CN102373044B - Oil displacement method suitable for MgCl2 water-type oil displacement agent - Google Patents
Oil displacement method suitable for MgCl2 water-type oil displacement agent Download PDFInfo
- Publication number
- CN102373044B CN102373044B CN2010102618195A CN201010261819A CN102373044B CN 102373044 B CN102373044 B CN 102373044B CN 2010102618195 A CN2010102618195 A CN 2010102618195A CN 201010261819 A CN201010261819 A CN 201010261819A CN 102373044 B CN102373044 B CN 102373044B
- Authority
- CN
- China
- Prior art keywords
- oil
- water
- displacing agent
- oil displacement
- mgcl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to an oil displacement method suitable for a MgCl2 water-type oil displacement agent. By the oil displacement 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 MgCl2 water-type oil displacement agent, underground dehydrated crude oil contacts the oil displacement agent under the MgCl2-type 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, Mg<2+> is more than 200 mg/L and Ca<2+> is more than 30 mg/L, so that crude oil in cores is displaced fully, wherein the oil displacement agent comprises the following components in percentage by mass: (1) 0.01 to 5.0 percent of N,N-double fatty acyl diamine dipropionate 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
Technical field
The present invention relates to a kind of MgCl of being applicable to
2The flooding method of water type 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 big more, and find is fewer and feweri; Two, also left in the exhausted oil reservoir have a substantial oil.Primary oil recovery (POR) but extraction 10～25% underground crude oil, secondary oil recovery (SOR) but extraction 15～25% underground crude oil, i.e. a primary oil recovery and secondary oil recovery extraction 25～50% underground crude oil.In order to guarantee oil supply steady in a long-term, 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 tensio-active agent is as host or as the auxiliary agent displacement of reservoir oil, all plays immeasurable effect to increasing substantially recovery ratio.Polymer displacement of reservoir oil tech is a kind of method of important raising oil recovery, compares with general water drive, and polymer flooding can quicken oil recovery process, improves economic benefit, and Processes and apparatus is simple, cost is lower.As an important technology in the chemical flooding, the ternary composite driving oil tech that polymkeric substance, tensio-active agent and alkali form has carried out some field tests in China and foreign countries, has obtained good oil displacement efficiency.But problems such as the fouling of producing well pit shaft is serious, extraction liquid difficult treatment that the adding of alkali causes occurring in the field test make ternary composite oil-displacing The Application of Technology prospect allow of no optimist.By contrast, do not use alkali in the binary combination flooding prescription that polymkeric substance and tensio-active agent form, the mining site operability is stronger, thereby is subjected to the approval in oil field.But because need not any alkali, crude oil PetroChina Company Limited. acids active substance can not be fully used, so that research and development have the novel surfactant and an alkali-free binary combination flooding prescription of high surface more is imperative.
The tensio-active agent industrialization product of external used for tertiary oil recovery mainly contains two big classes: the one, and sulfonated petro-leum is main tensio-active agent, the 2nd, alkylbenzene sulfonate is main tensio-active agent, this two classes tensio-active agent raw material is all taken from crude oil, raw material sources are wide, quantity is big, thereby also are the tensio-active agents of external tertiary oil recovery consumption maximum.Because sulfonate surfactant is 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 anion-nonionic amphoterics is one of focus of tertiary oil recovery (EOR) area research in recent years always, owing in its molecular structure two kinds of non-ionic groups of different nature and anionic group are designed in same surfactant molecule, make it have the advantage of negatively charged ion and nonionogenic tenside concurrently, have complementary advantages, excellent property, therefore shown good prospects for application, especially the binary combination flooding 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 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 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 positively charged ion 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 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 as 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, the alkali that contains high density, as sodium hydroxide, yellow soda ash etc., in use, to bringing huge injury in stratum and oil well etc., employed tensio-active agent is difficult for by biological degradation, and human body also there is certain hazardness, as: 1991, Zhao Guoxi was at " tensio-active agent physical chemistry " P495; 1994, disclosed content among Liu Chengzai " tensio-active agent complete works " P35.So at those harsh oil reservoirs, we ought to seek a kind of under alkali-free, high temperature (formation temperature is greater than 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 tertiary oil recovery.
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 new MgCl that is applicable to
2The flooding method of water type oil-displacing agent.This method will contain N, and the two carboxylate surface active agent oil-displacing agents of the two fatty acyl group diamines dipropionic acid two polyoxy Vinyl Ethers of N-are 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: a kind of MgCl that is applicable to
2The flooding method of water type oil-displacing agent, the oil-displacing agent that the displacement of reservoir oil is used is at 30～83 ℃ of displacement of reservoir oil temperature, total mineralization＞8000 mg/litre, Mg
2+＞200 mg/litre, Ca
2+The MgCl of＞30 mg/litre
2Type injects under the water condition, and underground dewatered oil is contacted with oil-displacing agent, and the abundant displacement of the crude oil in the rock core is come out, and wherein said 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 diamines dipropionic acid 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 one integer in 2～7; M is any one metal 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 xanthan gum.
