CN102277146A - 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 The development in society and economy, oil is just becoming more and more valuable as non-renewable resource.The problem that faces has one, and imbalance between supply and demand is outstanding, and the petroleum demand amount is big more big more, and find is fewer and feweri; Two, also left in the exhausted oil reservoir have a substantial oil.Primary oil recovery (POR) but extraction 10～25% underground crude oil, secondary oil recovery (SOR) but extraction 15～25% underground crude oil, 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 improve petroleum recovery technology that tertiary oil recovery (EOR) can make oil recovery factor improve 6～20% again by the intensified oil reduction measure, 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, all plays immeasurable effect to increasing substantially recovery ratio.Polymer displacement of reservoir oil tech is a kind of method of important raising oil recovery, compares with general water drive, and polymer flooding can quicken oil recovery process, improves economic benefit, and Processes and apparatus is simple, cost is lower.As an important technology in the chemical flooding, the ternary composite driving oil tech 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 problems such as the fouling of producing well pit shaft is serious, extraction liquid difficult treatment that the adding of alkali causes occurring in the field test make ternary composite oil-displacing The Application of Technology prospect allow of no optimist.By contrast, do not use alkali in the binary combination flooding prescription that polymkeric substance and tensio-active agent form, the mining site operability is stronger, thereby is subjected to the approval in oil field.But because need not any alkali, crude oil PetroChina Company Limited. acids active substance can not be fully used, so that research and development have the novel surfactant and an alkali-free binary combination flooding prescription of high surface more is imperative.
The tensio-active agent industrialization product of external used for tertiary oil recovery mainly contains two big 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 big, thereby also are the tensio-active agents of external tertiary oil recovery consumption maximum.Because sulfonate surfactant is anionic, it and the divalent cation (Ca in the local water
2+, Mg
2+Deng) can precipitate, work as Ca
2+, Mg
2+Just lose oil displacement efficiency when surpassing 300 μ g/g.For this reason, also continuing the suitable high saliferous of development research, high Ca abroad
2+, Mg
2+The tensio-active agent that the ion stratum is used comprises the research of betaine type amphoteric surfactant, Gemini surface active agent and sacrifice agent, and pays attention to the composite 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, owing to its Stability Analysis of Structures, metal ion is had huge legendary turtle cooperation usefulness, thereby can attempt being used for the oil reservoir displacement of reservoir oil of high salinity, comparatively high temps.In addition, another characteristics of betaine type amphoteric surfactant are that its foaming properties is influenced not quite by the pH of salinity and medium, thereby can be in salinity higher or be used for foam flooding in the pH scope widely, thereby cause great concern.Betaine type amphoteric surfactant with interface performance and rheological is expected to replace the alkali in the ternary composite driving prescription, under rational formula system, finally realizes binary displacement system, for the chemical flooding in oil field is opened up new approach.
In addition, in the existing ternary composite oil-displacing system, the alkali that contains high density, as sodium hydroxide, yellow soda ash etc., in use, to bringing huge injury in stratum and oil well etc., employed tensio-active agent is difficult for by biological degradation, and human body also there is certain hazardness, as: 1991, Zhao Guoxi was at " tensio-active agent physical chemistry " P495; 1994, disclosed content among Liu Chengzai " tensio-active agent complete works " P35.So at 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 the 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 improves the displacing surfactant system of oil recovery factor.
Summary of the invention
One of technical problem to be solved by this invention is that the oil-displacing agent that contains tensio-active agent in the prior art exists under the high temperature and high salt condition oil displacement efficiency poor, the corrosion that alkali brings stratum and oil well in working concentration height and the ternary composite driving and the problem of incrustation injury provide a kind of composition of new increased substantially recovery ratio.Said composition is used for oil displacement process, has alkali-free, does not have corrosion 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 provides preparation of compositions method a kind of and one of technical solution problem corresponding raising recovery ratio.
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 carboxylic acid type trimethyl-glycine;
(2) 0.01～3.0% polymkeric substance;
(3) 92.0～99.98% water;
Wherein the general molecular formula of component (1) is:
In the formula: R is C
5～C
15Alkyl, n is the adduction number of ethoxy group EO, its span is any one integer in 2～20; M is any one metal ion that is selected from potassium, sodium or the lithium.
