CN102220120A - Binary compound flooding compound and preparation method thereof - Google Patents
Binary compound flooding compound and preparation method thereof Download PDFInfo
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- CN102220120A CN102220120A CN2010101471992A CN201010147199A CN102220120A CN 102220120 A CN102220120 A CN 102220120A CN 2010101471992 A CN2010101471992 A CN 2010101471992A CN 201010147199 A CN201010147199 A CN 201010147199A CN 102220120 A CN102220120 A CN 102220120A
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Abstract
The invention relates to a binary compound flooding compound and a preparation method thereof, mainly solving the problems that the oil displacement agent containing surface active agents has poor oil displacement efficiency and high using concentration under the high-temperature and high-salt conditions, and corrosion and scale deposition to a stratum and an oil well, caused by alkali in the ternary compound flooding, happen in the prior art. The binary compound flooding compound comprises the following components in percentage by weight: (1) 0.01-5.0 percent of N,N-bi fatty acyl group diamine neopentanoic acid di-polyoxyethylene ether bisulphonate; (2) 0.01-3.0 percent of polymer; (3) 92.0-99.98 percent of formation water, wherein in the general molecular formula of the component (1), R1 is C9-C17 alkyl group, R2 is C2-C6 alkyl group, n is adding composite number of ethoxy groups (EO) and is one integer from 2-7; M is one metal ion of K, Na or Li; the polymer is selected from one of polyacrylamide with superhigh molecular weight (viscosityaverage molecular weight is 25,000,000), temperature-resisting and salt-resisting polymer or xanthogen gum, and water is selected from the formation water of the oil field. By the technical scheme, the problems are better solved, and the binary compound flooding compound is suitable for tertiary oil recovery production in the oil field.
Description
Technical field
The present invention relates to a kind of binary combination flooding composition and method of making the same.
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 anionic, it and the divalent cation (Ca in the local water
2+, Mg
2+Deng) can precipitate, work as Ca
2+, Mg
2+Just lose oil displacement efficiency when surpassing 300 μ g/g.For this reason, also continuing the suitable high saliferous of development research, high Ca abroad
2+, Mg
2+The tensio-active agent that the ion stratum is used comprises the research of 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 85 ℃), high salt (more than the salinity 40000mg/L) condition Stability Analysis of Structures, and can form 10 with crude oil
-3～10
-4The mN/m ultra low interfacial tension effectively improves the displacing surfactant system of oil recovery factor.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
One of technical problem to be solved by this invention is that the oil-displacing agent that contains tensio-active agent in the prior art exists under the high temperature and high salt condition oil displacement efficiency poor, the corrosion that alkali brings stratum and oil well in working concentration height and the ternary composite driving and the problem of incrustation injury provide a kind of new binary combination flooding composition.This method will contain N; the two fatty acyl group diamines neopentanoic acid two polyoxy Vinyl Ether disulfonate surfactant compositions of N-are used for oil displacement process; have alkali-free, do not have corrosion and incrustation injury, working concentration is low, the high characteristics of oil displacement efficiency under the high temperature and high salt condition.Two of technical problem to be solved by this invention provides one of a kind of and technical solution problem corresponding binary combination flooding preparation of compositions method.
In order one of to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of binary combination flooding composition comprises following component by percentage to the quality:
(1) 0.01～5.0% N, the two fatty acyl group diamines neopentanoic acid two polyoxy Vinyl Ether disulfonates of N-;
(2) 0.01～3.0% polymkeric substance;
(3) 92.0～99.98% local 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.
In the technique scheme, described local water total mineralization is preferably 16000～32000mg/L, Ca
2++ Mg
2+Be preferably 450～890mg/L; Polymkeric substance is selected from above-mentioned temperature resistant antisalt polymkeric substance; 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 fatty acyl group diamines neopentanoic acid two polyoxy Vinyl Ether disulfonates of N-
1Carbonatoms is preferably nine, 11,15 or 17, R
2Carbonatoms be preferably two, four or six.