In the technique scheme, displacement of reservoir oil temperature is preferably 45～75 ℃; Described injection water total mineralization is preferably 15000～32000 mg/litre, Mg
2+Be preferably 500～1200 mg/litre, Ca
2+Be preferably 200～500 mg/litre, the water type is MgCl
2Type; Polymkeric substance is selected from above-mentioned ultra-high-molecular aniouic polyacrylamide or modified polyacrylamide; The M preferred version is potassium and sodium, and more preferably scheme is for being selected from sodium; R
1It is to have best hydrophile-lipophile balance value at 3～4 o'clock that carbon number adds ratio preferable range that 1 sum and EO count n, and its aqueous solution can form 10 with crude oil
-3～10
-4Ultra low interfacial tension; N, the R in the two carboxylate salts of the two fatty acyl group diamines dipropionic acid 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 the two fatty acyl group diamines dipropionic acids of N-:
With the carbochain number of required proportioning is 10～18 lipid acid, thionyl chloride and N, and dinethylformamide (DMF) was 70～100 ℃ of reactions 2～5 hours, and excessive thionyl chloride is extracted in decompression out, and it is 10～18 fat acyl chloride that the transparent liquid that obtains is the carbochain number
1In addition be 2～6 diamines, methyl acrylate and solvent 1 with the carbochain number of required proportioning, the 4-dioxane mix all with after, 40～70 ℃ of reactions 2～5 hours, reduce pressure unreacted raw material of removal and solvent got diamines dipropionic acid methyl esters
2, regulate PH=9～10 with the sodium hydroxide solution of 50wt%, drip under the vigorous stirring
1, in 40～70 ℃ of reactions 2～6 hours, getting N again, the two carbochain numbers of N-are 10～18 fatty acyl group diamines dipropionic acid methyl esters
3, the ethanol of adding aequum is regulated PH=11～12 with the sodium hydroxide solution of 50wt%, and back flow reaction 2～6 hours gets N after the acidifying, and the two carbochain numbers of N-are 10～18 fatty acyl group diamines dipropionic acids.Wherein, preparation
1The time, 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; Preparation
2The time, solvent is 1, and 4-dioxane, consumption are 3～6 times of 2～6 diamines quality for the carbochain number, and the carbochain number is that 2～6 the diamines and the mol ratio of methyl acrylate are 1: 1.0～4.0; Preparation
3The time, the carbochain number is that the mol ratio that 10～18 fat acyl chloride and carbochain number are 2～6 diamines dipropionic acid methyl esters is 1.9～2.5: 1; Preparation N, when the two carbochain numbers of N-were 10～18 fatty acyl group diamines dipropionic acids, the ethanol consumption was 5～10 times of 2～6 diamines quality for the carbochain number.
(b) N, the preparation of the two fatty acyl group diamines dipropionic acid two polyoxy Vinyl Ethers of N-:
Step (a) the synthetic N of institute; the two carbochain numbers of N-are that 10～18 fatty acyl group diamines dipropionic acids 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 diamines dipropionic acids, two polyoxy Vinyl Ethers.Wherein, N, the two carbochain numbers of N-are that 10～18 fatty acyl group diamines dipropionic acids 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 diamines dipropionic acid quality.
(c) N, the preparation of the two carboxylate salts of the two fatty acyl group diamines dipropionic acid two polyoxy Vinyl Ethers of N-:
With step (b) the synthetic N of institute; the two carbochain numbers of N-are that 10～18 fatty acyl group diamines dipropionic acids, two polyoxy Vinyl Ethers are by required proportioning and sodium chloroacetate, potassium hydroxide or sodium hydroxide and Tetrabutyl amonium bromide catalyst mix; with toluene is solvent; 50～130 ℃ of temperature of reaction; reacted 3～15 hours; reaction finishes after aftertreatment gets N, the two carboxylate salts of the two fatty acyl group diamines dipropionic acid two polyoxy Vinyl Ethers of N-.Wherein, N, the two carbochain numbers of N-are mol ratio=1: 2～6: 2～8: 0.05～03 of 10～18 fatty acyl group diamines dipropionic acids, two polyoxy Vinyl Ethers, sodium chloroacetate, potassium hydroxide or sodium hydroxide and Tetrabutyl amonium bromide.
(d) with the N of aequum, the two carboxylate salts of the two fatty acyl group diamines dipropionic acid 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 oil-displacing agent.By percentage to the quality; N, the two carboxylate salts of the two fatty acyl group diamines dipropionic acid two polyoxy Vinyl Ethers 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%.
(e) be 10000～40000 mg/litre, Mg with total mineralization earlier
2+Be 300～1350 mg/litre, Ca
2+Be the MgCl of 50～800 mg/litre
2It is saturated with rock core that type injects water, measure the volume of voids (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%, behind metaideophone 0.3pv (rock pore volume) step (d) the synthetic 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) prepare in the step
1The time, the carbochain number is 10～18 lipid acid, thionyl chloride and N, the mol ratio of dinethylformamide is preferably 1: 1.2～and 2.0: 0.05～0.1; Preparation
2The time solvent be 1, it is 4～5 times of 2～6 diamines quality that 4-dioxane, consumption are preferably the carbochain number, the carbochain number be the mol ratio of 2～6 diamines and methyl acrylate be preferably 1: 2.2～3.0, temperature of reaction is preferably 50～60 ℃, and the reaction times is preferably 3～4 hours; Preparation
3The time, the carbochain number is that the mol ratio that 10～18 fat acyl chloride and carbochain number are 2～6 diamines dipropionic acid methyl esters is preferably 2.0～2.2: 1, and temperature of reaction is preferably 60～70 ℃, and the reaction times is preferably 3～4 hours; Preparation N, when the two carbochain numbers of N-were 10～18 fatty acyl group diamines dipropionic acids, it was 6～8 times of 2～6 diamines quality that the ethanol consumption is preferably the carbochain number, the reaction times is preferably 3～5 hours.(b) N, the two carbochain numbers of N-be 10～18 fatty acyl group diamines dipropionic acids and oxyethane mol ratio be preferably 1: 6～12, catalyst levels is preferably N, N-pair of carbochain numbers are 1.0～3.0% of 10～18 fatty acyl group diamines dipropionic acid quality.(c) N in the step; the two carbochain numbers of N-be the mol ratio of 10～18 fatty acyl group diamines dipropionic acids, two polyoxy Vinyl Ethers, sodium chloroacetate, sodium hydroxide (potassium hydroxide) and Tetrabutyl amonium bromide be preferably 1: 2.5～5.5: 3～7: 0.1～0.2; temperature of reaction is preferably 70～110 ℃, and the reaction times is preferably 5～12 hours.(d) by percentage to the quality, N, the consumption preferable range of the two carboxylate salts of the two fatty acyl group diamines dipropionic acid 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.(e) displacement of reservoir oil temperature is preferably 45～75 ℃; Inject the water total mineralization and be preferably 15000～32000 mg/litre, Mg
2+Be preferably 500～1200 mg/litre, Ca
2+Be preferably 200～500 mg/litre, the water type is MgCl
2Type.
