CN102373045B - Seawater-based oil displacement agent and preparation method thereof - Google Patents
Seawater-based oil displacement agent and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a seawater-based oil displacement agent and a preparation method thereof. By the seawater-based oil displacement agent, the problems of poor oil displacement efficiency, high using concentration and corrosion and scale depositing damage of alkali in alkali-surfactant-polymer (ASP) flooding to strata and oil wells at a high temperature and high salinity in a surfactant-containing oil displacement agent in the prior art are mainly solved. The seawater-based oil displacement agent comprises the following components in percentage by mass: (1) 0.01 to 5.0 percent of N,N-double fatty acyl diamine oxalic acid dipolyoxyethylene ether dicarboxylate, (2) 0.01 to 3.0 percent of polymer and (3) 92.0 to 99.98 percent of injection water, wherein the N,N-double fatty acyl diamine oxalic acid dipolyoxyethylene ether dicarboxylate has a molecular general formula shown in the specifications, R1 is alkyl having 9 to 17 carbon atoms, R2 is alkyl having 2 to 6 carbon atoms, n is the addition number of ethoxy groups EO and is an integral number ranging from 2 to 7, and M may be metal ions of potassium ions, sodium ions or lithium ions; polymer may be one or two of anionic polyacrylamide with superhigh molecular weight, modified polyacrylamide or xanthan gum; and water is selected from injection water in oil fields. Through the technical scheme, the problems are better solved. The method can be used for the production of tertiary oil recovery in the oil fields.
Description
Technical field
The present invention relates to a kind of seawater-based oil displacement agent and preparation method thereof.
Background technology
Along with socioeconomic development, people are to the continuous increase of petroleum demand amount and the minimizing of prospective oil, and 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 more large, 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, to satisfy human wants, must research and development improve petroleum recovery technology, tertiary oil recovery (EOR) can make oil recovery factor improve 6～20% by the intensified oil reduction measure again, and is 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 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 occurring in field test 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, do not use alkali in the binary combination flooding formula that polymkeric substance and tensio-active agent form, 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 injected 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 be fit to high saliferous, high Ca in continual exploitation research abroad
2+, Mg
2+The tensio-active agent that the ion stratum is used comprises the research of multi-functional tensio-active agent, Gemini surface active agent and sacrifice agent, and pays attention to the composition research of various tensio-active agents.
the anion-nonionic amphoterics is one of focus of tertiary oil recovery (EOR) area research in recent years always, owing in its molecular structure, two kinds of non-ionic groups of different nature and anionic group being designed in same surfactant molecule, make it have the advantage of negatively charged ion and nonionogenic tenside concurrently, have complementary advantages, excellent property, therefore shown good application prospect, especially the binary combination flooding system that exists for alkali-free, due to the obstruction of not only having avoided oil reservoir that there is no alkali, the problem such as fouling and corrosion, and can form ultra low interfacial tension with crude oil.In recent years, because Shuangzi (Gemini) tensio-active agent is by two hydrophilic radicals, two hydrophobic groupings and is connected and connects a base key and close the special construction compound that forms, has more good performance than conventional surfactant, make it have ultra low interfacial tension, low micelle-forming concentration, low Kraff point, good lime soap dispersing power, good a series of peculiar properties such as wettability, thereby cause great concern.Gemini tensio-active agent with interface performance and rheological is 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 the patent application at beginning of the thirties late 1920s, Degroot (De Groot) just once proposed the recovery ratio that the water soluble surfactant active helps to improve oil.
At present, the main Gemini surface active agent of domestic research and development is mainly the positively charged ion double quaternary ammonium salt type, as Chinese patent CN 1528853, CN 1817431, CN 1066137 etc. reported in succession that the bisamide type is cationic, fluorine-containing cationic type and contain the pyridyl cation Gemini surfactant.The absorption loss is large, the high in cost of production shortcoming because positively charged ion has, the research and development of anionic and non-ionic type Gemini surface active agent have in recent years also obtained increasing attention, have reported the synthetic of the asymmetric Shuangzi of a kind of negatively charged ion as Chinese patent CN 101073757.And to have salt tolerance poor due to aniorfic surfactant, and non-ionic type has the poor shortcoming of temperature tolerance, makes these products can't being applied at high temperature and high salt oil deposit.
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 that uses is difficult for being biodegradable, and human body also there is certain hazardness, as: 1991, Zhao Guoxi was at " tensio-active agent physical chemistry " P495; 1994, disclosed content in Liu Chengzai " tensio-active agent is complete works of " P35.So for those harsh oil reservoirs, we ought to seek a kind of under alkali-free, high temperature (formation temperature is greater than 65 ℃), high salt (more than salinity 30000mg/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.Of the present invention this in the alkali-free situation just, be suitable for the moon of high temperature and high salt oil deposit-non-Gemini surface active agent, its preparation method, binary is compound and the application in tertiary oil recovery.
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 prior art exists under the high temperature and high salt condition oil displacement efficiency poor, 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 new seawater-based oil displacement agent.The method will contain N, and the two carboxylate surface active agent oil-displacing agents of the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy Vinyl Ethers of N-are used for oil displacement process, have alkali-free, nothing 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 is to provide a kind of preparation method of the seawater-based oil displacement agent corresponding with one of technical solution problem.
In order one of to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of seawater-based oil displacement agent comprises following component by percentage to the quality:
(1) 0.01～5.0% N, the two carboxylate salts of the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy Vinyl Ethers of N-;
(2) 0.01～3.0% polymkeric substance;
(3) 92.0～99.98% injected water;
Wherein the general molecular formula of (1) component is:
In formula: R
1Be C
9～C
17Alkyl, R
2Be C
2～C
6Alkyl, n is the adduction number of ethoxy group EO, its span is any one integer in 2～7; M is any one metal ion that is selected from potassium, sodium or lithium; Polymkeric substance is selected from one or both in ultra-high-molecular aniouic polyacrylamide, modified polyacrylamide or xanthan gum.
In technique scheme, described injected water total mineralization is preferably 15000～32000 mg/litre, Ca
2++ Mg
2+Be preferably 750～1600 mg/litre; Polymkeric substance is selected from above-mentioned ultra-high-molecular aniouic polyacrylamide or modified polyacrylamide; The M preferred version is potassium and sodium, and more preferably scheme is for being selected from sodium; R
1It is to have best hydrophile-lipophile balance value at 3～4 o'clock that carbon number adds ratio preferable range that 1 sum and EO count n, and its aqueous solution can form 10 with crude oil
-3～10
-4Ultra low interfacial tension; N, the R in the two carboxylate salts of the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy Vinyl Ethers of N-
1Carbonatoms is preferably nine, 11,15 or 17, R
2Carbonatoms be preferably two, four or six.