For solve the problems of the technologies described above two, the technical solution adopted in the present invention is as follows: a kind of binary combination flooding preparation of compositions method may further comprise the steps:
(a) N, the preparation of the two fatty acyl group diamines neopentanoic 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 1 that the transparent liquid that obtains is the carbochain number; In addition be 2～6 diamines, methyl methacrylate and solvent 1 with the carbon 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 the diamines dimethylated methyl propionate
2, regulate PH=9～10 with alkaline solution, 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 dimethylated methyl propionates
3, the ethanol of adding aequum is regulated PH=11～12 with alkaline solution, 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 neopentanoic 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 methacrylate 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 dimethylated methyl propionates is 1.9～2.5: 1; Preparation N, when the two carbochain numbers of N-were 10～18 fatty acyl group diamines neopentanoic acids, 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 neopentanoic 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 neopentanoic 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 neopentanoic acids, two polyoxy Vinyl Ethers; Wherein, N, the two carbochain numbers of N-are that 10～18 fatty acyl group diamines neopentanoic 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 neopentanoic acid quality;
(c) N, the preparation of the two fatty acyl group diamines neopentanoic acid two polyoxy Vinyl Ether disulfonates of N-:
With step (b) the synthetic N of institute; the two carbochain numbers of N-are that 10～18 fatty acyl group diamines neopentanoic acids, two polyoxy Vinyl Ethers are by required proportioning and 3-chloro-2-hydroxypropionate sodium, 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 fatty acyl group diamines neopentanoic acid two polyoxy Vinyl Ether disulfonates of N-.Wherein, N, the two carbochain numbers of N-are mol ratio=1: 2～6: 2～8: 0.05～0.3 of 10～18 fatty acyl group diamines neopentanoic acids, two polyoxy Vinyl Ethers, 3-chloro-2-hydroxypropionate sodium, potassium hydroxide or sodium hydroxide and Tetrabutyl amonium bromide;
(d) with the N of aequum, the two fatty acyl group diamines neopentanoic acid two polyoxy Vinyl Ether disulfonates of N-, above-mentioned temperature resistant antisalt polymkeric substance and local water uniform mixing, stirring at room 1～3 hour obtains required composition.By percentage to the quality, N, the two fatty acyl group diamines neopentanoic acid two polyoxy Vinyl Ether disulfonates of N-, above-mentioned temperature resistant antisalt polymkeric substance and the proportioning of local water are 0.01～5.0%: 0.01～3.0%: 92.0～99.98%.
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 methacrylate 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 dimethylated methyl propionates 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 neopentanoic 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 neopentanoic 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 neopentanoic acid quality.(c) N in the step; the two carbochain numbers of N-be the mol ratio of 10～18 fatty acyl group diamines neopentanoic acids, two polyoxy Vinyl Ethers, 3-chloro-2-hydroxypropionate sodium, 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 fatty acyl group diamines neopentanoic acid two polyoxy Vinyl Ether disulfonates of N-is 0.03～1.0%, more preferably scope is 0.1～0.3%; Above-mentioned temperature resistant antisalt polymer loading preferable range is 0.05～0.5%; More preferably scope is 0.1～0.2%, and the reaction times is preferably 1.5～2.5 hours.
N in the prepared binary combination flooding composition of the present invention; the two fatty acyl group diamines neopentanoic acid two polyoxy Vinyl Ether 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 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 binary combination flooding composition of the present invention, under the alkali-free condition, can be used for formation temperature and be 85 ℃, salinity 16000～32000 mg/litre, Ca
2+, Mg
2+The Shengli Oil Field that is 450～890 mg/litre wins Tuo Er district's local water and crude oil; with consumption is 0.1～0.3wt%N; two fatty acyl group diamines neopentanoic acid two polyoxy Vinyl Ether disulfonates of N-and the above-mentioned temperature resistant antisalt polymer formation above-mentioned composition compound oil displacement agent of 0.1～0.2wt%; measure the dynamic interface tension value between this oil-displacing agent aqueous solution and the Shengli Oil Field victory Tuo Er district crude oil, can reach 10
-3～10
-4The ultra low interfacial tension of mN/m, can on the water drive basis, can reach 16.5% by (water drive improves oil recovery factor and reaches 40.9%) 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 infrared spectrum of the two fatty acyl group diamines neopentanoic acid two polyoxy Vinyl Ether disulfonates of N-.
The N of the present invention's preparation; the two fatty acyl group diamines neopentanoic acid two polyoxy Vinyl Ether disulfonates of N-can characterize by the following method: after synthetics is purified; use U.S. Nicolet-380 FT-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 are at wave number 720cm
-1The characteristic peak that waves in the chain alkyl C-H face appears because this peak is very wide; 1640cm
-1The acid amides I key band vC=O at place, 1058cm
-1Be to form owing to C-N is flexible; 1106cm
-1About the obvious broadening in peak located, and wave number moves on to 1117cm
-1The place, this peak is that the last C-O-C asymmetric stretch of EO bands of a spectrum cause owing to connected EO; 1350cm
-1About also broadening and obviously growing tall to some extent of peak, the characteristic peak of sulfonate is that the symmetrical stretching vibration of S=O is at 1155cm because the antisymmetric stretching vibration of S=O and the vibration of skeleton carbon cause
-1About, proved response has generated N really thus, the two fatty acyl group diamines neopentanoic acid two polyoxy Vinyl Ether disulfonates of N-.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
(a) N, the two lauroyl quadrol neopentanoic 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 drip methyl methacrylate 165.0 grams (1.65 moles), drip off and continue reaction 3 hours, unreacted methyl methacrylate and solvent 1 are removed in decompression, and 4-dioxane, residuum are the quadrol dimethylated methyl propionate.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 quadrol dimethylated methyl propionates 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 quadrol neopentanoic acid 306.2 grams of N-, molar yield 68.5%.