The N of the prepared displacement of reservoir oil of the present invention in the oil-displacing agent; the two carboxylate salts of the two fatty acyl group diamines dipropionic acid 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 anion surfactant concurrently and nonionogenic tenside; and symmetric Shuangzi constitutional features; it is low to make it have micelle-forming concentration again; it is strong to reduce the interfacial tension ability; features such as anti-high salinity and 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 MgCl that is applicable to of the present invention
2The flooding method of water type oil-displacing agent under the alkali-free condition, can be used for 45～75 ℃ of formation temperature, salinity 15000～32000 mg/litre, Mg
2+500～1200 mg/litre, Ca
2+The MgCl of 200～500 mg/litre
2The marine block of type Shengli Oil Field 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 carboxylate salts of the two fatty acyl group diamines dipropionic acid two polyoxy Vinyl Ethers of N-and 0.1～0.2wt% forms above-mentioned oil-displacing agent oil-displacing agent; measure the dynamic interface tension value between the marine block crude oil of this oil-displacing agent aqueous solution and Shengli Oil Field, can reach 10
-3～10
-4The ultra low interfacial tension of mN/m, can on the water drive basis, can reach 18.6% by (water drive improves oil recovery factor and reaches 60.9%) 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 diamines dipropionic acid two polyoxy Vinyl Ethers of N-.
The N of the present invention's preparation; the two carboxylate salts of the two fatty acyl group diamines dipropionic acid two polyoxy Vinyl Ethers of N-can characterize by the following method: after synthetics is purified; use U.S. Nicolet-380FT-IR spectrograph, adopt liquid-film method to carry out Infrared spectroscopy (sweep limit 4000～400cm
-1), be 2850～2950cm in wave number
-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 vC=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 diamines dipropionic acid two polyoxy Vinyl Ethers of N-.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
(a) N, the two lauroyl ethylene diamine dipropionic acids of N-synthetic
With lauric acid 300 grams (1.5 moles), sulfur oxychloride 267.8 grams (2.25 moles) and 4.5 gram DMF, add and be furnished with in 1000 milliliters of four-hole boiling flasks of sealing machine stirring, thermometer, prolong etc., after 3 hours, decompression steams excessive thionyl chloride, obtains lauroyl chloride in 90 ℃ of reactions.Another is furnished with and adds anhydrous ethylenediamine 45.0 grams (0.75 mole), 180 grams 1 in 2000 milliliters of four-hole boiling flasks of sealing machine stirring, thermometer, prolong, the 4-dioxane, be warming up to 50 ℃, slowly dropwise addition of acrylic acid methyl esters 141.9 restrains (1.65 moles), drip off and continue reaction 3 hours, unreacted methyl acrylate and solvent 1 are removed in decompression, and 4-dioxane, residuum are the ethylene diamine dipropionic acid methyl esters.With 50wt% sodium hydroxide conditioned reaction liquid PH=8～10; slowly drip lauroyl chloride under the vigorous stirring; constantly add simultaneously 50wt% sodium hydroxide with the PH that keeps reaction 8～10; drip off the back and continue reaction 3 hours in 60 ℃; get N, the two lauroyl ethylene diamine dipropionic acid methyl esters of N-continue to add 270 gram ethanol in reaction flask; transfer PH=11～12 with 50wt% sodium hydroxide again; refluxed 4 hours, cooling, filtration is desalted; pressure reducing and steaming ethanol; residuum is neutralized to strongly-acid with hydrochloric acid, and branch vibration layer gets N; two lauroyl ethylene diamine dipropionic acid 300.3 grams of N-, molar yield 70.5%.
(b) N, the two lauroyl ethylene diamine dipropionic acid two polyoxy Vinyl Ethers (n=4) of N-synthetic
With step (a) synthetic N; the basic cpd of two lauroyl ethylene diamine dipropionic acid 300.3 grams (0.529 mole) of N-, 3.5 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, be cooled to 80 ℃, the sulfuric acid (20wt%) that slowly drips the catalyst neutralisation theoretical amount makes the compound oxidizing calcium alkoxylating catalyst reaction solution system of high reactivity, highly selective, system temperature is heated to 80～90 ℃, open vacuum system, dehydration is 2 hours under high vacuum, uses nitrogen purging then 3～4 times, the system temperature of reaction is transferred to 140 ℃ slowly feed 186.4 gram (4.236 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 ethylene diamine dipropionic acid two polyoxy Vinyl Ethers (n=4) of N-419.5 grams, molar yield 86.2%.
(c) N, the two two carboxylate salts of lauroyl ethylene diamine dipropionic acid two polyoxy Vinyl Ethers (n=4) of N-synthetic
With step (b) the synthetic N of institute; the two lauroyl ethylene diamine dipropionic acid two polyoxy Vinyl Ethers (n=4) of N-419.5 grams (0.460 mole) and 155.3 gram (2.77 moles) potassium hydroxide, 214.6 gram (1.84 moles) sodium chloroacetates, 16.3 gram Tetrabutyl amonium bromides, 1500 milliliters of toluene are mixed in to be furnished with mechanical stirring, in 5000 milliliters the reactor of thermometer and reflux condensing tube, to be heated to 90 ℃ of reactions 8 hours.Cooling, neutralization divides and to remove inorganic salt, alkalize N, the two two carboxylate salts of lauroyl ethylene diamine dipropionic acid two polyoxy Vinyl Ethers (n=4) of N-, molar yield 87.8%.To synthetic N, the two two carboxylate salts of lauroyl ethylene diamine dipropionic acid two polyoxy Vinyl Ethers (n=4) of N-are used U.S. Nicolet-380FT-IR spectrograph, adopt liquid-film method to carry out Infrared spectroscopy (sweep limit 4000～400cm
-1), have all charateristic avsorption bands of Fig. 1.
(d) with step (c) synthetic N; the two two carboxylate salt 0.2wt% of lauroyl ethylene diamine dipropionic acid two polyoxy Vinyl Ethers (n=4) of N-, above-mentioned ultra-high-molecular aniouic polyacrylamide 0.15wt% and the marine block of 96.5wt% Shengli Oil Field inject water mixing stirring 2 hours, obtain a kind of MgCl that is applicable to of homogeneous transparent
2Type injects the oil-displacing agent of water.In 65 ℃ of temperature, salinity is 15000mg/L, Mg
2+Be 600mg/L, Ca
2+In the water for 200mg/L, the apparent viscosity that records this oil-displacing agent is 15.4mPa.s; Form the ultra low interfacial tension of 0.0006mN/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.
(e) earlier with salinity 15000mg/L, Mg
2+Be 600mg/L, Ca
2+(length is 30 centimetres, and diameter is 2.5 centimetres, and rate of permeation is 1.5 microns with rock core for the injection water of 200mg/L
2) saturated, the volume of voids (PV) of measuring rock core is 51.3%, 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%, behind metaideophone 0.3pv (rock pore volume) step (d) the synthetic oil-displacing agent, water drive records on the water drive basis and can improve oil recovery factor 18.6% again to moisture more than 98% again.
