CN102373041A

CN102373041A - Oil displacement method by use of seawater base oil displacement agent

Info

Publication number: CN102373041A
Application number: CN2010102607326A
Authority: CN
Inventors: 沈之芹; 吴国英; 沙鸥; 鲍新宁
Original assignee: China Petroleum and Chemical Corp; Sinopec Shanghai Research Institute of Petrochemical Technology
Current assignee: China Petroleum and Chemical Corp; Sinopec Shanghai Research Institute of Petrochemical Technology
Priority date: 2010-08-23
Filing date: 2010-08-23
Publication date: 2012-03-14
Anticipated expiration: 2030-08-23
Also published as: CN102373041B

Abstract

The invention relates to an oil displacement method by the use of a seawater base oil displacement agent and mainly solves the problem that a surfactant-containing oil displacement agent in the prior art has poor oil displacement efficiency and high concentration and alkali in alkali-surfactant-polymer flooding brings corrosion and deposit damage to stratum and oil well. According to the oil displacement method by the use of the seawater base oil displacement agent, underground dehydrated crude oil contacts with the seawater base oil displacement agent to fully displace the crude oil from the core under the injection water condition that the oil displacement temperature is 30-83 DEG C, the total salinity is greater than 8000mg/L and Ca<2+> + Mg<2+> is greater than 200mg/L. The seawater base oil displacement agent comprises the following components of: by weight, (1) 0.01-5.0% of N,N-double fatty acyl diamines diacetic acid dipolyoxyethylene ether double carboxylate; (2) 0.01-3.0% of a polymer; (3) 92.0-99.98% of injection water. The technical scheme greatly solves the problem and can be used for the tertiary oil recovery production in oil field.

Description

A kind of flooding method that uses the seawater base oil-displacing agent

Technical field

The present invention relates to a kind of flooding method that uses the seawater base oil-displacing agent.

Background technology

Along with The development in society and economy, 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 big more greatly 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, satisfy human wants that must research and development improve petroleum recovery technology, TOR (EOR) can make oil recovery factor improve 6～20% again through the intensified oil reduction measure, even more.

Chemical flooding is an important method that improves RF.Surfactant flooding is considered to improve by a relatively large margin a kind of chemical agent of RF, 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 RF.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 receives 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 the novel surfactant that research and development have a high surface more and alkali-free binary combination flooding are filled a prescription is imperative.

The tensio-active agent industrialization product of external used for tertiary oil recovery mainly contains two big types: the one, and sulfonated petro-leum is main tensio-active agent; The 2nd, sulfonated alkylbenzene is main tensio-active agent; These two types of tensio-active agent raw materials are all taken from crude oil; Raw material sources are wide, quantity is big, thereby also are the maximum tensio-active agents of external TOR consumption.Because sulfonate surfactant is an anionic, it and divalent cation (inject the Ca of 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 multi-functional tensio-active agent, Gemini surface active agent and sacrifice agent, and pays attention to the composite research of various tensio-active agents.

The moon-nonionic amphoterics is one of focus of TOR (EOR) area research in recent years always; Owing in its molecular structure two kinds of non-ionic groups of different nature and anionic group are designed in same surfactant molecule; Make it have the advantage of negatively charged ion and nonionogenic tenside concurrently; Therefore mutual supplement with each other's advantages, excellent property have shown good prospects for application, the binary combination flooding system that especially exists to alkali-free; Owing to do not have the existence of alkali not only to avoid the problems such as obstruction, fouling and corrosion of oil reservoir, and can form ultra low interfacial tension with crude oil.In recent years; Because Shuangzi (Gemini) tensio-active agent is to be connected base key with one and to be closed the special construction compound that forms by two hydrophilic radicals, two hydrophobic groupings; 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 prescription, under rational formula system, finally realizes binary displacement system, for the chemical flooding in oil field is opened up new approach.

In the patented claim at beginning of the thirties late 1920s, Degroot (De Groot) just once proposed the RF that the water soluble surfactant active helps to improve oil.

At present; The main Gemini surface active agent of domestic research and development mainly is the positively charged ion double quaternary ammonium salt type, has reported in succession that like Chinese patent CN 1528853, CN 1817431, CN 1066137 etc. the bisamide type is cationic, fluorine-containing cationic and contain the pyridyl cation Gemini surfactant.Shortcomings such as the absorption loss is big because positively charged ion has, cost height; 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 like Chinese patent CN 101073757.And since aniorfic surfactant to have salt tolerance poor, and non-ionic type has the shortcoming of temperature tolerance difference, makes that these products can't being applied at high temperature and high salt oil deposit.

In addition, in the existing ternary composite oil-displacing system, contain the alkali of high density; Like 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 the is complete works of " P35.So to those harsh oil reservoirs, we ought to seek a kind of under alkali-free, high temperature (FT is greater than 65 ℃), high salt (more than the 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 just under the alkali-free situation, be suitable for high temperature and high salt oil deposit the moon-non-Gemini surface active agent, its preparation method, binary is compound and the application in TOR.

Summary of the invention

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 flooding method of new use seawater base oil-displacing agent.This method will contain N; The seawater base oil-displacing agent of the two carboxylate surface active agents of the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy Vinyl Ethers of N-is used for oil displacement process; Have alkali-free, do not have corrosion and incrustation injury, working concentration is low, the high characteristics of oil displacement efficiency under the high temperature and high salt condition.

In order to solve the problems of the technologies described above, the technical scheme that the present invention adopts is following: a kind of flooding method that uses the seawater base oil-displacing agent, with the seawater base oil-displacing agent at 30～83 ℃ of displacement of reservoir oil temperature, total mineralization＞8000mg/L, Ca ²⁺+ Mg ²⁺Under the injection water condition of＞200mg/L, underground dewatered oil is contacted with the seawater base oil-displacing agent, the abundant displacement of the crude oil in the rock core is come out, wherein said seawater base oil-displacing 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% injection water;

Wherein the general molecular formula of (1) component is:

In the 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 integer in 2～7; M is any one metals ion that is selected from potassium, sodium or the lithium; Polymkeric substance is selected from one or both in ultra-high-molecular aniouic polyacrylamide, modified polyacrylamide or the XG 550.