(b) N, the two lauroyl quadrol neopentanoic acid two polyoxy Vinyl Ethers (n=4) of N-synthetic
With step (a) synthetic N; the basic cpd of two lauroyl quadrol neopentanoic acid 306.2 grams (0.514 mole) of N-, 3.4 gram calcium adds to be furnished with in the high-pressure reactor of condensing works, whipping appts and gas distributor; when limit logical nitrogen limit heating is made 135 ℃; add 20 gram water, stirring reaction 1 hour.After removing moisture content, be cooled to 80 ℃, the sulfuric acid (20wt%) that slowly drips the catalyst neutralisation theoretical amount makes the compound oxidizing calcium alkoxylating catalyst reaction solution system of high reactivity, highly selective, system temperature is heated to 80～90 ℃, 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 181.1 gram (4.116 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 quadrol neopentanoic acid two polyoxy Vinyl Ethers (n=4) of N-428.3 grams, molar yield 87.9%.
(c) N, two lauroyl quadrol neopentanoic acid two polyoxy Vinyl Ether (n=4) disulfonates of N-synthetic
With step (b) the synthetic N of institute; the two lauroyl quadrol neopentanoic acid two polyoxy Vinyl Ethers (n=4) of N-428.3 grams (0.452 mole) and 152.3 gram (2.72 moles) potassium hydroxide, 355.4 gram (1.81 moles) 3-chloro-2-hydroxypropionate sodiums, 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, two lauroyl quadrol neopentanoic acid two polyoxy Vinyl Ether (n=4) disulfonates of N-, molar yield 75.8%.To synthetic N, two lauroyl quadrol neopentanoic acid two polyoxy Vinyl Ether (n=4) disulfonates 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; two lauroyl quadrol neopentanoic acid two polyoxy Vinyl Ether (n=4) the disulfonate 0.15wt% of N-, above-mentioned temperature resistant antisalt polymkeric substance 0.15wt% and 97.0wt% Shengli Oil Field win Tuo Er district and win local water and mix stirring 2 hours, obtain the composition that a kind of displacement of reservoir oil of homogeneous transparent is used.At 85 ℃ of temperature, salinity 32000mg/L, Ca
2++ Mg
2+In the water of 890mg/L, the apparent viscosity that records this composition is 15.3mPa.s; Said composition and Shengli Oil Field win the ultra low interfacial tension that forms 0.0035mN/m between the Tuo Er district 0-141 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.
[embodiment 2]
(a) N, the two lauroyl hexanediamine neopentanoic 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 neopentanoic acid 328.6 grams of N-, molar yield 67.2%.
(b) N, the two lauroyl hexanediamine neopentanoic acid two polyoxy Vinyl Ethers (n=3) of N-synthetic
With [embodiment 1] (b); difference is with the N of 328.6 grams (0.504 mole); the two lauroyl hexanediamine neopentanoic acids of N-substitute 306.2 gram (0.514 mole) N; the usage quantity of the two lauroyl quadrol neopentanoic acids of N-, oxyethane is 133.1g (3.024 moles); the usage quantity of the basic cpd of calcium is 7.5 grams; get N, the two lauroyl hexanediamine neopentanoic acid two polyoxy Vinyl Ethers (n=3) of N-409.5 grams, molar yield 88.2%.
(c) N, two lauroyl hexanediamine neopentanoic acid two polyoxy Vinyl Ether (n=3) disulfonates of N-synthetic
With step (b) the synthetic N of institute; the two lauroyl hexanediamine neopentanoic acid two polyoxy Vinyl Ethers (n=3) of N-409.5 grams (0.447 mole) and 100.5 gram (1.79 moles) potassium hydroxide, 377.3 gram (1.92 moles) 3-chloro-2-hydroxypropionate sodiums, 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 100 ℃ of reactions 6 hours.Cooling, neutralization divides and to remove inorganic salt, alkalize N, two lauroyl hexanediamine neopentanoic acid two polyoxy Vinyl Ether (n=3) disulfonates of N-, molar yield 75.5%.To synthetic N, two lauroyl hexanediamine neopentanoic acid two polyoxy Vinyl Ether (n=3) disulfonates 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; two lauroyl hexanediamine neopentanoic acid two polyoxy Vinyl Ether (n=3) the disulfonate 0.2wt% of N-, above-mentioned temperature resistant antisalt polymkeric substance 0.15wt% and 96.5wt% Shengli Oil Field win Tuo Er district and win local water and mix stirring 2 hours, obtain the composition that a kind of displacement of reservoir oil of homogeneous transparent is used.At 85 ℃ of temperature, salinity 24000mg/L, Ca
2++ Mg
2+In the water of 667mg/L, the apparent viscosity that records this composition is 15.8mPa.s; Said composition and Shengli Oil Field win the ultra low interfacial tension that forms 0.0028mN/m between the Tuo Er district 0-141 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.