[embodiment 2]
(a) N, the two lauroyl hexanediamine dipropionic acids of N-synthetic
With [embodiment 1] (a), difference substitutes 45.0 gram (0.75 mole) anhydrous ethylenediamines with the anhydrous hexanediamine of 87.0 grams (0.75 mole), and all the other are identical, get N, two lauroyl hexanediamine dipropionic acid 328.5 grams of N-, molar yield 70.2%.
(b) N, the two lauroyl hexanediamine dipropionic acid two polyoxy Vinyl Ethers (n=3) of N-synthetic
With [embodiment 1] (b); difference is with the N of 328.5 grams (0.578 mole); the two lauroyl hexanediamine dipropionic acids of N-substitute 300.3 gram (0.529 mole) N; the usage quantity of the two lauroyl ethylene diamine dipropionic acids of N-, oxyethane is 152.7g (3.470 moles); the usage quantity of the basic cpd of calcium is 8.6 grams;) N, the two lauroyl hexanediamine dipropionic acid two polyoxy Vinyl Ethers (n=3) of N-446.0 grams, molar yield 86.9%.
(c) N, the two two carboxylate salts of lauroyl hexanediamine dipropionic acid two polyoxy Vinyl Ethers (n=3) of N-synthetic
With step (b) the synthetic N of institute; the two lauroyl hexanediamine dipropionic acid two polyoxy Vinyl Ethers (n=3) of N-446.0 grams (0.503 mole) and 113.0 gram (2.014 moles) potassium hydroxide, 251.7 gram (2.16 moles) sodium chloroacetates, 18.3 gram Tetrabutyl amonium bromides, 1500 milliliters of toluene are mixed in to be furnished with mechanical stirring, in 5000 milliliters the reactor of thermometer and reflux condensing tube, to be heated to 100 ℃ of reactions 6 hours.Cooling, neutralization divides and to remove inorganic salt, alkalize N, the two two carboxylate salts of lauroyl hexanediamine dipropionic acid two polyoxy Vinyl Ethers (n=3) of N-, molar yield 87.4%.To synthetic N, the two two carboxylate salts of lauroyl hexanediamine dipropionic acid two polyoxy Vinyl Ethers (n=3) of N-are used U.S. Nicolet-380FT-IR spectrograph, adopt liquid-film method to carry out Infrared spectroscopy (sweep limit 4000～400cm
-1), have all charateristic avsorption bands of Fig. 1.
(d) with step (c) synthetic N; the two two carboxylate salt 0.1wt% of lauroyl hexanediamine dipropionic acid two polyoxy Vinyl Ethers (n=3) 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 2.5 hours, obtain a kind of MgCl that is applicable to of homogeneous transparent
2Type injects the oil-displacing agent of water.In 65 ℃ of temperature, salinity is 15000mg/L, Mg
2+Be 600mg/L, Ca
2+In the water for 200mg/L, the apparent viscosity that records this oil-displacing agent is 15.8mPa.s; Form the ultra low interfacial tension of 0.0052mN/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.
(e) earlier with salinity 15000mg/L, Mg
2+Be 600mg/L, Ca
2+(length is 30 centimetres, and diameter is 2.5 centimetres, and rate of permeation is 1.5 microns with rock core for the injection water of 200mg/L
2) saturated, measure the volume of voids (PV) 528% of rock core, 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 55.8%, behind metaideophone 0.3pv (rock pore volume) step (d) the synthetic 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) N, the two ten acyl group butanediamine dipropionic acids of N-synthetic
With [embodiment 1] (a); difference substitutes 300.0 gram (1.5 moles) lauric acid with the capric acid of 261.0 grams (1.5 moles); anhydrous butanediamine with 66.0 grams (0.75 mole) substitutes 45.0 gram (0.75 mole) anhydrous ethylenediamines; all the other are identical; get N; the two ten acyl group butanediamine dipropionic acids of N-285.2 grams, molar yield 69.9%.
(b) N, two ten acyl group butanediamine dipropionic acids, the two polyoxy Vinyl Ethers (n=3) of N-synthetic
With [embodiment 1] (b); difference is with the N of 285.2 grams (0.524 mole); the two ten acyl group butanediamine dipropionic acids of N-substitute 300.3 gram (0.529 mole) N; the usage quantity of the two lauroyl ethylene diamine dipropionic acids of N-, oxyethane is 138.3g (3.144 moles); the usage quantity of the basic cpd of calcium is 6.7 grams; get N, the two ten acyl group butanediamine dipropionic acids of N-two polyoxy Vinyl Ethers (n=3) 360.6 grams, molar yield 85.6%.
(c) N, the two two carboxylate salts of ten acyl group butanediamine dipropionic acids, two polyoxy Vinyl Ethers (n=3) of N-synthetic
With step (b) the synthetic N of institute; the two ten acyl group butanediamine dipropionic acids of N-two polyoxy Vinyl Ethers (n=3) 360.6 grams (0.448 mole) and 100.3 gram (1.79 moles) potassium hydroxide, 263.3 gram (1.34 moles) sodium chloroacetates, 18.8 gram Tetrabutyl amonium bromides, 1500 milliliters of toluene are mixed in to be furnished with mechanical stirring, in 5000 milliliters the reactor of thermometer and reflux condensing tube, to be heated to 80 ℃ of reactions 8 hours.Cooling, neutralization divides and to remove inorganic salt, alkalize N, the two two carboxylate salts of ten acyl group butanediamine dipropionic acids, two polyoxy Vinyl Ethers (n=3) of N-, molar yield 86.5%.To synthetic N, the two two carboxylate salts of ten acyl group butanediamine dipropionic acids, two polyoxy Vinyl Ethers (n=3) of N-are used U.S. Nicolet-380FT-IR spectrograph, adopt liquid-film method to carry out Infrared spectroscopy (sweep limit 4000～400cm
-1), have all charateristic avsorption bands of Fig. 1.
