CN102277146B - Composition for improving recovery ratio substantially and preparation method thereof - Google Patents
Composition for improving recovery ratio substantially and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a composition for improving a recovery ratio substantially and a preparation method thereof. The invention mainly aims to solve the problems of poor oil displacement efficiency, high using concentration and corrosion and scale depositing damage to strata and oil wells due to alkali in ternary combination flooding under the condition of high temperature and high salt in a surfactant-containing oil displacement agent in the prior art. The oil displacement composition for tertiary oil recovery comprises the following components in percentage by weight: 0.01 to 5.0 percent of alkylphenol ethoxylate carboxylate betaine surfactant, 0.01 to 3.0 percent of polymer and 92.0 to 99.98 percent of water, wherein a molecular general formula of the alkylphenol ethoxylate carboxylate betaine surfactant is shown as the specification, R is alkyl having 5 to 15 carbon atoms, n which is the addition number of ethoxy groups is one integral number of between 2 and 20; M may be one of potassium, sodium and lithium; and the polymer may be one of polyacrylamide with ultrahigh molecular weight, a temperature-resistant and salt-resistant polymer A and xanthan gum. By the technical scheme, the problems are better solved. The composition can be used for the production of tertiary oil recovery in oil fields.
Description
Technical field
The present invention relates to a kind of composition and method of making the same that increases substantially recovery ratio.
Background technology
Along with socioeconomic development, oil is just becoming more and more valuable as non-renewable resource.The problem faced has one, and imbalance between supply and demand is outstanding, and the petroleum demand amount is more larger, and find is fewer and feweri; Two, also left in exhausted oil reservoir have a substantial oil.Primary oil recovery (POR) but the underground crude oil of extraction 10～25%, secondary oil recovery (SOR) but the underground crude oil of extraction 15～25%, i.e. a primary oil recovery and secondary oil recovery extraction 25～50% underground crude oil.In order to guarantee oil supply steady in a long-term, must research and development to improve petroleum recovery technology, tertiary oil recovery (EOR), by the intensified oil reduction measure, can make oil recovery factor improve 6～20% again, even more.
Chemical flooding is an important method that improves recovery ratio.Surfactant flooding is considered to improve by a relatively large margin a kind of chemical agent of recovery ratio, applied widely, tool development prospect.No matter tensio-active agent is as host or as the auxiliary agent displacement of reservoir oil, to increasing substantially recovery ratio, all plays immeasurable effect.Polymer displacement of reservoir oil tech is a kind of method of important raising oil recovery, with general water drive, compares, and polymer flooding can accelerate oil recovery process, improves economic benefit, and Processes and apparatus is simple, cost is lower.As an important technology in chemical flooding, the ASP Oil-Displacing Technology that polymkeric substance, tensio-active agent and alkali form has carried out some field tests in China and foreign countries, has obtained good oil displacement efficiency.But the adding of alkali cause in field test occurring the problems such as the fouling of producing well pit shaft is serious, Produced Liquid difficult treatment, make the application prospect of ASP Oil-Displacing Technology allow of no optimist.By contrast, in the binary combination flooding formula that polymkeric substance and tensio-active agent form, do not use alkali, the mining site operability is stronger, thereby is subject to the approval in oil field.But due to need not any alkali, crude oil PetroChina Company Limited. acids active substance can not be fully used, so that research and development have novel surfactant and an alkali-free binary combination flooding formula of high surface more is imperative.
The Surfactant Industry product of external used for tertiary oil recovery mainly contains two large classes: the one, and sulfonated petro-leum is main tensio-active agent, the 2nd, alkylbenzene sulfonate is main tensio-active agent, this two classes tensio-active agent raw material is all taken from crude oil, raw material sources are wide, quantity is large, thereby are also the tensio-active agents of external tertiary oil recovery consumption maximum.Because sulfonate surfactant is anionic, it and the divalent cation (Ca in local water
2+, Mg
2+deng) can precipitate, work as Ca
2+, Mg
2+just lose oil displacement efficiency while surpassing 300 μ g/g.For this reason, also in continual exploitation research, be applicable to high saliferous, high Ca abroad
2+, Mg
2+the tensio-active agent that the ion stratum is used, comprise the research of betaine type amphoteric surfactant, Gemini surface active agent and sacrifice agent, and focus on the composition research of various tensio-active agents.