For solve the problems of the technologies described above two, the technical solution adopted in the present invention is as follows: a kind of preparation method of seawater-based oil displacement agent comprises the following steps:
(a) N, the preparation of N-two fatty acyl diamines:
be 10～18 lipid acid with the carbochain number of required proportioning, thionyl chloride and N, dinethylformamide DMF was 70～100 ℃ of reactions 2～5 hours, excessive thionyl chloride is extracted in decompression out, it is 10～18 fat acyl chloride that the transparent liquid that obtains is the carbochain number, after adding the carbochain number to be the dilution with toluene of 10～18 lipid acid quality 1/2nd, be warming up to 60～90 ℃, be 2～6 diamines with the carbochain number by required proportioning, pyridine and consumption are that the carbochain number is that slowly to splash into the carbochain number after the toluene of 10～18 lipid acid quality 1/2nd mixes be in 10～18 fat acyl chloride solution, reacted 2～5 hours, obtain the white powder solid chemical compound through aftertreatment, wherein, the carbochain number is 10～18 lipid acid, thionyl chloride and N, the mol ratio of dinethylformamide is 1: 1.0～2.0: 0.03～0.1, and the carbochain number is that 10～18 fat acyl chloride, carbochain number are that 2～6 diamines and the mol ratio of pyridine are 2.0～4.0: 1: 1.5～3.5,
(b) N, the preparation of the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA)s of N-:
The N that step (a) is synthesized, the two carbochain numbers of N-are 10～18 fatty acyl diamines by after required proportioning and sodium hydroxide or potassium hydroxide, Tetrabutyl amonium bromide catalyst mix, to add N, after the tetrahydrofuran (THF) dilution that the two carbochain numbers of N-are 10～18 fatty acyl diamines quality 1/2nd, be heated to back flow reaction 2～8 hours, add again the sodium chloroacetate of required proportioning to continue back flow reaction 6～14 hours, get the white powder solid through aftertreatment.Wherein, N, the mol ratio that the two carbochain numbers of N-are 10～18 fatty acyl diamines, sodium chloroacetate, sodium hydroxide or potassium hydroxide and Tetrabutyl amonium bromide=1: 2～9: 3～9: 0.02～0.07;
(c) N, the preparation of the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy Vinyl Ethers of N-:
The N that step (b) is synthesized, the two carbochain numbers of N-are that 10～18 fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA)s and oxyethane are 85～160 ℃ by required proportioning in temperature of reaction, pressure is less than under 0.80MPa gauge pressure condition, the basic cpd of calcium is catalyzer, react to get N, the two carbochain numbers of N-are 10～18 fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy Vinyl Ethers; Wherein, N, the two carbochain numbers of N-are that 10～18 fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA)s and oxyethane mol ratio are 1: 4～14, and catalyst levels is N, and the two carbochain numbers of N-are 0.5～5.0% of 10～18 fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) quality;
(d) N, the preparation of the two carboxylate salts of the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy Vinyl Ethers of N-:
The N that step (c) is synthesized, the two carbochain numbers of N-are that 10～18 fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy Vinyl Ethers are by required proportioning and sodium chloroacetate, potassium hydroxide or sodium hydroxide and Tetrabutyl amonium bromide catalyst mix, take toluene as solvent, 50～130 ℃ of temperature of reaction, reacted 3～15 hours, reaction finishes to get N by aftertreatment, the two carboxylate salts of the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy Vinyl Ethers of N-; Wherein, N, the mol ratio that the two carbochain numbers of N-are 10～18 fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy Vinyl Ethers, sodium chloroacetate, potassium hydroxide or sodium hydroxide and Tetrabutyl amonium bromide=1: 2～6: 2～8: 0.05～0.3;
(e) with the N of aequum, the two carboxylate salts of the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy Vinyl Ethers of N-, above-mentioned ultra-high-molecular aniouic polyacrylamide or modified polyacrylamide and injected water evenly mix, stirring at room 1～3 hour obtains required composition; By percentage to the quality, N, the two carboxylate salts of the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy Vinyl Ethers of N-, above-mentioned modified polyacrylamide and the proportioning of injected water are 0.01～5.0%: 0.01～3.0%: 92.0～99.98%.
In technique scheme, (a) in step, the carbochain number is 10～18 lipid acid, thionyl chloride and N, the mol ratio of dinethylformamide is preferably 1: 1.2～and 2.0: 0.05～0.1, the carbochain number is that 10～18 fat acyl chloride, carbochain number are that 2～6 diamines and the mol ratio of pyridine are preferably 2.5～3.5: 1: 2～3.The temperature of reaction of preparation acyl chlorides is preferably 80～95 ℃, and the temperature of reaction of preparation acid amides is preferably 70～90 ℃.(b) N in step, the two carbochain numbers of N-be the mol ratio of 10～18 fatty acyl diamines, sodium chloroacetate, sodium hydroxide (potassium hydroxide) and Tetrabutyl amonium bromide be preferably 1: 3～8: 4～8: 0.03～0.06.(c) N, the two carbochain numbers of N-be 10～18 fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA)s and oxyethane mol ratio be preferably 1: 6～12, catalyst levels is N, N-pair of carbochain numbers are 1.0～3.0% of 10～18 fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) quality.(d) N in step; the two carbochain numbers of N-be the mol ratio of 10～18 fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy Vinyl Ethers, sodium chloroacetate, sodium hydroxide (potassium hydroxide) and Tetrabutyl amonium bromide be preferably 1: 2.5～5.5: 3～7: 0.1～0.2; temperature of reaction is preferably 70～110 ℃, and the reaction times is preferably 5～12 hours.(e) by percentage to the quality, N, the consumption preferable range of the two carboxylate salts of the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy Vinyl Ethers of N-is 0.03～1.0%, more preferably scope is 0.1～0.3%; The consumption preferable range of above-mentioned ultra-high-molecular aniouic polyacrylamide or modified polyacrylamide is 0.05～0.5%; More preferably scope is 0.1～0.2%, and the reaction times is preferably 1.5～2.5 hours.
N in the prepared seawater-based oil displacement agent of the present invention, the two carboxylate salts of the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy Vinyl Ethers of N-, owing to containing simultaneously aerobic ethene non-ionic group and carboxylate anion group in its molecular structure, make the salt tolerant advantage of its heat resistance that has anion surfactant concurrently and nonionogenic tenside, and symmetrical Shuangzi constitutional features, make it have micelle-forming concentration again low, reduce the interfacial tension ability strong, the features such as the rheological of anti-high salinity and uniqueness and visco-elasticity-viscosifying action, has more good performance than conventional surfactant.Do not contain aromatic ring structure in its molecule in addition, be easier to biological degradation, therefore less to the harm of human body and environment, be a kind of green surfactant that is suitable for the used for tertiary oil recovery of high temperature and high salt oil deposit.
Adopt seawater-based oil displacement agent of the present invention, under the alkali-free condition, can be used for formation temperature and be 65 ℃, salinity 15000～32000 mg/litre, Ca
2++ Mg
2+Be the MgCl of 750～1600 mg/litre
2Type Shengli Oil Field field of razor clam island block injected water and crude oil; take consumption as 0.1～0.3wt%N; above-mentioned ultra-high-molecular aniouic polyacrylamide or the modified polyacrylamide of the two carboxylate salts of the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy Vinyl Ethers of N-and 0.1～0.2wt% forms the above-mentioned composition oil-displacing agent; measure the dynamic interface tension value between this oil-displacing agent aqueous solution and Shengli Oil Field field of razor clam island block crude oil, can reach 10
-3～10
-4The ultra low interfacial tension of mN/m, through physical simulation displacement test Lab-evaluation this oil-displacing agent on high temperature, high salinity reservoir can be on the water drive basis (water drive improves oil recovery factor and reaches 60.5%) improve oil recovery factor and can reach 18.9%, obtained technique effect preferably.