In the technique scheme, displacement of reservoir oil temperature is preferably 45～75 ℃, and described injection water total mineralization is preferably 15000～32000 mg/litre, Ca ²⁺+ Mg ²⁺Be preferably 750～1600 mg/litre; Polymkeric substance is preferably 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, its water-soluble fluid power and crude oil formation 10 at 3～4 o'clock that carbon number adds ratio preferable range that 1 sum and EO count n ^-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.

This flooding method specifically may further comprise the steps:

(a) N, the preparation of N-two fatty acyl diamines:

With the carbochain number of required proportioning 10～18 lipid acid, 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 and be the dilution with toluene of 10～18 lipid acid quality 1/2nd, being warming up to 60～90 ℃, is that 2～6 diamines, 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 the fat acyl chloride solution by required proportioning with the carbochain number; Reacted 2～5 hours, and obtained 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 the 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-:

Step (a) the synthetic N of institute; The two carbochain numbers of N-are 10～18 fatty acyl diamines by after required proportioning and sodium hydroxide or Pottasium Hydroxide, the Tetrabutyl amonium bromide catalyst mix; To add N, after the 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; The sodium chloroacetate that adds required proportioning again continued back flow reaction 6～14 hours, got the white powder solid through aftertreatment.Wherein, N, the two carbochain numbers of N-are mol ratio=1: 2～9: 3～9: 0.02～0.07 of 10～18 fatty acyl diamines, sodium chloroacetate, sodium hydroxide (Pottasium Hydroxide) and Tetrabutyl amonium bromide.

(c) N, the preparation of the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy Vinyl Ethers of N-:

Step (b) the synthetic N of institute; 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 the 0.80MPa gauge pressure condition; The basic cpd of calcium is a catalyzer, react N, the two carbochain numbers of N-are 10～18 fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA)s, 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-:

With step (c) the synthetic N of institute; The two carbochain numbers of N-are that 10～18 fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA)s, two polyoxy Vinyl Ethers are by required proportioning and sodium chloroacetate, Pottasium Hydroxide or sodium hydroxide and Tetrabutyl amonium bromide catalyst mix; With toluene is solvent, 50～130 ℃ of temperature of reaction, reacts 3～15 hours; Reaction finishes after aftertreatment gets N, 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 two carbochain numbers of N-are mol ratio=1: 2～6: 2～8: 0.05～0.3 of 10～18 fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA)s, two polyoxy Vinyl Ethers, sodium chloroacetate, Pottasium Hydroxide or sodium hydroxide and Tetrabutyl amonium bromide.

(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 inject the water uniform mixing; Stirring at room 1～3 hour obtains required seawater base oil-displacing agent.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 injection water is 0.01～5.0%: 0.01～3.0%: 92.0～99.98%.

(f) be 10000～40000mg/L, Ca with total mineralization earlier ²⁺+ Mg ²⁺The injection water that is 400～1800mg/L is saturated with rock core; Measure the volume of voids (PV) of rock core; Carry out saturatedly then with dewatered oil, under 40～80 ℃ of temperature, carry out imitation oil displacement experiment test: first water drive is to moisture 94%, behind metaideophone 0.3pv (rock pore volume) step (f) the synthetic seawater base oil-displacing agent; Water drive is calculated the percentage ratio that improves oil recovery factor to moisture more than 98%.

In the technique scheme; (a) the carbochain number is 10～18 lipid acid, thionyl chloride and N in the step; 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 the 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 the step, the two carbochain numbers of N-be the mol ratio of 10～18 fatty acyl diamines, sodium chloroacetate, sodium hydroxide (Pottasium 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 the step; The two carbochain numbers of N-be the mol ratio of 10～18 fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA)s, two polyoxy Vinyl Ethers, sodium chloroacetate, sodium hydroxide (Pottasium 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%; Above-mentioned ultra-high-molecular aniouic polyacrylamide or modified polyacrylamide consumption preferable range are 0.05～0.5%; More preferably scope is 0.1～0.2%, and the reaction times is preferably 1.5～2.5 hours.(f) displacement of reservoir oil temperature is preferably 45～75 ℃; The local water total mineralization is preferably 15000～32000mg/L, Ca ²⁺+ Mg ²⁺Be preferably 750～1600mg/L.

The prepared displacement of reservoir oil of the present invention is with the N in the compsn; The two carboxylate salts of the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy Vinyl Ethers of N-; Owing to contain aerobic ethene non-ionic group and carboxylate anion group simultaneously in its molecular structure; Make the salt tolerant advantage of its heat resistance that has AS concurrently and nonionogenic tenside; And symmetric Shuangzi constitutional features, make again its have micelle-forming concentration low, reduce strong, anti-high salinity of IT ability and characteristics such as particular rheological properties and visco-elasticity-viscosifying action, have 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 the flooding method of use seawater base oil-displacing agent of the present invention, under the alkali-free condition, can be used for 45～75 ℃ of FTs, 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 injects water and crude oil; With consumption is 0.1～0.3wt%N; Above-mentioned ultra-high-molecular aniouic polyacrylamide or the modified polyacrylamide of the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy Vinyl Ether disulfonates of N-and 0.1～0.2wt% forms the above-mentioned compsn oil-displacing agent; Measure the dynamic interface tension value between this oil-displacing agent aqueous solution and the Shengli Oil Field field of razor clam island block crude oil, can reach 10 ^-3～10 ^-4The ultra low interfacial tension of mN/m; Can on the water drive basis, can reach 18.9% by (water drive improves oil recovery factor and reaches 60.8%) raising oil recovery factor through the indoor evaluation of physical simulation displacement test at this oil-displacing agent on high temperature, the high salinity reservoir, obtain better technical effect.

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 through following method: after synthetics is purified; Use U.S. Nicolet-380FT-IR spectrograph, adopt liquid-film method to carry out IR 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 the alkyl chain, 1475cm appear in the place ^-1C-H flexural vibration on the alkyl chain, 1856～1505cm ^-1A big broad peak, comprised the charateristic avsorption band of three kinds of ν C=O, 1418cm ^-1The peak is the III key band C-N stretching, extension of acid amides in the place, 1106cm ^-1Locate a broad peak, this peak is that the last C-O-C asymmetric stretch of EO bands of a spectrum cause 985cm owing to connected EO ^-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-.

Through embodiment the present invention is done further elaboration below.