In recent years, it is found that the betaine type surfactivity had good table, interfacial activity, can form than low interfacial tension at water-oil interface.Simultaneously, due to its Stability Analysis of Structures, metal ion is had to huge legendary turtle cooperation use, thereby can attempt the oil reservoir displacement of reservoir oil for high salinity, comparatively high temps.In addition, another characteristics of betaine type amphoteric surfactant are that its foaming properties is affected not quite by the pH of salinity and medium, thus can be in salinity higher or in pH scope widely for foam flooding, thereby cause great concern.Betaine type amphoteric surfactant with interface performance and rheological, be expected to replace the alkali in the ternary composite driving formula, under rational formula system, finally realizes binary displacement system, for the chemical flooding in oil field is opened up new approach.
In addition, in existing ternary composite oil-displacing system, the alkali that contains high density, as sodium hydroxide, sodium carbonate etc., in use, to bringing huge injury in stratum and oil well etc., the tensio-active agent used is difficult for being biodegradable, and human body is also had to certain hazardness, as: 1991, Zhao Guoxi was at " tensio-active agent physical chemistry " P495; 1994, disclosed content in Liu Cheng " tensio-active agent complete works " P35.So for those harsh oil reservoirs, we ought to seek a kind of under alkali-free, high temperature (formation temperature is greater than 85 ℃), high salt (more than salinity 40000mg/L) condition Stability Analysis of Structures, and can form 10 with crude oil
-3～10
-4the mN/m ultra low interfacial tension, effectively improve the displacing surfactant system of oil recovery factor.
Summary of the invention
One of technical problem to be solved by this invention is containing the oil-displacing agent of tensio-active agent, to exist under the high temperature and high salt condition oil displacement efficiency poor in prior art, the corrosion that in the high and ternary composite driving of working concentration, alkali brings stratum and oil well and the problem of incrustation injury, provide a kind of composition of new increased substantially recovery ratio.Said composition, for oil displacement process, has alkali-free, corrosion-free and incrustation injury, and working concentration is low, the high characteristics of oil displacement efficiency under the high temperature and high salt condition.Two of technical problem to be solved by this invention is to provide a kind of preparation method of composition of the raising recovery ratio corresponding with one of technical solution problem.
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 composition that increases substantially recovery ratio comprises following component by weight percentage:
(1) 0.01～5.0% alkylphenol polyoxyethylene ether carboxylate type betaine;
(2) 0.01～3.0% polymkeric substance;
(3) 92.0～99.98% water;
Wherein the general molecular formula of component (1) is:
In formula: R is C
5～C
15alkyl, the adduction number that n is ethoxy group EO, its span is any one integer in 2～20; M is any one metal ion be selected from potassium, sodium or lithium.
