CN102373913B - High-efficiency anti-magnesium ion oil displacement method - Google Patents
High-efficiency anti-magnesium ion oil displacement method Download PDFInfo
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Abstract
The invention relaters to a high-efficiency anti-magnesium ion oil displacement method, mainly aiming at the problems of the prior art that the surface active agent containing oil displacement agent is bad in oil displacement efficiency and high in use concentration under the conditions of high temperature and high salt, and alkali in the ternary composite asp flooding causes corrosion and scaling damage to the stratum and an oil well. By the adoption of the high-efficiency anti-magnesium ion oil displacement method, underground dehydrated crude oil contacts the displacement agent to sufficiently displace the crude oil in a drill core under the conditions of MgCl2 type injected water that the oil displacement temperature is 30-83 DEG C, the total mineralization degree is more than 8000 milligram/L, the Mg2<+> is more than 200 milligram/L, and the Ca2<+> is more than 30 milligram/L, wherein the displacement agent comprises the following components in percentage by mass: (1) 0.01-5.0% of N, N-di-fatty acyl diamine dimethyl propionate di-polyoxyethylene ether di-sulfonate; (2) 0.01-3.0% of polymer; and (3) 92.0-99.98% of injected water. By adopting the technical scheme, the problems can be better solved, and the method can be used for the tertiary oil recovery production of an oil field.
Description
Technical field
The present invention relates to a kind of flooding method of high efficiency anti-magnesium ions.
Background technology
Along with socioeconomic development, people are to the continuous increase of oil demand amount and the minimizing of petroleum reserves, and oil is just becoming more and more valuable as non-renewable resource.The problem facing has one, and imbalance between supply and demand is outstanding, and oil demand amount is more larger, and find is fewer and feweri; Two, also left in exhausted oil reservoir have a substantial oil.Primary oil recovery (POR) can the underground crude oil of extraction 10～25%, and secondary oil recovery (SOR) can the underground crude oil of extraction 15～25%, i.e. a primary oil recovery and secondary oil recovery extraction 25～50% underground crude oil.In order to guarantee oil supply steady in a long-term, to meet human wants, must research and development improve petroleum recovery technology, tertiary oil recovery (EOR), by intensified oil reduction measure, can make oil recovery factor improve 6～20% again, even more.
Chemical flooding is an important method that improves recovery ratio.Surfactant flooding is considered to improve by a relatively large margin recovery ratio, a kind of chemical agent applied widely, most with prospects.No matter surfactant is as host or as the auxiliary agent displacement of reservoir oil, to increasing substantially recovery ratio, all plays immeasurable effect.Polymer displacement of reservoir oil tech is a kind of method of important raising oil recovery, compares with general water drive, and polymer displacement of reservoir oil can accelerate oil recovery process, improves economic benefit, and Processes and apparatus is simple, cost is lower.As an important technology in chemical flooding, the ASP Oil-Displacing Technology that polymer, surfactant and alkali form has carried out some field tests in China and foreign countries, has obtained good oil displacement efficiency.But adding of alkali causes occurring the application prospect of ASP Oil-Displacing Technology being allowed of no optimist the problems such as the fouling of producing well pit shaft is serious, Produced Liquid difficult treatment in field test.By contrast, in the binary combination flooding formula that polymer and surfactant form, do not use alkali, mining site operability is stronger, thereby is subject to the approval in oil field.But due to need not be any Jian， crude oil PetroChina Company Limited. acids active material can not be fully used, so that research and development have novel surfactant and the alkali-free binary combination flooding formula of high surface is more imperative.
The Surfactant Industry product of external used for tertiary oil recovery mainly contains two large classes: the one, and petroleum sulfonate is main surfactant, the 2nd, alkylbenzenesulfonate is main surfactant, this two classes surfactant raw material is all taken from crude oil, raw material sources are wide, quantity is large, thereby are also the surfactants of external tertiary oil recovery consumption maximum.Because sulfonate surfactant is anionic, it and the bivalent cation (Ca in injected water
2+, Mg
2+deng) can precipitate, work as Ca
2+, Mg
2+while surpassing 300 μ g/g, just lose oil displacement efficiency.For this reason, also in continual exploitation research, be applicable to high saliferous, high Ca abroad
2+, Mg
2+the surfactant that ion stratum is used, comprises the research of multi-functional surfactant, Gemini surface active agent and sacrifice agent, and focuses on the composition research of various surfactants.