[embodiment 3]
(a) N, the two ten acyl group butanediamine neopentanoic 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 neopentanoic acids of N-283.3 grams, molar yield 66.5%.
(b) N, two ten acyl group butanediamine neopentanoic acids, the two polyoxy Vinyl Ethers (n=3) of N-synthetic
With [embodiment 1] (b); difference is with the N of 283.3 grams (0.499 mole); the two ten acyl group butanediamine neopentanoic acids of N-substitute 306.2 gram (0.514 mole) N; the usage quantity of the two lauroyl quadrol neopentanoic acids of N-, oxyethane is 131.7g (2.994 moles); the usage quantity of the basic cpd of calcium is 6.4 grams; get N, the two ten acyl group butanediamine neopentanoic acids of N-two polyoxy Vinyl Ethers (n=3) 371.6 grams, molar yield 89.5%.
(c) N, two ten acyl group butanediamine neopentanoic acids, two polyoxy Vinyl Ether (n=3) disulfonates of N-synthetic
With step (b) the synthetic N of institute; the two ten acyl group butanediamine neopentanoic acids of N-two polyoxy Vinyl Ethers (n=3) 371.6 grams (0.447 mole) and 100.3 gram (1.79 moles) potassium hydroxide, 263.3 gram (1.34 moles) 3-chloro-2-hydroxypropionate sodiums, 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, two ten acyl group butanediamine neopentanoic acids, two polyoxy Vinyl Ether (n=3) disulfonates of N-, molar yield 73.5%.To synthetic N, two ten acyl group butanediamine neopentanoic acids, two polyoxy Vinyl Ether (n=3) disulfonates 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; two ten acyl group butanediamine neopentanoic acids, two polyoxy Vinyl Ether (n=3) the disulfonate 0.15wt% of N-, above-mentioned temperature resistant antisalt polymkeric substance 0.15wt% and 97.0wt% Shengli Oil Field win Tuo Er district and win local water and mix stirring 2 hours, obtain the composition that a kind of displacement of reservoir oil of homogeneous transparent is used.At 85 ℃ of temperature, salinity 32000mg/L, Ca
2++ Mg
2+In the water of 890mg/L, the apparent viscosity that records this composition is 15.7mPa.s; Said composition and Shengli Oil Field win the ultra low interfacial tension that forms 0.0041mN/m between the Tuo Er district 0-141 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.
[embodiment 4]
(a) N, the two palmitoyl quadrol neopentanoic 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 drip methyl methacrylate 187.5 grams (1.875 moles), drip off and continue reaction 4 hours, unreacted methyl methacrylate and solvent 1 are removed in decompression, and 4-dioxane, residuum are the quadrol dimethylated methyl propionate.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 quadrol dimethylated methyl propionates 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 quadrol neopentanoic acid 360.0 grams of N-, molar yield 67.8%.
(b) N, the two palmitoyl quadrol neopentanoic acid two polyoxy Vinyl Ethers (n=5) of N-synthetic
With [embodiment 1] (b); difference is with the N of 360.0 grams (0.508 mole); the two palmitoyl quadrol neopentanoic acids of N-substitute 306.2 gram (0.514 mole) N; the usage quantity of the two lauroyl quadrol neopentanoic acids of N-, oxyethane is 223.5g (5.08 moles); the usage quantity of the basic cpd of calcium is 6.6 grams; get N, the two palmitoyl quadrol neopentanoic acid two polyoxy Vinyl Ethers (n=5) of N-497.4 grams, molar yield 85.3%.
