CN102373039B

CN102373039B - Oil displacement method suitable for seawater base

Info

Publication number: CN102373039B
Application number: CN2010102607186A
Authority: CN
Inventors: 沈之芹; 张卫东; 杨一青; 李斌
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: 2013-08-14
Anticipated expiration: 2030-08-23
Also published as: CN102373039A

Abstract

The invention relates to an oil displacement method suitable for a seawater base. By the method, 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. In the oil displacement method suitable for the seawater base, underground dehydrated crude oil contacts an oil displacement composition under the injection water conditions that the oil displacement temperature is between 30 and 83 DEG C, the total mineralization is more than 8,000 mg/L, Ca<2+> and Mg<2+> are more than 200 mg/L, so that crude oil in cores is displaced fully, wherein the oil displacement composition 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 disulfonate, (2) 0.01 to 3.0 percent of polymer and (3) 92.0 to 99.98 percent of injection water. Through the technical scheme, the problems are better solved. The method can be used for the production of tertiary oil recovery in oil fields.

Description

Be applicable to the flooding method of seawater base

Technical field

The present invention relates to a kind of flooding method that is applicable to seawater base.

Background technology

Along with The development in society and economy, people are to the continuous increase of oil demand amount and the minimizing of petroleum reserves, 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 oil demand amount is more big more big, 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, tertiary oil recovery (EOR) can make oil recovery factor improve 6～20% again by the intensified oil reduction measure, even more.

Chemical flooding is an important method that improves recovery ratio.Surfactant flooding is considered to improve by a relatively large margin a kind of chemical agent of recovery ratio, applied widely, tool development prospect.No matter surfactant 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 displacement of reservoir oil can accelerate 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 polymer, surfactant 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 polymer and surfactant form, the mining site operability is stronger, thereby is subjected to the approval in oil field.But because need not any alkali, crude oil PetroChina Company Limited. acids active material can not be fully used, so that research and development have novel surfactant and an alkali-free binary combination flooding prescription of high surface more is imperative.

The surfactant industrialization product of external used for tertiary oil recovery mainly contains two big classes: the one, and petroleum sulfonate is main surfactant, the 2nd, alkylbenzenesulfonate is main surfactant, this two classes surfactant raw material is all taken from crude oil, raw material sources are wide, quantity is big, thereby also are the surfactants of external tertiary oil recovery consumption maximum.Because sulfonate surfactant is anionic, it and bivalent 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 developmental research, high Ca abroad ²⁺, Mg ²⁺The surfactant that the ion stratum is used comprises the research of multi-functional surfactant, Gemini surface active agent and sacrifice agent, and pays attention to the composite research of various surfactants.

The moon-nonionic amphoteric surfactant 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 are designed in same surfactant molecule, make it have the advantage of anion and non-ionic surface active agent concurrently, have complementary advantages, function admirable, therefore shown good prospects for application, especially the binary composite displacement system that exists at alkali-free, not only do not avoided the obstruction of oil reservoir owing to there is the existence of alkali, problem such as fouling and corrosion, and can form ultralow interfacial tension with crude oil.In recent years, because Shuangzi (Gemini) surfactant 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 ultralow interfacial tension, low critical micelle concentration, low Kraff point, good lime soap dispersing power, good a series of peculiar properties such as wettability, thereby cause great concern.Gemini surfactant with interface performance and rheological characteristic 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 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 mainly is the cation double quaternary ammonium salt type, has reported in succession that as Chinese patent CN 1528853, CN 1817431, CN 1066137 etc. the bisamide type is cationic, fluorine-containing cationic and contain the pyridine radicals cation Gemini surfactant.Shortcomings such as the absorption loss is big because cation has, cost height, the research and development of anionic and nonionic Gemini surface active agent have in recent years also obtained increasing attention, have reported the synthetic of the asymmetric Shuangzi of a kind of anion as Chinese patent CN 101073757.And since anionic surfactant to have salt tolerance poor, and nonionic 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, the alkali that contains high concentration, as NaOH, sodium carbonate etc., in use, to bringing huge injury in stratum and oil well etc., employed surfactant is difficult for by biodegradation, and human body also there is certain harmfulness, as: 1991, Zhao Guoxi was at " surfactant physical chemistry " P495; 1994, disclosed content among Liu Chengzai " surfactant complete works " P35.So at those harsh oil reservoirs, we ought to seek a kind of under alkali-free, high temperature (formation temperature is greater than 65 ℃), high salt (more than salinity 30000 mg/litre) condition Stability Analysis of Structures, and can form 10 with crude oil ^-3～10 ^-4The mN/m ultralow interfacial tension effectively improves the displacing surfactant system of oil recovery factor.Of the present invention this under the alkali-free situation just, 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 tertiary oil recovery.

Summary of the invention

Technical problem to be solved by this invention is that the oil displacement agent that contains surfactant in the prior art exists under the high temperature and high salt condition oil displacement efficiency poor, problems such as the corrosion that alkali brings stratum and oil well in working concentration height and the ternary composite driving and incrustation injury provide a kind of new flooding method that is applicable to seawater base.This method will contain N, and the composition of the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy vinethene disulfonates of N-is used for oil displacement process, have alkali-free, not have corrosion and incrustation injury, and working concentration is low, characteristics such as oil displacement efficiency height under the high temperature and high salt condition.

In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: be applicable to the flooding method of seawater base, at 30～83 ℃ of displacement of reservoir oil temperature, total salinity＞8000mg/L, Ca ²⁺+ Mg ²⁺Under the injection water condition of＞200mg/L, underground dewatered oil is contacted with displacement of reservoir oil composition, the abundant displacement of the crude oil in the rock core is come out, wherein said displacement of reservoir oil composition comprises following component by percentage to the quality:

(1) 0.01～5.0% N, the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy vinethene disulfonates of N-;

(2) 0.01～3.0% polymer;

(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 one integer in 2～7; M is any one metal ion that is selected from potassium, sodium or the lithium; Polymer is selected from one or both in ultra-high-molecular aniouic polyacrylamide, modified polyacrylamide or the xanthans.