Anion-nonionic amphoteric surfactant is one of focus of tertiary oil recovery (EOR) area research in recent years always, owing in its molecular structure, two kinds of non-ionic groups of different nature and anionic group being designed in same surfactant molecule, make it have the advantage of anion and non-ionic surface active agent concurrently, have complementary advantages, function admirable, therefore shown good application prospect, especially the binary composite displacement system existing for alkali-free, owing to there is no the obstruction of not only having avoided oil reservoir of alkali, the problem such as fouling and corrosion, and can form ultralow interfacial tension with crude oil.In recent years, because Shuangzi (Gemini) surfactant is to be connected base key with one and to be closed the special construction compound forming by two hydrophilic radicals, two hydrophobic groupings, than conventional surfactant, there is more good performance, make it there are ultralow interfacial tension, low critical micelle concentration, low Kraff point, good lime soap dispersing power, good a series of peculiar properties such as wettability, thereby cause great concern.The Gemini surfactant with interface performance and rheological characteristic, is expected to replace the alkali in ternary composite driving formula, under rational formula system, finally realizes binary displacement system, for the chemical flooding in oil field is opened up new approach.
In the patent application at beginning of the thirties late 1920s, Degroot (De Groot) just once proposed the recovery ratio that water soluble surfactant active contributes to improve oil.
At present, the main Gemini surface active agent of domestic research and development is mainly cation double quaternary ammonium salt type, as Chinese patent CN 1528853, CN 1817431, CN 1066137 etc. have reported that bisamide type is cationic in succession, fluorine-containing cationic type and containing pyridine radicals cation Gemini surfactant.Because cation has, absorption loss is large, high in cost of production shortcoming, the research and development of anionic and nonionic Gemini surface active agent in recent years have also obtained increasing attention, as Chinese patent CN 101073757 has reported the synthetic of the asymmetric Shuangzi of a kind of anion.And to have salt tolerance poor due to anionic surfactant, and nonionic has the poor shortcoming of temperature tolerance, makes these products cannot being applied at high temperature and high salt oil deposit.
In addition, in existing ternary composite oil-displacing system, the alkali that contains high concentration, as NaOH, sodium carbonate etc., in use, to bringing huge injury in stratum and oil well etc., the surfactant using is difficult for being biodegradable, and human body is also had to certain harmfulness, as: 1991, Zhao Guoxi was at < < surfactant physical chemistry > > P495; 1994, Liu Cheng is disclosed content in the complete works of > > of < < surfactant P35.So for those harsh oil reservoirs, we ought to seek a kind of under alkali-free, high temperature (formation temperature is greater than 65 ℃), high salt (more than salinity 30000mg/L) condition Stability Analysis of Structures, and can form 10 with crude oil
-3～10
-4mN/m ultralow interfacial tension, effectively improves the displacing surfactant system of oil recovery factor.Of the present invention this in alkali-free situation just, be suitable for high temperature and high salt oil deposit the moon-non-Gemini surface active agent, its preparation method, binary is compound and the application in tertiary oil recovery.
Summary of the invention
Technical problem to be solved by this invention is containing the oil displacement agent of surfactant, to exist under high temperature and high salt condition oil displacement efficiency poor in prior art, the corrosion that in the high and ternary composite driving of working concentration, alkali brings stratum and oil well and the problem of incrustation injury, provide a kind of flooding method of new high efficiency anti-magnesium ions.The method will be containing N; the two fatty acyl group diamines neopentanoic acid two APEO disulfonate surfactant oil displacement agents of N-are for oil displacement process; have alkali-free, corrosion-free and incrustation injury, working concentration is low, the high feature of oil displacement efficiency under 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 flooding method of high efficiency anti-magnesium ions, by oil displacement agent at 30～83 ℃ of displacement of reservoir oil temperature, total salinity > 8000 mg/litre, Mg
2+> 200 mg/litre, Ca
2+the MgCl of > 30 mg/litre
2under type injected water condition, underground dewatered oil is contacted with oil displacement agent, by the abundant displacement of the crude oil in rock core out, wherein said oil displacement agent comprises following component by percentage to the quality:
The N of (1) 0.01～5.O%, the two fatty acyl group diamines neopentanoic acid two APEO disulfonates of N-;
(2) 0.01～3.0% polymer;
(3) 92.0～99.98% injected water;
Wherein the general molecular formula of (1) component is:
In formula: R
1for C
9～C
17alkyl, R
2for 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 being selected from potassium, sodium or lithium; Polymer is selected from one or both in ultra high molecular weight anion-type polyacrylamide, modified polyacrylamide or xanthans.