In technique scheme, the total mineralization preferable range of water is 16000～40000mg/L, Ca
2++ Mg
2+preferable range is 0～1200mg/L.Polymkeric substance is selected from super high molecular weight polyacrylamide and temperature resistant antisalt polymer A, and (by acrylamide, 2-acrylamide-2-methylpro panesulfonic acid, 2-acrylamido dodecyl sodium sulfonate and four kinds of monomer copolymerizations of allyl group oleyl ether, formed, its molar percentage preferable range is (76～83): (7～18): (5～8): a kind of 1) or in xanthan gum.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: a kind of preparation method who increases substantially the composition of recovery ratio comprises the following steps:
A) preparation of haloalkyl phenol polyethenoxy ether:
By alkylphenol polyoxyethylene and thionyl chloride, in mol ratio, be 0.1～5: 1, temperature of reaction is 20～150 ℃, reacts 4～12 hours, and reaction obtains the haloalkyl phenol polyethenoxy ether after finishing after treatment;
B) alkylphenol polyoxyethylene-N, the preparation of N-dimethyl amine:
By haloalkyl phenol polyethenoxy ether and the dimethylamine agueous solution of synthesized in a), in temperature, be 30～150 ℃, to react 2～20 hours, reaction obtains alkylphenol polyoxyethylene-N, the N-dimethyl amine after finishing after treatment;
C) preparation of alkylphenol polyoxyethylene ether hydroxyl sulfonate type betaine:
By b) in the alkylphenol polyoxyethylene-N of synthesized, N-dimethyl amine and sodium chloroacetate, under 60～100 ℃, react and within 2～8 hours, obtain target product;
D) alkylphenol polyoxyethylene ether carboxylate type betaine of aequum, above-mentioned temperature resistant antisalt polymer A and water are evenly mixed, stirring at room 1～3 hour, obtain required composition, by weight percentage, the proportioning of alkylphenol polyoxyethylene ether carboxylate type betaine, above-mentioned temperature resistant antisalt polymer A water is 0.01～5.0%: 0.01～3.0%: 92.0～99.98%.
In technique scheme, a) in the step, the mol ratio preferable range of alkylphenol polyoxyethylene and excessive thionyl chloride is 1～3: 1, and the temperature of reaction preferable range is 50～120 ℃, and the reaction times preferable range is 10 hours; B) in step, the temperature preferable range is 70～90 ℃, and the reaction times preferable range is 10 hours; C) step reaction temperature and reaction times preferable range are under 60～80 ℃ 2～3 hours, then are warming up under 85～100 ℃ and continue reaction 2～4 hours.(d) in step, by weight percentage, the consumption preferable range of alkylphenol polyoxyethylene ether carboxylate type betaine is 0.03～1.0%, and more preferably scope is 0.1～0.3%; Above-mentioned temperature resistant antisalt polymer A molecular weight preferable range is 1,500 ten thousand～2,500 ten thousand, and the consumption preferable range is 0.05～0.5%; More preferably scope is 0.1～0.2%, and the churning time preferable range is 1.5～2.5 hours.
Alkylphenol polyoxyethylene ether carboxylate type betaine in the composition of the increased substantially recovery ratio that the present invention is prepared, owing to containing zwitterion group and nonionic block in its molecular structure simultaneously, make the salt tolerant advantage of its heat resistance that has ionic surface active agent concurrently and nonionogenic tenside, there are again the features such as micelle-forming concentration is low, reduction interfacial tension ability is strong, anti-high salinity, there is the performance more better than conventional surfactant.
Adopting the present invention can increase substantially the composition of recovery ratio, under the alkali-free condition, is that 70 ℃, salinity surpass 30000 mg/litre, Ca for formation temperature
2+, Mg
2+be Shengli Oil Field Crude Oil at Sea and the water of 420～1170 mg/litre, the consumption of take forms the above-mentioned composition oil-displacing agent as 0.1～0.3wt% alkylphenol polyoxyethylene ether carboxylate type betaine and the above-mentioned temperature resistant antisalt polymer A of 0.1～0.2wt%, measure the dynamic interface tension value between this oil-displacing agent aqueous solution and Shengli Oil Field Crude Oil at Sea, can reach 10
-3the ultra low interfacial tension of mN/m can improve oil recovery factor through physical simulation displacement test Lab-evaluation this oil-displacing agent on high temperature, high salinity reservoir and can reach 10% left and right on the water drive basis, has obtained technique effect preferably.