Description of drawings
Fig. 1 is N, the infared spectrum of the two carboxylate salts of the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy Vinyl Ethers of N-.
The N of the present invention's preparation; the two carboxylate salts of the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy Vinyl Ethers of N-can characterize by the following method: after synthetics is purified; use U.S. Nicolet-380FT-IR spectrograph, adopt liquid-film method to carry out Infrared spectroscopy (sweep limit 4000～400cm
-1), be 2953cm in wave number
-1, 2919cm
-1, 2850cm
-1Methyl and the flexible characteristic peak of methylene radical C-H on alkyl chain, 1475cm appear in the place
-1C-H flexural vibration on alkyl chain, 1856～1505cm
-1A large broad peak, comprised the charateristic avsorption band of three kinds of vC=O, 1418cm
-1In the place, the peak is the III key band C-N stretching, extension of acid amides, 1106cm
-1Locate a broad peak, this peak is owing to having connected EO, and the upper C-O-C asymmetric stretch of EO bands of a spectrum cause, 985cm
-1Peak disappear, this peak usually associates relevantly with terminal hydroxyl, proved response has generated N really thus, the two carboxylate salts of the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy Vinyl Ethers of N-.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
(a) two 12 (bay) acyl group quadrol is synthetic
With lauric acid 300 grams (1.5 moles), sulfur oxychloride 267.8 grams (2.25 moles) and 4.5 gram DMF, add in 2000 milliliters of four-hole boiling flasks being furnished with sealing machine stirring, thermometer, prolong etc., in 90 ℃ the reaction 3 hours after, decompression steams excessive thionyl chloride, obtains lauroyl chloride.When temperature is down to 60 ℃, add dry toluene 150 grams, after stirring, slowly drip the mixed solution that is formed by anhydrous ethylenediamine 30.0 grams (0.5 mole), anhydrous pyridine 99.0 grams (1.25 moles) and dry toluene 150 grams, control temperature less than 60 ℃, drip off and be warming up to 85 ℃ of reactions 2 hours.Cooling, filter, crude product gets white powder solid, molar yield 97.1% with ethyl alcohol recrystallization after vacuum-drying.
(b) N, the two lauroyl ethylenediamine-N,N'-diacetic acid(EDDA)s of N-synthetic
Bimonthly osmanthus acyl group quadrol 200 grams (0.47 mole) that step (a) is synthetic, 400 gram tetrahydrofuran (THF)s, 112.8 grams (2.82 moles) sodium hydroxide and 7.5 gram Tetrabutyl amonium bromides; add be furnished with mechanical stirring, in the there-necked flask of 2000 milliliters of thermometer and reflux condensing tube, quaternization 4 hours are heated to reflux.Dividing after slightly cooling and adding total amount five times is the sodium chloroacetate solid of 219.0 grams (1.88 moles), keeps back flow reaction 10 hours.Cooling, be neutralized to reaction solution with hydrochloric acid and be strongly-acid, be cooled to room temperature, suction filtration, to neutral, vacuum-drying gets white powder solid 165.0 grams, molar yield 65.0% with the distilled water wash solid.
(c) N, the two lauroyl ethylenediamine-N,N'-diacetic acid(EDDA) two polyoxy Vinyl Ethers (n=4) of N-synthetic
With the synthetic N of step (b); the basic cpd of two lauroyl ethylenediamine-N,N'-diacetic acid(EDDA) 165.0 grams (0.305 mole) of N-, 2.0 gram calcium add be furnished with condensing works, in the high-pressure reactor of whipping appts and gas distributor; when limit logical nitrogen limit heating is made 135 ℃; add 20 gram water, stirring reaction 1 hour.After removing moisture content, be cooled to 80 ℃, the sulfuric acid (20wt%) that slowly drips the catalyst neutralisation theoretical amount makes the compound oxidizing calcium alkoxylating catalyst reaction solution system of high reactivity, highly selective, system temperature is heated to 80～90 ℃, open vacuum system, dehydration is 2 hours under high vacuum, then uses nitrogen purging 3～4 times, the system temperature of reaction is transferred to 140 ℃ slowly pass into 107.6 grams (2.444 moles) oxyethane, control pressure≤0.60MPa.Reaction is used the nitrogen purging system after finishing, and cooling rear neutralization, dehydration get N, two lauroyl ethylenediamine-N,N'-diacetic acid(EDDA) two polyoxy Vinyl Ether (n=4) 268.5 grams of N-, molar yield 98.5%.
(d) N, the two lauroyl ethylenediamine-N,N'-diacetic acid(EDDA) two two carboxylate salts of polyoxy Vinyl Ether (n=4) of N-synthetic
The N that step (c) is synthesized; two lauroyl ethylenediamine-N,N'-diacetic acid(EDDA) two polyoxy Vinyl Ether (n=4) 268.5 grams (0.30 mole) of N-and 101.1 grams (1.80 moles) potassium hydroxide, 139.8 grams (1.20 moles) sodium chloroacetate, 10.8 gram Tetrabutyl amonium bromides, 1000 milliliters of toluene are mixed in to be furnished with mechanical stirring, in the there-necked flask of 2000 milliliters of thermometer and reflux condensing tube, to be heated to 90 ℃ of reactions 8 hours.Cooling, neutralization divides and removes inorganic salt, the N that alkalizes to get, and two lauroyl ethylenediamine-N,N'-diacetic acid(EDDA) two two carboxylate salt 276.0 grams of polyoxy Vinyl Ether (n=4) of N-, molar yield is 87.3%.To synthetic N, the two lauroyl ethylenediamine-N,N'-diacetic acid(EDDA) two two carboxylate salts of polyoxy Vinyl Ether (n=4) of N-are used U.S. Nicolet-380FT-IR spectrograph, adopt liquid-film method to carry out Infrared spectroscopy (sweep limit 4000～400cm
-1), have all charateristic avsorption bands of Fig. 1.
(e) with the synthetic N of step (d); the two lauroyl ethylenediamine-N,N'-diacetic acid(EDDA) two two carboxylate salt 0.15wt% of polyoxy Vinyl Ether (n=4) of N-, above-mentioned modified polyacrylamide 0.15wt% and 97.0wt% Shengli Oil Field field of razor clam island block injected water mix and blend 2 hours obtain a kind of seawater-based oil displacement agent that is applicable to of homogeneous transparent.At 65 ℃ of temperature, salinity 31500mg/L, Ca
2++ Mg
2+In the water of 1600mg/L, the apparent viscosity that records this seawater-based oil displacement agent is 15.0mPa.s; Form the ultra low interfacial tension of 0.0019mN/m between this seawater-based oil displacement agent and Shengli Oil Field field of razor clam island block dewatered oil.Apparent viscosity is by the BROODFIELD II type viscometer determining of U.S. Brookfield company, and the TX500 type rotation that interfacial tension is produced by Texas ,Usa university is dripped interfacial tensimeter and measured.
[embodiment 2]
(a) two 12 (bay) acyl group hexanediamine is synthetic
With [embodiment 1] (a), difference substitutes 30.0 grams (0.5 mole) anhydrous ethylenediamine with the anhydrous hexanediamine of 58.0 grams (0.5 mole), and all the other are identical, gets white powder solid, molar yield 95.6% after vacuum-drying.