In the technique scheme, displacement of reservoir oil temperature is preferably 45～75 ℃, and described injection water total salinity is preferably 15000～32000 mg/litre, Ca ²⁺+ Mg ²⁺Be preferably 750～1600 mg/litre; Polymer 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 hydrophilic lipophilic balance 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 ^-4Ultralow interfacial tension; N, the R in the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy vinethene disulfonates of N- ₁Carbon number is preferably nine, 11,15 or 17, R ₂Carbon number 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:

Be 10～18 aliphatic 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 transparency liquid that obtains is the carbochain number, after adding the carbochain number and be the dilution with toluene of 10～18 aliphatic 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 aliphatic acid quality 1/2nd mixes be in 10～18 the fat acyl chloride solution, reacted 2～5 hours, and obtained the white powder solid chemical compound through post processing.Wherein, the carbochain number is 10～18 aliphatic 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-be 10～18 fatty acyl diamines by required proportioning and NaOH or potassium hydroxide TBAB catalyst mix after, to add N, after the oxolane 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 post processing.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, NaOH (potassium hydroxide) and TBAB.

(c) N, the preparation of the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy vinethenes 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 oxirane are 85～160 ℃ by required proportioning in reaction temperature; pressure is less than under the 0.80MPa gauge pressure condition; the alkali compounds of calcium is catalyzer; react N, the two carbochain numbers of N-are 10～18 fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA)s, two polyoxy vinethenes.Wherein, N, the two carbochain numbers of N-are that 10～18 fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA)s and oxirane mol ratio are 1: 4～14, and catalyst amount 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) dichloro-N, the preparation of the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy vinethenes of N-:

The N that step (c) is synthesized; the two carbochain numbers of N-be 10～18 fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA)s, two polyoxy vinethenes, thionyl chloride, pyridine by required proportioning 70～100 ℃ of reactions 3～10 hours; excessive thionyl chloride is extracted in decompression out; in and layering remove inorganic salts; vacuum drying gets dichloro-N, and the two carbochain numbers of N-are 10～18 fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA)s, two polyoxy vinethenes.Wherein, N, the mol ratio that the two carbochain numbers of N-are 10～18 fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA)s, two polyoxy vinethenes, thionyl chloride and pyridine is 1: 2.0～6.0: 1.0～5.0.

(e) N, the preparation of the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy vinethene disulfonates of N-:

The dichloro-N that step (d) is synthesized; the two N of N-; the two carbochain numbers of N-are that 10～18 fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA)s, two polyoxy vinethenes place reactor; the mixture and the water that add solvent ethylene glycol, sulfonating agent sodium sulfite or sodium sulfite and the sodium hydrogensulfite of required proportioning; reacted 3～9 hours down at 90～150 ℃; get thick product N through post processing again, the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy vinethene disulfonates of N-.Wherein, sulfonated reagent is the mixture of sodium sulfite or sodium sulfite and sodium hydrogensulfite; dichloro-N; the two N of N-; the mol ratio that the two carbochain numbers of N-are 10～18 fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA)s, two polyoxy vinethenes and sulfonated reagent is 1: 2.5～5.0; the ethylene glycol consumption is 8～16% of reactant quality, and water consumption is 10～40% of reactant quality.

(f) with the N of aequum, the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy vinethene disulfonates of N-, above-mentioned ultra-high-molecular aniouic polyacrylamide or modified polyacrylamide and inject water and evenly mix, stirring at room 1～3 hour obtains required composition.Wherein, by percentage to the quality; N, the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy vinethene disulfonates of N-, above-mentioned ultra-high-molecular aniouic polyacrylamide or modified polyacrylamide and the proportioning of injecting water are 0.01～5.0%: 0.01～3.0%: 92.0～99.98%.

(g) be 10000～40000mg/L, Ca with total salinity earlier ²⁺+ Mg ²⁺The injection water that is 400～1800mg/L is saturated with rock core, measure the voids volume (PV) of rock core, carry out saturated with dewatered oil then, carry out the imitation oil displacement experiment test under 40～80 ℃ of temperature: first water drive is to moisture 94%, the synthetic displacement of reservoir oil of metaideophone 0.3pv (rock pore volume) step (f) with composition after, water drive is calculated the percentage that improves oil recovery factor to moisture more than 98%.

In the technique scheme, (a) the carbochain number is 10～18 aliphatic 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 diamines and the mol ratio of pyridine are preferably 2.5～3.5: 1: 2～3.The reaction temperature of preparation acyl chlorides is preferably 80～95 ℃, and the reaction temperature 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, NaOH (potassium hydroxide) and TBAB 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 oxirane mol ratio be preferably 1: 6～12, catalyst amount 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 vinethenes, thionyl chloride and pyridine be preferably 1: 3.0～4.5: 2.0～4.0, reaction temperature is preferably 75～90 ℃, the reaction time is preferably 4～8 hours.(e) dichloro-N; 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 vinethenes and sulfonated reagent be preferably 1: 3～4.5; the ethylene glycol consumption is preferably 10～14% of reactant quality; water consumption is preferably 15～30% of reactant quality; reaction temperature is preferably 110～140 ℃, and the reaction time is preferably 4～8 hours.(f) by percentage to the quality, N, the consumption preferable range of the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy vinethene disulfonates 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 time is preferably 1.5～2.5 hours.(g) displacement of reservoir oil temperature is preferably 45～75 ℃; The formation water total salinity is preferably 15000～32000mg/L, Ca ²⁺+ Mg ²⁺Be preferably 750～1600mg/L.

N in the flooding method that is applicable to seawater base that the present invention is prepared; the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy vinethene disulfonates of N-; owing to contain aerobic ethene non-ionic group and azochlorosulfonate acid anion group simultaneously in its molecular structure; make the salt tolerant advantage of its heat resistance that has anion surfactant concurrently and non-ionic surface active agent; and the Shuangzi architectural feature of symmetry; it is low to make it have critical micelle concentration again; it is strong to reduce the interfacial tension ability; features such as anti-high salinity and particular rheological properties and viscoplasticity-viscosifying action have more good performance than conventional surfactant.Do not contain aromatic ring structure in its molecule in addition, be easier to biodegradation, 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 that is applicable to seawater base of the present invention, under the alkali-free condition, can be used for formation temperature and be 45～75 ℃, salinity 15000～32000 mg/litre, Ca ²⁺+ Mg ²⁺Be the MgCl of 750～1600 mg/litre ₂The marine block of type Shengli Oil Field injects water and crude oil; be 0.1～0.3wt%N with consumption; 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 vinethene disulfonates of N-and 0.1～0.2wt% forms the above-mentioned composition oil displacement agent; measure the dynamic interface tension value between the marine block crude oil of this oil displacement agent aqueous solution and Shengli Oil Field, can reach 10 ^-3～10 ^-4The ultralow interfacial tension of mN/m, can on the water drive basis, can reach 18.7% by (water drive improves oil recovery factor and reaches 60.8%) raising oil recovery factor through the indoor evaluation of physical analogy displacement experiment at this oil displacement 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 fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy vinethene disulfonates of N-.