Synthetic product of the present invention can characterize by the following method, and by after purification of products, application U.S. Nicolet-5700 infrared spectrometer, adopt liquid-film method to carry out Infrared spectroscopy (surface sweeping scope 4000～400cm
-1), and spectrogram is contrasted with the standard infrared spectrum, determine the chemical structure of sample, to reach the Infrared Characterization to compound of the present invention.The infrared spectrum that Fig. 1 is alkylphenol polyoxyethylene carboxylic acid sodium type trimethyl-glycine.In Fig. 1,3350cm
-1the stretching vibration (being mainly that product is the aqueous solution) that left and right place is-OH, 1600cm
-1the place, left and right is phenyl ring, 1249cm
-1place is aryl oxide C-O-C, 1070～1160cm
-1place has EO to exist, 1083～1192cm
-1place is the stretching vibration of C-N, 1550～1610cm
-1for-the COO-stretching vibration, prove that the synthetic product of the present invention is a kind of alkylphenol polyoxyethylene ether carboxylate type betaine really.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
1) chloro amyl group (R=5) phenol polyethenoxy (n=2) ether is synthetic
In being housed, the four-hole round-bottomed flask of reflux condensate device, thermometer, agitator and gas absorbing device adds 100g amyl group (R=5) phenol polyethenoxy (n=2) ether and 57g pyridine, be heated to 70 ℃ under stirring, slowly drip the 85g thionyl chloride with dropping funnel, react 10 hours under 90 ℃ after dropwising.After reaction finishes, by standing, the cooling layering of reactant, upper organic phase is target product, and lower floor is solid hydrochloric acid pyridinium salt.Sodium hydroxide solution with 30% is neutralized to neutrality or weakly alkaline by upper organic phase, separate inorganic salt, by hot saturated common salt water washing 5～6 times for upper organic phase, obtain intermediate product chloro amyl group (R=5) phenol polyethenoxy (n=2) ether after drying again, yield is 88%.
2) amyl group (R=5) phenol polyethenoxy (n=2) ether-N, N-dimethyl amine synthetic
Chloro amyl group (R=5) phenol polyethenoxy (n=2) ether 70g synthetic in step (1) is added in the four-hole boiling flask with reflux condensate device, thermometer, agitator, be heated to 77 ℃, with ethanol, dimethylamine agueous solution (33wt%) is diluted to 16wt% (be mainly and prevent dimethylamine transition volatilization), then with dropping funnel, slowly drip in flask, after dropwising 1 hour, add the hydrogen chloride gas of 2g solid sodium hydroxide in order to the absorption reaction generation in system, and measure now system pH; After reacting again 1 hour, then add the 2g solid sodium hydroxide, make system remain weakly alkaline, react after 10 hours and finish, stratification.Upper strata is organic phase, and lower floor is water.The upper organic phase underpressure distillation is removed to unnecessary dimethylamine, ethanol, then use hot saturated common salt water washing 5～6 times, obtain target intermediate product amyl group (R=5) phenol polyethenoxy (n=2) ether-N, the N-dimethyl amine, yield is 83%.
3) amyl group (R=5) phenol polyethenoxy (n=2) ether carboxylic acid sodium trimethyl-glycine is synthetic
By step 2) in synthetic amyl group (R=5) phenol polyethenoxy (n=2) ether-N, N-dimethyl amine 40g joins in the four-hole boiling flask with reflux condensate device, thermometer, agitator, be heated to 70 ℃, slowly drip 70% sodium chloroacetate aqueous solution 66g, under 70 ℃, reaction is after 2 hours, be warming up to 90 ℃ and continue reaction 6 hours until reaction finishes, during add appropriate normal-butyl bromination ammonium and ethanol, to guarantee two-phase, fully mix.After reaction finishes, ethanol and a small amount of water are fallen in underpressure distillation, obtain thick liquid, are ultimate aim product amyl group (R=5) phenol polyethenoxy (n=2) ether carboxylic acid sodium trimethyl-glycine.
4) the marine block water of synthetic amyl group (R=5) phenol polyethenoxy (n=2) ether carboxylic acid sodium trimethyl-glycine 0.15wt%, temperature resistant antisalt polymer A (molecular weight 2,500 ten thousand) 0.15wt% and the 97.0wt% Shengli Oil Field mix and blend 2 hours by step (3), obtain the composition that a kind of displacement of reservoir oil of homogeneous transparent is used.At temperature 70 C, salinity 30000mg/L, Ca
2++ Mg
2+in the water of 890mg/L, the apparent viscosity that records this composition is 15.5mPa.s; Form the ultra low interfacial tension of 0.0091mN/m between the marine block crude oil of said composition and Shengli Oil Field.Apparent viscosity is by the BROODFIELD II type viscometer determining of U.S. Brookfield company, and interfacial tensimeter mensuration is dripped in the TX500 type rotation that interfacial tension is produced by Texas ,Usa university.