(d) with step (c) synthetic N; the two two carboxylate salt 025wt% of ten acyl group butanediamine dipropionic acids, two polyoxy Vinyl Ethers (n=3) of N-, above-mentioned modified polyacrylamide 0.2wt% and the marine block of 95.5wt% Shengli Oil Field inject water mixing stirring 25 hours, obtain a kind of MgCl that is applicable to of homogeneous transparent
2Type injects the oil-displacing agent of water.In 70 ℃ of temperature, salinity is 32000mg/L, Mg
2+Be 1200mg/L, Ca
2+In the water for 400mg/L, the apparent viscosity that records this oil-displacing agent is 14.7mPa.s; Form the ultra low 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.
(e) earlier with salinity 32000mg/L, Mg
2+Be 1200mg/L, Ca
2+(length is 30 centimetres, and diameter is 2.5 centimetres, and rate of permeation is 1.5 microns with rock core for the injection water of 400mg/L
2) saturated, the volume of voids (PV) of measuring rock core is 53.2%, 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 56.9%, behind metaideophone 0.3pv (rock pore volume) step (d) the synthetic 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 4]
(a) N, the two palmitoyl ethylene diamine dipropionic acids of N-synthetic
With palmitinic acid 422.4 grams (1.65 moles), sulfur oxychloride 235.6 grams (1.875 moles) and 6.3 gram DMF, add and be furnished with in 1000 milliliters of four-hole boiling flasks of sealing machine stirring, thermometer, prolong etc., in 80 ℃ the reaction 5 hours after, decompression steams excessive thionyl chloride, obtains palmityl chloride.Another is furnished with and adds anhydrous ethylenediamine 45.0 grams (0.75 mole), 225 grams 1 in 2000 milliliters of four-hole boiling flasks of sealing machine stirring, thermometer, prolong, the 4-dioxane, be warming up to 60 ℃, slowly dropwise addition of acrylic acid methyl esters 161.3 restrains (1.875 moles), drip off and continue reaction 4 hours, unreacted methyl acrylate and solvent 1 are removed in decompression, and 4-dioxane, residuum are the ethylene diamine dipropionic acid methyl esters.With 50wt% sodium hydroxide conditioned reaction liquid PH=8～10; slowly drip lauroyl chloride under the vigorous stirring; constantly add simultaneously 50wt% sodium hydroxide with the PH that keeps reaction 8～10; drip off the back and continue reaction 4 hours in 70 ℃; get N, the two palmitoyl ethylene diamine dipropionic acid methyl esters of N-continue to add 360 gram ethanol in reaction flask; transfer PH=11～12 with 50wt% sodium hydroxide again; refluxed 4 hours, cooling, filtration is desalted; pressure reducing and steaming ethanol; residuum is neutralized to strongly-acid with hydrochloric acid, and branch vibration layer gets N; two palmitoyl ethylene diamine dipropionic acid 354.5 grams of N-, molar yield 69.5%.
(b) N, the two palmitoyl ethylene diamine dipropionic acid two polyoxy Vinyl Ethers (n=5) of N-synthetic
With [embodiment 1] (b); difference is with the N of 354.5 grams (0.521 mole); the two palmitoyl ethylene diamine dipropionic acids of N-substitute 300.3 gram (0.529 mole) N; the usage quantity of the two lauroyl ethylene diamine dipropionic acids of N-, oxyethane is 229.2g (5.21 moles); the usage quantity of the basic cpd of calcium is 6.8 grams; get N, the two palmitoyl ethylene diamine dipropionic acid two polyoxy Vinyl Ethers (n=5) of N-497.8 grams, molar yield 84.7%.
(c) N, the two two carboxylate salts of palmitoyl ethylene diamine dipropionic acid two polyoxy Vinyl Ethers (n=5) of N-synthetic
With step (b) the synthetic N of institute; the two palmitoyl ethylene diamine dipropionic acid two polyoxy Vinyl Ethers (n=5) of N-497.8 grams (0.441 mole) and 106.0 gram (265 moles) sodium hydroxide, 205.3 gram (1.76 moles) sodium chloroacetates, 17.6 gram Tetrabutyl amonium bromides, 1500 milliliters of toluene are mixed in to be furnished with mechanical stirring, in 5000 milliliters the reactor of thermometer and reflux condensing tube, to be heated to 100 ℃ of reactions 8 hours.Cooling, neutralization divides and to remove inorganic salt, alkalize N, the two two carboxylate salts of palmitoyl ethylene diamine dipropionic acid two polyoxy Vinyl Ethers (n=5) of N-, molar yield 85.9%.To synthetic N, the two two carboxylate salts of palmitoyl ethylene diamine dipropionic acid two polyoxy Vinyl Ethers (n=5) of N-are used U.S. Nicolet-380FT-IR spectrograph, adopt liquid-film method to carry out Infrared spectroscopy (sweep limit 4000～400cm
-1), have all charateristic avsorption bands of Fig. 1.
(d) with step (c) synthetic N; the two two carboxylate salt 0.15wt% of palmitoyl ethylene diamine dipropionic acid two polyoxy Vinyl Ethers (n=5) of N-, above-mentioned modified polyacrylamide 0.2wt% and the marine block of 96.5wt% Shengli Oil Field inject water mixing stirring 2.5 hours, obtain a kind of MgCl that is applicable to of homogeneous transparent
2Type injects the oil-displacing agent of water.In 80 ℃ of temperature, salinity is 32000mg/L, Mg
2+Be 1200mg/L, Ca
2+In the water for 400mg/L, the apparent viscosity that records this oil-displacing agent is 14.0mPa.s; Form the ultra low interfacial tension of 0.0023mN/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.
(e) earlier with salinity 32000mg/L, Mg
2+Be 1200mg/L, Ca
2+(length is 30 centimetres, and diameter is 2.5 centimetres, and rate of permeation is 1.5 microns with rock core for the injection water of 400mg/L
2) saturated, the volume of voids (PV) of measuring rock core is 52.9%, 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 59.8%, behind metaideophone 0.3pv (rock pore volume) step (d) the synthetic oil-displacing agent, water drive records on the water drive basis and can improve oil recovery factor 16.8% again to moisture more than 98% again.
[embodiment 5]
(a) N, the two palmitoyl butanediamine dipropionic acids of N-synthetic
With [embodiment 4] (a), difference substitutes 45.0 gram (0.75 mole) anhydrous ethylenediamines with the anhydrous butanediamine of 66.0 grams (0.75 mole), and all the other are identical, get N, two palmitoyl butanediamine dipropionic acid 364.8 grams of N-, molar yield 68.7%.