In technique scheme, displacement of reservoir oil temperature is preferably 45～75 ℃; Described injected water total salinity is preferably 15000～32000 mg/litre, Mg
2+be preferably 500～1200 mg/litre, Ca
2+be preferably 200～500 mg/litre, water type is MgCl
2type; Polymer is selected from above-mentioned ultra high molecular weight anion-type polyacrylamide or modified polyacrylamide; M preferred version is potassium and sodium, and more preferably scheme is for being selected from sodium; R
1it is 2～4 that carbon number adds the ratio preferable range that 1 sum and EO count n, has best hydrophilic lipophilic balance when this ratio is preferably 3～4, and its aqueous solution can form 10 with crude oil
-3～10
-4ultralow interfacial tension; N, the R in the two fatty acyl group diamines neopentanoic acid two APEO disulfonates of N-
1carbon number is preferably nine, 11,15 or 17, R
2carbon number be preferably two, four or six.
This flooding method specifically comprises the following steps:
(a) N, the preparation of the two fatty acyl group diamines neopentanoic acids of N-:
The aliphatic acid, thionyl chloride and the N that by the carbochain number of required proportioning, are 10～18, dinethylformamide (DMF) was 70～100 ℃ of reactions 2～5 hours, excessive thionyl chloride is extracted in decompression out, and it is 10～18 fat acyl chloride that the transparency liquid obtaining is carbochain number
1.Another diamines, methyl methacrylate and the solvent Isosorbide-5-Nitrae-dioxane that is 2～6 by the carbon number of required proportioning mix all with after, 40～70 ℃ of reactions 2～5 hours, the reduce pressure unreacted raw material of removal and solvent obtained diamines dimethylated methyl propionate
2, with the sodium hydroxide solution of 50wt%, regulate PH=9～10, under vigorous stirring, drip
1, then in 40～70 ℃ of reactions 2～6 hours, obtaining N, the two carbochain numbers of N-are 10～18 fatty acyl group diamines dimethylated methyl propionates
3, add the ethanol of aequum, with the sodium hydroxide solution of 50wt%, regulate PH=11～12, back flow reaction 2～6 hours, after acidifying N, the two carbochain numbers of N-are 10～18 fatty acyl group diamines neopentanoic acids.Wherein, preparation
1time, the mol ratio of the aliphatic acid that carbochain number is 10～18, thionyl chloride and DMF is 1: 1.0～2.0: 0.03～0.1; Preparation
2time, solvent is Isosorbide-5-Nitrae-dioxane, and consumption is that carbochain number is 3～6 times of 2～6 diamines quality, and the diamines that carbochain number is 2～6 and the mol ratio of methyl methacrylate are 1: 1.0～4.0; Preparation
3time, the fat acyl chloride that carbochain number is 10～18 and carbochain number are that the mol ratio of 2～6 diamines dimethylated methyl propionates is 1.9～2.5: 1; Preparation N, when the two carbochain numbers of N-are 10～18 fatty acyl group diamines neopentanoic acid, ethanol consumption is that carbochain number is 5～10 times of 2～6 diamines quality.
(b) N, the preparation of two fatty acyl group diamines neopentanoic acid two APEOs of N-:
The N of step (a) synthesized; the two carbochain numbers of N-are that 10～18 fatty acyl group diamines neopentanoic acids and oxirane are 85～160 ℃ by required proportioning in reaction temperature; pressure is less than under 0.80MPa gauge pressure condition; the alkali compounds of calcium is catalyzer; react to obtain N, the two carbochain numbers of N-are 10～18 fatty acyl group diamines neopentanoic acid two APEOs.Wherein, N, the two carbochain numbers of N-are that 10～18 fatty acyl group diamines neopentanoic acids and oxirane mol ratio are 1: 4～14, and catalyst amount is N, and the two carbochain numbers of N-are 0.5～5.0% of 10～18 fatty acyl group diamines neopentanoic acid quality.