(c) N, two palmitoyl quadrol neopentanoic acid two polyoxy Vinyl Ether (n=5) disulfonates of N-synthetic
With step (b) the synthetic N of institute; the two palmitoyl quadrol neopentanoic acid two polyoxy Vinyl Ethers (n=5) of N-497.4 grams (0.433 mole) and 103.6 gram (2.60 moles) sodium hydroxide, 339.9 gram (1.73 moles) 3-chloro-2-hydroxypropionate sodiums, 17.3 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 8 hours.Cooling, neutralization divides and to remove inorganic salt, alkalize N, two palmitoyl quadrol neopentanoic acid two polyoxy Vinyl Ether (n=5) disulfonates of N-, molar yield 72.9%.To synthetic N, two palmitoyl quadrol neopentanoic acid two polyoxy Vinyl Ether (n=5) disulfonates 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; two palmitoyl quadrol neopentanoic acid two polyoxy Vinyl Ether (n=5) the disulfonate 0.1wt% of N-, above-mentioned temperature resistant antisalt polymkeric substance 0.2wt% and 97.0wt% Shengli Oil Field win Tuo Er district and win local water and mix stirring 2 hours, obtain the composition that a kind of displacement of reservoir oil of homogeneous transparent is used.At 85 ℃ of temperature, salinity 16000mg/L, Ca
2++ Mg
2+In the water of 450mg/L, the apparent viscosity that records this composition is 15.2mPa.s; Said composition and Shengli Oil Field win the ultra low interfacial tension that forms 0.0007mN/m between the Tuo Er district 0-141 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.
[embodiment 5]
(a) N, the two palmitoyl butanediamine neopentanoic 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 neopentanoic acid 362.7 grams of N-, molar yield 65.7%.
(b) N, the two palmitoyl butanediamine neopentanoic acid two polyoxy Vinyl Ethers (n=4) of N-synthetic
With [embodiment 1] (b); difference is with the N of 362.7 grams (0.493 mole); the two palmitoyl butanediamine neopentanoic acids of N-substitute 306.2 gram (0.514 mole) N; the usage quantity of the two lauroyl quadrol neopentanoic acids of N-, oxyethane is 173.5g (3.944 moles); the usage quantity of the basic cpd of calcium is 7.4 grams; get N, the two palmitoyl butanediamine neopentanoic acid two polyoxy Vinyl Ethers (n=4) of N-456.5 grams, molar yield 85.1%.
(c) N, two palmitoyl butanediamine neopentanoic acid two polyoxy Vinyl Ether (n=4) disulfonates of N-synthetic
With step (b) the synthetic N of institute; the two palmitoyl butanediamine neopentanoic acid two polyoxy Vinyl Ethers (n=4) of N-456.5 grams (0.420 mole) and 102.9 gram (2.57 moles) sodium hydroxide, 290.5 gram (1.48 moles) 3-chloro-2-hydroxypropionate sodiums, 19.9 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, two palmitoyl butanediamine neopentanoic acid two polyoxy Vinyl Ether (n=4) disulfonates of N-, molar yield 71.1%.To synthetic N, two palmitoyl butanediamine neopentanoic acid two polyoxy Vinyl Ether (n=4) disulfonates of N-are used U.S. Nicolet-380 FT-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; two palmitoyl butanediamine neopentanoic acid two polyoxy Vinyl Ether (n=4) the disulfonate 0.25wt% of N-, above-mentioned temperature resistant antisalt polymkeric substance 0.15wt% and 96.0wt% Shengli Oil Field win Tuo Er district and win local water and mix stirring 2 hours, obtain the composition that a kind of displacement of reservoir oil of homogeneous transparent is used.At 85 ℃ of temperature, salinity 24000mg/L, Ca
2++ Mg
2+In the water of 667mg/L, the apparent viscosity that records this composition is 15.9mPa.s; Said composition and Shengli Oil Field win the ultra low interfacial tension that forms 0.0012mN/m between the Tuo Er district 0-141 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.
[embodiment 6]
(a) N, the two stearoyl quadrol neopentanoic 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 drip methyl methacrylate 225.0 grams (2.25 moles), drip off and continue reaction 4 hours, unreacted methyl methacrylate and solvent 1 are removed in decompression, and 4-dioxane, residuum are the quadrol dimethylated methyl propionate.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 quadrol dimethylated methyl propionates 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 quadrol neopentanoic acid 384.5 grams of N-, molar yield 67.1%.
(b) N, the two stearoyl quadrol neopentanoic acid two polyoxy Vinyl Ethers (n=6) of N-synthetic
With [embodiment 1] (b); difference is with the N of 384.5 grams (0.503 mole); the two stearoyl quadrol neopentanoic acids of N-substitute 306.2 gram (0.514 mole) N; the usage quantity of the two lauroyl quadrol neopentanoic acids of N-, oxyethane is 265.6g (6.036 moles); the usage quantity of the basic cpd of calcium is 5.6 grams; get N, the two stearoyl quadrol neopentanoic acid two polyoxy Vinyl Ethers (n=6) of N-547.2 grams, molar yield 84.2%.