Embodiment

[embodiment 1]

(a) two 12 (bay) acyl group quadrol is synthetic

With LAURIC ACID 99 MIN 300 grams (1.5 moles), sulfur oxychloride 267.8 grams (2.25 moles) and 4.5 gram DMF; Add and be furnished with in 2000 milliliters of four-hole boiling flasks of sealing machine stirring, TM, prolong etc.; After 3 hours, decompression steams excessive thionyl chloride, obtains lauroyl chloride in 90 ℃ of reactions.When temperature is reduced to 60 ℃; Add exsiccant toluene 150 grams; After stirring; Slowly drip the mixed solution of being made up of anhydrous ethylenediamine 30.0 grams (0.5 mole), anhydrous pyridine 99.0 grams (1.25 moles) and exsiccant toluene 150 grams, controlled temperature drips off and is warming up to 85 ℃ of reactions 2 hours less than 60 ℃.Cooling is filtered, and bullion gets white powder solid, molar yield 97.1% with ethyl alcohol recrystallization after the vacuum-drying.

(b) N, the two lauroyl ethylenediamine-N,N'-diacetic acid(EDDA)s of N-synthetic

With the bimonthly osmanthus of step (a) synthetic acyl group quadrol 200 grams (0.47 mole), 400 gram THFs, 112.8 gram (2.82 moles) sodium hydroxide and 7.5 gram Tetrabutyl amonium bromides; Add and be furnished with in 2000 milliliters the there-necked flask of mechanical stirring, TM and reflux condensing tube, be heated to the backflow quaternization 4 hours.Slightly the cooling back is divided and is added the sodium chloroacetate solid that total amount is 219.0 grams (1.88 moles) for five times, keeps back flow reaction 10 hours.Cooling is neutralized to reaction solution with hydrochloric acid and is strongly-acid, is cooled to room temperature, suction filtration, and 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 step (b) synthetic N; The basic cpd of two lauroyl ethylenediamine-N,N'-diacetic acid(EDDA) 165.0 grams (0.305 mole) of N-, 2.0 gram calcium adds to be furnished with in the high-pressure reactor of condensing works, 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 ℃; The open vacuum system, dehydration is 2 hours under high vacuum, uses nitrogen purging then 3～4 times; The system temperature of reaction is transferred to 140 ℃ slowly feed 107.6 gram (2.444 moles) oxyethane, control pressure≤0.60MPa.Reaction is used the nitrogen purging system after finishing, and cooling post neutralization, dehydration get N, the two lauroyl ethylenediamine-N,N'-diacetic acid(EDDA) two polyoxy Vinyl Ethers (n=4) of N-268.5 grams, molar yield 98.5%.

(d) N, the two two carboxylate salts of lauroyl ethylenediamine-N,N'-diacetic acid(EDDA) two polyoxy Vinyl Ethers (n=4) of N-synthetic

With step (c) the synthetic N of institute; The two lauroyl ethylenediamine-N,N'-diacetic acid(EDDA) two polyoxy Vinyl Ethers (n=4) of N-268.5 grams (0.30 mole) and 101.1 gram (1.80 moles) Pottasium Hydroxide, 139.8 gram (1.20 moles) sodium chloroacetates, 10.8 gram Tetrabutyl amonium bromides, 1000 milliliters of toluene are mixed in to be furnished with mechanical stirring, in 2000 milliliters the there-necked flask of TM and reflux condensing tube, to be heated to 90 ℃ of reactions 8 hours.Cooling, neutralization divides and to remove inorganic salt, alkalize N, two carboxylate salts 276.0 grams of the two lauroyl ethylenediamine-N,N'-diacetic acid(EDDA) two polyoxy Vinyl Ethers (n=4) of N-, molar yield is 87.3%.To synthetic N, the two two carboxylate salts of lauroyl ethylenediamine-N,N'-diacetic acid(EDDA) two polyoxy Vinyl Ethers (n=4) of N-are used U.S. Nicolet-380FT-IR spectrograph, adopt liquid-film method to carry out IR spectroscopy (sweep limit 4000～400cm ^-1), have all charateristic avsorption bands of Fig. 1.

(e) with step (d) synthetic N; The two two carboxylate salt 0.15wt% of lauroyl ethylenediamine-N,N'-diacetic acid(EDDA) two polyoxy Vinyl Ethers (n=4) of N-, above-mentioned modified polyacrylamide 0.15wt% and 97.0wt% Shengli Oil Field field of razor clam island block inject water to be mixed and stirred 2 hours, and what obtain a kind of homogeneous transparent is applicable to the seawater base oil-displacing agent.At 65 ℃ of temperature, salinity 31500mg/L, Ca ²⁺+ Mg ²⁺In the water of 1600mg/L, the AV that records this seawater base oil-displacing agent is 15.0mPa.s; Form the ultra low interfacial tension of 0.0019mN/m between this seawater base oil-displacing agent and the Shengli Oil Field field of razor clam island block dewatered oil.AV is by the BROODFIELD II type viscometer determining of U.S. Brookfield company, and IT is dripped interfacial tensimeter mensuration by the TX500 type rotation that Texas ,Usa university produces.

(f) earlier with salinity 31500mg/L, Ca ²⁺+ Mg ²⁺(length is 30 centimetres to the injection water of 1600mg/L, and diameter is 2.5 centimetres, and rate of permeation is 1.5 microns with rock core ²) saturated; The volume of voids (PV) of measuring rock core is 52.1%, carries out saturatedly then with Shengli Oil Field field of razor clam island block dewatered oil, and under 65 ℃ of constant temperature, carry out the imitation oil displacement experiment test: first water drive is to moisture 94%; Record water drive and improve oil recovery factor 58.7%; Behind metaideophone 0.3pv (rock pore volume) step (e) the synthetic seawater base oil-displacing agent, water drive records on the water drive basis and can improve oil recovery factor 17.2% again to moisture more than 98% again.

[embodiment 2]

(a) two 12 (bay) acyl group hexanediamine is synthetic

With [embodiment 1] (a), difference substitutes 30.0 gram (0.5 mole) anhydrous ethylenediamines with the anhydrous hexanediamine of 58.0 grams (0.5 mole), and all the other are identical, get white powder solid, molar yield 95.6% after the vacuum-drying.