The N of the present invention's preparation; the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy vinethene disulfonates of N-can characterize by the following method: after synthetic is purified; use U.S. Nicolet-380 FT-IR spectrometer, adopt liquid-film method to carry out infrared spectrum analysis (sweep limits 4000～400cm ^-1), as shown in Figure 1, be 2953cm in wave number ^-1, 2919cm ^-1, 2850cm ^-1Methyl and the flexible characteristic peak of methylene C-H on the alkyl chain, 1475cm appear in the place ^-1C-H flexural vibrations on the alkyl chain, 1634cm ^-1Locating strong peak is the I key band ν C=O of acid amides, 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 1350cm owing to connected EO ^-1About the peak also to some extent broadening with grow tall, the characteristic peak of sulfonate, the symmetrical stretching vibration of S=O is at 1155cm ^-1About, antisymmetric stretching vibration is at 1345cm ^-1About, so 1116cm ^-1The peak at place is owing to C-O-C asymmetric stretch bands of a spectrum stack on the symmetrical stretching vibration of S=O and the EO causes 1350cm ^-1About the peak be because the antisymmetric stretching vibration of S=O and the vibration of skeleton carbon cause, and proved response has generated N really thus, the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy vinethene disulfonates of N-

The present invention is further elaborated below by embodiment.

The specific embodiment

[embodiment 1]

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

With laurate 300 grams (1.5 moles), thionyl chloride 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, thermometer, condensation pipe etc., after 3 hours, decompression steams excessive thionyl chloride, obtains lauroyl chloride in 90 ℃ of reactions.When temperature is down to 60 ℃, add dry toluene 150 grams, after stirring, slowly drip the mixed liquor of being formed by anhydrous ethylenediamine 30.0 grams (0.5 mole), anhydrous pyridine 99.0 grams (1.25 moles) and dry toluene 150 grams, the control temperature drips off and is warming up to 85 ℃ of reactions 2 hours less than 60 ℃.Cooling is filtered, and crude product gets white powder solid, molar yield 97.1% with ethyl alcohol recrystallization after the vacuum drying.

(b) N, the two dodecanoyl EDDAs of N-synthetic

Bimonthly osmanthus acyl group ethylenediamine 200 grams (0.47 mole) that step (a) is synthetic, 400 gram oxolanes, 112.8 gram (2.82 moles) NaOH and 7.5 gram TBABs; add and be furnished with in 2000 milliliters the there-necked flask of mechanical agitation, thermometer 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 reactant liquor with hydrochloric acid and is highly 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 distilled water washing solid.

(c) N, the two dodecanoyl EDDA two polyoxy vinethenes (n=4) of N-synthetic

With the synthetic N of step (b); the alkali compounds of two dodecanoyl 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 unit, mixing plant 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 reactant liquor system of high activity, high selectivity, system temperature is heated to 80～90 ℃, open vacuum system, dehydration is 2 hours under high vacuum, purges 3～4 times with nitrogen then, the system reaction temperature is transferred to 140 ℃ slowly feed 107.6 gram (2.444 moles) oxirane, controlled pressure≤0.60MPa.Reaction purges system with nitrogen after finishing, and the neutralization of cooling back, dehydration get N, the two dodecanoyl EDDA two polyoxy vinethenes (n=4) of N-268.5 grams, molar yield 98.5%.

(d) dichloro-N, the two dodecanoyl EDDA two polyoxy vinethenes (n=4) of N-synthetic

The N that step (c) is synthesized; the two dodecanoyl EDDA two polyoxy vinethenes (n=4) of N-268.5 grams (0.30 mole); 50.4 gram (0.63 mole) pyridine places backflow is housed; stir; in 1000 milliliters of there-necked flasks of gas absorbing device; under agitation slowly thionyl chloride 125.0 restrains (1.05 moles); 85 ℃ of reactions 6 hours; reaction finishes the excessive thionyl chloride of back pressure reducing and steaming; the residue cooling; standing demix; the upper strata is neutralized to neutrality with 15% sodium hydroxide solution; divide and remove inorganic salts; organic layer washes with water 5～6 times again; vacuum drying gets dichloro-N; the two dodecanoyl EDDA two polyoxy vinethenes (n=4) of N-243.9 grams, molar yield 87.5%.

(e) N, two dodecanoyl EDDA two polyoxy vinethene (n=4) disulfonates of N-synthetic

The dichloro-N that step (d) is synthesized; the two dodecanoyl EDDA two polyoxy vinethenes (n=4) of N-243.9 grams (0.263 mole) place autoclave; add 60 gram ethylene glycol, 80 gram water, 81.6 gram sodium sulfites (0.79 mole) and 16.6 gram sodium hydrogensulfites (0.132 mole); reaction is 6 hours under 130 ℃ of temperature; reaction finishes the back decompression distillation and boils off most of moisture; add an amount of isopropyl alcohol standing over night in the mixture; the inorganic salts that filtering is precipitated out add the further filtering inorganic salts of an amount of carrene again.Solvent is removed in decompression, gets N, two dodecanoyl EDDA two polyoxy vinethene (n=4) disulfonates of N-, and the product quality mark is 90.2%.To synthetic N, two dodecanoyl EDDA two polyoxy vinethene (n=4) disulfonates of N-are used U.S. Nicolet-380 FT-IR spectrometer, adopt liquid-film method to carry out infrared spectrum analysis (sweep limits 4000～400cm ^-1), have all characteristic absorption peaks of Fig. 1.

(f) with the synthetic N of step (e); two dodecanoyl EDDA two polyoxy vinethene (n=4) the disulfonate 0.15wt% of N-, above-mentioned modified polyacrylamide 0.15wt% and the marine block of 97.0wt% Shengli Oil Field inject water mixing stirring 2 hours, obtain a kind of flooding method that is applicable to seawater base 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 composition is 14.6mPa.s; Form the ultralow interfacial tension of 0.0022mN/m between the marine block IFA-8 of said composition and the Shengli Oil Field well dewatered oil.Apparent viscosity is by the BROODFIELD II type viscometer determining of U.S. Brookfield company, and interfacial tension is dripped interfacial tensimeter mensuration by the TX500 type rotation that Texas ,Usa university produces.

(g) 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 permeability is 1.5 microns with rock core ²) saturated, the voids volume (PV) of measuring rock core is 53.3%, carry out saturated with the marine block IFA-8 of Shengli Oil Field well dewatered oil then, carry out the imitation oil displacement experiment test under 65 ℃ of constant temperature: first water drive is to moisture 94%, record water drive and improve oil recovery factor 57.2%, again the synthetic displacement of reservoir oil of metaideophone 0.3pv (rock pore volume) step (f) with composition after, water drive records on the water drive basis and can improve oil recovery factor 16.3% again to moisture more than 98%.