(b) N, the two lauroyl hexanediamine oxalic acid of N-synthetic
Bimonthly osmanthus acyl group hexanediamine 225.6 grams (0.47 mole) that step (a) is synthetic, 450 gram tetrahydrofuran (THF)s, 105.3 grams (1.88 moles) potassium hydroxide and 4.5 gram Tetrabutyl amonium bromides; add be furnished with mechanical stirring, in the there-necked flask of 2000 milliliters of thermometer and reflux condensing tube, quaternization 3 hours are heated to reflux.Dividing after slightly cooling and adding total amount five times is the sodium chloroacetate solid of 164.3 grams (1.41 moles), keeps back flow reaction 9 hours.Cooling, be neutralized to reaction solution with hydrochloric acid and be strongly-acid, be cooled to room temperature, suction filtration, to neutral, vacuum-drying gets white powder solid 171.4 grams, molar yield 61.2% with the distilled water wash solid.
(c) N, the two lauroyl hexanediamine oxalic acid two polyoxy Vinyl Ethers (n=3) of N-synthetic
With [embodiment 1] (c); difference is with the N of 171.4 grams (0.288 mole); the two lauroyl hexanediamine oxalic acid of N-substitute 165.0 grams (0.305 mole) N; the usage quantity of the two lauroyl ethylenediamine-N,N'-diacetic acid(EDDA)s of N-, oxyethane is 76.0g (1.728 moles); the usage quantity of the basic cpd of calcium is 4.3 grams; get N, two lauroyl hexanediamine oxalic acid two polyoxy Vinyl Ether (n=3) 240.7 grams of N-, molar yield 97.2%.
(d) N, the two lauroyl hexanediamine oxalic acid two two carboxylate salts of polyoxy Vinyl Ether (n=3) of N-synthetic
The N that step (c) is synthesized; two lauroyl hexanediamine oxalic acid two polyoxy Vinyl Ether (n=3) 240.7 grams (0.28 mole) of N-and 62.8 grams (1.12 moles) potassium hydroxide, 139.8 grams (1.20 moles) sodium chloroacetate, 10.2 gram Tetrabutyl amonium bromides, 1000 milliliters of toluene are mixed in to be furnished with mechanical stirring, in the there-necked flask of 2000 milliliters of thermometer and reflux condensing tube, to be heated to 100 ℃ of reactions 6 hours.Cooling, neutralization divides and removes inorganic salt, the N that alkalizes to get, and two lauroyl hexanediamine oxalic acid two two carboxylate salt 248.1 grams of polyoxy Vinyl Ether (n=3) of N-, molar yield is 86.7%.To synthetic N, the two lauroyl hexanediamine oxalic acid two two carboxylate salts of polyoxy Vinyl Ether (n=3) of N-are used U.S. Nicolet-380FT-IR spectrograph, adopt liquid-film method to carry out Infrared spectroscopy (sweep limit 4000～400cm
-1), have all charateristic avsorption bands of Fig. 1.
(e) with the synthetic N of step (d); the two lauroyl hexanediamine oxalic acid two two carboxylate salt 0.2wt% of polyoxy Vinyl Ether (n=3) of N-, above-mentioned ultra-high-molecular aniouic polyacrylamide 0.15wt% and 96.5wt% Shengli Oil Field field of razor clam island block injected water mix and blend 2 hours obtain a kind of seawater-based oil displacement agent of homogeneous transparent.At 65 ℃ of temperature, salinity 21000mg/L, Ca
2++ Mg
2+In the water of 1067mg/L, the apparent viscosity that records this seawater-based oil displacement agent is 15.5mPa.s; Form the ultra low interfacial tension of 0.0038mN/m between this seawater-based oil displacement agent and Shengli Oil Field field of razor clam island block dewatered oil.Apparent viscosity is by the BROODFIELD II type viscometer determining of U.S. Brookfield company, and the TX500 type rotation that interfacial tension is produced by Texas ,Usa university is dripped interfacial tensimeter and measured.
[embodiment 3]
(a) two ten (last of the ten Heavenly stems) acyl group butanediamine is synthetic
With [embodiment 1] (a), difference substitutes 300.0 grams (1.5 moles) lauric acid with the capric acid of 261.0 grams (1.5 moles), anhydrous butanediamine with 44.0 grams (0.5 mole) substitutes 30.0 grams (0.5 mole) anhydrous ethylenediamine, all the other are identical, get white powder solid, molar yield 96.7% after vacuum-drying.
(b) N, the two ten acyl group butanediamine oxalic acid of N-synthetic
Two decanoyl butanediamine 186.1 grams (0.47 mole) that step (a) is synthetic, 400 gram tetrahydrofuran (THF)s, 112.8 grams (2.82 moles) sodium hydroxide and 7.5 gram Tetrabutyl amonium bromides; add be furnished with mechanical stirring, in the there-necked flask of 2000 milliliters of thermometer and reflux condensing tube, quaternization 3 hours are heated to reflux.Dividing after slightly cooling and adding total amount five times is the sodium chloroacetate solid of 219.0 grams (1.88 moles), keeps back flow reaction 12 hours.Cooling, be neutralized to reaction solution with hydrochloric acid and be strongly-acid, be cooled to room temperature, suction filtration, to neutral, vacuum-drying gets white powder solid 152.5 grams, molar yield 63.4% with the distilled water wash solid.
(c) N, the two ten acyl group butanediamine oxalic acid two polyoxy Vinyl Ethers (n=3) of N-synthetic
With [embodiment 1] (c); difference is with the N of 152.5 grams (0.298 mole); the two ten acyl group butanediamine oxalic acid of N-substitute 165.0 grams (0.305 mole) N; the usage quantity of the two lauroyl ethylenediamine-N,N'-diacetic acid(EDDA)s of N-, oxyethane is 78.6g (1.788 moles); the usage quantity of the basic cpd of calcium is 3.8 grams; get N, two ten acyl group butanediamine oxalic acid two polyoxy Vinyl Ether (n=3) 225.5 grams of N-, molar yield 97.5%.
(d) N, the two ten acyl group butanediamine oxalic acid two two carboxylate salts of polyoxy Vinyl Ether (n=3) of N-synthetic
The N that step (c) is synthesized; two ten acyl group butanediamine oxalic acid two polyoxy Vinyl Ether (n=3) 225.5 grams (0.29 mole) of N-and 65.1 grams (1.16 moles) potassium hydroxide, 101.4 grams (0.87 mole) sodium chloroacetate, 12.2 gram Tetrabutyl amonium bromides, 1000 milliliters of toluene are mixed in to be furnished with mechanical stirring, in the there-necked flask of 2000 milliliters of thermometer and reflux condensing tube, to be heated to 80 ℃ of reactions 8 hours.Cooling, neutralization divides and removes inorganic salt, the N that alkalizes to get, and two ten acyl group butanediamine oxalic acid two two carboxylate salt 231.2 grams of polyoxy Vinyl Ether (n=3) of N-, molar yield is 85.0%.To synthetic N, the two ten acyl group butanediamine oxalic acid two two carboxylate salts of polyoxy Vinyl Ether (n=3) of N-are used U.S. Nicolet-380FT-IR spectrograph, adopt liquid-film method to carry out Infrared spectroscopy (sweep limit 4000～400cm
-1), have all charateristic avsorption bands of Fig. 1.