(c) N, two stearoyl quadrol neopentanoic acid two polyoxy Vinyl Ether (n=6) disulfonates of N-synthetic
With step (b) the synthetic N of institute; the two stearoyl quadrol neopentanoic acid two polyoxy Vinyl Ethers (n=6) of N-547.2 grams (0.424 mole) and 101.6 gram (2.54 moles) sodium hydroxide, 416.7 gram (2.12 moles) 3-chloro-2-hydroxypropionate sodiums, 26.9 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, two stearoyl quadrol neopentanoic acid two polyoxy Vinyl Ether (n=6) disulfonates of N-, molar yield 72.3%.To synthetic N, two stearoyl quadrol neopentanoic acid two polyoxy Vinyl Ether (n=6) disulfonates of N-are used U.S. Nicolet-380 FT-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; two stearoyl quadrol neopentanoic acid two polyoxy Vinyl Ether (n=6) the disulfonate 0.2wt% of N-, above-mentioned temperature resistant antisalt polymkeric substance 0.1wt% and 97.0wt% Shengli Oil Field win Tuo Er district and win local water and mix stirring 2 hours, obtain the composition that a kind of displacement of reservoir oil of homogeneous transparent is used.At 85 ℃ of temperature, salinity 32000mg/L, Ca
2++ Mg
2+In the water of 890mg/L, the apparent viscosity that records this composition is 15.7mPa.s; Said composition and Shengli Oil Field win the ultra low interfacial tension that forms 0.0005mN/m between the Tuo Er district 0-141 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.
[embodiment 7]
(a) N, the two stearoyl hexanediamine neopentanoic acids of N-synthetic
With [embodiment 6] (a), difference substitutes anhydrous ethylenediamine 45.0 grams (0.75 mole) with the anhydrous hexanediamine of 87.0 grams (0.75 mole), and all the other are identical, get N, two stearoyl hexanediamine neopentanoic acid 398.5 grams of N-, molar yield 64.8%.(b) N, the two stearoyl hexanediamine neopentanoic acid two polyoxy Vinyl Ethers (n=5) of N-synthetic
With [embodiment 1] (b); difference is with the N of 398.5 grams (0.486 mole); the two stearoyl hexanediamine neopentanoic acids of N-substitute 306.2 gram (0.514 mole) N; the usage quantity of the two lauroyl quadrol neopentanoic acids of N-, oxyethane is 213.8g (4.86 moles); the usage quantity of the basic cpd of calcium is 6.0 grams; get N, the two stearoyl hexanediamine neopentanoic acid two polyoxy Vinyl Ethers (n=5) of N-507.6 grams, molar yield 82.9%.
(c) N, two stearoyl hexanediamine neopentanoic acid two polyoxy Vinyl Ether (n=5) disulfonates of N-synthetic
With step (b) the synthetic N of institute; the two stearoyl hexanediamine neopentanoic acid two polyoxy Vinyl Ethers (n=5) of N-507.6 grams (0.403 mole) and 159.6 gram (2.80 moles) potassium hydroxide, 392.5 gram (2.00 moles) 3-chloro-2-hydroxypropionate sodiums, 26.1 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, two stearoyl hexanediamine neopentanoic acid two polyoxy Vinyl Ether (n=5) disulfonates of N-, molar yield 70.6%.To synthetic N, two stearoyl hexanediamine neopentanoic acid two polyoxy Vinyl Ether (n=5) disulfonates of N-are used U.S. Nicolet-380 FT-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; two stearoyl hexanediamine neopentanoic acid two polyoxy Vinyl Ether (n=5) the disulfonate 0.15wt% of N-, above-mentioned temperature resistant antisalt polymkeric substance 0.15wt% and 97.0wt% Shengli Oil Field win Tuo Er district and win local water and mix stirring 2 hours, obtain the composition that a kind of displacement of reservoir oil of homogeneous transparent is used.At 85 ℃ of temperature, salinity 16000mg/L, Ca
2++ Mg
2+In the water of 450mg/L, the apparent viscosity that records this composition is 16.1mPa.s; Said composition and Shengli Oil Field win the ultra low interfacial tension that forms 0.0056mN/m between the Tuo Er district 0-141 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.
[embodiment 8～14]
With [embodiment 1～7] synthetic binary combination flooding composition, be 30 centimetres in length, diameter is 2.5 centimetres, rate of permeation is 1.5 microns
2Rock core on carry out imitation oil displacement experiment test.Win Tuo Er district local water with Shengli Oil Field earlier and be driven to moisture 92%, record water drive and can improve oil recovery factor 39.8～40.9%, again behind the binary combination flooding composition of metaideophone 0.3pv (rock pore volume) [embodiment 1～7], water drive is to moisture 100%, record on the water drive basis and can improve oil recovery factor 14.3～16.5% again, the results are shown in Table shown in 1.