[embodiment 2]

(a) two 12 (bay) acyl group hexamethylene diamine is synthetic

With [embodiment 1] (a), difference substitutes 30.0 gram (0.5 mole) anhydrous ethylenediamines with the anhydrous hexamethylene diamine 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 dodecanoyl hexamethylene diamine oxalic acid of N-synthetic

Bimonthly osmanthus acyl group hexamethylene diamine 225.6 grams (0.47 mole) that step (a) is synthetic, 450 gram oxolanes, 105.3 gram (1.88 moles) potassium hydroxide and 4.5 gram TBABs; add and be furnished with in 2000 milliliters the there-necked flask of mechanical agitation, thermometer 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 reactant liquor with hydrochloric acid and is highly 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 distilled water washing solid.

(c) N, the two dodecanoyl hexamethylene diamine oxalic acid two polyoxy vinethenes (n=3) of N-synthetic

With [embodiment 1] (c); difference is with the N of 171.4 grams (0.288 mole); the two dodecanoyl hexamethylene diamine oxalic acid of N-substitute 165.0 gram (0.305 mole) N; the use amount of the two dodecanoyl EDDAs of N-, oxirane is 76.0g (1.728 moles); the use amount of the alkali compounds of calcium is 4.3 grams; get N, the two dodecanoyl hexamethylene diamine oxalic acid two polyoxy vinethenes (n=3) of N-240.7 grams, molar yield 97.2%.

(d) dichloro-N, the two dodecanoyl hexamethylene diamine oxalic acid two polyoxy vinethenes (n=3) of N-synthetic

The N that step (c) is synthesized; the two dodecanoyl hexamethylene diamine oxalic acid two polyoxy vinethenes (n=3) of N-240.7 grams (0.28 mole), 66.9 gram (0.84 mole) pyridines place in 1000 milliliters of there-necked flasks that backflow, stirring, gas absorbing device are housed; under agitation slowly thionyl chloride 133.4 restrains (1.12 moles); all the other operations with [embodiment 1] (d); vacuum drying gets dichloro-N; the two dodecanoyl hexamethylene diamine oxalic acid two polyoxy vinethenes (n=3) of N-218.5 grams, molar yield 87.0%.

(e) N, two dodecanoyl hexamethylene diamine oxalic acid two polyoxy vinethene (n=3) disulfonates of N-synthetic

The dichloro-N that step (d) is synthesized; the two dodecanoyl hexamethylene diamine oxalic acid two polyoxy vinethenes (n=3) of N-218.5 grams (0.24 mole) place autoclave; add 60 gram ethylene glycol, 100 gram water, 65.2 gram sodium sulfites (0.63 mole) and 13.2 gram sodium hydrogensulfites (0.10 mole); reaction is 8 hours under 110 ℃ of temperature; all the other operations with [embodiment 1] (e); get N; two dodecanoyl hexamethylene diamine oxalic acid two polyoxy vinethene (n=3) disulfonates of N-, the product quality mark is 90.0%.To synthetic N, two dodecanoyl hexamethylene diamine oxalic acid two polyoxy vinethene (n=3) disulfonates of N-are used U.S. Nicolet-380FT-IR spectrometer, adopt liquid-film method to carry out infrared spectrum analysis (sweep limits 4000～400cm ^-1), have all characteristic absorption peaks of Fig. 1.

(f) with the synthetic N of step (e); two dodecanoyl hexamethylene diamine oxalic acid two polyoxy vinethene (n=3) the disulfonate 0.2wt% of N-, above-mentioned modified polyacrylamide 0.15wt% and the marine block of 96.5wt% Shengli Oil Field inject water mixing stirring 2.5 hours, obtain a kind of flooding method that is applicable to seawater base of homogeneous transparent.At 70 ℃ of temperature, salinity 21000mg/L, Ca ²⁺+ Mg ²⁺In the water of 1067mg/L, the apparent viscosity that records this composition is 14.9mPa.s; Form the ultralow interfacial tension of 0.0004mN/m between the marine block IFA-8 of said composition and the Shengli Oil Field well dewatered oil.Apparent viscosity is by the BROODFIELD II type viscometer determining of U.S. Brookfield company, and interfacial tension is dripped interfacial tensimeter mensuration by the TX500 type rotation that Texas ,Usa university produces.

(g) 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 permeability is 1.5 microns with rock core ²) saturated, the voids volume (PV) of measuring rock core is 52.1%, carry out saturated with the marine block IFA-8 of Shengli Oil Field well dewatered oil then, carry out the imitation oil displacement experiment test under 70 ℃ of constant temperature: first water drive is to moisture 94%, record water drive and improve oil recovery factor 56.6%, again the synthetic displacement of reservoir oil of metaideophone 0.3pv (rock pore volume) step (f) with composition after, water drive records on the water drive basis and can improve oil recovery factor 17.3% again to moisture more than 98%.

[embodiment 3]

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

With [embodiment 1] (a), difference substitutes 300.0 gram (1.5 moles) laurate with the capric acid of 261.0 grams (1.5 moles), anhydrous butanediamine 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 butanediamine oxalic acid of N-synthetic

Two capryl butanediamine 186.1 grams (0.47 mole) that step (a) is synthetic, 400 gram oxolanes, 112.8 gram (2.82 moles) NaOH and 7.5 gram TBABs; add and be furnished with in 2000 milliliters the there-necked flask of mechanical agitation, thermometer 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 reactant liquor with hydrochloric acid and is highly 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 distilled water washing solid.

(c) N, two ten acyl group butanediamine oxalic acid, the two polyoxy vinethenes (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 gram (0.305 mole) N; the use amount of the two dodecanoyl EDDAs of N-, oxirane is 78.6g (1.788 moles); the use amount of the alkali compounds of calcium is 3.8 grams; get N, the two ten acyl group butanediamine oxalic acid of N-two polyoxy vinethenes (n=3) 225.5 grams, molar yield 97.5%.