(c) N, the preparation of the two fatty acyl group diamines neopentanoic acid two APEO disulfonates of N-:
By the N of step (b) synthesized; the two carbochain numbers of N-are that 10～18 fatty acyl group diamines neopentanoic acid two APEOs are by required proportioning and 3-chlorine-2-hydroxyl propanesulfonate, potassium hydroxide or NaOH and TBAB catalyst mix; take toluene as solvent; 50～130 ℃ of reaction temperatures; react 3～15 hours; reaction finishes to obtain N by post processing, the two fatty acyl group diamines neopentanoic acid two APEO disulfonates of N-.Wherein, N, the two carbochain numbers of N-are mol ratio=1 of 10～18 fatty acyl group diamines neopentanoic acid two APEOs, 3-chlorine-2-hydroxyl propanesulfonate, potassium hydroxide or NaOH and TBAB: 2～6: 2～8: 0.05～0.3.
(d) by the N of aequum; the two fatty acyl group diamines neopentanoic acid two APEO disulfonates of N-, above-mentioned ultra high molecular weight anion-type polyacrylamide or modified polyacrylamide and injected water evenly mix; stirring at room 1～3 hour, obtains required oil displacement agent.By percentage to the quality; N, the two fatty acyl group diamines neopentanoic acid two APEO disulfonates of N-, above-mentioned ultra high molecular weight anion-type polyacrylamide or the proportioning of modified polyacrylamide and injected water are 0.01～5.0%: 0.01～3.0%: 92.0～99.98%.
(e) first take total salinity as 10000～40000 mg/litre, Mg
2+be 300～1350 mg/litre, Ca
2+be the MgCl of 50～800 mg/litre
2type injected water is saturated by rock core, measure the voids volume (PV) of rock core, then with dewatered oil, carry out saturated, at 40～80 ℃ of temperature, carry out imitation oil displacement experiment test: first water drive is to moisture 94%, after the synthetic oil displacement agent of metaideophone 0.3pv (rock pore volume) step (d), water drive, to moisture more than 98%, is calculated the percentage that improves oil recovery factor.
In technique scheme, (a) in step, prepare
1time, the mol ratio of the aliphatic acid that carbochain number is 10～18, thionyl chloride and DMF is preferably 1: 1.2～and 2.0: 0.05～0.1; Preparation
2time solvent be 1,4-dioxane, it is 4～5 times of 2～6 diamines quality that consumption is preferably carbochain number, the diamines that carbochain number is 2～6 and the mol ratio of methyl methacrylate be preferably 1: 2.2～and 3.0, reaction temperature is preferably 50～60 ℃, and the reaction time is preferably 3～4 hours; Preparation
3time, the fat acyl chloride that carbochain number is 10～18 and carbochain number are that the mol ratio of 2～6 diamines dimethylated methyl propionates is preferably 2.0～2.2: 1, and reaction temperature is preferably 60～70 ℃, and the reaction time is preferably 3～4 hours; Preparation N, when the two carbochain numbers of N-are 10～18 fatty acyl group diamines neopentanoic acid, it is 6～8 times of 2～6 diamines quality that ethanol consumption is preferably carbochain number, the reaction time is preferably 3～5 hours.(b) N, the two carbochain numbers of N-be 10～18 fatty acyl group diamines neopentanoic acids and oxirane mol ratio be preferably 1: 6～12, catalyst amount 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 step; the two carbochain numbers of N-be the mol ratio of 10～18 fatty acyl group diamines neopentanoic acid two APEOs, 3-chlorine-2-hydroxyl propanesulfonate, NaOH (potassium hydroxide) and TBAB be preferably 1: 2.5～5.5: 3～7: 0.1～0.2; reaction temperature is preferably 70～110 ℃, and the reaction time 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 APEO disulfonates of N-is 0.03～1.0%, more preferably scope is 0.1～0.3%; Above-mentioned ultra high molecular weight anion-type polyacrylamide or modified polyacrylamide consumption preferable range are 0.05～0.5%; More preferably scope is 0.1～0.2%, and the reaction time is preferably 1.5～2.5 hours.(e) displacement of reservoir oil temperature is preferably 45～75 ℃; Injected water total salinity is preferably 15000～32000 mg/litre, Mg
2+be preferably 500～1200 mg/litre, Ca
2+be preferably 200～500 mg/litre, water type is MgCl
2type.