[embodiment 2]
Synthesizing of nonyl (R=9) phenol polyethenoxy ether (n=10) carboxylic acid sodium type trimethyl-glycine
1) chloro nonyl (R=9) phenol polyethenoxy (n=10) ether is synthetic
In being housed, the four-hole round-bottomed flask of reflux condensate device, thermometer, agitator and gas absorbing device adds 100g nonyl (R=9) phenol polyethenoxy (n=10) ether and 22g pyridine, be heated to 70 ℃ under stirring, slowly drip the 32.5g thionyl chloride with dropping funnel, react 8 hours under 70 ℃ after dropwising.After reaction finishes, by standing, the cooling layering of reactant, upper organic phase is target product, and lower floor is solid hydrochloric acid pyridinium salt.Sodium hydroxide solution with 30% is neutralized to neutrality or weakly alkaline by upper organic phase, separate inorganic salt, by hot saturated common salt water washing 5～6 times for upper organic phase, obtain intermediate product chloro nonyl (R=9) phenol polyethenoxy (n=10) ether after drying again, yield is 85%.
2) nonyl (R=9) phenol polyethenoxy (n=10) ether-N, N-dimethyl amine synthetic
Chloro nonyl (R=9) phenol polyethenoxy (n=10) ether 70g synthetic in step (1) is added in the four-hole boiling flask with reflux condensate device, thermometer, agitator, be heated to 85 ℃, with ethanol, dimethylamine agueous solution (33wt%) is diluted to 16wt% (be mainly and prevent dimethylamine transition volatilization), then with dropping funnel, slowly drip in flask, after dropwising 1 hour, add the hydrogen chloride gas of 2g solid sodium hydroxide in order to the absorption reaction generation in system, and measure now system pH; After reacting again 1 hour, then add the 2g solid sodium hydroxide, make system remain weakly alkaline, react after 6 hours and finish, stratification.Upper strata is organic phase, and lower floor is water.The upper organic phase underpressure distillation is removed to unnecessary dimethylamine, ethanol, then use hot saturated common salt water washing 5～6 times, obtain target intermediate product nonyl (R=9) phenol polyethenoxy (n=10) ether-N, the N-dimethyl amine, yield is 80%.
3) nonyl (R=9) phenol polyethenoxy (n=10) ether carboxylic acid sodium trimethyl-glycine is synthetic
By step 2) in synthetic nonyl (R=9) phenol polyethenoxy (n=10) ether-N, N-dimethyl amine 56g joins in the four-hole boiling flask with reflux condensate device, thermometer, agitator, be heated to 70 ℃, slowly drip sodium chloroacetate aqueous solution 76g, under 70 ℃, reaction is after 2 hours, be warming up to 90 ℃ and continue reaction 6 hours until reaction finishes, during add appropriate normal-butyl bromination ammonium and ethanol, to guarantee two-phase, fully mix.After reaction finishes, ethanol and a small amount of water are fallen in underpressure distillation, obtain thick liquid, are ultimate aim product nonyl (R=9) phenol polyethenoxy (n=10) ether carboxylic acid sodium trimethyl-glycine.
4), by step (3) synthetic nonyl (R=9) phenol polyethenoxy (n=10) ether carboxylic acid sodium trimethyl-glycine 0.15wt%, temperature resistant antisalt polymer A (molecular weight 2,500 ten thousand) 0.15wt% and the marine block water of 97.0wt% Shengli Oil Field mix and blend 2 hours, obtain the composition that a kind of displacement of reservoir oil of homogeneous transparent is used.At temperature 70 C, salinity 30000mg/L, Ca
2++ Mg
2+in the water of 1100mg/L, the apparent viscosity that records this composition is 14.8mPa.s; Form the ultra low interfacial tension of 0.0068mN/m between the marine block crude oil of said composition and Shengli Oil Field.Apparent viscosity is by the BROODFIELD II type viscometer determining of U.S. Brookfield company, and interfacial tensimeter mensuration is dripped in the TX500 type rotation that interfacial tension is produced by Texas ,Usa university.