(d) dichloro-N, two ten acyl group butanediamine oxalic acid, the two polyoxy vinethenes (n=3) of N-synthetic

The N that step (c) is synthesized; the two ten acyl group butanediamine oxalic acid of N-two polyoxy vinethenes (n=3) 225.5 grams (0.29 mole), 69.3 gram (0.87 mole) pyridines place in 1000 milliliters of there-necked flasks that backflow, stirring, gas absorbing device are housed; under agitation slowly thionyl chloride 138.2 restrains (1.16 moles); all the other operations with [embodiment 1] (d); vacuum drying gets dichloro-N; the two ten acyl group butanediamine oxalic acid of N-two polyoxy vinethenes (n=3) 209.1 grams, molar yield 88.7%.

(e) N, two ten acyl group butanediamine oxalic acid, two polyoxy vinethene (n=3) disulfonates of N-synthetic

The dichloro-N that step (d) is synthesized; the two ten acyl group butanediamine oxalic acid of N-two polyoxy vinethenes (n=3) 209.1 grams (0.26 mole) place autoclave; add 60 gram ethylene glycol, 90 gram water, 70.6 gram sodium sulfites (0.68 mole) and 14.3 gram sodium hydrogensulfites (0.11 mole); reaction is 7 hours under 120 ℃ of temperature; all the other operations with [embodiment 1] (e); get N; two ten acyl group butanediamine oxalic acid, two polyoxy vinethene (n=3) disulfonates of N-, the product quality mark is 91.2%.To synthetic N, two ten acyl group butanediamine oxalic acid, two polyoxy vinethene (n=3) disulfonates of N-are used U.S. Nicolet-380FT-IR spectrometer, adopt liquid-film method to carry out infrared spectrum analysis (sweep limits 4000～400cm ^-1), have all characteristic absorption peaks of Fig. 1.

(f) with the synthetic N of step (e); two ten acyl group butanediamine oxalic acid, two polyoxy vinethene (n=3) the disulfonate 0.1wt% of N-, above-mentioned modified polyacrylamide 0.2wt% and the marine block of 97.0wt% Shengli Oil Field inject water mixing stirring 2.5 hours, obtain a kind of flooding method that is applicable to seawater base of homogeneous transparent.At 80 ℃ of temperature, salinity 31500mg/L, Ca ²⁺+ Mg ²⁺In the water of 1600mg/L, the apparent viscosity that records this composition is 14.0mPa.s; Form the ultralow interfacial tension of 0.0041mN/m between the marine block IFA-8 of said composition and the Shengli Oil Field well dewatered oil.Apparent viscosity is by the BROODFIELD II type viscometer determining of U.S. Brookfield company, and interfacial tension is dripped interfacial tensimeter mensuration by the TX500 type rotation that Texas ,Usa university produces.

(g) 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 permeability is 1.5 microns with rock core ²) saturated, the voids volume (PV) of measuring rock core is 51.8%, carry out saturated with the marine block IFA-8 of Shengli Oil Field well dewatered oil then, carry out the imitation oil displacement experiment test under 80 ℃ of constant temperature: first water drive is to moisture 94%, record water drive and improve oil recovery factor 60.7%, again the synthetic displacement of reservoir oil of metaideophone 0.3pv (rock pore volume) step (f) with composition after, water drive records on the water drive basis and can improve oil recovery factor 15.7% again to moisture more than 98%.

[embodiment 4]

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

With palmitic acid 320 grams (1.25 moles), thionyl chloride 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, thermometer, condensation pipe etc., after 5 hours, decompression steams excessive thionyl chloride, obtains palmitoyl chloride in 80 ℃ of reactions.When temperature is down to 60 ℃, add dry toluene 160 grams, after stirring, slowly drip the mixed liquor of being formed by anhydrous ethylenediamine 30.0 grams (0.5 mole), anhydrous pyridine 79.2 grams (1.0 moles) and dry toluene 160 grams, the control temperature drips off and is warming up to 75 ℃ of reactions 3 hours less than 60 ℃.Cooling is filtered, and crude product gets white powder solid, molar yield 91.3% with ethyl alcohol recrystallization after the vacuum drying.

(b) N, the two hexadecanoyl group EDDAs of N-synthetic

Two palmityl ethylenediamines 251.9 grams (0.47 mole) that step (a) is synthetic, 504 gram oxolanes, 94.0 gram (2.35 moles) NaOH and 6.0 gram TBABs; add and be furnished with in 2000 milliliters the there-necked flask of mechanical agitation, thermometer 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 reactant liquor with hydrochloric acid and is highly 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 distilled water washing solid.

(c) N, the two hexadecanoyl group EDDA two polyoxy vinethenes (n=5) of N-synthetic

With [embodiment 1] (c); difference is with the N of 190.9 grams (0.293 mole); the two hexadecanoyl group EDDAs of N-substitute 165.0 gram (0.305 mole) N; the use amount of the two dodecanoyl EDDAs of N-, oxirane is 128.9g (2.93 moles); the use amount of the alkali compounds of calcium is 3.8 grams; get N, the two hexadecanoyl group EDDA two polyoxy vinethenes (n=5) of N-304.9 grams, molar yield 95.3%.

(d) dichloro-N, the two hexadecanoyl group EDDA two polyoxy vinethenes (n=5) of N-synthetic

The N that step (c) is synthesized; the two hexadecanoyl group EDDA two polyoxy vinethenes (n=5) of N-304.9 grams (0.28 mole), 78.1 gram (0.98 mole) pyridines place in 1000 milliliters of there-necked flasks that backflow, stirring, gas absorbing device are housed; under agitation slowly thionyl chloride 116.7 restrains (0.98 mole); 75 ℃ of reactions 8 hours; all the other operations with [embodiment 1] (d); vacuum drying gets dichloro-N; the two hexadecanoyl group EDDA two polyoxy vinethenes (n=5) of N-271.5 grams, molar yield 85.9%.

(e) N, two hexadecanoyl group EDDA two polyoxy vinethene (n=5) disulfonates of N-synthetic

The dichloro-N that step (d) is synthesized; the two hexadecanoyl group EDDA two polyoxy vinethenes (n=5) of N-271.5 grams (0.240 mole) place autoclave; add 65 gram ethylene glycol, 110 gram water, 74.9 gram sodium sulfites (0.72 mole) and 15.1 gram sodium hydrogensulfites (0.12 mole); reaction is 7 hours under 120 ℃ of temperature; all the other operations with [embodiment 1] (e); get N; two hexadecanoyl group EDDA two polyoxy vinethene (n=5) disulfonates of N-, the product quality mark is 90.0%.To synthetic N, two hexadecanoyl group EDDA two polyoxy vinethene (n=5) disulfonates of N-are used U.S. Nicolet-380FT-IR spectrometer, adopt liquid-film method to carry out infrared spectrum analysis (sweep limits 4000～400cm ^-1), have all characteristic absorption peaks of Fig. 1.