In the 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 (formed by acrylamide, 2-acrylamido-2-methyl propane sulfonic acid, 2-acrylamido dodecyl sodium sulfonate and four kinds of monomer copolymerizations of allyl group oleyl ether, its molar percentage preferable range is (76～83): (7～18): (5～8): a kind of 1) or in the 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 of compositions method that increases substantially recovery ratio may further comprise the steps:
A) preparation of haloalkyl phenol polyethenoxy ether:
Is 0.1～5: 1 with alkylphenol polyoxyethylene and thionyl chloride in mol ratio, and 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:
With institute's synthetic haloalkyl phenol polyethenoxy ether in a) and dimethylamine agueous solution, be 30～150 ℃ in temperature, react 2～20 hours, obtain alkylphenol polyoxyethylene-N after treatment, the N-dimethyl amine after the reaction end;
C) preparation of alkylphenol polyoxyethylene hydroxy sulfonate type trimethyl-glycine:
With b) in the synthetic alkylphenol polyoxyethylene-N of institute, N-dimethyl amine and sodium chloroacetate react and obtained target product in 2～8 hours under 60～100 ℃;
D) with the alkylphenol polyoxyethylene carboxylic acid type trimethyl-glycine of aequum, above-mentioned temperature resistant antisalt polymer A and water uniform mixing, stirring at room 1～3 hour, obtain required composition, by weight percentage, the proportioning of alkylphenol polyoxyethylene carboxylic acid type trimethyl-glycine, above-mentioned temperature resistant antisalt polymer A water is 0.01～5.0%: 0.01～3.0%: 92.0～99.98%.
In the technique scheme, a) the mol ratio preferable range of alkylphenol polyoxyethylene and excessive thionyl chloride is 1～3: 1 in the step, and the temperature of reaction preferable range is 50～120 ℃, and the reaction times preferable range is 10 hours; B) the temperature preferable range is 70～90 ℃ in the step, and the reaction times preferable range is 10 hours; C) step reaction temperature and reaction times preferable range be 60～80 ℃ 2～3 hours down, be warming up to 85～100 ℃ then and continue reaction 2～4 hours down.(d) in the step, by weight percentage, the consumption preferable range of alkylphenol polyoxyethylene carboxylic acid type trimethyl-glycine 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 carboxylic acid type trimethyl-glycine in the composition of the increased substantially recovery ratio that the present invention is prepared, owing to contain zwitterion group and nonionic block simultaneously in its molecular structure, make the salt tolerant advantage of its heat resistance that has ionic surface active agent concurrently and nonionogenic tenside, have features such as micelle-forming concentration is low, reduction interfacial tension ability is strong, anti-high salinity again, have the performance more better than conventional surfactant.
Adopt the present invention can increase substantially the composition of recovery ratio, under the alkali-free condition, be used for formation temperature and be 70 ℃, salinity and surpass 30000 mg/litre, Ca
2+, Mg
2+Be the marine crude oil of Shengli Oil Field and the water of 420～1170 mg/litre, with consumption is that the above-mentioned temperature resistant antisalt polymer A of 0.1～0.3wt% alkylphenol polyoxyethylene carboxylic acid type trimethyl-glycine and 0.1～0.2wt% forms the above-mentioned composition oil-displacing agent, measure the dynamic interface tension value between the marine crude oil of this oil-displacing agent aqueous solution and Shengli Oil Field, can reach 10
-3The ultra low interfacial tension of mN/m can improve oil recovery factor through the indoor evaluation of physical simulation displacement test at this oil-displacing agent on high temperature, the high salinity reservoir and can reach about 10% on the water drive basis, obtained better technical effect.
Synthetic product of the present invention can characterize by the following method, after purification of products, uses U.S. Nicolet-5700 infrared spectrometer, adopts liquid-film method to carry out Infrared spectroscopy (surface sweeping scope 4000～400cm
-1), and spectrogram and standard infrared spectrum contrasted, determine the chemical structure of sample, to reach Infrared Characterization to compound of the present invention.Fig. 1 is the infrared spectrum of alkylphenol polyoxyethylene carboxylic acid sodium type trimethyl-glycine.Among Fig. 1,3350cm
-1About locate stretching vibration (mainly being that product is the aqueous solution) for-OH, 1600cm
-1About locate to be phenyl ring, 1249cm
-1The place is aryl oxide C-O-C, 1070～1160cm
-1The place has EO to have 1083～1192cm
-1The place is the stretching vibration of C-N, 1550～1610cm
-1For-the COO-stretching vibration, prove that synthetic product of the present invention is a kind of alkylphenol polyoxyethylene carboxylic acid type trimethyl-glycine really.