[comparative example 1]
With [embodiment 1] (d); difference substitutes 0.15wt%N with the petroleum sodium sulfonate (Wuxi refinery) of 0.15wt%; two lauroyl quadrol neopentanoic acid two polyoxy Vinyl Ether (n=4) disulfonates of N-; all the other are identical; the apparent viscosity that records this composition is 14.2mPa.s, and said composition and Shengli Oil Field win the interfacial tension that forms 0.0712mN/m between the Tuo Er district 0-141 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.
The above-mentioned displacement of reservoir oil composition that makes carries out the displacement of reservoir oil with the method with [embodiment 8], records water drive and can improve oil recovery factor 40.2%, can improve oil recovery factor 10.3% again on the water drive basis behind the above-mentioned displacement of reservoir oil composition of metaideophone, the results are shown in Table shown in 1.
[comparative example 2]
With [embodiment 1] (d), difference substitutes the above-mentioned temperature resistant antisalt polymkeric substance of 0.15wt% with the super high molecular weight polyacrylamide (viscosity-average molecular weight is 2,500 ten thousand) of 0.15wt%, all the other are identical, the apparent viscosity that records this composition is 10.5mPa.s, and said composition and Shengli Oil Field win the interfacial tension that forms 0.0459mN/m between the Tuo Er district 0-141 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.
The above-mentioned displacement of reservoir oil composition that makes carries out the displacement of reservoir oil with the method with [embodiment 8], records water drive and can improve oil recovery factor 40.3%, can improve oil recovery factor 9.1% again on the water drive basis behind the above-mentioned displacement of reservoir oil composition of metaideophone, the results are shown in Table shown in 1.
Table 1 different compositions wins Tuo Er district oil displacement test result to Shengli Oil Field
| Sequence number | Tensio-active agent title and consumption, wt% | Polymkeric substance title and consumption, wt% | Water drive improves oil recovery factor, % | Composition drives and improves oil recovery factor again, % |
| Embodiment 8 | N, two lauroyl quadrol neopentanoic acid two polyoxy Vinyl Ether (n=4) disulfonates 0.15 of N- | Above-mentioned temperature resistant antisalt polymkeric substance 0.15 | 40.2 | 15.8 |
| Embodiment 9 | N, two lauroyl hexanediamine neopentanoic acid two polyoxy Vinyl Ether (n=3) disulfonates 0.2 of N- | The same 0.15 | 39.8 | 15.5 |
| Embodiment 10 | N, two ten acyl group butanediamine neopentanoic acids, two polyoxy Vinyl Ether (n=3) disulfonates 0.15 of N- | The same 0.15 | 40.1 | 14.7 |
| Embodiment 11 | N, two palmitoyl quadrol neopentanoic acid two polyoxy Vinyl Ether (n=5) disulfonates 0.1 of N- | The same 0.2 | 40.5 | 16.5 |
| Embodiment 12 | N, two palmitoyl hexanediamine neopentanoic acid two polyoxy Vinyl Ether (n=4) disulfonates 0.25 of N- | The same 0.15 | 40.9 | 14.3 |
| Embodiment 13 | N, two stearoyl quadrol neopentanoic acid two polyoxy Vinyl Ether (n=6) disulfonates 0.2 of N- | The same 0.1 | 40.3 | 15.2 |
| Embodiment 14 | N, two stearoyl hexanediamine neopentanoic acid two polyoxy Vinyl Ether (n=5) disulfonates 0.15 of N- | The same 0.15 | 40.8 | 15.9 |
| Comparative example 1 | Petroleum sodium sulfonate (Wuxi refinery) 0.15 | The same 0.15 | 40.2 | 10.3 |
| Comparative example 2 | N, two lauroyl quadrol neopentanoic acid two polyoxy Vinyl Ether (n=4) disulfonates 0.15 of N- | Super high molecular weight polyacrylamide (viscosity-average molecular weight is 2,500 ten thousand) 0.15 | 40.3 | 9.1 |
Claims (8)
1. binary combination flooding composition comprises following component by percentage to the quality:
(1) 0.01～5.0% N, the two fatty acyl group diamines neopentanoic acid two polyoxy Vinyl Ether disulfonates of N-;
(2) 0.01～3.0% polymkeric substance;
(3) 92.0～99.98% local 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.
2. binary combination flooding composition according to claim 1, the total mineralization that it is characterized in that described local water is 16000～40000mg/L, Ca
2++ Mg
2+Be 450～1000mg/L.
3. binary combination flooding composition according to claim 1 is characterized in that described polymkeric substance is selected from the temperature resistant antisalt polymkeric substance.