(b) N, the two palmitoyl butanediamine dipropionic acid two polyoxy Vinyl Ethers (n=4) of N-synthetic
With [embodiment 1] (b); difference is with the N of 364.8 grams (0.515 mole); the two palmitoyl butanediamine dipropionic acids of N-substitute 300.3 gram (0.529 mole) N; the usage quantity of the two lauroyl ethylene diamine dipropionic acids of N-, oxyethane is 1814g (4.122 moles); the usage quantity of the basic cpd of calcium is 7.7 grams; get N, the two palmitoyl butanediamine dipropionic acid two polyoxy Vinyl Ethers (n=4) of N-461.3 grams, molar yield 84.5%.
(c) N, the two two carboxylate salts of palmitoyl butanediamine dipropionic acid two polyoxy Vinyl Ethers (n=4) of N-synthetic
With step (b) the synthetic N of institute; the two palmitoyl butanediamine dipropionic acid two polyoxy Vinyl Ethers (n=4) of N-4613 grams (0435 mole) and 106.5 gram (2.66 moles) sodium hydroxide, 178.6 gram (1.53 moles) sodium chloroacetates, 20.6 gram Tetrabutyl amonium bromides, 1600 milliliters of toluene are mixed in to be furnished with mechanical stirring, in 5000 milliliters the reactor of thermometer and reflux condensing tube, to be heated to 100 ℃ of reactions 10 hours.Cooling, neutralization divides and to remove inorganic salt, alkalize N, the two two carboxylate salts of palmitoyl butanediamine dipropionic acid two polyoxy Vinyl Ethers (n=4) of N-, molar yield 85.5%.To synthetic N, the two two carboxylate salts of palmitoyl butanediamine dipropionic acid two polyoxy Vinyl Ethers (n=4) of N-are used U.S. Nicolet-380FT-IR spectrograph, adopt liquid-film method to carry out Infrared spectroscopy (sweep limit 4000～400cm
-1), have all charateristic avsorption bands of Fig. 1.
(d) with step (c) synthetic N; the two two carboxylate salt 0.15wt% of palmitoyl butanediamine dipropionic acid two polyoxy Vinyl Ethers (n=4) 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 MgCl that is applicable to of homogeneous transparent
2Type injects the oil-displacing agent of water.In 70 ℃ of temperature, salinity is 21000mg/L, Mg
2+Be 900mg/L, Ca
2+In the water for 300mg/L, the apparent viscosity that records this oil-displacing agent is 14.6mPa.s; Form the ultra low interfacial tension of 0.0032mN/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.
(e) earlier with salinity 21000mg/L, Mg
2+Be 900mg/L, Ca
2+(length is 30 centimetres, and diameter is 2.5 centimetres, and rate of permeation is 1.5 microns with rock core for the injection water of 300mg/L
2) saturated, the volume of voids (PV) of measuring rock core is 51.7%, 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 70 ℃ of constant temperature: first water drive is to moisture 94%, record water drive and improve oil recovery factor 60.9%, behind metaideophone 0.3pv (rock pore volume) step (d) the synthetic oil-displacing agent, water drive records on the water drive basis and can improve oil recovery factor 17.0% again to moisture more than 98% again.
[embodiment 6]
(a) N, the two stearoyl ethylene diamine dipropionic acids of N-synthetic
With 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 1000 milliliters of four-hole boiling flasks of sealing machine stirring, thermometer, prolong etc., after 3 hours, decompression steams excessive thionyl chloride, obtains stearyl chloride in 95 ℃ of reactions.Another is furnished with and adds anhydrous ethylenediamine 45.0 grams (0.75 mole), 225 grams 1 in 2000 milliliters of four-hole boiling flasks of sealing machine stirring, thermometer, prolong, the 4-dioxane, be warming up to 60 ℃, slowly dropwise addition of acrylic acid methyl esters 193.5 restrains (2.25 moles), drip off and continue reaction 4 hours, unreacted methyl acrylate and solvent 1 are removed in decompression, and 4-dioxane, residuum are the ethylene diamine dipropionic acid methyl esters.With 50wt% sodium hydroxide conditioned reaction liquid PH=8～10; slowly drip lauroyl chloride under the vigorous stirring; constantly add simultaneously 50wt% sodium hydroxide with the PH that keeps reaction 8～10; drip off the back and continue reaction 3 hours in 70 ℃; get N, the two stearoyl ethylene diamine dipropionic acid methyl esters of N-continue to add 315 gram ethanol in reaction flask; transfer PH=11～12 with 50wt% sodium hydroxide again; refluxed 4 hours, cooling, filtration is desalted; pressure reducing and steaming ethanol; residuum is neutralized to strongly-acid with hydrochloric acid, and branch vibration layer gets N; two stearoyl ethylene diamine dipropionic acid 377.0 grams of N-, molar yield 68.3%.
(b) N, the two stearoyl ethylene diamine dipropionic acid two polyoxy Vinyl Ethers (n=6) of N-synthetic
With [embodiment 1] (b); difference is with the N of 377.0 grams (0.512 mole); the two stearoyl ethylene diamine dipropionic acids of N-substitute 300.3 gram (0.529 mole) N; the usage quantity of the two lauroyl ethylene diamine dipropionic acids of N-, oxyethane is 270.3g (6.144 moles); the usage quantity of the basic cpd of calcium is 5.7 grams; get N, the two stearoyl ethylene diamine dipropionic acid two polyoxy Vinyl Ethers (n=6) of N-542.3 grams, molar yield 83.8%.
(c) N, the two two carboxylate salts of stearoyl ethylene diamine dipropionic acid two polyoxy Vinyl Ethers (n=6) of N-synthetic
With step (b) the synthetic N of institute; the two stearoyl ethylene diamine dipropionic acid two polyoxy Vinyl Ethers (n=6) of N-542.3 grams (0.429 mole) and 102.8 gram (2.57 moles) sodium hydroxide, 249.9 gram (2.14 moles) sodium chloroacetates, 27.2 gram Tetrabutyl amonium bromides, 1800 milliliters of toluene are mixed in to be furnished with mechanical stirring, in 5000 milliliters the reactor of thermometer and reflux condensing tube, to be heated to 110 ℃ of reactions 12 hours.Cooling, neutralization divides and to remove inorganic salt, alkalize N, the two two carboxylate salts of stearoyl ethylene diamine dipropionic acid two polyoxy Vinyl Ethers (n=6) of N-, molar yield 84.7%.To synthetic N, the two two carboxylate salts of stearoyl ethylene diamine dipropionic acid two polyoxy Vinyl Ethers (n=6) of N-are used U.S. Nicolet-380FT-IR spectrograph, adopt liquid-film method to carry out Infrared spectroscopy (sweep limit 4000～400cm
-1), have all charateristic avsorption bands of Fig. 1.