(b) N, the two lauroyl hexanediamine oxalic acid of N-synthetic

With the bimonthly osmanthus of step (a) synthetic acyl group hexanediamine 225.6 grams (0.47 mole), 450 gram THFs, 105.3 gram (1.88 moles) Pottasium Hydroxide and 4.5 gram Tetrabutyl amonium bromides; Add and be furnished with in 2000 milliliters the there-necked flask of mechanical stirring, TM and reflux condensing tube, be heated to the backflow quaternization 3 hours.Slightly the cooling back is divided and is added the sodium chloroacetate solid that total amount is 164.3 grams (1.41 moles) for five times, keeps back flow reaction 9 hours.Cooling is neutralized to reaction solution with hydrochloric acid and is strongly-acid, is cooled to room temperature, suction filtration, and 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), and the two lauroyl hexanediamine oxalic acid of N-substitute 165.0 gram (0.305 mole) N, and 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, the two lauroyl hexanediamine oxalic acid two polyoxy Vinyl Ethers (n=3) of N-240.7 grams, molar yield 97.2%.

(d) N, the two two carboxylate salts of lauroyl hexanediamine oxalic acid two polyoxy Vinyl Ethers (n=3) of N-synthetic

With step (c) the synthetic N of institute; The two lauroyl hexanediamine oxalic acid two polyoxy Vinyl Ethers (n=3) of N-240.7 grams (0.28 mole) and 62.8 gram (1.12 moles) Pottasium Hydroxide, 139.8 gram (1.20 moles) sodium chloroacetates, 10.2 gram Tetrabutyl amonium bromides, 1000 milliliters of toluene are mixed in to be furnished with mechanical stirring, in 2000 milliliters the there-necked flask of TM and reflux condensing tube, to be heated to 100 ℃ of reactions 6 hours.Cooling, neutralization divides and to remove inorganic salt, alkalize N, two carboxylate salts 248.1 grams of the two lauroyl hexanediamine oxalic acid two polyoxy Vinyl Ethers (n=3) of N-, molar yield is 86.7%.To synthetic N, the two two carboxylate salts of lauroyl hexanediamine oxalic acid two polyoxy Vinyl Ethers (n=3) of N-are used U.S. Nicolet-380FT-IR spectrograph, adopt liquid-film method to carry out IR spectroscopy (sweep limit 4000～400cm ^-1), have all charateristic avsorption bands of Fig. 1.

(e) with step (d) synthetic N; The two two carboxylate salt 0.2wt% of lauroyl hexanediamine oxalic acid two polyoxy Vinyl Ethers (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 inject water mixing stirring 2 hours, obtain a kind of seawater base oil-displacing agent of homogeneous transparent.At 65 ℃ of temperature, salinity 21000mg/L, Ca ²⁺+ Mg ²⁺In the water of 1067mg/L, the AV that records this seawater base oil-displacing agent is 15.5mPa.s; Form the ultra low interfacial tension of 0.0038mN/m between this seawater base oil-displacing agent and the Shengli Oil Field field of razor clam island block dewatered oil.AV is by the BROODFIELD II type viscometer determining of U.S. Brookfield company, and IT is dripped interfacial tensimeter mensuration by the TX500 type rotation that Texas ,Usa university produces.

(f) earlier with salinity 21000mg/L, Ca ²⁺+ Mg ²⁺(length is 30 centimetres to the injection water of 1067mg/L, and diameter is 2.5 centimetres, and rate of permeation is 1.5 microns with rock core ²) saturated; The volume of voids (PV) of measuring rock core is 53.2%, carries out saturatedly then with Shengli Oil Field field of razor clam island block dewatered oil, and under 65 ℃ of constant temperature, carry out the imitation oil displacement experiment test: first water drive is to moisture 94%; Record water drive and improve oil recovery factor 57.3%; Behind metaideophone 0.3pv (rock pore volume) step (e) the synthetic seawater base oil-displacing agent, water drive records on the water drive basis and can improve oil recovery factor 17.6% again to moisture more than 98% again.

[embodiment 3]

(a) two ten (last of the ten Heavenly stems) acyl group tetramethylenediamine is synthetic

With [embodiment 1] (a); Difference substitutes 300.0 gram (1.5 moles) LAURIC ACID 99 MIN with the capric acid of 261.0 grams (1.5 moles); Anhydrous tetramethylenediamine with 44.0 grams (0.5 mole) substitutes 30.0 gram (0.5 mole) anhydrous ethylenediamines; All the other are identical, get white powder solid, molar yield 96.7% after the vacuum-drying.

(b) N, the two ten acyl group tetramethylenediamine oxalic acid of N-synthetic

With two decanoyl tetramethylenediamine 186.1 grams (0.47 mole) of step (a) synthetic, 400 gram THFs, 112.8 gram (2.82 moles) sodium hydroxide and 7.5 gram Tetrabutyl amonium bromides; Add and be furnished with in 2000 milliliters the there-necked flask of mechanical stirring, TM and reflux condensing tube, be heated to the backflow quaternization 3 hours.Slightly the cooling back is divided and is added the sodium chloroacetate solid that total amount is 219.0 grams (1.88 moles) for five times, keeps back flow reaction 12 hours.Cooling is neutralized to reaction solution with hydrochloric acid and is strongly-acid, is cooled to room temperature, suction filtration, and to neutral, vacuum-drying gets white powder solid 152.5 grams, molar yield 63.4% with the distilled water wash solid.

(c) N, two ten acyl group tetramethylenediamine oxalic acid, the 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), and the two ten acyl group tetramethylenediamine oxalic acid of N-substitute 165.0 gram (0.305 mole) N, and 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, the two ten acyl group tetramethylenediamine oxalic acid of N-two polyoxy Vinyl Ethers (n=3) 225.5 grams, molar yield 97.5%.

(d) N, the two two carboxylate salts of ten acyl group tetramethylenediamine oxalic acid, two polyoxy Vinyl Ethers (n=3) of N-synthetic

With step (c) the synthetic N of institute; The two ten acyl group tetramethylenediamine oxalic acid of N-two polyoxy Vinyl Ethers (n=3) 225.5 grams (0.29 mole) and 65.1 gram (1.16 moles) Pottasium Hydroxide, 101.4 gram (0.87 mole) sodium chloroacetates, 12.2 gram Tetrabutyl amonium bromides, 1000 milliliters of toluene are mixed in to be furnished with mechanical stirring, in 2000 milliliters the there-necked flask of TM and reflux condensing tube, to be heated to 80 ℃ of reactions 8 hours.Cooling, neutralization divides and to remove inorganic salt, alkalize N, two carboxylate salts 231.2 grams of two ten acyl group tetramethylenediamine oxalic acid, the two polyoxy Vinyl Ethers (n=3) of N-, molar yield is 85.0%.To synthetic N, the two two carboxylate salts of ten acyl group tetramethylenediamine oxalic acid, two polyoxy Vinyl Ethers (n=3) of N-are used U.S. Nicolet-380 FT-IR spectrograph, adopt liquid-film method to carry out IR spectroscopy (sweep limit 4000～400cm ^-1), have all charateristic avsorption bands of Fig. 1.