(e) with the synthetic N of step (d); the two ten acyl group butanediamine oxalic acid two two carboxylate salt 0.15wt% of polyoxy Vinyl Ether (n=3) of N-, above-mentioned modified polyacrylamide 0.15wt% and 97.0wt% Shengli Oil Field field of razor clam island block injected water mix and blend 1.5 hours obtain a kind of seawater-based oil displacement agent of homogeneous transparent.At 65 ℃ of temperature, salinity 15000mg/L, Ca
2++ Mg
2+In the water of 800mg/L, the apparent viscosity that records this seawater-based oil displacement agent is 16.0mPa.s; Form the ultra low interfacial tension of 0.0041mN/m between this seawater-based oil displacement agent and Shengli Oil Field field of razor clam island block dewatered oil.Apparent viscosity is by the BROODFIELD II type viscometer determining of U.S. Brookfield company, and the TX500 type rotation that interfacial tension is produced by Texas ,Usa university is dripped interfacial tensimeter and measured.
[embodiment 4]
(a) two 16 (palm) acyl group quadrol is synthetic
With palmitinic acid 320 grams (1.25 moles), sulfur oxychloride 178.5 grams (1.5 moles) and 4.8 gram DMF, add in 2000 milliliters of four-hole boiling flasks being furnished with sealing machine stirring, thermometer, prolong etc., in 80 ℃ the reaction 5 hours after, decompression steams excessive thionyl chloride, obtains palmityl chloride.When temperature is down to 60 ℃, add dry toluene 160 grams, after stirring, slowly drip the mixed solution that is formed by anhydrous ethylenediamine 30.0 grams (0.5 mole), anhydrous pyridine 79.2 grams (1.0 moles) and dry toluene 160 grams, control temperature less than 60 ℃, drip off and be warming up to 75 ℃ of reactions 3 hours.Cooling, filter, crude product gets white powder solid, molar yield 91.3% with ethyl alcohol recrystallization after vacuum-drying.
(b) N, the two palmitoyl ethylenediamine-N,N'-diacetic acid(EDDA)s of N-synthetic
Two palmitoyl quadrol 251.9 grams (0.47 mole) that step (a) is synthetic, 504 gram tetrahydrofuran (THF)s, 94.0 grams (2.35 moles) sodium hydroxide and 6.0 gram Tetrabutyl amonium bromides; add be furnished with mechanical stirring, in the there-necked flask of 2000 milliliters of thermometer and reflux condensing tube, quaternization 6 hours are heated to reflux.Dividing after slightly cooling and adding total amount five times is the sodium chloroacetate solid of 164.3 grams (1.41 moles), keeps back flow reaction 12 hours.Cooling, be neutralized to reaction solution with hydrochloric acid and be strongly-acid, be cooled to room temperature, suction filtration, to neutral, vacuum-drying gets white powder solid 190.9 grams, molar yield 62.3% with the distilled water wash solid.
(c) N, the two palmitoyl ethylenediamine-N,N'-diacetic acid(EDDA) two polyoxy Vinyl Ethers (n=5) of N-synthetic
With [embodiment 1] (c); difference is with the N of 190.9 grams (0.293 mole); the two palmitoyl ethylenediamine-N,N'-diacetic acid(EDDA)s of N-substitute 165.0 grams (0.305 mole) N; the usage quantity of the two lauroyl ethylenediamine-N,N'-diacetic acid(EDDA)s of N-, oxyethane is 128.9g (2.93 moles); the usage quantity of the basic cpd of calcium is 3.8 grams; get N, two palmitoyl ethylenediamine-N,N'-diacetic acid(EDDA) two polyoxy Vinyl Ether (n=5) 304.9 grams of N-, molar yield 95.3%.
(d) N, the two palmitoyl ethylenediamine-N,N'-diacetic acid(EDDA) two two carboxylate salts of polyoxy Vinyl Ether (n=5) of N-synthetic
The N that step (c) is synthesized; two palmitoyl ethylenediamine-N,N'-diacetic acid(EDDA) two polyoxy Vinyl Ether (n=5) 304.9 grams (0.28 mole) of N-and 67.0 grams (1.68 moles) sodium hydroxide, 130.5 grams (1.12 moles) sodium chloroacetate, 11.5 gram Tetrabutyl amonium bromides, 1000 milliliters of toluene are mixed in to be furnished with mechanical stirring, in the there-necked flask of 2000 milliliters of thermometer and reflux condensing tube, to be heated to 100 ℃ of reactions 8 hours.Cooling, neutralization divides and removes inorganic salt, the N that alkalizes to get, and two palmitoyl ethylenediamine-N,N'-diacetic acid(EDDA) two two carboxylate salt 298.5 grams of polyoxy Vinyl Ether (n=5) of N-, molar yield is 85.0%.To synthetic N, the two ten acyl group butanediamine oxalic acid two two carboxylate salts of polyoxy Vinyl Ether (n=5) of N-are used U.S. Nicolet-380FT-IR spectrograph, adopt liquid-film method to carry out Infrared spectroscopy (sweep limit 4000～400cm
-1), have all charateristic avsorption bands of Fig. 1.
(e) with the synthetic N of step (d); the two ten acyl group butanediamine oxalic acid two two carboxylate salt 0.25wt% of polyoxy Vinyl Ether (n=5) of N-, above-mentioned modified polyacrylamide 0.15wt% and 96.0wt% Shengli Oil Field field of razor clam island block injected water mix and blend 2.5 hours obtain a kind of seawater-based oil displacement agent of homogeneous transparent.At 65 ℃ of temperature, salinity 31500mg/L, Ca
2++ Mg
2+In the water of 1600mg/L, the apparent viscosity that records this seawater-based oil displacement agent is 14.8mPa.s; Form the ultra low interfacial tension of 0.0005mN/m between this seawater-based oil displacement agent and Shengli Oil Field field of razor clam island block dewatered oil.Apparent viscosity is by the BROODFIELD II type viscometer determining of U.S. Brookfield company, and the TX500 type rotation that interfacial tension is produced by Texas ,Usa university is dripped interfacial tensimeter and measured.
[embodiment 5]
(a) two 16 (palm) acyl group butanediamine is synthetic
With [embodiment 4] (a), difference substitutes 30.0 grams (0.5 mole) anhydrous ethylenediamine with the anhydrous butanediamine of 44.0 grams (0.5 mole), and all the other are identical, gets white powder solid, molar yield 94.2% after vacuum-drying.
(b) N, the two palmitoyl butanediamine oxalic acid of N-synthetic
Two palmitoyl butanediamine 265.1 grams (0.47 mole) that step (a) is synthetic, 530 gram tetrahydrofuran (THF)s, 112.8 grams (2.82 moles) sodium hydroxide and 9.0 gram Tetrabutyl amonium bromides; add be furnished with mechanical stirring, in the there-necked flask of 2000 milliliters of thermometer and reflux condensing tube, quaternization 6 hours are heated to reflux.Dividing after slightly cooling and adding total amount five times is the sodium chloroacetate solid of 328.5 grams (2.82 moles), keeps back flow reaction 10 hours.Cooling, be neutralized to reaction solution with hydrochloric acid and be strongly-acid, be cooled to room temperature, suction filtration, to neutral, vacuum-drying gets white powder solid 195.6 grams, molar yield 61.2% with the distilled water wash solid.