4. polymkeric substance according to claim 3, it is characterized in that described temperature resistant antisalt polymkeric substance is formed by acrylamide, 2-acrylamido-2-methyl propane sulfonic acid, 2-acrylamido dodecyl sodium sulfonate and four kinds of monomer copolymerizations of allyl group oleyl ether, its molar percentage is 76: 18: 5: 1.
5. binary combination flooding composition according to claim 1 is characterized in that described N, the R in the two fatty acyl group diamines neopentanoic acid two polyoxy Vinyl Ether disulfonates of N-
1Carbonatoms is nine, 11,13,15 or 17.
6. binary combination flooding composition according to claim 1 is characterized in that described N, the two fatty acyl group diamines neopentanoic acid two polyoxy Vinyl Ether disulfonate N of N-, the R in the two carboxylate salts of the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy Vinyl Ethers of N-
2Carbonatoms be two, four or six.
7. binary combination flooding composition according to claim 1 is characterized in that described N, the R in the two fatty acyl group diamines neopentanoic acid two polyoxy Vinyl Ether disulfonates of N-
1Carbon number adds 1 sum, and EO counts the ratio of n between 2～4.
8. the described binary combination flooding preparation of compositions of claim 1 method may further comprise the steps:
(a) N, the preparation of the two fatty acyl group diamines neopentanoic 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 methacrylate and solvent 1 with the carbon 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 the diamines dimethylated methyl propionate
2, regulate PH=9～10 with 5 alkaline solutions, 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 dimethylated methyl propionates
3, the ethanol of adding aequum is regulated PH=11～12 with alkaline solution, 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 neopentanoic 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 methacrylate 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 dimethylated methyl propionates is 1.9～2.5: 1; Preparation N, when the two carbochain numbers of N-were 10～18 fatty acyl group diamines neopentanoic acids, 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 neopentanoic 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 neopentanoic 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 neopentanoic acids, two polyoxy Vinyl Ethers; Wherein, N, the two carbochain numbers of N-are that 10～18 fatty acyl group diamines neopentanoic 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 neopentanoic acid quality;
(c) N, the preparation of the two fatty acyl group diamines neopentanoic acid two polyoxy Vinyl Ether disulfonates of N-:
With step (b) the synthetic N of institute; the two carbochain numbers of N-are that 10～18 fatty acyl group diamines neopentanoic acids, two polyoxy Vinyl Ethers are by required proportioning and 3-chloro-2-hydroxypropionate sodium, 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 fatty acyl group diamines neopentanoic acid two polyoxy Vinyl Ether disulfonates of N-.Wherein, N, the two carbochain numbers of N-are mol ratio=1: 2～6: 2～8: 0.05～0.3 of 10～18 fatty acyl group diamines neopentanoic acids, two polyoxy Vinyl Ethers, 3-chloro-2-hydroxypropionate sodium, potassium hydroxide or sodium hydroxide and Tetrabutyl amonium bromide;
(d) with the N of aequum, the two fatty acyl group diamines neopentanoic acid two polyoxy Vinyl Ether disulfonates of N-, above-mentioned temperature resistant antisalt polymkeric substance and local water uniform mixing, stirring at room 1～3 hour obtains required composition.By percentage to the quality, N, the two fatty acyl group diamines neopentanoic acid two polyoxy Vinyl Ether disulfonates of N-, above-mentioned temperature resistant antisalt polymkeric substance and the proportioning of local water are 0.01～5.0%: 0.01～3.0%: 92.0～99.98%.
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| CN109135711A (en) * | 2018-10-09 | 2019-01-04 | 西南石油大学 | The opposite association polymer compound oil displacement agent of monomer charge and single hop plug flooding method |
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| CN105461854A (en) * | 2015-12-16 | 2016-04-06 | 长江大学 | Fluorine-containing double-tail hydrophobically associating polymer and preparation thereof |
| CN107298470A (en) * | 2016-10-19 | 2017-10-27 | 烟台智本知识产权运营管理有限公司 | A kind of degreaser of oil field binary combination flooding output water |
| CN109135711A (en) * | 2018-10-09 | 2019-01-04 | 西南石油大学 | The opposite association polymer compound oil displacement agent of monomer charge and single hop plug flooding method |
| CN109135711B (en) * | 2018-10-09 | 2021-09-14 | 西南石油大学 | Monomer charge-oppositely-associated polymer composite oil displacement agent and single-plug oil displacement method |
| CN111763153A (en) * | 2019-04-02 | 2020-10-13 | 中国石油天然气股份有限公司 | Dodecyl polyoxyethylene ether sodium sulfate-diglucoside peptide compound and composite oil displacement agent |
| CN111763153B (en) * | 2019-04-02 | 2022-08-30 | 中国石油天然气股份有限公司 | Dodecyl polyoxyethylene ether sodium sulfate-diglucoside peptide compound and composite oil displacement agent |
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