(e) with step (d) synthetic N; The two two carboxylate salt 0.15wt% of ten acyl group tetramethylenediamine oxalic acid, two polyoxy Vinyl Ethers (n=3) of N-, above-mentioned modified polyacrylamide 0.15wt% and 97.0wt% Shengli Oil Field field of razor clam island block inject water mixing stirring 1.5 hours, obtain a kind of seawater base oil-displacing agent of homogeneous transparent.At 70 ℃ of temperature, salinity 15000mg/L, Ca ²⁺+ Mg ²⁺In the water of 800mg/L, the AV that records this seawater base oil-displacing agent is 15.5mPa.s; Form the ultra low interfacial tension of 0.0032mN/m between this seawater base oil-displacing agent and the Shengli Oil Field field of razor clam island block dewatered oil.AV is by the BROODFIELD II type viscometer determining of U.S. Brookfield company, and IT is dripped interfacial tensimeter mensuration by the TX500 type rotation that Texas ,Usa university produces.

(f) earlier with salinity 15000mg/L, Ca ²⁺+ Mg ²⁺(length is 30 centimetres to the injection water of 800mg/L, and diameter is 2.5 centimetres, and rate of permeation is 1.5 microns with rock core ²) saturated; The volume of voids (PV) of measuring rock core is 52.7%, carries out saturatedly then with Shengli Oil Field field of razor clam island block dewatered oil, and under 70 ℃ of constant temperature, carry out the imitation oil displacement experiment test: first water drive is to moisture 94%; Record water drive and improve oil recovery factor 59.2%; Behind metaideophone 0.3pv (rock pore volume) step (e) the synthetic seawater base oil-displacing agent, water drive records on the water drive basis and can improve oil recovery factor 17.9% again to moisture more than 98% again.

[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 and be furnished with in 2000 milliliters of four-hole boiling flasks of sealing machine stirring, TM, prolong etc.; After 5 hours, decompression steams excessive thionyl chloride, obtains palmityl chloride in 80 ℃ of reactions.When temperature is reduced to 60 ℃; Add exsiccant toluene 160 grams; After stirring; Slowly drip the mixed solution of being made up of anhydrous ethylenediamine 30.0 grams (0.5 mole), anhydrous pyridine 79.2 grams (1.0 moles) and exsiccant toluene 160 grams, controlled temperature drips off and is warming up to 75 ℃ of reactions 3 hours less than 60 ℃.Cooling is filtered, and bullion gets white powder solid, molar yield 91.3% with ethyl alcohol recrystallization after the vacuum-drying.

(b) N, the two palmitoyl ethylenediamine-N,N'-diacetic acid(EDDA)s of N-synthetic

With two palmitoyl quadrol 251.9 grams (0.47 mole) of step (a) synthetic, 504 gram THFs, 94.0 gram (2.35 moles) sodium hydroxide and 6.0 gram Tetrabutyl amonium bromides; Add and be furnished with in 2000 milliliters the there-necked flask of mechanical stirring, TM and reflux condensing tube, be heated to the backflow quaternization 6 hours.Slightly the cooling back is divided and is added the sodium chloroacetate solid that total amount is 164.3 grams (1.41 moles) for five times, keeps back flow reaction 12 hours.Cooling is neutralized to reaction solution with hydrochloric acid and is strongly-acid, is cooled to room temperature, suction filtration, and 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), and the two palmitoyl ethylenediamine-N,N'-diacetic acid(EDDA)s of N-substitute 165.0 gram (0.305 mole) N, and 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, the two palmitoyl ethylenediamine-N,N'-diacetic acid(EDDA) two polyoxy Vinyl Ethers (n=5) of N-304.9 grams, molar yield 95.3%.

(d) N, the two two carboxylate salts of palmitoyl ethylenediamine-N,N'-diacetic acid(EDDA) two polyoxy Vinyl Ethers (n=5) of N-synthetic

With step (c) the synthetic N of institute; The two palmitoyl ethylenediamine-N,N'-diacetic acid(EDDA) two polyoxy Vinyl Ethers (n=5) of N-304.9 grams (0.28 mole) and 67.0 gram (1.68 moles) sodium hydroxide, 130.5 gram (1.12 moles) sodium chloroacetates, 11.5 gram Tetrabutyl amonium bromides, 1000 milliliters of toluene are mixed in to be furnished with mechanical stirring, in 2000 milliliters the there-necked flask of TM and reflux condensing tube, to be heated to 100 ℃ of reactions 8 hours.Cooling, neutralization divides and to remove inorganic salt, alkalize N, two carboxylate salts 298.5 grams of the two palmitoyl ethylenediamine-N,N'-diacetic acid(EDDA) two polyoxy Vinyl Ethers (n=5) of N-, molar yield is 85.0%.To synthetic N, the two two carboxylate salts of ten acyl group tetramethylenediamine oxalic acid, two polyoxy Vinyl Ethers (n=5) of N-are used U.S. Nicolet-380 FT-IR spectrograph, adopt liquid-film method to carry out IR spectroscopy (sweep limit 4000～400cm ^-1), have all charateristic avsorption bands of Fig. 1.

(e) with step (d) synthetic N; The two two carboxylate salt 0.25wt% of ten acyl group tetramethylenediamine oxalic acid, two polyoxy Vinyl Ethers (n=5) of N-, above-mentioned modified polyacrylamide 0.15wt% and 96.0wt% Shengli Oil Field field of razor clam island block inject water mixing stirring 2.5 hours, obtain a kind of seawater base oil-displacing agent of homogeneous transparent.At 80 ℃ of temperature, salinity 31500mg/L, Ca ²⁺+ Mg ²⁺In the water of 1600mg/L, the AV that records this seawater base oil-displacing agent is 14.0mPa.s; Form the ultra low interfacial tension of 0.0003mN/m between this seawater base oil-displacing agent and the Shengli Oil Field field of razor clam island block dewatered oil.AV is by the BROODFIELD II type viscometer determining of U.S. Brookfield company, and IT is dripped interfacial tensimeter mensuration by the TX500 type rotation that Texas ,Usa university produces.