N in the prepared oil displacement agent of the present invention, the two fatty acyl group diamines neopentanoic acid two APEO disulfonates of N-, owing to containing aerobic ethene non-ionic group and azochlorosulfonate acid anion group in its molecular structure simultaneously, make the salt tolerant advantage of its heat resistance that has anion surfactant concurrently and non-ionic surface active agent, and symmetrical Shuangzi architectural feature, make it have again critical micelle concentration low, reduce interfacial tension ability strong, the features such as the rheological characteristic of resistance to high salinity and uniqueness and viscoplasticity-viscosifying action, than conventional surfactant, there is more good performance.In its molecule, do not contain aromatic ring structure in addition, be easier to biodegradation, therefore less to the harm of human body and environment, be a kind of green surfactant that is suitable for the used for tertiary oil recovery of high temperature and high salt oil deposit.
Adopt the flooding method of high efficiency anti-magnesium ions of the present invention, under alkali-free condition, can be used for 45～75 ℃ of formation temperatures, salinity 15000～32000 mg/litre, Mg
2+500～1200 mg/litre, Ca
2+the MgCl of 200～500 mg/litre
2the marine block injected water of type Shengli Oil Field and crude oil; take consumption as 0.1～0.3wt%N; above-mentioned ultra high molecular weight anion-type polyacrylamide or the modified polyacrylamide of the two fatty acyl group diamines neopentanoic acid two APEO disulfonates of N-and 0.1～0.2wt% forms above-mentioned compound oil displacement agent; measure the dynamic interface tension value between the marine block crude oil of this oil displacement agent aqueous solution and Shengli Oil Field, can reach 10
-3～10
-4the ultralow interfacial tension of mN/m, through physical analogy displacement experiment Lab-evaluation this oil displacement agent on high temperature, high salinity reservoir, can on water drive basis, can reach 18.5% by (water drive improves oil recovery factor and reaches 60.5%) raising oil recovery factor, obtain good technique effect.
Accompanying drawing explanation
Fig. 1 is N, the infrared spectrum of the two fatty acyl group diamines neopentanoic acid two APEO disulfonates of N-.
N prepared by the present invention; the two fatty acyl group diamines neopentanoic acid two APEO disulfonates of N-can characterize by the following method: after synthetic is purified; application U.S. Nicolet-380FT-IR spectrometer, adopts liquid-film method to carry out infrared spectrum analysis (sweep limits 4000～400cm
-1), in wave number, be 2850～2950cm
-1there is methyl and the flexible characteristic peak of methylene C-H on alkyl chain, 1475cm in place
-1c-H flexural vibrations on alkyl chain, at wave number 720cm
-1occur that the characteristic peak waving in chain alkyl C-H face is because this peak is very wide; 1640cm
-1the acid amides I key band vC=O at place, 1058cm
-1because C-N is flexible, form; 1106cm
-1the obvious broadening in peak at place, left and right, and wave number moves on to 1117cm
-1place, this peak is owing to having connected EO, the upper C-O-C asymmetric stretch of EO bands of a spectrum cause; 1350cm
-1the peak of left and right is broadening and obviously growing tall to some extent also, and the characteristic peak of sulfonate is that antisymmetric stretching vibration and the vibration of skeleton carbon due to S=O causes, and the symmetrical stretching vibration of S=O is at 1155cm
-1left and right, proved response has generated N really thus, the two fatty acyl group diamines neopentanoic acid two APEO disulfonates of N-.
Below by embodiment, the present invention is further elaborated.
The specific embodiment
[embodiment 1]
(a) N, the two dodecanoyl ethylenediamine neopentanoic acids of N-synthetic
By 300 grams of laurate (1.5 moles), thionyl chloride 267.8 grams of (2.25 moles) and 4.5 grams of DMF, add in 1000 milliliters of four-hole boiling flasks being furnished with sealing machine stirring, thermometer, condensation pipe etc., in 90 ℃, react after 3 hours, decompression steams excessive thionyl chloride, obtains lauroyl chloride.Another is furnished with and in 2000 milliliters of four-hole boiling flasks of sealing machine stirring, thermometer, condensation pipe, adds 45.0 grams of anhydrous ethylenediamines (0.75 mole), 180 gram 1,4-dioxane, be warming up to 50 ℃, slowly drip 165.0 grams of methyl methacrylates (1.65 moles), drip off and continue reaction 3 hours, unreacted methyl methacrylate and solvent Isosorbide-5-Nitrae-dioxane are removed in decompression, and residue is ethylenediamine dimethylated methyl propionate.With 50wt% NaOH, regulate reactant liquor PH=8～10, under vigorous stirring, slowly drip lauroyl chloride, constantly add simultaneously 50wt% NaOH with the PH that maintains reaction 8～10, after dripping off, in 60 ℃, continue reaction 3 hours, obtain N, the two dodecanoyl ethylenediamine dimethylated methyl propionates of N-, continuation adds 270 grams of ethanol in reaction bulb, with 50wt% NaOH, adjust PH=11～12 again, reflux 4 hours, cooling, filtration is desalted, pressure reducing and steaming ethanol, residue is neutralized to highly acid with hydrochloric acid, branch vibration layer, obtain N, 306.2 grams of the two dodecanoyl ethylenediamine neopentanoic acids of N-, molar yield 68.5%.