[embodiment 3]
Synthesizing of dodecyl phenol polyethenoxy ether (n=20) carboxylic acid sodium type trimethyl-glycine
1) chlorinated dodecane base phenol polyethenoxy (n=20) ether is synthetic
In being housed, the four-hole round-bottomed flask of reflux condensate device, thermometer, agitator and gas absorbing device adds 100g dodecyl phenol polyethenoxy (n=20) ether and 13g pyridine, be heated to 60 ℃ under stirring, slowly drip the 18.7g thionyl chloride with dropping funnel, react 10 hours under 80 ℃ after dropwising.After reaction finishes, by standing, the cooling layering of reactant, upper organic phase is target product, and lower floor is solid hydrochloric acid pyridinium salt.Sodium hydroxide solution with 30% is neutralized to neutrality or weakly alkaline by upper organic phase, separate inorganic salt, by hot saturated common salt water washing 5～6 times for upper organic phase, obtain intermediate product chlorinated dodecane base phenol polyethenoxy (n=20) ether after drying again, yield is 81%.
2) dodecyl phenol polyethenoxy (n=20) ether-N, N-dimethyl amine synthetic
Chlorinated dodecane base phenol polyethenoxy (n=20) ether 70g synthetic in step (1) is added in the four-hole boiling flask with reflux condensate device, thermometer, agitator, be heated to 80 ℃, with ethanol, dimethylamine agueous solution (33wt%) is diluted to 16wt% (be mainly and prevent dimethylamine transition volatilization), then with dropping funnel, slowly drip in flask, after dropwising 1 hour, add the hydrogen chloride gas of 2g solid sodium hydroxide in order to the absorption reaction generation in system, and measure now system pH; After reacting again 1 hour, then add the 2g solid sodium hydroxide, make system remain weakly alkaline, react after 10 hours and finish, stratification.Upper strata is organic phase, and lower floor is water.The upper organic phase underpressure distillation is removed to unnecessary dimethylamine, ethanol, then use hot saturated common salt water washing 5～6 times, obtain target intermediate product dodecyl phenol polyethenoxy (n=20) ether-N, the N-dimethyl amine, yield is 83%.
3) dodecyl phenol polyethenoxy (n=20) ether carboxylic acid sodium trimethyl-glycine is synthetic
By step 2) in synthetic dodecyl phenol polyethenoxy (n=20) ether-N, N-dimethyl amine 40g joins in the four-hole boiling flask with reflux condensate device, thermometer, agitator, be heated to 75 ℃, slowly drip 70% sodium chloroacetate aqueous solution 60g, under 75 ℃, reaction is after 2 hours, be warming up to 85 ℃ and continue reaction 4 hours until reaction finishes, during add appropriate normal-butyl bromination ammonium and ethanol, to guarantee two-phase, fully mix.After reaction finishes, ethanol and a small amount of water are fallen in underpressure distillation, obtain thick liquid, are ultimate aim product dodecyl phenol polyethenoxy (n=20) ether carboxylic acid sodium trimethyl-glycine.
4) the marine block water of dodecyl phenol polyethenoxy (n=20) ether carboxylic acid sodium trimethyl-glycine 0.15wt%, temperature resistant antisalt polymer A (molecular weight 2,500 ten thousand) 0.15wt% and 97.0wt% Shengli Oil Field mix and blend is 2 hours, obtains the composition that a kind of displacement of reservoir oil of homogeneous transparent is used.At temperature 70 C, salinity 30000mg/L, Ca
2++ Mg
2+in the water of 580mg/L, the apparent viscosity that records this composition is 18.5mPa.s.; Form the ultra low interfacial tension of 0.0056mN/m between the marine block crude oil of said composition and Shengli Oil Field.Apparent viscosity is by the BROODFIELD II type viscometer determining of U.S. Brookfield company, and interfacial tensimeter mensuration is dripped in the TX500 type rotation that interfacial tension is produced by Texas ,Usa university.