(f) earlier with salinity 31500mg/L, Ca ²⁺+ Mg ²⁺(length is 30 centimetres to the injection water of 1600mg/L, and diameter is 2.5 centimetres, and rate of permeation is 1.5 microns with rock core ²) saturated; The volume of voids (PV) of measuring rock core is 53.3%, carries out saturatedly then with Shengli Oil Field field of razor clam island block dewatered oil, and under 80 ℃ of constant temperature, carry out the imitation oil displacement experiment test: first water drive is to moisture 94%; Record water drive and improve oil recovery factor 60.5%; Behind metaideophone 0.3pv (rock pore volume) step (e) the synthetic seawater base oil-displacing agent, water drive records on the water drive basis and can improve oil recovery factor 16.6% again to moisture more than 98% again.

[embodiment 5]

(a) two 16 (palm) acyl group tetramethylenediamine is synthetic

With [embodiment 4] (a), difference substitutes 30.0 gram (0.5 mole) anhydrous ethylenediamines with the anhydrous tetramethylenediamine of 44.0 grams (0.5 mole), and all the other are identical, get white powder solid, molar yield 94.2% after the vacuum-drying.

(b) N, the two palmitoyl tetramethylenediamine oxalic acid of N-synthetic

With two palmitoyl tetramethylenediamine 265.1 grams (0.47 mole) of step (a) synthetic, 530 gram THFs, 112.8 gram (2.82 moles) sodium hydroxide and 9.0 gram Tetrabutyl amonium bromides; Add and be furnished with in 2000 milliliters the there-necked flask of mechanical stirring, TM and reflux condensing tube, be heated to the backflow quaternization 6 hours.Slightly the cooling back is divided and is added the sodium chloroacetate solid that total amount is 328.5 grams (2.82 moles) for five times, keeps back flow reaction 10 hours.Cooling is neutralized to reaction solution with hydrochloric acid and is strongly-acid, is cooled to room temperature, suction filtration, and 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 tetramethylenediamine 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 tetramethylenediamine oxalic acid of N-substitute 165.0 gram (0.305 mole) N, and the usage quantity of the two lauroyl ethylenediamine-N,N'-diacetic acid(EDDA)s of N-, oxyethane is 101.4g (2.304 moles), gets N; The two palmitoyl tetramethylenediamine oxalic acid two polyoxy Vinyl Ethers (n=4) of N-282.1 grams, molar yield 94.9%.

(d) N, the two two carboxylate salts of palmitoyl tetramethylenediamine oxalic acid two polyoxy Vinyl Ethers (n=4) of N-synthetic

With step (c) the synthetic N of institute; The two palmitoyl tetramethylenediamine oxalic acid two polyoxy Vinyl Ethers (n=4) of N-282.1 grams (0.27 mole) and 66.1 gram (1.65 moles) sodium hydroxide, 110.7 gram (0.95 mole) sodium chloroacetates, 12.8 gram Tetrabutyl amonium bromides, 1000 milliliters of toluene are mixed in to be furnished with mechanical stirring, in 2000 milliliters the there-necked flask of TM and reflux condensing tube, to be heated to 100 ℃ of reactions 10 hours.Cooling, neutralization divides and to remove inorganic salt, alkalize N, two carboxylate salts 264.0 grams of the two palmitoyl tetramethylenediamine oxalic acid two polyoxy Vinyl Ethers (n=4) of N-, molar yield is 81.9%.To synthetic N, the two two carboxylate salts of palmitoyl tetramethylenediamine oxalic acid two polyoxy Vinyl Ethers (n=4) of N-are used U.S. Nicolet-380FT-IR spectrograph, adopt liquid-film method to carry out IR spectroscopy (sweep limit 4000～400cm ^-1), have all charateristic avsorption bands of Fig. 1.

(e) with step (d) synthetic N; The two two carboxylate salt 0.15wt% of palmitoyl tetramethylenediamine oxalic acid two polyoxy Vinyl Ethers (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 inject water mixing stirring 2.5 hours, obtain a kind of seawater base oil-displacing agent of homogeneous transparent.At 40 ℃ of temperature, salinity 21000mg/L, Ca ²⁺Mg ²⁺In the water of 1067mg/L, the AV that records this seawater base oil-displacing agent is 16.3mPa.s; Form the ultra low interfacial tension of 0.0063mN/m between this seawater base oil-displacing agent and the Shengli Oil Field field of razor clam island block dewatered oil.AV is by the BROODFIELD II type viscometer determining of U.S. Brookfield company, and IT is dripped interfacial tensimeter mensuration by the TX500 type rotation that Texas ,Usa university produces.

(f) earlier with salinity 21000mg/L, Ca ²⁺+ Mg ²⁺(length is 30 centimetres to the injection water of 1067mg/L, and diameter is 2.5 centimetres, and rate of permeation is 1.5 microns with rock core ²) saturated; The volume of voids (PV) of measuring rock core is 51.6%, carries out saturatedly then with Shengli Oil Field field of razor clam island block dewatered oil, and under 40 ℃ of constant temperature, carry out the imitation oil displacement experiment test: first water drive is to moisture 94%; Record water drive and improve oil recovery factor 55.5%; Behind metaideophone 0.3pv (rock pore volume) step (e) the synthetic seawater base oil-displacing agent, water drive records on the water drive basis and can improve oil recovery factor 18.5% again to moisture more than 98% again.

[embodiment 6]

(a) two 18 (tristearin) acyl group quadrol is synthetic

With Triple Pressed Stearic Acid 497 grams (1.75 moles), sulfur oxychloride 374.9 grams (3.15 moles) and 7.5 gram DMF; Add and be furnished with in 2000 milliliters of four-hole boiling flasks of sealing machine stirring, TM, prolong etc.; After 3 hours, decompression steams excessive thionyl chloride, obtains stearyl chloride in 95 ℃ of reactions.When temperature is reduced to 60 ℃; Add exsiccant toluene 249 grams; After stirring; Slowly drip the mixed solution of being made up of anhydrous ethylenediamine 30.0 grams (0.5 mole), anhydrous pyridine 118.8 grams (1.5 moles) and exsiccant toluene 249 grams, controlled temperature drips off and is warming up to 70 ℃ of reactions 5 hours less than 60 ℃.Cooling is filtered, and bullion gets white powder solid, molar yield 94.7% with ethyl alcohol recrystallization after the vacuum-drying.