(d) with step (c) synthetic N; the two two carboxylate salt 015wt% of stearoyl ethylene diamine dipropionic acid two polyoxy Vinyl Ethers (n=6) of N-, above-mentioned modified polyacrylamide 0.2wt% and the marine block of 96.5wt% Shengli Oil Field inject water mixing stirring 2 hours, obtain a kind of MgCl that is applicable to of homogeneous transparent
2Type injects the oil-displacing agent of water.In 70 ℃ of temperature, salinity is 21000mg/L, Mg
2+Be 900mg/L, Ca
2+In the water for 300mg/L, the apparent viscosity that records this oil-displacing agent is 14.5mPa.s; Form the ultra low interfacial tension of 0.0027mN/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.
(e) earlier with salinity 21000mg/L, Mg
2+Be 900mg/L, Ca
2+(length is 30 centimetres, and diameter is 2.5 centimetres, and rate of permeation is 1.5 microns with rock core for the injection water of 300mg/L
2) saturated, the volume of voids (PV) of measuring rock core is 52.2%, 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 59.2%, behind metaideophone 0.3pv (rock pore volume) step (d) the synthetic oil-displacing agent, water drive records on the water drive basis and can improve oil recovery factor 17.4% again to moisture more than 98% again.
[embodiment 7]
(a) N, the two stearoyl hexanediamine dipropionic acids of N-synthetic
With [embodiment 6] (a), difference substitutes anhydrous ethylenediamine 45.0 grams (075 mole) with the anhydrous hexanediamine of 87.0 grams (0.75 mole), and all the other are identical, get N, two stearoyl hexanediamine dipropionic acid 383.1 grams of N-, molar yield 64.5%.
(b) N, the two stearoyl hexanediamine dipropionic acid two polyoxy Vinyl Ethers (n=5) of N-synthetic
With [embodiment 1] (b); difference is with the N of 383.1 grams (0.484 mole); the two stearoyl hexanediamine dipropionic acids of N-substitute 300.3 gram (0.529 mole) N; the usage quantity of the two lauroyl ethylene diamine dipropionic acids of N-, oxyethane is 212.9g (4.84 moles); the usage quantity of the basic cpd of calcium is 6.0 grams; get N, the two stearoyl hexanediamine dipropionic acid two polyoxy Vinyl Ethers (n=5) of N-484.2 grams, molar yield 81.2%.
(c) N, the two two carboxylate salts of stearoyl hexanediamine dipropionic acid two polyoxy Vinyl Ethers (n=5) of N-synthetic
With step (b) the synthetic N of institute; the two stearoyl hexanediamine dipropionic acid two polyoxy Vinyl Ethers (n=5) of N-484.2 grams (0.393 mole) and 153.2 gram (2.73 moles) potassium hydroxide, 227.2 gram (1.95 moles) sodium chloroacetates, 25.5 gram Tetrabutyl amonium bromides, 1800 milliliters of toluene are mixed in to be furnished with mechanical stirring, in 5000 milliliters the reactor of thermometer and reflux condensing tube, to be heated to 110 ℃ of reactions 12 hours.Cooling, neutralization divides and to remove inorganic salt, alkalize N, the two two carboxylate salts of stearoyl hexanediamine dipropionic acid two polyoxy Vinyl Ethers (n=5) of N-, molar yield 83.5%.To synthetic N, the two two carboxylate salts of stearoyl hexanediamine dipropionic acid two polyoxy Vinyl Ethers (n=5) of N-are used U.S. Nicolet-380FT-IR spectrograph, adopt liquid-film method to carry out Infrared spectroscopy (sweep limit 4000～400cm
-1), have all charateristic avsorption bands of Fig. 1.
(d) with step (c) synthetic N; the two two carboxylate salt 0.1wt% of stearoyl hexanediamine dipropionic acid two polyoxy Vinyl Ethers (n=5) of N-, above-mentioned ultra-high-molecular aniouic polyacrylamide 0.1wt% and the marine block of 98.0wt% Shengli Oil Field inject water mixing stirring 1.5 hours, obtain a kind of MgCl that is applicable to of homogeneous transparent
2Type injects the oil-displacing agent of water.In 40 ℃ of temperature, salinity is 15000mg/L, Mg
2+Be 600mg/L, Ca
2+In the water for 200mg/L, the apparent viscosity that records this oil-displacing agent is 15.4mPa.s; Form the ultra low interfacial tension of 0.0042mN/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.
(e) earlier with salinity 15000mg/L, Mg
2+Be 600mg/L, Ca
2+(length is 30 centimetres, and diameter is 2.5 centimetres, and rate of permeation is 1.5 microns with rock core for the injection water of 200mg/L
2) saturated, the volume of voids (PV) of measuring rock core is 53.5%, 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 60.2%, behind metaideophone 0.3pv (rock pore volume) step (d) the synthetic oil-displacing agent, water drive records on the water drive basis and can improve oil recovery factor 18.2% again to moisture more than 98% again.
[comparative example 1]
With [embodiment 1] (d); difference substitutes 0.2wt%N with the petroleum sodium sulfonate (Wuxi refinery) of 0.2wt%; the two two carboxylate salts of lauroyl ethylene diamine dipropionic acid two polyoxy Vinyl Ethers (n=4) of N-; all the other are identical; the apparent viscosity that records this oil-displacing agent is 14.9mPa.s, forms the interfacial tension of 0.0367mN/m between the marine block IFA-8 of this oil-displacing agent 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] (e), record water drive and improve oil recovery factor 60.1%, metaideophone is above-mentioned with behind the oil-displacing agent, records on the water drive basis to improve oil recovery factor 13.1% again.
[comparative example 2]
With [embodiment 1] (d), 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 1,500 ten thousand) of 0.15wt%, all the other are identical, the apparent viscosity that records this composition is 11.5mPa.s, forms the interfacial tension of 0.0076mN/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] (e), record water drive and improve oil recovery factor 59.2%, behind the above-mentioned oil-displacing agent of metaideophone, record on the water drive basis and can improve oil recovery factor 13.4% again.