The present invention is further elaborated below by embodiment.
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, dropwise the back and reacted 10 hours down at 90 ℃.Layering is left standstill, cooled off to reaction with reactant after finishing, and upper organic phase is a target product, and lower floor is a solid hydrochloric acid pyridinium salt.Sodium hydroxide solution with 30% is neutralized to neutrality or weakly alkaline with upper organic phase, tell inorganic salt, with upper organic phase hot saturated common salt water washing 5～6 times, obtain intermediate product chloro amyl group (R=5) phenol polyethenoxy (n=2) ether after the drying again, yield is 88%.
2) amyl group (R=5) phenol polyethenoxy (n=2) ether-N, N-dimethyl amine synthetic
Synthetic chloro amyl group (R=5) phenol polyethenoxy (n=2) ether 70g adding in the step (1) is had in the four-hole boiling flask of 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), slowly drip in the flask with dropping funnel then, after dropwising 1 hour, in system, add the hydrogen chloride gas that the 2g solid sodium hydroxide generates in order to absorption reaction, and measure system pH this moment; After reacting 1 hour again, add the 2g solid sodium hydroxide again, the system that makes remains weakly alkaline, reacts after 10 hours and finishes, standing demix.The upper strata is an organic phase, and lower floor is a water.Unnecessary dimethylamine, ethanol are removed in the upper organic phase underpressure distillation, use hot saturated common salt water washing 5～6 times then, obtain target intermediate product amyl group (R=5) phenol polyethenoxy (n=2) ether-N, N-dimethyl amine, yield are 83%.
3) amyl group (R=5) phenol polyethenoxy (n=2) ether carboxylic acid sodium trimethyl-glycine is synthetic
With step 2) middle synthetic amyl group (R=5) phenol polyethenoxy (n=2) ether-N, N-dimethyl amine 40g joins in the four-hole boiling flask that has reflux condensate device, thermometer, agitator, be heated to 70 ℃, the sodium chloroacetate aqueous solution 66g of slow dropping 70%, after reacting 2 hours under 70 ℃, be warming up to 90 ℃ and continue reaction 6 hours and finish until reaction, during add an amount of normal-butyl bromination ammonium and ethanol, to guarantee the two-phase thorough mixing.After reaction finished, ethanol and less water were 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 step (3) 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 97.0wt% Shengli Oil Field is mixed stirred 2 hours, obtain the composition that a kind of displacement of reservoir oil of homogeneous transparent is used.At 70 ℃ of temperature, 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 tension is dripped interfacial tensimeter mensuration by the TX500 type rotation that Texas ,Usa university produces.
[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, dropwise the back and reacted 8 hours down at 70 ℃.Layering is left standstill, cooled off to reaction with reactant after finishing, and upper organic phase is a target product, and lower floor is a solid hydrochloric acid pyridinium salt.Sodium hydroxide solution with 30% is neutralized to neutrality or weakly alkaline with upper organic phase, tell inorganic salt, with upper organic phase hot saturated common salt water washing 5～6 times, obtain intermediate product chloro nonyl (R=9) phenol polyethenoxy (n=10) ether after the drying again, yield is 85%.
2) nonyl (R=9) phenol polyethenoxy (n=10) ether-N, N-dimethyl amine synthetic
Synthetic chloro nonyl (R=9) phenol polyethenoxy (n=10) ether 70g adding in the step (1) is had in the four-hole boiling flask of 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), slowly drip in the flask with dropping funnel then, after dropwising 1 hour, in system, add the hydrogen chloride gas that the 2g solid sodium hydroxide generates in order to absorption reaction, and measure system pH this moment; After reacting 1 hour again, add the 2g solid sodium hydroxide again, the system that makes remains weakly alkaline, reacts after 6 hours and finishes, standing demix.The upper strata is an organic phase, and lower floor is a water.Unnecessary dimethylamine, ethanol are removed in the upper organic phase underpressure distillation, use hot saturated common salt water washing 5～6 times then, obtain target intermediate product nonyl (R=9) phenol polyethenoxy (n=10) ether-N, N-dimethyl amine, yield are 80%.