(b) N, the two stearoyl ethylenediamine-N,N'-diacetic acid(EDDA)s of N-synthetic

With step (a) synthetic stearic bicine diester base quadrol 278.2 grams (0.47 mole), 556.4 gram THFs, 112.8 gram (2.82 moles) sodium hydroxide and 6.0 gram Tetrabutyl amonium bromides; Add and be furnished with in 2000 milliliters the there-necked flask of mechanical stirring, TM and reflux condensing tube, be heated to the backflow quaternization 4 hours.Slightly the cooling back is divided and is added the sodium chloroacetate solid that total amount is 328.5 grams (2.82 moles) for five times, keeps back flow reaction 10 hours.Cooling is neutralized to reaction solution with hydrochloric acid and is strongly-acid, is cooled to room temperature, suction filtration, and 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), and the two stearoyl ethylenediamine-N,N'-diacetic acid(EDDA)s of N-substitute 165.0 gram (0.305 mole) N, and 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, the two stearoyl ethylenediamine-N,N'-diacetic acid(EDDA) two polyoxy Vinyl Ethers (n=6) of N-300.8 grams, molar yield 93.6%.

(d) N, the two two carboxylate salts of stearoyl ethylenediamine-N,N'-diacetic acid(EDDA) two polyoxy Vinyl Ethers (n=6) of N-synthetic

With step (c) the synthetic N of institute; The two stearoyl ethylenediamine-N,N'-diacetic acid(EDDA) two polyoxy Vinyl Ethers (n=6) of N-300.8 grams (0.24 mole) and 80.8 gram (1.44 moles) Pottasium Hydroxide, 139.8 gram (1.2 moles) sodium chloroacetates, 15.2 gram Tetrabutyl amonium bromides, 1000 milliliters of toluene are mixed in to be furnished with mechanical stirring, in 2000 milliliters the there-necked flask of TM and reflux condensing tube, to be heated to 110 ℃ of reactions 12 hours.Cooling, neutralization divides and to remove inorganic salt, alkalize N, two carboxylate salts 271.8 grams of the two stearoyl ethylenediamine-N,N'-diacetic acid(EDDA) two polyoxy Vinyl Ethers (n=6) of N-, molar yield is 81.0%.To synthetic N, the two two carboxylate salts of stearoyl ethylenediamine-N,N'-diacetic acid(EDDA) two polyoxy Vinyl Ethers (n=6) of N-are used U.S. Nicolet-380 FT-IR spectrograph, adopt liquid-film method to carry out IR spectroscopy (sweep limit 4000～400cm ^-1), have all charateristic avsorption bands of Fig. 1.

(e) with step (d) synthetic N; The two two carboxylate salt 0.2wt% of stearoyl ethylenediamine-N,N'-diacetic acid(EDDA) two polyoxy Vinyl Ethers (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 inject water mixing stirring 2 hours, obtain a kind of seawater base oil-displacing agent of homogeneous transparent.At 65 ℃ of temperature, salinity 15000mg/L, Ca ²⁺+ Mg ²⁺In the water of 800mg/L, the AV that records this seawater base oil-displacing agent is 16.1mPa.s; Form the ultra low interfacial tension of 0.0008mN/m between this seawater base oil-displacing agent and the Shengli Oil Field field of razor clam island block dewatered oil.AV is by the BROODFIELD II type viscometer determining of U.S. Brookfield company, and IT is dripped interfacial tensimeter mensuration by the TX500 type rotation that Texas ,Usa university produces.

(f) earlier with salinity 15000mg/L, Ca ²⁺+ Mg ²⁺(length is 30 centimetres to the injection water of 800mg/L, and diameter is 2.5 centimetres, and rate of permeation is 1.5 microns with rock core ²) saturated; The volume of voids (PV) of measuring rock core is 51.2%, carries out saturatedly then with Shengli Oil Field field of razor clam island block dewatered oil, and under 65 ℃ of constant temperature, carry out the imitation oil displacement experiment test: first water drive is to moisture 94%; Record water drive and improve oil recovery factor 56.8%; Behind metaideophone 0.3pv (rock pore volume) step (e) the synthetic seawater base oil-displacing agent, water drive records on the water drive basis and can improve oil recovery factor 18.9% again to moisture more than 98% again.

[embodiment 7]

(a) two 18 (tristearin) acyl group hexanediamine is synthetic

With [embodiment 6] (a), difference substitutes 30.0 gram (0.5 mole) anhydrous ethylenediamines with the anhydrous hexanediamine of 58.0 grams (0.5 mole), and all the other are identical, get white powder solid, yield 96.3% after the vacuum-drying.

(b) N, the two stearoyl hexanediamine oxalic acid of N-synthetic

With step (a) synthetic stearic bicine diester base hexanediamine 304.6 grams (0.47 mole), 609 gram THFs, 210.6 gram (3.76 moles) sodium hydroxide and 7.5 gram Tetrabutyl amonium bromides; Add and be furnished with in 2000 milliliters the there-necked flask of mechanical stirring, TM and reflux condensing tube, be heated to the backflow quaternization 4 hours.Slightly the sodium chloroacetate solid that adds total amount 438.0 grams (3.76 moles) for five times is divided in the cooling back, keeps back flow reaction 10 hours.Cooling is neutralized to reaction solution with hydrochloric acid and is strongly-acid, is cooled to room temperature, suction filtration, and 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), and the two stearoyl hexanediamine oxalic acid of N-substitute 165.0 gram (0.305 mole) N, and 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, the two stearoyl hexanediamine oxalic acid two polyoxy Vinyl Ethers (n=5) of N-271.2 grams, molar yield 92.7%.