(f) with the synthetic N of step (e); two hexadecanoyl group EDDA two polyoxy vinethene (n=5) the disulfonate 0.1wt% of N-, above-mentioned ultra-high-molecular aniouic polyacrylamide 0.2wt% and the marine block of 97.0wt% Shengli Oil Field inject water mixing stirring 2.0 hours, obtain a kind of flooding method that is applicable to seawater base of homogeneous transparent.At 70 ℃ of temperature, salinity 15750mg/L, Ca ²⁺+ Mg ²⁺In the water of 800mg/L, the apparent viscosity that records this composition is 15.6mPa.s; Form the ultralow interfacial tension of 0.0028mN/m between the marine block IFA-8 of said composition and the Shengli Oil Field well dewatered oil.Apparent viscosity is by the BROODFIELD II type viscometer determining of U.S. Brookfield company, and interfacial tension is dripped interfacial tensimeter mensuration by the TX500 type rotation that Texas ,Usa university produces.

(g) earlier with salinity 15750mg/L, Ca ²⁺+ Mg ²⁺(length is 30 centimetres to the injection water of 800mg/L, and diameter is 2.5 centimetres, and permeability is 1.5 microns with rock core ²) saturated, the voids volume (PV) of measuring rock core is 51.1%, carry out saturated with the marine block IFA-8 of Shengli Oil Field well dewatered oil then, carry out the imitation oil displacement experiment test under 70 ℃ of constant temperature: first water drive is to moisture 94%, record water drive and improve oil recovery factor 58.1%, again the synthetic displacement of reservoir oil of metaideophone 0.3pv (rock pore volume) step (f) with composition after, water drive records on the water drive basis and can improve oil recovery factor 18.1% again to moisture more than 98%.

[embodiment 5]

(a) two hexadecylic acids (palm) acyl group butanediamine is synthetic

With [embodiment 4] (a), difference substitutes 30.0 gram (0.5 mole) anhydrous ethylenediamines with the anhydrous butanediamine 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 hexadecanoyl group butanediamine oxalic acid of N-synthetic

Two palmityl butanediamine 265.1 grams (0.47 mole) that step (a) is synthetic, 530 gram oxolanes, 112.8 gram (2.82 moles) NaOH and 9.0 gram TBABs; add and be furnished with in 2000 milliliters the there-necked flask of mechanical agitation, thermometer 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 reactant liquor with hydrochloric acid and is highly 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 distilled water washing solid.

(c) N, the two hexadecanoyl group butanediamine oxalic acid two polyoxy vinethenes (n=4) of N-synthetic

With [embodiment 1] (c); difference is with the N of 195.6 grams (0.288 mole); the two hexadecanoyl group butanediamine oxalic acid of N-substitute 165.0 gram (0.305 mole) N; the use amount of the two dodecanoyl EDDAs of N-, oxirane is 101.4g (2.304 moles); get N; the two hexadecanoyl group butanediamine oxalic acid two polyoxy vinethenes (n=4) of N-282.1 grams, molar yield 94.9%.

(d) dichloro-N, the two hexadecanoyl group butanediamine oxalic acid two polyoxy vinethenes (n=4) of N-synthetic

The N that step (c) is synthesized; the two hexadecanoyl group butanediamine oxalic acid two polyoxy vinethenes (n=4) of N-281.2 grams (0.27 mole), 51.6 gram (0.65 mole) pyridines place in 1000 milliliters of there-necked flasks that backflow, stirring, gas absorbing device are housed; under agitation slowly thionyl chloride 92.8 restrains (0.78 mole); 90 ℃ of reactions 4 hours; all the other operations with [embodiment 1] (d); vacuum drying gets dichloro-N; the two hexadecanoyl group butanediamine oxalic acid two polyoxy vinethenes (n=4) of N-234.1 grams, molar yield 84.0%.

(e) N, two hexadecanoyl group butanediamine oxalic acid two polyoxy vinethene (n=4) disulfonates of N-synthetic

The dichloro-N that step (d) is synthesized; the two hexadecanoyl group butanediamine oxalic acid two polyoxy vinethenes (n=4) of N-234.1 grams (0.219 mole) place autoclave; add 60 gram ethylene glycol, 150 gram water, 87.8 gram sodium sulfites (0.85 mole) and 17.7 gram sodium hydrogensulfites (0.14 mole); reaction is 6 hours under 130 ℃ of temperature; all the other operations with [embodiment 1] (e); get N; two hexadecanoyl group hexamethylene diamine oxalic acid two polyoxy vinethene (n=4) disulfonates of N-, the product quality mark is 89.0%.To synthetic N, two hexadecanoyl group hexamethylene diamine oxalic acid two polyoxy vinethene (n=4) disulfonates of N-are used U.S. Nicolet-380FT-IR spectrometer, adopt liquid-film method to carry out infrared spectrum analysis (sweep limits 4000～400cm ^-1), have all characteristic absorption peaks of Fig. 1.

(f) with the synthetic N of step (e); two hexadecanoyl group hexamethylene diamine oxalic acid two polyoxy vinethene (n=4) the disulfonate 0.25wt% of N-, above-mentioned ultra-high-molecular aniouic polyacrylamide 0.15wt% and the marine block of 96.0wt% Shengli Oil Field inject water mixing stirring 1.5 hours, obtain a kind of flooding method that is applicable to seawater base of homogeneous transparent.At 40 ℃ of temperature, salinity 21000mg/L, Ca ²⁺+ Mg ²⁺In the water of 1067mg/L, the apparent viscosity that records this composition is 16.5mPa.s; Form the ultralow interfacial tension of 0.0009mN/m between the marine block IFA-8 of said composition and the Shengli Oil Field well dewatered oil.Apparent viscosity is by the BROODFIELD II type viscometer determining of U.S. Brookfield company, and interfacial tension is dripped interfacial tensimeter mensuration by the TX500 type rotation that Texas ,Usa university produces.

(g) 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 permeability is 1.5 microns with rock core ²) saturated, the voids volume (PV) of measuring rock core is 53.6%, carry out saturated with the marine block IFA-8 of Shengli Oil Field well dewatered oil then, carry out the imitation oil displacement experiment test under 40 ℃ of constant temperature: first water drive is to moisture 94%, record water drive and improve oil recovery factor 60.1%, again the synthetic displacement of reservoir oil of metaideophone 0.3pv (rock pore volume) step (f) with composition after, water drive records on the water drive basis and can improve oil recovery factor 18.6% again to moisture more than 98%.