(b) N, two dodecanoyl ethylenediamine neopentanoic acid two APEOs (n=4) of N-synthetic
By the synthetic N of step (a); the alkali compounds of two 306.2 grams (0.514 moles) of dodecanoyl ethylenediamine neopentanoic acid of N-, 3.4 grams of calcium add be furnished with condensing unit, in the high-pressure reactor of mixing plant and gas distributor; when limit logical nitrogen limit heating is made 135 ℃; add 20 grams of water, stirring reaction 1 hour.Remove after moisture content, be cooled to 80 ℃, the sulfuric acid (20wt%) that slowly drips catalyst neutralisation theoretical amount makes the compound oxidizing calcium alkoxylating catalyst reactant liquor system of high activity, high selectivity, system temperature is heated to 80～90 ℃, open vacuum system, under high vacuum, dewater 2 hours, then use nitrogen blowing 3～4 times, system reaction temperature is adjusted to 140 ℃ and slowly passes into 181.1 grams of (4.116 moles) oxirane, controlled pressure≤0.60MPa.After reaction finishes, use nitrogen blowing system, cooling rear neutralization, dehydration, obtain N, 428.3 grams of two dodecanoyl ethylenediamine neopentanoic acid two APEOs (n=4) of N-, molar yield 87.9%.
(c) N, two dodecanoyl ethylenediamine neopentanoic acid two APEOs (n=4) disulfonates of N-synthetic
By the N of step (b) synthesized; two dodecanoyl ethylenediamine neopentanoic acid two APEOs (n=4) of N-428.3 grams (0.452 mole) and 152.3 grams of (2.72 moles) potassium hydroxide, 355.4 grams of (1.81 moles) 3-chlorine-2-hydroxyl propanesulfonates, 16.3 grams of TBABs, 1500 milliliters of toluene are mixed in to be furnished with mechanical agitation, in the reactor of 5000 milliliters of thermometer and reflux condensing tube, to be heated to 90 ℃ of reactions 8 hours.Cooling, neutralization, divides and removes inorganic salts, the N that alkalizes to obtain, two dodecanoyl ethylenediamine neopentanoic acid two APEOs (n=4) disulfonates of N-, molar yield 75.8%.To synthetic N, two dodecanoyl ethylenediamine neopentanoic acid two APEOs (n=4) disulfonates of N-, application U.S. Nicolet-380FT-IR spectrometer, adopts liquid-film method to carry out infrared spectrum analysis (sweep limits 4000～400cm
-1), there is all characteristic absorption peaks of Fig. 1.
(d) by the synthetic N of step (c); two dodecanoyl ethylenediamine neopentanoic acid two APEOs (n=4) the disulfonate 0.2wt% of N-, above-mentioned ultra high molecular weight anion-type polyacrylamide 0.15wt% and the marine block injected water of 96.5wt% Shengli Oil Field mix and blend 2 hours, obtain a kind of high efficiency anti-magnesium ions oil displacement agent of homogeneous transparent.In 65 ℃ of temperature, salinity, be 15000mg/L, Mg
2+for 600mg/L, Ca
2+in water for 200mg/L, the apparent viscosity that records this oil displacement agent is 15.9mPa.s; Between the marine block IFA-8 of this oil displacement agent and Shengli Oil Field well dewatered oil, form the ultralow interfacial tension of 0.0004mN/m.Apparent viscosity is by the BROODFIELD II type viscometer determining of U.S. Brookfield company, and the TX500 type rotation interfacial tensimeter that interfacial tension is produced by Texas ,Usa university is measured.