(c) N, the two palmitoyl butanediamine oxalic acid two polyoxy Vinyl Ethers (n=4) of N-synthetic
With [embodiment 1] (c); difference is with the N of 195.6 grams (0.288 mole); the two palmitoyl butanediamine oxalic acid of N-substitute 165.0 grams (0.305 mole) N; the usage quantity of the two lauroyl ethylenediamine-N,N'-diacetic acid(EDDA)s of N-, oxyethane is 101.4g (2.304 moles); get N; two palmitoyl butanediamine oxalic acid two polyoxy Vinyl Ether (n=4) 282.1 grams of N-, molar yield 94.9%.
(d) N, the two palmitoyl butanediamine oxalic acid two two carboxylate salts of polyoxy Vinyl Ether (n=4) of N-synthetic
The N that step (c) is synthesized; two palmitoyl butanediamine oxalic acid two polyoxy Vinyl Ether (n=4) 282.1 grams (0.27 mole) of N-and 66.1 grams (1.65 moles) sodium hydroxide, 110.7 grams (0.95 mole) sodium chloroacetate, 12.8 gram Tetrabutyl amonium bromides, 1000 milliliters of toluene are mixed in to be furnished with mechanical stirring, in the there-necked flask of 2000 milliliters of thermometer and reflux condensing tube, to be heated to 100 ℃ of reactions 10 hours.Cooling, neutralization divides and removes inorganic salt, the N that alkalizes to get, and two palmitoyl butanediamine oxalic acid two two carboxylate salt 264.0 grams of polyoxy Vinyl Ether (n=4) of N-, molar yield is 81.9%.To synthetic N, the two palmitoyl butanediamine oxalic acid two two carboxylate salts of polyoxy Vinyl Ether (n=4) of N-are used U.S. Nicolet-380FT-IR spectrograph, adopt liquid-film method to carry out Infrared spectroscopy (sweep limit 4000～400cm
-1), have all charateristic avsorption bands of Fig. 1.
(e) with the synthetic N of step (d); the two palmitoyl butanediamine oxalic acid two two carboxylate salt 0.15wt% of polyoxy Vinyl Ether (n=4) of N-, above-mentioned ultra-high-molecular aniouic polyacrylamide 0.1wt% and 97.5wt% Shengli Oil Field field of razor clam island block injected water mix and blend 2.5 hours obtain a kind of seawater-based oil displacement agent of homogeneous transparent.At 65 ℃ of temperature, salinity 21000mg/L, Ca
2++ Mg
2+In the water of 1067mg/L, the apparent viscosity that records this seawater-based oil displacement agent is 14.7mPa.s; Form the ultra low interfacial tension of 0.0052mN/m between this seawater-based oil displacement agent and Shengli Oil Field field of razor clam island block dewatered oil.Apparent viscosity is by the BROODFIELD II type viscometer determining of U.S. Brookfield company, and the TX500 type rotation that interfacial tension is produced by Texas ,Usa university is dripped interfacial tensimeter and measured.
[embodiment 6]
(a) two 18 (tristearin) acyl group quadrol is synthetic
With stearic acid 497 grams (1.75 moles), sulfur oxychloride 374.9 grams (3.15 moles) and 7.5 gram DMF, add in 2000 milliliters of four-hole boiling flasks being furnished with sealing machine stirring, thermometer, prolong etc., in 95 ℃ the reaction 3 hours after, decompression steams excessive thionyl chloride, obtains stearyl chloride.When temperature is down to 60 ℃, add dry toluene 249 grams, after stirring, slowly drip the mixed solution that is formed by anhydrous ethylenediamine 30.0 grams (0.5 mole), anhydrous pyridine 118.8 grams (1.5 moles) and dry toluene 249 grams, control temperature less than 60 ℃, drip off and be warming up to 70 ℃ of reactions 5 hours.Cooling, filter, crude product gets white powder solid, molar yield 94.7% with ethyl alcohol recrystallization after vacuum-drying.
(b) N, the two stearoyl ethylenediamine-N,N'-diacetic acid(EDDA)s of N-synthetic
Stearic bicine diester base quadrol 278.2 grams (0.47 mole) that step (a) is synthetic, 556.4 gram tetrahydrofuran (THF)s, 112.8 grams (2.82 moles) sodium hydroxide and 6.0 gram Tetrabutyl amonium bromides; add be furnished with mechanical stirring, in the there-necked flask of 2000 milliliters of thermometer and reflux condensing tube, quaternization 4 hours are heated to reflux.Dividing after slightly cooling and adding total amount five times is the sodium chloroacetate solid of 328.5 grams (2.82 moles), keeps back flow reaction 10 hours.Cooling, be neutralized to reaction solution with hydrochloric acid and be strongly-acid, be cooled to room temperature, suction filtration, to neutral, vacuum-drying gets white powder solid 184.0 grams, molar yield 55.3% with the distilled water wash solid.
(c) N, the two stearoyl ethylenediamine-N,N'-diacetic acid(EDDA) two polyoxy Vinyl Ethers (n=6) of N-synthetic
With [embodiment 1] (c); difference is with the N of 184.0 grams (0.260 mole); the two stearoyl ethylenediamine-N,N'-diacetic acid(EDDA)s of N-substitute 165.0 grams (0.305 mole) N; the usage quantity of the two lauroyl ethylenediamine-N,N'-diacetic acid(EDDA)s of N-, oxyethane is 137.8g (3.132 moles); the usage quantity of the basic cpd of calcium is 2.9 grams; get N, two stearoyl ethylenediamine-N,N'-diacetic acid(EDDA) two polyoxy Vinyl Ether (n=6) 300.8 grams of N-, molar yield 93.6%.
(d) N, the two stearoyl ethylenediamine-N,N'-diacetic acid(EDDA) two two carboxylate salts of polyoxy Vinyl Ether (n=6) of N-synthetic
The N that step (c) is synthesized; two stearoyl ethylenediamine-N,N'-diacetic acid(EDDA) two polyoxy Vinyl Ether (n=6) 300.8 grams (0.24 mole) of N-and 80.8 grams (1.44 moles) potassium hydroxide, 139.8 grams (1.2 moles) sodium chloroacetate, 15.2 gram Tetrabutyl amonium bromides, 1000 milliliters of toluene are mixed in to be furnished with mechanical stirring, in the there-necked flask of 2000 milliliters of thermometer and reflux condensing tube, to be heated to 110 ℃ of reactions 12 hours.Cooling, neutralization divides and removes inorganic salt, the N that alkalizes to get, and two stearoyl ethylenediamine-N,N'-diacetic acid(EDDA) two two carboxylate salt 271.8 grams of polyoxy Vinyl Ether (n=6) of N-, molar yield is 81.0%.To synthetic N, the two stearoyl ethylenediamine-N,N'-diacetic acid(EDDA) two two carboxylate salts of polyoxy Vinyl Ether (n=6) of N-are used U.S. Nicolet-380FT-IR spectrograph, adopt liquid-film method to carry out Infrared spectroscopy (sweep limit 4000～400cm
-1), have all charateristic avsorption bands of Fig. 1.