[embodiment 4～6]
The composition of increased substantially recovery ratio prepared by [embodiment 1～3], be 30 centimetres in length, and diameter is 2.5 centimetres, and rate of permeation is 1.5 microns
2rock core on carry out the imitation oil displacement experiment test.First with the marine block local water of Shengli Oil Field, be driven to moisture 92%, record water drive and can improve oil recovery factor 40.3～41.4%, again after the composition of the increased substantially recovery ratio of metaideophone 0.3pv (rock pore volume) [embodiment 1～3], water drive is to moisture 100%, record on the water drive basis and can improve again oil recovery factor 10～11.2%, the results are shown in Table shown in 1.
[comparative example 1]
With [embodiment 1] (d), difference substitutes 0.15wt% alkylphenol polyoxyethylene carboxylic acid sodium trimethyl-glycine with the oil-based betaine of 0.15wt%, all the other are identical, the apparent viscosity that records this composition is 14.2mPa.s, forms the interfacial tension of 0.0812mN/m between said composition and Shengli Oil Field Crude Oil at Sea.Apparent viscosity is by the BROODFIELD II type viscometer determining of U.S. Brookfield company, and interfacial tensimeter mensuration is dripped in the TX500 type rotation that interfacial tension is produced by Texas ,Usa university.
The above-mentioned displacement of reservoir oil composition made carries out the displacement of reservoir oil with the method with [embodiment 4], records water drive and can improve oil recovery factor 40.3%, after the above-mentioned displacement of reservoir oil composition of metaideophone, can improve oil recovery factor 5.6% on the water drive basis again, the results are shown in Table shown in 1.
[comparative example 2]
With [embodiment 1] (d), difference be take the super high molecular weight polyacrylamide (viscosity-average molecular weight is 2,500 ten thousand) of 0.15wt% and is substituted the above-mentioned temperature resistant antisalt polymer A (molecular weight 2,500 ten thousand) of 0.15wt%, all the other are identical, the apparent viscosity that records this composition is 10.5mPa.s, forms the interfacial tension of 0.0523mN/m between said composition and Shengli Oil Field Crude Oil at Sea.Apparent viscosity is by the BROODFIELD II type viscometer determining of U.S. Brookfield company, and interfacial tensimeter mensuration is dripped in the TX500 type rotation that interfacial tension is produced by Texas ,Usa university.
The above-mentioned displacement of reservoir oil composition made carries out the displacement of reservoir oil with the method with [embodiment 4], records water drive and can improve oil recovery factor 40.5%, after the above-mentioned displacement of reservoir oil composition of metaideophone, can improve oil recovery factor 6.2% on the water drive basis again, the results are shown in Table shown in 1.