(e) first with salinity 15000mg/L, Mg
2+for 600mg/L, Ca
2+for the injected water of 200mg/L, by rock core, (length is 30 centimetres, and diameter is 2.5 centimetres, and permeability is 1.5 microns
2) saturated, the voids volume (PV) of measuring rock core is 52.1%, then with the marine block IFA-8 of Shengli Oil Field well dewatered oil, carry out saturated, under 65 ℃ of constant temperature, carry out imitation oil displacement experiment test: first water drive is to moisture 94%, record water drive and improve oil recovery factor 58.6%, after the synthetic oil displacement agent of metaideophone 0.3pv (rock pore volume) step (d), water drive, to moisture more than 98%, record on water drive basis and can improve oil recovery factor 18.5% again again.
[embodiment 2]
(a) N, the two dodecanoyl hexamethylene diamine neopentanoic acids of N-synthetic
With [embodiment 1] (a); difference substitutes 45.0 grams of (0.75 mole) anhydrous ethylenediamines with the anhydrous hexamethylene diamine of 87.0 grams (0.75 moles), and all the other are identical, obtain N; 328.6 grams of the two dodecanoyl hexamethylene diamine neopentanoic acids of N-, molar yield 67.2%.
(b) N, two dodecanoyl hexamethylene diamine neopentanoic acid two APEOs (n=3) of N-synthetic
With [embodiment 1] (b); difference is with the N of 328.6 grams (0.504 moles); the two dodecanoyl hexamethylene diamine neopentanoic acids of N-substitute 306.2 grams of (0.514 mole) N; the use amount of the two dodecanoyl ethylenediamine neopentanoic acids of N-, oxirane is 133.1g (3.024 moles); the use amount of the alkali compounds of calcium is 7.5 grams; obtain N, 409.5 grams of two dodecanoyl hexamethylene diamine neopentanoic acid two APEOs (n=3) of N-, molar yield 88.2%.
(c) N, two dodecanoyl hexamethylene diamine neopentanoic acid two APEOs (n=3) disulfonates of N-synthetic
By the N of step (b) synthesized; two dodecanoyl hexamethylene diamine neopentanoic acid two APEOs (n=3) of N-409.5 grams (0.447 mole) and 100.5 grams of (1.79 moles) potassium hydroxide, 377.3 grams of (1.92 moles) 3-chlorine-2-hydroxyl propanesulfonates, 16.3 grams of TBABs, 1500 milliliters of toluene are mixed in to be furnished with mechanical agitation, in the reactor of 5000 milliliters of thermometer and reflux condensing tube, to be heated to 100 ℃ of reactions 6 hours.Cooling, neutralization, divides and removes inorganic salts, the N that alkalizes to obtain, two dodecanoyl hexamethylene diamine neopentanoic acid two APEOs (n=3) disulfonates of N-, molar yield 75.5%.To synthetic N, two dodecanoyl hexamethylene diamine neopentanoic acid two APEOs (n=3) disulfonates of N-, application U.S. Nicolet-380FT-IR spectrometer, adopts liquid-film method to carry out infrared spectrum analysis (sweep limits 4000～400cm
-1), there is all characteristic absorption peaks of Fig. 1.
(d) by the synthetic N of step (c); two dodecanoyl hexamethylene diamine neopentanoic acid two APEOs (n=3) the disulfonate 0.15wt% of N-, above-mentioned ultra high molecular weight anion-type polyacrylamide 0.15wt% and the marine block injected water of 97.0wt% Shengli Oil Field mix and blend 2.5 hours, obtain a kind of high efficiency anti-magnesium ions oil displacement agent of homogeneous transparent.In temperature 70 C, salinity, be 21000mg/L, Mg
2+for 900mg/L, Ca
2+in water for 300mg/L, the apparent viscosity that records this oil displacement agent is 15.1mPa.s; Between the marine block IFA-8 of this oil displacement agent and Shengli Oil Field well dewatered oil, form the ultralow interfacial tension of 0.0038mN/m.Apparent viscosity is by the BROODFIELD II type viscometer determining of U.S. Brookfield company, and the TX500 type rotation interfacial tensimeter that interfacial tension is produced by Texas ,Usa university is measured.