(d) N, the two two carboxylate salts of stearoyl hexanediamine oxalic acid two polyoxy Vinyl Ethers (n=5) of N-synthetic

With step (c) the synthetic N of institute; The two stearoyl hexanediamine oxalic acid two polyoxy Vinyl Ethers (n=5) of N-271.2 grams (0.23 mole) and 90.3 gram (1.61 moles) Pottasium Hydroxide, 134.0 gram (1.15 moles) sodium chloroacetates, 15.0 gram Tetrabutyl amonium bromides, 1000 milliliters of toluene are mixed in to be furnished with mechanical stirring, in 2000 milliliters the there-necked flask of TM and reflux condensing tube, to be heated to 110 ℃ of reactions 12 hours.Cooling, neutralization divides and to remove inorganic salt, alkalize N, two carboxylate salts 246.6 grams of the two stearoyl hexanediamine oxalic acid two polyoxy Vinyl Ethers (n=5) of N-, molar yield is 78.5%.To synthetic N, the two two carboxylate salts of stearoyl hexanediamine oxalic acid two polyoxy Vinyl Ethers (n=5) of N-are used U.S. Nicolet-380 FT-IR spectrograph, adopt liquid-film method to carry out IR spectroscopy (sweep limit 4000～400cm ^-1), have all charateristic avsorption bands of Fig. 1.

(e) with step (d) synthetic N; The two two carboxylate salt 0.15wt% of stearoyl hexanediamine oxalic acid two polyoxy Vinyl Ethers (n=5) of N-, above-mentioned modified polyacrylamide 0.2wt% and 96.5wt% Shengli Oil Field field of razor clam island block inject water mixing stirring 2.5 hours, obtain a kind of seawater base oil-displacing agent of homogeneous transparent.At 70 ℃ of temperature, salinity 21000mg/L, Ca ²⁺+ Mg ²⁺In the water of 1067mg/L, the AV that records this seawater base oil-displacing agent is 16.0mPa.s; Form the ultra low interfacial tension of 0.0012mN/m between this seawater base oil-displacing agent and the Shengli Oil Field field of razor clam island block dewatered oil.AV is by the BROODFIELD II type viscometer determining of U.S. Brookfield company, and IT is dripped interfacial tensimeter mensuration by the TX500 type rotation that Texas ,Usa university produces.

(f) earlier with salinity 21000mg/L, Ca ²⁺+ Mg ²⁺(length is 30 centimetres to the injection water of 1067mg/L, and diameter is 2.5 centimetres, and rate of permeation is 1.5 microns with rock core ²) saturated; The volume of voids (PV) of measuring rock core is 53.3%, carries out saturatedly then with Shengli Oil Field field of razor clam island block dewatered oil, and under 70 ℃ of constant temperature, carry out the imitation oil displacement experiment test: first water drive is to moisture 94%; Record water drive and improve oil recovery factor 60.8%; Behind metaideophone 0.3pv (rock pore volume) step (e) the synthetic seawater base oil-displacing agent, water drive records on the water drive basis and can improve oil recovery factor 17.3% again to moisture more than 98% again.

[comparative example 1]

With [embodiment 1] (e); Difference substitutes 0.15wt%N with the petroleum sodium sulfonate (Wuxi refinery) of 0.15wt%; The two two carboxylate salts of lauroyl ethylenediamine-N,N'-diacetic acid(EDDA) two polyoxy Vinyl Ethers (n=4) of N-; All the other are identical, and the AV that records this seawater base oil-displacing agent is 14.1mPa.s, form the IT of 0.0352mN/m between said composition and the Shengli Oil Field field of razor clam island block dewatered oil.AV is by the BROODFIELD II type viscometer determining of U.S. Brookfield company, and IT is dripped interfacial tensimeter mensuration by the TX500 type rotation that Texas ,Usa university produces.

With [embodiment 1] (f), record water drive and improve oil recovery factor 56.8%, behind the above-mentioned seawater base oil-displacing agent of metaideophone, record on the water drive basis and can improve oil recovery factor 12.1% again.

[comparative example 2]

With [embodiment 1] (e); Difference substitutes the above-mentioned ultra-high-molecular aniouic polyacrylamide (viscosity-average molecular weight is 2,400 ten thousand) of 0.15wt% with the high molecular weight polyacrylamide (viscosity-average molecular weight is 1,800 ten thousand) of 0.15wt%; All the other are identical; The AV that records this seawater base oil-displacing agent is 11.6mPa.s, forms the IT of 0.0072mN/m between this seawater base oil-displacing agent and the Shengli Oil Field field of razor clam island block dewatered oil.AV is by the BROODFIELDII type viscometer determining of U.S. Brookfield company, and IT is dripped interfacial tensimeter mensuration by the TX500 type rotation that Texas ,Usa university produces.

With [embodiment 1] (f), record water drive and improve oil recovery factor 58.3%, behind the above-mentioned seawater base oil-displacing agent of metaideophone, record on the water drive basis and can improve oil recovery factor 11.8% again.

Claims

1. flooding method that uses the seawater base oil-displacing agent is at 30～83 ℃ of displacement of reservoir oil temperature, total mineralization＞8000mg/L, Ca ²⁺+ Mg ²⁺Under the injection water condition of＞200mg/L; Underground dewatered oil is contacted with the seawater base oil-displacing agent; The abundant displacement of crude oil in the rock core is come out; Wherein said seawater base oil-displacing 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% injection water;

Wherein the general molecular formula of (1) component is:

2. the flooding method of use seawater base oil-displacing agent according to claim 1 is characterized in that described displacement of reservoir oil temperature is 40～80 ℃.

3. the flooding method of use seawater base oil-displacing agent according to claim 1, the total mineralization that is characterised in that described injection water is 10000～40000 mg/litre, Ca ²⁺+ Mg ²⁺Be 400～1800 mg/litre, the water type is MgCl ₂Type.

4. the flooding method of use seawater base oil-displacing agent according to claim 1; It is characterized in that described polymkeric substance is selected from ultra-high-molecular aniouic polyacrylamide, modified polyacrylamide; Ultra-high-molecular aniouic polyacrylamide wherein; Its viscosity-average molecular weight is 2,400 ten thousand; Modified polyacrylamide is formed by acrylic amide, 2-acrylamido-2-methyl propane sulfonic acid, three kinds of monomer copolymerizations of 2-acrylamido dodecyl sodium sulfonate, and its molar percentage is 80: 18: 2, and its viscosity-average molecular weight is 15,000,000.

5. the flooding method of use seawater base oil-displacing 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.

6. the flooding method of use seawater base oil-displacing 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.

7. the flooding method of use seawater base oil-displacing 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 ratio that 1 sum and EO adduction count n between 2～4.