(e) with the synthetic N of step (d); the two stearoyl ethylenediamine-N,N'-diacetic acid(EDDA) two two carboxylate salt 0.2wt% of polyoxy Vinyl Ether (n=6) of N-, above-mentioned ultra-high-molecular aniouic polyacrylamide 0.15wt% and 96.5wt% Shengli Oil Field field of razor clam island block injected water mix and blend 2 hours obtain a kind of seawater-based oil displacement agent of homogeneous transparent.At 65 ℃ of temperature, salinity 15000mg/L, Ca
2++ Mg
2+In the water of 800mg/L, the apparent viscosity that records this seawater-based oil displacement agent is 16.1mPa.s; Form the ultra low interfacial tension of 0.0008mN/m between this seawater-based oil displacement agent and Shengli Oil Field field of razor clam island block dewatered oil.Apparent viscosity is by the BROODFIELD II type viscometer determining of U.S. Brookfield company, and the TX500 type rotation that interfacial tension is produced by Texas ,Usa university is dripped interfacial tensimeter and measured.
[embodiment 7]
(a) two 18 (tristearin) acyl group hexanediamine is synthetic
With [embodiment 6] (a), difference substitutes 30.0 grams (0.5 mole) anhydrous ethylenediamine with the anhydrous hexanediamine of 58.0 grams (0.5 mole), and all the other are identical, gets white powder solid, yield 96.3% after vacuum-drying.
(b) N, the two stearoyl hexanediamine oxalic acid of N-synthetic
Stearic bicine diester base hexanediamine 304.6 grams (0.47 mole) that step (a) is synthetic, 609 gram tetrahydrofuran (THF)s, 210.6 grams (3.76 moles) sodium hydroxide and 7.5 gram Tetrabutyl amonium bromides; add be furnished with mechanical stirring, in the there-necked flask of 2000 milliliters of thermometer and reflux condensing tube, quaternization 4 hours are heated to reflux.Divide the sodium chloroacetate solid that adds total amount 438.0 grams (3.76 moles) for five times after slightly cooling, kept back flow reaction 10 hours.Cooling, be neutralized to reaction solution with hydrochloric acid and be strongly-acid, be cooled to room temperature, suction filtration, to neutral, vacuum-drying gets white powder solid 185.6 grams, molar yield 51.7% with the distilled water wash solid.
(c) N, the two stearoyl hexanediamine oxalic acid two polyoxy Vinyl Ethers (n=5) of N-synthetic
With [embodiment 1] (c); difference is with the N of 185.6 grams (0.243 mole); the two stearoyl hexanediamine oxalic acid of N-substitute 165.0 grams (0.305 mole) N; the usage quantity of the two lauroyl ethylenediamine-N,N'-diacetic acid(EDDA)s of N-, oxyethane is 106.9g (2.43 moles); the usage quantity of the basic cpd of calcium is 3.0 grams; get N, two stearoyl hexanediamine oxalic acid two polyoxy Vinyl Ether (n=5) 271.2 grams of N-, molar yield 92.7%.
(d) N, the two stearoyl hexanediamine oxalic acid two two carboxylate salts of polyoxy Vinyl Ether (n=5) of N-synthetic
The N that step (c) is synthesized; two stearoyl hexanediamine oxalic acid two polyoxy Vinyl Ether (n=5) 271.2 grams (0.23 mole) of N-and 90.3 grams (1.61 moles) potassium hydroxide, 134.0 grams (1.15 moles) sodium chloroacetate, 15.0 gram Tetrabutyl amonium bromides, 1000 milliliters of toluene are mixed in to be furnished with mechanical stirring, in the there-necked flask of 2000 milliliters of thermometer and reflux condensing tube, to be heated to 110 ℃ of reactions 12 hours.Cooling, neutralization divides and removes inorganic salt, the N that alkalizes to get, and two stearoyl hexanediamine oxalic acid two two carboxylate salt 246.6 grams of polyoxy Vinyl Ether (n=5) of N-, molar yield is 78.5%.To synthetic N, the two stearoyl hexanediamine oxalic acid two two carboxylate salts of polyoxy Vinyl Ether (n=5) of N-are used U.S. Nicolet-380FT-IR spectrograph, adopt liquid-film method to carry out Infrared spectroscopy (sweep limit 4000～400cm
-1), have all charateristic avsorption bands of Fig. 1.
(e) with the synthetic N of step (d); the two stearoyl hexanediamine oxalic acid two two carboxylate salt 0.15wt% of polyoxy Vinyl Ether (n=5) of N-, above-mentioned modified polyacrylamide 0.2wt% and 96.5wt% Shengli Oil Field field of razor clam island block injected water mix and blend 2.5 hours obtain a kind of seawater-based oil displacement agent of homogeneous transparent.At 65 ℃ of temperature, salinity 21000mg/L, Ca
2++ Mg
2+In the water of 1067mg/L, the apparent viscosity that records this seawater-based oil displacement agent is 16.3mPa.s; Form the ultra low interfacial tension of 0.0009mN/m between this seawater-based oil displacement agent and Shengli Oil Field field of razor clam island block dewatered oil.Apparent viscosity is by the BROODFIELD II type viscometer determining of U.S. Brookfield company, and the TX500 type rotation that interfacial tension is produced by Texas ,Usa university is dripped interfacial tensimeter and measured.
[embodiment 8～14]
The seawater-based oil displacement agent that [embodiment 1～7] is synthetic is 30 centimetres in length, and diameter is 2.5 centimetres, and rate of permeation is 1.5 microns
2Rock core on carry out imitation oil displacement experiment test.First be driven to moisture 94% with Shengli Oil Field field of razor clam island block injected water, record water drive and can improve oil recovery factor 55.5～60.5%, again after the seawater-based oil displacement agent of metaideophone 0.3pv (rock pore volume) [embodiment 1～7], water drive is to moisture more than 98%, record on the water drive basis and can improve again oil recovery factor 16.6～18.9%, the results are shown in Table shown in 1.
[comparative example 1]
With [embodiment 1] (e); difference substitutes 0.15wt%N with the petroleum sodium sulfonate (Wuxi refinery) of 0.15wt%; the two lauroyl ethylenediamine-N,N'-diacetic acid(EDDA) two two carboxylate salts of polyoxy Vinyl Ether (n=4) of N-; all the other are identical; the apparent viscosity that records this seawater-based oil displacement agent is 14.1mPa.s, forms the interfacial tension of 0.0352mN/m between this seawater-based oil displacement agent and Shengli Oil Field field of razor clam island block dewatered oil.Apparent viscosity is by the BROODFIELD II type viscometer determining of U.S. Brookfield company, and the TX500 type rotation that interfacial tension is produced by Texas ,Usa university is dripped interfacial tensimeter and measured.
The above-mentioned seawater-based oil displacement agent that makes records water drive and can improve oil recovery factor 56.8% to carry out the displacement of reservoir oil with the method for [embodiment 8], can improve oil recovery factor 12.1% on the water drive basis after the above-mentioned seawater-based oil displacement agent of metaideophone again, the results are shown in Table shown in 1.