[embodiment 6]

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

With stearic acid 497 grams (1.75 moles), thionyl chloride 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, thermometer, condensation pipe etc., after 3 hours, decompression steams excessive thionyl chloride, obtains stearyl chloride in 95 ℃ of reactions.When temperature is down to 60 ℃, add dry toluene 249 grams, after stirring, slowly drip the mixed liquor of being formed by anhydrous ethylenediamine 30.0 grams (0.5 mole), anhydrous pyridine 118.8 grams (1.5 moles) and dry toluene 249 grams, the control temperature drips off and is warming up to 70 ℃ of reactions 5 hours less than 60 ℃.Cooling is filtered, and crude product gets white powder solid, molar yield 94.7% with ethyl alcohol recrystallization after the vacuum drying.

(b) N, the two octadecanoyl EDDAs of N-synthetic

Stearic bicine diester base ethylenediamine 278.2 grams (0.47 mole) that step (a) is synthetic, 556.4 gram oxolanes, 112.8 gram (2.82 moles) NaOH and 6.0 gram TBABs; add and be furnished with in 2000 milliliters the there-necked flask of mechanical agitation, thermometer 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 reactant liquor with hydrochloric acid and is highly 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 distilled water washing solid.

(c) N, the two octadecanoyl EDDA two polyoxy vinethenes (n=6) of N-synthetic

With [embodiment 1] (c); difference is with the N of 184.0 grams (0.260 mole); the two octadecanoyl EDDAs of N-substitute 165.0 gram (0.305 mole) N; the use amount of the two dodecanoyl EDDAs of N-, oxirane is 137.8g (3.132 moles); the use amount of the alkali compounds of calcium is 2.9 grams; get N, the two octadecanoyl EDDA two polyoxy vinethenes (n=6) of N-300.8 grams, molar yield 93.6%.

(d) dichloro-N, the two octadecanoyl EDDA two polyoxy vinethenes (n=6) of N-synthetic

The N that step (c) is synthesized; the two octadecanoyl EDDA two polyoxy vinethenes (n=6) of N-300.8 grams (0.24 mole), 40.3 gram (0.50 mole) pyridines place in 1000 milliliters of there-necked flasks that backflow, stirring, gas absorbing device are housed; under agitation slowly thionyl chloride 100.0 restrains (0.84 mole); 90 ℃ of reactions 5 hours; all the other operations with [embodiment 1] (d); vacuum drying gets dichloro-N; the two octadecanoyl EDDA two polyoxy vinethenes (n=6) of N-253.0 grams, molar yield 82.8%.

(e) N, two octadecanoyl EDDA two polyoxy vinethene (n=6) disulfonates of N-synthetic

The dichloro-N that step (d) is synthesized; the two octadecanoyl EDDA two polyoxy vinethenes (n=6) of N-253.0 grams (0.20 mole) place autoclave; add 70 gram ethylene glycol, 80 gram water, 71.7 gram sodium sulfites (0.69 mole) and 14.5 gram sodium hydrogensulfites (0.12 mole); reaction is 5 hours under 140 ℃ of temperature; all the other operations with [embodiment 1] (e); get N; two octadecanoyl EDDA two polyoxy vinethene (n=6) disulfonates of N-, the product quality mark is 90.5%.To synthetic N, two octadecanoyl EDDA two polyoxy vinethene (n=6) disulfonates of N-are used U.S. Nicolet-380FT-IR spectrometer, adopt liquid-film method to carry out infrared spectrum analysis (sweep limits 4000～400cm ^-1), have all characteristic absorption peaks of Fig. 1.

(f) with the synthetic N of step (e); two octadecanoyl EDDA two polyoxy vinethene (n=6) the disulfonate 0.2wt% of N-, above-mentioned modified polyacrylamide 0.1wt% and the marine block of 97.0wt% Shengli Oil Field inject water mixing stirring 1.5 hours, obtain a kind of flooding method that is applicable to seawater base 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 composition is 14.4mPa.s; Form the ultralow interfacial tension of 0.0017mN/m between the marine block IFA-8 of said composition and the Shengli Oil Field well dewatered oil.Apparent viscosity is by the BROODFIELD II type viscometer determining of U.S. Brookfield company, and interfacial tension is dripped interfacial tensimeter mensuration by the TX500 type rotation that Texas ,Usa university produces.

(g) 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 permeability is 1.5 microns with rock core ²) saturated, the voids volume (PV) of measuring rock core is 52.7%, carry out saturated with the marine block IFA-8 of Shengli Oil Field well dewatered oil then, carry out the imitation oil displacement experiment test under 65 ℃ of constant temperature: first water drive is to moisture 94%, record water drive and improve oil recovery factor 60.8%, again the synthetic displacement of reservoir oil of metaideophone 0.3pv (rock pore volume) step (f) with composition after, water drive records on the water drive basis and can improve oil recovery factor 16.0% again to moisture more than 98%.

[embodiment 7]

(a) two 18 (tristearin) acyl group hexamethylene diamine is synthetic

With [embodiment 6] (a), difference substitutes 30.0 gram (0.5 mole) anhydrous ethylenediamines with the anhydrous hexamethylene diamine 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 octadecanoyl hexamethylene diamine oxalic acid of N-synthetic

Stearic bicine diester base hexamethylene diamine 304.6 grams (0.47 mole) that step (a) is synthetic, 609 gram oxolanes, 210.6 gram (3.76 moles) NaOH and 7.5 gram TBABs; add and be furnished with in 2000 milliliters the there-necked flask of mechanical agitation, thermometer 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 reactant liquor with hydrochloric acid and is highly 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 distilled water washing solid.

(c) N, the two octadecanoyl hexamethylene diamine oxalic acid two polyoxy vinethenes (n=5) of N-synthetic

With [embodiment 1] (c); difference is with the N of 185.6 grams (0.243 mole); the two octadecanoyl hexamethylene diamine oxalic acid of N-substitute 165.0 gram (0.305 mole) N; the use amount of the two dodecanoyl EDDAs of N-, oxirane is 106.9g (2.43 moles); the use amount of the alkali compounds of calcium is 3.0 grams; get N, the two octadecanoyl hexamethylene diamine oxalic acid two polyoxy vinethenes (n=5) of N-271.2 grams, molar yield 92.7%.