Table 1 different compositions is to the marine block oil displacement test of Shengli Oil Field result
| Sequence number | Tensio-active agent title and consumption, wt% | Polymkeric substance title and consumption, wt% | Water drive improves oil recovery factor, % | Composition drives and improves oil recovery factor, % again |
| Embodiment 4 | Amyl group (R=5) phenol polyethenoxy (n=2) ether carboxylic acid sodium trimethyl-glycine | Above-mentioned temperature resistant antisalt polymers A0.15 | 41.2 | 10.2 |
| Embodiment 5 | Nonyl (R=9) phenol polyethenoxy (n=10) ether carboxylic acid sodium trimethyl-glycine | The same 0.15 | 40.6 | 11.1 |
| Embodiment 6 | Dodecyl phenol polyethenoxy (n=20) ether carboxylic acid sodium trimethyl-glycine | The same 0.15 | 41.4 | 10.8 |
| Comparative example 1 | Oil-based betaine | The same 0.15 | 40.3 | 5.6 |
| Comparative example 2 | Amyl group (R=5) phenol polyethenoxy (n=2) ether carboxylic acid sodium trimethyl-glycine 0.15 | Super high molecular weight polyacrylamide (viscosity-average molecular weight is 2,500 ten thousand) 0.15 | 40.5 | 6.2 |
Claims (5)
1. the composition that can increase substantially recovery ratio comprises following component by weight percentage:
(1) 0.01～5.0% alkyl phenol polyoxyethylene ether carboxylate type beet alkali surface activator;
(2) 0.01～3.0% polymkeric substance;
(3) 92.0～99.98% water;
Wherein the general molecular formula of (1) component is:
In formula: R is C
5～C
15alkyl, the adduction number that n is ethoxy group EO, its span is any one integer in 2～20; M is any one metal ion be selected from potassium, sodium or lithium; Described polymkeric substance is the temperature resistant antisalt polymer A, wherein the temperature resistant antisalt polymer A is formed by acrylamide, 2-acrylamide-2-methylpro panesulfonic acid, 2-acrylamido dodecyl sodium sulfonate and four kinds of monomer copolymerizations of allyl group oleyl ether, its molar percentage is (76～83): (7～18): (5～8): 1, and molecular weight is 15,000,000～25,000,000.
2. the composition that increases substantially recovery ratio according to claim 1, the total mineralization that it is characterized in that described water is 16000～40000mg/L, Ca
2++ Mg
2+be 0～1200mg/L.
3. the preparation method who increases substantially the composition of recovery ratio claimed in claim 1 comprises the following steps:
A) preparation of haloalkyl phenol polyethenoxy ether:
By alkylphenol polyoxyethylene and thionyl chloride, in mol ratio, be 0.1～5:1, temperature of reaction is 20～150 ℃, reacts 4～12 hours, and reaction obtains the haloalkyl phenol polyethenoxy ether after finishing after treatment;
B) alkylphenol polyoxyethylene-N, the preparation of N-dimethyl amine:
By haloalkyl phenol polyethenoxy ether and the dimethylamine agueous solution of synthesized in a), in temperature, be 30～150 ℃, to react 2～20 hours, reaction obtains alkylphenol polyoxyethylene-N, the N-dimethyl amine after finishing after treatment;
C) preparation of alkylphenol polyoxyethylene ether hydroxyl sulfonate type betaine:
By b) in the alkylphenol polyoxyethylene-N of synthesized, N-dimethyl amine and sodium chloroacetate, under 60～100 ℃, react and within 2～8 hours, obtain target product;
D) alkylphenol polyoxyethylene ether carboxylate type betaine of aequum, above-mentioned temperature resistant antisalt polymer A and water are evenly mixed, stirring at room 1～3 hour, obtain required composition, by weight percentage, alkylphenol polyoxyethylene ether carboxylate type betaine, above-mentioned temperature resistant antisalt polymer A, the proportioning of water are 0.01～5.0%:0.01～3.0%:92.0～99.98%.
4. the preparation method who increases substantially the composition of recovery ratio according to claim 3, is characterized in that a) step reaction temperature preferable range is 50～120 ℃, and the reaction times is preferably 10 hours; B) in step, preferred temperature is 70～90 ℃, and the reaction times is preferably 10 hours; C) step reaction temperature and reaction times be preferably 70 ℃ lower 2 hours, then be warming up under 90 ℃ and continue reaction 2～6 hours; (d), in step, by weight percentage, the consumption preferable range of alkylphenol polyoxyethylene ether carboxylate type betaine is 0.03～1.0%; Above-mentioned temperature resistant antisalt polymer A molecular weight is preferably 2,500 ten thousand, and the consumption preferable range is 0.05～0.5%; Churning time is preferably 1.5～2.5 hours.
5. the preparation method who increases substantially the composition of recovery ratio according to claim 4, is characterized in that in (d) step, and by weight percentage, the consumption preferable range of alkylphenol polyoxyethylene ether carboxylate type betaine is 0.1～0.3%; Above-mentioned temperature resistant antisalt polymer A preferable range is 0.1～0.2%.
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