Claims (7)
1. one kind is applicable to MgCl
2The flooding method of water type oil-displacing agent, the oil-displacing agent that the displacement of reservoir oil is used is at 30～83 ℃ of displacement of reservoir oil temperature, total mineralization＞8000 mg/litre, Mg
2+＞200 mg/litre, Ca
2+The MgCl of＞30 mg/litre
2Type injects under the water condition, and underground dewatered oil is contacted with oil-displacing agent, and the abundant displacement of the crude oil in the rock core is come out, and wherein said 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 diamines dipropionic acid 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 one integer in 2～7; M is any one metal 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 xanthan gum.
2. the MgCl that is applicable to according to claim 1
2The flooding method of water type oil-displacing agent is characterized in that described displacement of reservoir oil temperature is 40～80 ℃.
3. the MgCl that is applicable to according to claim 1
2The flooding method of water type oil-displacing agent, the total mineralization that it is characterized in that described injection water is 10000～40000 mg/litre, Mg
2+Be 300～1350 mg/litre, Ca
2+Be 50～800 mg/litre, the water type is MgCl
2Type.
4. the MgCl that is applicable to according to claim 1
2The flooding method of water type oil-displacing agent, 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 acrylamide, 2-acrylamido-2-methyl propane sulfonic acid, three kinds of monomer copolymerizations of 2-acrylamido dodecyl sodium sulfonate, its molar percentage is 80: 18: 2, and its viscosity-average molecular weight is 15,000,000.
5. the MgCl that is applicable to according to claim 1
2The flooding method of water type oil-displacing agent is characterized in that described N, the R in the two carboxylate salts of the two fatty acyl group diamines dipropionic acid two polyoxy Vinyl Ethers of N-
1Carbonatoms is nine, 11,13,15 or 17.
6. the MgCl that is applicable to according to claim 1
2The flooding method of water type oil-displacing agent is characterized in that described N, the R in the two carboxylate salts of the two fatty acyl group diamines dipropionic acid two polyoxy Vinyl Ethers of N-
2Carbonatoms be two, four or six.
7. the MgCl that is applicable to according to claim 1
2The flooding method of water type oil-displacing agent is characterized in that described N, the R in the two carboxylate salts of the two fatty acyl group diamines dipropionic acid two polyoxy Vinyl Ethers of N-
1Carbon number adds 1 sum and the EO adduction is counted the ratio of n between 2～4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102618195A CN102373044B (en) | 2010-08-23 | 2010-08-23 | Oil displacement method suitable for MgCl2 water-type oil displacement agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102618195A CN102373044B (en) | 2010-08-23 | 2010-08-23 | Oil displacement method suitable for MgCl2 water-type oil displacement agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102373044A CN102373044A (en) | 2012-03-14 |
| CN102373044B true CN102373044B (en) | 2013-07-31 |
Family
ID=45792281
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010102618195A Active CN102373044B (en) | 2010-08-23 | 2010-08-23 | Oil displacement method suitable for MgCl2 water-type oil displacement agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102373044B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1528853A (en) * | 2003-10-09 | 2004-09-15 | 西南石油学院 | Cation dual surface active agent capable of using displacement agent |
| CN102220123A (en) * | 2010-04-15 | 2011-10-19 | 中国石油化工股份有限公司 | Oil displacement method for tertiary oil recovery |
-
2010
- 2010-08-23 CN CN2010102618195A patent/CN102373044B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1528853A (en) * | 2003-10-09 | 2004-09-15 | 西南石油学院 | Cation dual surface active agent capable of using displacement agent |
| CN102220123A (en) * | 2010-04-15 | 2011-10-19 | 中国石油化工股份有限公司 | Oil displacement method for tertiary oil recovery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102373044A (en) | 2012-03-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102220118B (en) | Oil displacement composition and preparation method thereof | |
| CN102220119B (en) | Oil displacing method for reservoirs with high temperature and salinity | |
| CN102277146B (en) | Composition for improving recovery ratio substantially and preparation method thereof | |
| CN102220121B (en) | Composition capable of improving recovery ratio considerably and preparation method thereof | |
| CN102219897B (en) | Disulfonate gemini surfactant with high temperature and salt resistance and preparation method thereof | |
| CN102218282B (en) | Dual-carboxylate gemini surfactant resistant to high temperature and high salt and preparation method thereof | |
| CN102219714B (en) | N,N-dual fat acyl diamine diacetate dipolyoxyethylene ether bisulphonate and preparation method thereof | |
| CN102220859B (en) | Oil flooding method for greatly improving recovery rate of crude oil | |
| CN103032055B (en) | Use the flooding method containing the cloudy non-surfactant composition of sulfonate | |
| CN103031119B (en) | Sulfonate-containing anionic/nonionic surfactant composition and preparation method | |
| CN102220123B (en) | Oil displacement method for tertiary oil recovery | |
| CN102220860B (en) | Polymer-surfactant binary compound oil displacement method | |
| CN102277148B (en) | Composition for improving recovery ratio of crude oil and preparation method thereof | |
| CN102220120B (en) | Binary compound flooding compound and preparation method thereof | |
| CN104559985B (en) | The displacement of reservoir oil is applied in poly- table pack object and its tertiary oil recovery | |
| CN102373046B (en) | High efficiency anti-magnesium ions oil displacement agent and its preparation method | |
| CN102277147A (en) | Oil displacement method for high-temperature high-salt oil reservoir | |
| CN102220124B (en) | Oil displacement compound for tertiary oil recovery and preparation method thereof | |
| CN102373913B (en) | High-efficiency anti-magnesium ion oil displacement method | |
| CN102219896B (en) | N,N-difattyacyl diamino diacetoxyl dipolyoxyethylene ether dicarboxylate and preparation method thereof | |
| CN102373043B (en) | Displacement agent suitable for MgCl2 injection water and preparation method thereof | |
| CN102373044B (en) | Oil displacement method suitable for MgCl2 water-type oil displacement agent | |
| CN102373045B (en) | Seawater-based oil displacement agent and preparation method thereof | |
| CN102373040B (en) | Composition suitable for seawater-based oil displacement and its preparation method | |
| CN102373041B (en) | Oil displacement method by use of seawater base oil displacement agent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |