flooding finish, raw materials quality part is composed as follows:
Alkylolamide 40-55 part, bipolarity based surfactants 10-50 part, water 100-200 part.Wherein,
Described alkylolamide is Oleum Cocois alkylolamide, fatty monoethanol amide or Oleum Cocois diethanolamine, wherein preferred Oleum Cocois alkylolamide;
Described bipolarity based surfactants is alkyl two propyloic rice azoles quinolines, alkyl alcohol polyoxyethylene ether sulfate, alkylphenol polyoxyethylene vitriol, sulphonic acid betaine, carboxylic acid trimethyl-glycine or two alkyl diphenyl ether sulfonate, wherein preferred sulphonic acid betaine.
Preferably, a kind of temperature resistant antisalt low-tension foam flooding finish, raw materials quality part is composed as follows:
Alkylolamide 40-50 part, bipolarity based surfactants 20-30 part, water 100-160 part.
Further preferred, a kind of temperature resistant antisalt low-tension foam flooding finish, raw materials quality part is composed as follows:
42 parts of Oleum Cocois alkylolamides, 28 parts of sulphonic acid betaines, 130 parts in water.
Above-mentioned alkylolamide, bipolarity based surfactants are all selected prior art products for use, and market is on sale.Wherein,
Preferably, the Oleum Cocois alkylolamide makes as follows: in synthesis reaction vessel, quantitatively add Oleum Cocois, temperature is controlled at 60-100 ℃, by Oleum Cocois and diethanolamine mass ratio is to reactor in to add diethanolamine at 2.0～1.0: 1, stir, add the KOH of reactant total mass 0.3-1%, be warming up to 100-150 ℃ of reaction 4-6 hour.
The above-mentioned a kind of temperature resistant antisalt low-tension foam flooding finish preparation method of the present invention, step is as follows:
Above-mentioned alkylolamide, bipolarity tensio-active agent are added to the water, under 40-60 ℃, continue stirring until dissolving fully, promptly.
Preferably, a kind of temperature resistant antisalt low-tension foam flooding finish preparation method joins above-mentioned alkylolamide, bipolarity tensio-active agent in the water of 1/3～1/2 total amount, under 40-60 ℃, continue stirring until dissolving fully, water with surplus adds again, stirs, promptly.
The application of temperature resistant antisalt low-tension foam flooding finish of the present invention, being used for temperature 50-120 ℃, salinity is 0-100, the tertiary oil recovery under the 000ppm condition.During application, it is that 0.05-0.3wt% injects the down-hole that product of the present invention is assigned to concentration, enters the stratum the generation foam is mixed in the shaft bottom with air or nitrogen after.Compare with other prior art conventional foam agent, oil water interfacial tension is by 10
-2MN.m
-1Reduce to 10
-3MN.m
-1, to compare with the interfacial agent that prior art is commonly used, 50 ℃ of following half foam life periods were brought up to more than 40 minutes by 15 minutes, and indoor model improves recovery ratio and reaches more than 15%.Temperature resistant antisalt low-tension foam flooding finish of the present invention is suitable for calcium ions and magnesium ions total concn 0-1,000ppm.
Temperature resistant antisalt low-tension foaming agent of the present invention has following excellent results:
1, low-tension foaming agent of the present invention, adopt the weak alkylolamide of polar head grappling effect, making surfactant molecule present " lying down " formula on bubble film arranges, therefore the network structure interfacial film stable foam liquid film that utilizes hydrophobic chain to be staggered to form all keeps higher froth stability in conventional temperature to high temperature.
2, low-tension foaming agent of the present invention adopts the high alkylolamide of high bipolarity based surfactants of interface efficient and interphase density composite, obtains high interface and renders a service, and can make the interfacial tension of crude oil and water reduce to ultralow.
3, low-tension foaming agent of the present invention, adopt the good bipolarity based surfactants of salt resistance composite, make the higher salinity of system tolerance, and can utilize of the absorption of the further modulometer surface-active agent of salinity, under high salinity, obtain higher interfacial activity at water-oil interface.
Embodiment
The present invention will be further described below in conjunction with embodiment, but be not limited thereto.
Embodiment 1:
A kind of temperature resistant antisalt low-tension foam flooding finish, raw materials quality part is composed as follows:
42 parts of coconut acid diethanolamides, 28 parts of sulphonic acid betaines, 130 parts in water.Wherein, coconut acid diethanolamide prepares by the following method:
In the 1000L synthesis reaction vessel, add 366 kilograms of Oleum Cocois, in above-mentioned synthesis reaction vessel, add 234 kilograms of diethanolamine while stirring, keeping temperature is 80 ℃, 15g potassium hydroxide after stirring is warming up to 120 ℃ of reactions 5 hours, gets coconut acid diethanolamide.
By mass parts, get 42 parts of above-mentioned coconut acid diethanolamides, add 28 parts of sulphonic acid betaines, add 50 parts of water, under 50 ℃, be stirred to dissolving fully, add 80 parts of water again, stir and promptly get low-tension foam flooding finish, label is LIF-1.
Embodiment 2:
A kind of temperature resistant antisalt low-tension foam flooding finish, raw materials quality part is composed as follows:
49 parts of coconut acid diethanolamides, 21 parts of alkyl alcohol polyoxyethylene ether sulfates, 150 parts in water.Wherein, coconut acid diethanolamide makes by embodiment 1, and the alkyl alcohol polyoxyethylene ether sulfate is a Taiyuan Fa Kai company product, and model is AE3S.
By mass parts, get 49 parts of coconut acid diethanolamides, add 21 parts of alkyl alcohol polyoxyethylene ether sulfates, add 50 parts of water, under 50 ℃, be stirred to dissolving fully, add 100 parts of water again, stir, promptly get low-tension foaming oil oil-displacing agent, label is LIF-2.
Embodiment 3: froth stability and the test of shutoff profile control
It is 0.3% the aqueous solution that foaming agent is formulated as concentration, adopt the air-flow method to produce foam, the frothing machine controlled temperature is 50 ℃, measures lather volume and gets the foam attenuation curve over time, getting the time that lather volume decays to original volume one half is half foam life period, is labeled as t
1/2Froth stability and transformation period are proportional.
Adopt 80-200 order quartz sand filling 55cm simulation core barrel, core volume of voids 32%, rate of permeation 1.5 darcies after water saturation, are injected the aqueous solution and N with the speed of 10ml/min and 160ml/min respectively
2, measure core barrel entrance and exit terminal pressure, get original pressure difference Δ P
Initially=P
Inlet-P
Outlet, inject 0.3% the foaming agent aqueous solution and N then with same speed
2, get pressure difference Δ P
Foam=P
Inlet-P
Outlet, calculate resistance factor δ=Δ P
Foam/ Δ P
InitiallyIn the mensuration process, whole flow process is in temperature T=120 ℃.Foamy shut-off capacity and resistance factor are proportional.
The foaming agent sulfonated is used in contrast, commercial disignation AOS, and market is buied, and Xi'an south wind chemical industry company limited produces.Contrast interfacial agent sulfonated petro-leum PS-1, market is buied, and wins international petroleum chemical industry Group Co.,Ltd in the Shengli Oil Field and produces.
Experimental result is as follows:
Embodiment 4: the interfacial activity of foaming agent
Interfacial tensimeter is dripped in the TEXAS-500 rotation be adjusted to 50 ℃, according to GB SY/T5370-1999 method, measure the interfacial tension of 0.3% foaming agent and comparative sample solution and Shengli Oil Field Sheng Tuo district crude oil, minimum interfacial tension is designated as γ min.Water all adopts Shengli Oil Field to win the block local water that sticks together.The foaming agent strength of solution is 0.3%.
Experimental result is as follows:
Embodiment 5: foam system improves the oil recovery factor effect
Adopt 80-200 order quartz sand filling 55cm simulation core barrel, core volume of voids 28-34%, rate of permeation 1.0-1.8 darcy, after water saturation, saturated Shengli Oil Field wins the crude oil that sticks together, at 80 ℃ down after aging 48 hours, moisture 98% with 80 ℃ of hot-water displacements to output liquid, inject 80 ℃ of hot water and N with the speed of 10ml/min and 160ml/min again
2, displacement 5PV injects 80 ℃ of 0.5% foaming agent aqueous solution and N with the speed of 10ml/min and 160ml/min then
2, displacement to output liquid water ratio is 98%.Flow process all is under 80 ℃ in the entire test.
Test-results is as follows:
Claims (9)
1. temperature resistant antisalt low-tension foam flooding finish is characterized in that raw materials quality part is composed as follows:
Alkylolamide 40-55 part, bipolarity based surfactants 10-50 part, water 100-200 part; Wherein,
Described alkylolamide is Oleum Cocois alkylolamide, fatty monoethanol amide or Oleum Cocois diethanolamine;
Described bipolarity based surfactants is alkyl two propyloic rice azoles quinolines, alkyl alcohol polyoxyethylene ether sulfate, alkylphenol polyoxyethylene vitriol, sulphonic acid betaine, carboxylic acid trimethyl-glycine or two alkyl diphenyl ether sulfonate.
2. oil-displacing agent as claimed in claim 1 is characterized in that raw materials quality part is composed as follows:
Alkylolamide 40-50 part, bipolarity based surfactants 20-30 part, water 100-160 part.
3. oil-displacing agent as claimed in claim 1 or 2 is characterized in that described alkylolamide is the Oleum Cocois alkylolamide.
4. oil-displacing agent as claimed in claim 3 is characterized in that described Oleum Cocois alkylolamide makes by the following method:
In synthesis reaction vessel, quantitatively add Oleum Cocois, temperature is controlled at 60-100 ℃, by Oleum Cocois and diethanolamine mass ratio is to reactor in to add diethanolamine at 2.0～1.0: 1,, stir, the KOH that adds reactant total mass 0.3-1wt% is warming up to 100-150 ℃ of reaction 4-6 hour.
5. oil-displacing agent as claimed in claim 1 or 2 is characterized in that described bipolarity based surfactants is a sulphonic acid betaine.
6. oil-displacing agent as claimed in claim 1 is characterized in that, raw materials quality part is composed as follows:
42 parts of Oleum Cocois alkylolamides, 28 parts of sulphonic acid betaines, 130 parts in water.
7. the preparation method of each described oil-displacing agent of claim 1～5, step is as follows: above-mentioned alkylolamide, bipolarity tensio-active agent are added to the water, continue stirring until dissolving fully under 40-60 ℃, promptly.
8. the preparation method of each described oil-displacing agent of claim 1～5, wherein above-mentioned alkylolamide, bipolarity tensio-active agent are joined in the water of 1/3～1/2 total amount, continue stirring until dissolving fully under 40-60 ℃, the water with surplus adds again, stir, promptly.
9. the application of each described oil-displacing agent of claim 1～6, being used for temperature 50-120 ℃, salinity is 0-100, the tertiary oil recovery under the 000ppm condition.
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