3) nonyl (R=9) phenol polyethenoxy (n=10) ether carboxylic acid sodium trimethyl-glycine is synthetic
With step 2) middle synthetic nonyl (R=9) phenol polyethenoxy (n=10) ether-N, N-dimethyl amine 56g joins in the four-hole boiling flask that has reflux condensate device, thermometer, agitator, be heated to 70 ℃, slowly drip sodium chloroacetate aqueous solution 76g, after reacting 2 hours under 70 ℃, be warming up to 90 ℃ and continue reaction 6 hours and finish until reaction, during add an amount of normal-butyl bromination ammonium and ethanol, to guarantee the two-phase thorough mixing.After reaction finished, ethanol and less water were 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) 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 are mixed stirred 2 hours, obtain the composition that a kind of displacement of reservoir oil of homogeneous transparent is used.At 70 ℃ of temperature, 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 tension is dripped interfacial tensimeter mensuration by the TX500 type rotation that Texas ,Usa university produces.
[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, dropwise the back and reacted 10 hours down at 80 ℃.Layering is left standstill, cooled off to reaction with reactant after finishing, and upper organic phase is a target product, and lower floor is a solid hydrochloric acid pyridinium salt.Sodium hydroxide solution with 30% is neutralized to neutrality or weakly alkaline with upper organic phase, tell inorganic salt, with upper organic phase hot saturated common salt water washing 5～6 times, obtain intermediate product chlorinated dodecane base phenol polyethenoxy (n=20) ether after the drying again, yield is 81%.
2) dodecyl phenol polyethenoxy (n=20) ether-N, N-dimethyl amine synthetic
Synthetic chlorinated dodecane base phenol polyethenoxy (n=20) ether 70g adding in the step (1) is had in the four-hole boiling flask of 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), slowly drip in the flask with dropping funnel then, after dropwising 1 hour, in system, add the hydrogen chloride gas that the 2g solid sodium hydroxide generates in order to absorption reaction, and measure system pH this moment; After reacting 1 hour again, add the 2g solid sodium hydroxide again, the system that makes remains weakly alkaline, reacts after 10 hours and finishes, standing demix.The upper strata is an organic phase, and lower floor is a water.Unnecessary dimethylamine, ethanol are removed in the upper organic phase underpressure distillation, use hot saturated common salt water washing 5～6 times then, obtain target intermediate product dodecyl phenol polyethenoxy (n=20) ether-N, N-dimethyl amine, yield are 83%.
3) dodecyl phenol polyethenoxy (n=20) ether carboxylic acid sodium trimethyl-glycine is synthetic
With step 2) middle synthetic dodecyl phenol polyethenoxy (n=20) ether-N, N-dimethyl amine 40g joins in the four-hole boiling flask that has reflux condensate device, thermometer, agitator, be heated to 75 ℃, the sodium chloroacetate aqueous solution 60g of slow dropping 70%, after reacting 2 hours under 75 ℃, be warming up to 85 ℃ and continue reaction 4 hours and finish until reaction, during add an amount of normal-butyl bromination ammonium and ethanol, to guarantee the two-phase thorough mixing.After reaction finished, ethanol and less water were 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 mixes and stirred 2 hours, obtains the composition that a kind of displacement of reservoir oil of homogeneous transparent is used.At 70 ℃ of temperature, 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 tension is dripped interfacial tensimeter mensuration by the TX500 type rotation that Texas ,Usa university produces.
[embodiment 4～6]
With the composition of increased substantially recovery ratio of [embodiment 1～3] preparation, be 30 centimetres in length, diameter is 2.5 centimetres, rate of permeation is 1.5 microns
2Rock core on carry out imitation oil displacement experiment test.Be driven to moisture 92% with the marine block local water of Shengli Oil Field earlier, record water drive and can improve oil recovery factor 40.3～41.4%, again behind 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 oil recovery factor 10～11.2% again, 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 the marine 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 tension is dripped interfacial tensimeter mensuration by the TX500 type rotation that Texas ,Usa university produces.
The above-mentioned displacement of reservoir oil composition that makes carries out the displacement of reservoir oil with the method with [embodiment 4], records water drive and can improve oil recovery factor 40.3%, can improve oil recovery factor 5.6% again on the water drive basis behind the above-mentioned displacement of reservoir oil composition of metaideophone, the results are shown in Table shown in 1.