(d) dichloro-N, the two octadecanoyl hexamethylene diamine oxalic acid two polyoxy vinethenes (n=5) of N-synthetic

The N that step (c) is synthesized; the two octadecanoyl hexamethylene diamine oxalic acid two polyoxy vinethenes (n=5) of N-271.2 grams (0.225 mole), 72.4 gram (0.90 mole) pyridines place in 1000 milliliters of there-necked flasks that backflow, stirring, gas absorbing device are housed; under agitation slowly thionyl chloride 120.1 restrains (1.01 moles); all the other operations with [embodiment 1] (d); vacuum drying gets dichloro-N; the two octadecanoyl hexamethylene diamine oxalic acid two polyoxy vinethenes (n=5) of N-227.8 grams, molar yield 81.6%.

(e) N, two octadecanoyl hexamethylene diamine oxalic acid two polyoxy vinethene (n=5) disulfonates of N-synthetic

The dichloro-N that step (d) is synthesized; the two octadecanoyl EDDA two polyoxy vinethenes (n=5) of N-227.8 grams (0.184 mole) place autoclave; add 60 gram ethylene glycol, 90 gram water, 57.4 gram sodium sulfites (0.552 mole) and 11.6 gram sodium hydrogensulfites (0.092 mole); reaction is 7 hours under 140 ℃ of temperature; all the other operations with [embodiment 1] (e); get N; two octadecanoyl hexamethylene diamine oxalic acid two polyoxy vinethene (n=5) disulfonates of N-, the product quality mark is 87.8%.To synthetic N, two octadecanoyl hexamethylene diamine oxalic acid two polyoxy vinethene (n=5) disulfonates of N-are used U.S. Nicolet-380FT-IR spectrometer, adopt liquid-film method to carry out infrared spectrum analysis (sweep limits 4000～400cm ^-1), have all characteristic absorption peaks of Fig. 1.

(f) with the synthetic N of step (e); two octadecanoyl hexamethylene diamine oxalic acid two polyoxy vinethene (n=5) the disulfonate 0.15wt% of N-, above-mentioned ultra-high-molecular aniouic polyacrylamide 0.15wt% and the marine block of 97.0wt% Shengli Oil Field inject water mixing stirring 2.0 hours, obtain a kind of flooding method that is applicable to seawater base of homogeneous transparent.At 65 ℃ of temperature, salinity 15750mg/L, Ca ²⁺+ Mg ²⁺In the water of 800mg/L, the apparent viscosity that records this composition is 15.6mPa.s; Form the ultralow interfacial tension of 0.0046mN/m between the marine block IFA-8 of said composition and the Shengli Oil Field well dewatered oil.Apparent viscosity is by the BROODFIELD II type viscometer determining of U.S. Brookfield company, and interfacial tension is dripped interfacial tensimeter mensuration by the TX500 type rotation that Texas ,Usa university produces.

(g) earlier with salinity 15750mg/L, Ca ²⁺+ Mg ²⁺(length is 30 centimetres to the injection water of 800mg/L, and diameter is 2.5 centimetres, and permeability is 1.5 microns with rock core ²) saturated, the voids volume (PV) of measuring rock core is 52.8%, carry out saturated with the marine block IFA-8 of Shengli Oil Field well dewatered oil then, carry out the imitation oil displacement experiment test under 65 ℃ of constant temperature: first water drive is to moisture 94%, record water drive and improve oil recovery factor 58.7%, again the synthetic displacement of reservoir oil of metaideophone 0.3pv (rock pore volume) step (f) with composition after, water drive records on the water drive basis and can improve oil recovery factor 18.7% again to moisture more than 98%.

[comparative example 1]

With [embodiment 1] (f); difference substitutes 0.15wt%N with the petroleum sodium sulfonate (Wuxi oil refinery) of 0.15wt%; two dodecanoyl EDDA two polyoxy vinethene (n=4) disulfonates of N-; all the other are identical; the apparent viscosity that records this composition is 14.3mPa.s, forms the interfacial tension of 0.0236mN/m between the marine block IFA-8 of said composition and the Shengli Oil Field well dewatered oil.Apparent viscosity is by the BROODFIELD II type viscometer determining of U.S. Brookfield company, and interfacial tension is dripped interfacial tensimeter mensuration by the TX500 type rotation that Texas ,Usa university produces.

With [embodiment 1] (g), record water drive and improve oil recovery factor 56.9%, the above-mentioned displacement of reservoir oil of metaideophone with composition after, record on the water drive basis and can improve oil recovery factor 11.3% again.

[comparative example 2]

With [embodiment 1] (f), difference substitutes the above-mentioned ultra-high-molecular aniouic polyacrylamide (viscosity average molecular weigh is 2,300 ten thousand) of 0.15wt% with the high molecular weight polyacrylamide (viscosity average molecular weigh is 1,800 ten thousand) of 0.15wt%, all the other are identical, the apparent viscosity that records this composition is 12.5mPa.s, forms the interfacial tension of 0.0089mN/m between the marine block IFA-8 of said composition and the Shengli Oil Field well dewatered oil.Apparent viscosity is by the BROODFIELD II type viscometer determining of U.S. Brookfield company, and interfacial tension is dripped interfacial tensimeter mensuration by the TX500 type rotation that Texas ,Usa university produces.

With [embodiment 1] (g), record water drive and improve oil recovery factor 57.2%, the above-mentioned displacement of reservoir oil of metaideophone with composition after, record on the water drive basis and can improve oil recovery factor 12.5% again.

Claims

1. flooding method that is applicable to seawater base is at 30～83 ℃ of displacement of reservoir oil temperature, total salinity＞8000mg/L, Ca ²⁺+ Mg ²⁺Under the injection water condition of＞200mg/L, underground dewatered oil is contacted with displacement of reservoir oil composition, the abundant displacement of the crude oil in the rock core is come out, wherein said displacement of reservoir oil composition comprises following component by percentage to the quality:

(2) 0.01～3.0% polymer;

(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 one integer in 2～7; M is any one metal ion that is selected from potassium, sodium or the lithium; Polymer is selected from one or both in modified polyacrylamide or the xanthans; Described modified polyacrylamide is formed by acrylamide, 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 weigh is 15,000,000.

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

3. the flooding method that is applicable to seawater base according to claim 1, the total salinity 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 that is applicable to seawater base according to claim 1 is characterized in that described N, the R in the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy vinethene disulfonates of N- ₁Carbon number is nine, 11,13,15 or 17.

5. the flooding method that is applicable to seawater base according to claim 1 is characterized in that described N, the R in the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy vinethene disulfonates of N- ₂Carbon number be two, four or six.

6. the flooding method that is applicable to seawater base according to claim 1 is characterized in that described N, the R in the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy vinethene disulfonates of N- ₁Carbon number adds 1 sum and the EO adduction is counted the ratio of n between 2～4.