[comparative example 2]
With [embodiment 1] (e), difference substitutes the above-mentioned ultra-high-molecular aniouic polyacrylamide (viscosity-average molecular weight is as 2,400 ten thousand) of 0.15wt% take the high molecular weight polyacrylamide (viscosity-average molecular weight is as 1,800 ten thousand) of 0.15wt%, all the other are identical, the apparent viscosity that records this seawater-based oil displacement agent is 11.6mPa.s, forms the interfacial tension of 0.0072mN/m between this seawater-based oil displacement agent and Shengli Oil Field field of razor clam island block dewatered oil.Apparent viscosity is by the BROODFIELDII type viscometer determining of U.S. Brookfield company, and the TX500 type rotation that interfacial tension is produced by Texas ,Usa university is dripped interfacial tensimeter and measured.
The above-mentioned seawater-based oil displacement agent that makes records water drive and can improve oil recovery factor 58.3% to carry out the displacement of reservoir oil with the method for [embodiment 8], can improve oil recovery factor 11.8% on the water drive basis after the above-mentioned seawater-based oil displacement agent of metaideophone again, the results are shown in Table shown in 1.
The different oil-displacing agents of table 1 are to Shengli Oil Field field of razor clam island block oil displacement test result
Claims (6)
1. seawater-based oil displacement agent comprises following component by percentage to the quality:
(1) 0.01～5.0% N, the two carboxylate salts of the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy Vinyl Ethers of N-;
(2) 0.01～3.0% polymkeric substance;
(3) 92.0～99.98% injected water;
Wherein the general molecular formula of (1) component is:
In formula: R
1Be C
9～C
17Alkyl, R
2Be C
2～C
6Alkylidene group, n is the adduction number of ethoxy group EO, its span is any one integer in 2～7; M is any one metal ion that is selected from potassium, sodium or lithium; Described polymkeric substance is selected from one or both in ultra-high-molecular aniouic polyacrylamide, modified polyacrylamide or xanthan gum; Described ultra-high-molecular aniouic polyacrylamide, its viscosity-average molecular weight is 2,400 ten thousand, modified polyacrylamide is formed by acrylamide, 2-acrylamide-2-methylpro panesulfonic acid, three kinds of monomer copolymerizations of 2-acrylamido dodecyl sodium sulfonate, its molar percentage is 80: 18: 2, and its viscosity-average molecular weight is 15,000,000.
2. seawater-based oil displacement agent according to claim 1, the total mineralization that it is characterized in that described injected water is 10000～40000 mg/litre, Ca
2++ Mg
2+Be 400～1800 mg/litre, the water type is MgCl
2Type.
3. seawater-based oil displacement agent according to claim 1, is characterized in that described N, the R in the two carboxylate salts of the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy Vinyl Ethers of N-
1Carbonatoms is nine, 11,13,15 or 17.
4. seawater-based oil displacement agent according to claim 1, is characterized in that described N, the R in the two carboxylate salts of the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy Vinyl Ethers of N-
2Carbonatoms be two, four or six.
5. seawater-based oil displacement agent according to claim 1, is characterized in that described N, the R in the two carboxylate salts of the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy Vinyl Ethers of N-
1Carbon number adds 1 sum, and EO counts the ratio of n between 2～4.
6. the preparation method of seawater-based oil displacement agent claimed in claim 1 comprises the following steps:
(a) N, the preparation of N-two fatty acyl diamines:
be 10～18 lipid acid with the carbochain number of required proportioning, thionyl chloride and N, dinethylformamide DMF was 70～100 ℃ of reactions 2～5 hours, excessive thionyl chloride is extracted in decompression out, it is 10～18 fat acyl chloride that the transparent liquid that obtains is the carbochain number, after adding the carbochain number to be the dilution with toluene of 10～18 lipid acid quality 1/2nd, be warming up to 60～90 ℃, be 2～6 diamines with the carbochain number by required proportioning, pyridine and consumption are that the carbochain number is that slowly to splash into the carbochain number after the toluene of 10～18 lipid acid quality 1/2nd mixes be in 10～18 fat acyl chloride solution, reacted 2～5 hours, obtain the white powder solid chemical compound through aftertreatment, wherein, the carbochain number is 10～18 lipid acid, thionyl chloride and N, the mol ratio of dinethylformamide is 1: 1.0～2.0: 0.03～0.1, and the carbochain number is that 10～18 fat acyl chloride, carbochain number are that 2～6 diamines and the mol ratio of pyridine are 2.0～4.0: 1: 1.5～3.5,
(b) N, the preparation of the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA)s of N-:
The N that step (a) is synthesized, the two carbochain numbers of N-are 10～18 fatty acyl diamines by after required proportioning and sodium hydroxide or potassium hydroxide, Tetrabutyl amonium bromide catalyst mix, to add N, after the tetrahydrofuran (THF) dilution that the two carbochain numbers of N-are 10～18 fatty acyl diamines quality 1/2nd, be heated to back flow reaction 2～8 hours, add again the sodium chloroacetate of required proportioning to continue back flow reaction 6～14 hours, get the white powder solid through aftertreatment; Wherein, N, the mol ratio that the two carbochain numbers of N-are 10～18 fatty acyl diamines, sodium chloroacetate, sodium hydroxide or potassium hydroxide and Tetrabutyl amonium bromide=1: 2～9: 3～9: 0.02～0.07;
(c) N, the preparation of the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy Vinyl Ethers of N-:
The N that step (b) is synthesized, the two carbochain numbers of N-are that 10～18 fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA)s and oxyethane are 85～160 ℃ by required proportioning in temperature of reaction, pressure is less than under 0.80MPa gauge pressure condition, the basic cpd of calcium is catalyzer, react to get N, the two carbochain numbers of N-are 10～18 fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy Vinyl Ethers; Wherein, N, the two carbochain numbers of N-are that 10～18 fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA)s and oxyethane mol ratio are 1: 4～14, and catalyst levels is N, and the two carbochain numbers of N-are 0.5～5.0% of 10～18 fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) quality;
(d) N, the preparation of the two carboxylate salts of the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy Vinyl Ethers of N-:
The N that step (c) is synthesized, the two carbochain numbers of N-are that 10～18 fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy Vinyl Ethers are by required proportioning and sodium chloroacetate, potassium hydroxide or sodium hydroxide and Tetrabutyl amonium bromide catalyst mix, take toluene as solvent, 50～130 ℃ of temperature of reaction, reacted 3～15 hours, reaction finishes to get N by aftertreatment, the two carboxylate salts of the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy Vinyl Ethers of N-; Wherein, N, the mol ratio that the two carbochain numbers of N-are 10～18 fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy Vinyl Ethers, sodium chloroacetate, potassium hydroxide or sodium hydroxide and Tetrabutyl amonium bromide=1: 2～6: 2～8: 0.05～0.3;
(e) with the N of aequum, the two carboxylate salts of the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy Vinyl Ethers of N-, above-mentioned ultra-high-molecular aniouic polyacrylamide or modified polyacrylamide and injected water evenly mix, stirring at room 1～3 hour obtains required composition; By percentage to the quality; N, the proportioning of the two carboxylate salts of the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy Vinyl Ethers of N-, ultra-high-molecular aniouic polyacrylamide or modified polyacrylamide and injected water is 0.01～5.0%: 0.01～3.0%: 92.0～99.98%.
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