[comparative example 2]
With [embodiment 1] (d), difference substitutes the above-mentioned temperature resistant antisalt polymer A (molecular weight 2,500 ten thousand) of 0.15wt% with the super high molecular weight polyacrylamide (viscosity-average molecular weight is 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 the marine 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 tension is dripped interfacial tensimeter mensuration by the TX500 type rotation that Texas ,Usa university produces.
The above-mentioned displacement of reservoir oil composition that makes carries out the displacement of reservoir oil with the method with [embodiment 4], records water drive and can improve oil recovery factor 40.5%, can improve oil recovery factor 6.2% again on the water drive basis behind the above-mentioned displacement of reservoir oil composition of metaideophone, 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 (6)
1. composition that can increase substantially recovery ratio comprises following component by weight percentage:
(1) 0.01～5.0% alkylphenol-polyethenoxy carboxylic acid 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 the formula: R is C
5～C
15Alkyl, n is the adduction number of ethoxy group EO, its span is any one integer in 2～20; M is any one metal ion that is selected from potassium, sodium or the lithium.
2. the composition that increases substantially recovery ratio according to claim 1 is characterized in that described total mineralization is 16000～40000mg/L, Ca
2++ Mg
2+Be 0～1200mg/L.
3. the composition that increases substantially recovery ratio according to claim 1 is characterized in that described polymkeric substance is selected from a kind of in super high molecular weight polyacrylamide and temperature resistant antisalt polymer A or the xanthan gum.
4. according to the described temperature resistant antisalt polymer A of claim 3, it is characterized in that described its molar percentage that is formed by acrylamide, 2-acrylamido-2-methyl propane sulfonic acid, 2-acrylamido dodecyl sodium sulfonate and four kinds of monomer copolymerizations of allyl group oleyl ether is (76～83): (7～18): (5～8): 1, molecular weight is 15,000,000～25,000,000.
5. the described preparation of compositions method that increases substantially recovery ratio of claim 1 may further comprise the steps:
A) preparation of haloalkyl phenol polyethenoxy ether:
Is 0.1～5: 1 with alkylphenol polyoxyethylene and thionyl chloride in mol ratio, and 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:
With institute's synthetic haloalkyl phenol polyethenoxy ether in a) and dimethylamine agueous solution, be 30～150 ℃ in temperature, react 2～20 hours, obtain alkylphenol polyoxyethylene-N after treatment, the N-dimethyl amine after the reaction end;
C) preparation of alkylphenol polyoxyethylene hydroxy sulfonate type trimethyl-glycine:
With b) in the synthetic alkylphenol polyoxyethylene-N of institute, N-dimethyl amine and sodium chloroacetate react and obtained target product in 2～8 hours under 60～100 ℃;
D) with the alkylphenol polyoxyethylene carboxylic acid type trimethyl-glycine of aequum, above-mentioned temperature resistant antisalt polymer A and water uniform mixing, stirring at room 1～3 hour, obtain required composition, by weight percentage, the proportioning of alkylphenol polyoxyethylene carboxylic acid type trimethyl-glycine, above-mentioned temperature resistant antisalt polymer A water is 0.01～5.0%: 0.01～3.0%: 92.0～99.98%.
6. the preparation of compositions method that increases substantially recovery ratio according to claim 5, it is characterized in that the mol ratio of alkylphenol polyoxyethylene and excessive thionyl chloride is preferably 1～3 in a) step: 1, the temperature of reaction preferable range is 50～120 ℃, and the reaction times is preferably 10 hours; B) preferred temperature is 70～90 ℃ in the step, and the reaction times is preferably 10 hours; C) step reaction temperature and reaction times be preferably 70 ℃ following 2 hours, be warming up to 90 ℃ then and continue down reaction 2～6 hours.(d) in the step, by weight percentage, the consumption preferable range of alkylphenol polyoxyethylene carboxylic acid type trimethyl-glycine is 0.03～1.0%, and more preferably scope is 0.1～0.3%; It is 0.05～0.5% that above-mentioned temperature resistant antisalt polymer A molecular weight is preferably 2500 general-purpose amount preferable range; More preferably scope is 0.1～0.2%, and churning time is preferably 1.5～2.5 hours.
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