(e) first with salinity 21000mg/L, Mg
2+for 900mg/L, Ca
2+for the injected water of 300mg/L, by rock core, (length is 30 centimetres, and diameter is 2.5 centimetres, and permeability is 1.5 microns
2) saturated, the voids volume (PV) of measuring rock core is 52.5%, then with the marine block IFA-8 of Shengli Oil Field well dewatered oil, carry out saturated, under 70 ℃ of constant temperature, carry out imitation oil displacement experiment test: first water drive is to moisture 94%, record water drive and improve oil recovery factor 60.5%, after the synthetic oil displacement agent of metaideophone 0.3pv (rock pore volume) step (d), water drive, to moisture more than 98%, record on water drive basis and can improve oil recovery factor 17.2% again again.
[embodiment 3]
(a) N, the two ten acyl group butanediamine neopentanoic acids of N-synthetic
With [embodiment 1] (a); difference substitutes 300.0 grams of (1.5 moles) laurate with the capric acid of 261.0 grams (1.5 moles); anhydrous butanediamine with 66.0 grams (0.75 moles) substitutes 45.0 grams of (0.75 mole) anhydrous ethylenediamines; all the other are identical; obtain N; 283.3 grams of the two ten acyl group butanediamine neopentanoic acids of N-, molar yield 66.5%.
(b) N, two ten acyl group butanediamine neopentanoic acid two APEOs (n=3) of N-synthetic
With [embodiment 1] (b); difference is with the N of 283.3 grams (0.499 moles); the two ten acyl group butanediamine neopentanoic acids of N-substitute 306.2 grams of (0.514 mole) N; the use amount of the two dodecanoyl ethylenediamine neopentanoic acids of N-, oxirane is 131.7g (2.994 moles); the use amount of the alkali compounds of calcium is 6.4 grams; obtain N, 371.6 grams of two ten acyl group butanediamine neopentanoic acid two APEOs (n=3) of N-, molar yield 89.5%.
(c) N, two ten acyl group butanediamine neopentanoic acid two APEOs (n=3) disulfonates of N-synthetic
By the N of step (b) synthesized; two ten acyl group butanediamine neopentanoic acid two APEOs (n=3) of N-371.6 grams (0.447 mole) and 100.3 grams of (1.79 moles) potassium hydroxide, 263.3 grams of (1.34 moles) 3-chlorine-2-hydroxyl propanesulfonates, 18.8 grams of TBABs, 1500 milliliters of toluene are mixed in to be furnished with mechanical agitation, in the reactor of 5000 milliliters of thermometer and reflux condensing tube, to be heated to 80 ℃ of reactions 8 hours.Cooling, neutralization, divides and removes inorganic salts, the N that alkalizes to obtain, two ten acyl group butanediamine neopentanoic acid two APEOs (n=3) disulfonates of N-, molar yield 73.5%.To synthetic N, two ten acyl group butanediamine neopentanoic acid two APEOs (n=3) disulfonates of N-, application U.S. Nicolet-380FT-IR spectrometer, adopts liquid-film method to carry out infrared spectrum analysis (sweep limits 4000～400cm
-1), there is all characteristic absorption peaks of Fig. 1.
(d) by the synthetic N of step (c); two ten acyl group butanediamine neopentanoic acid two APEOs (n=3) the disulfonate 0.15wt% of N-, above-mentioned modified polyacrylamide 0.15wt% and the marine block injected water of 97.0wt% Shengli Oil Field mix and blend 1.5 hours, obtain a kind of high efficiency anti-magnesium ions oil displacement agent of homogeneous transparent.In 65 ℃ of temperature, salinity, be 32000mg/L, Mg
2+for 1200mg/L, Ca
2+in water for 400mg/L, the apparent viscosity that records this oil displacement agent is 14.5mPa.s; Between the marine block IFA-8 of this oil displacement agent and Shengli Oil Field well dewatered oil, form the ultralow interfacial tension of 0.0018mN/m.Apparent viscosity is by the BROODFIELD II type viscometer determining of U.S. Brookfield company, and the TX500 type rotation interfacial tensimeter that interfacial tension is produced by Texas ,Usa university is measured.
(e) first with salinity 32000mg/L, Mg
2+for 1200mg/L, Ca
2+for the water of 400mg/L, by rock core, (length is 30 centimetres, diameter is 2.5 centimetres, permeability is 1.5 micron 2) saturated, the voids volume (PV) of measuring rock core is 53.1%, then with the marine block IFA-8 of Shengli Oil Field well dewatered oil, carry out saturated, under 65 ℃ of constant temperature, carry out imitation oil displacement experiment test: first water drive is to moisture 94%, record water drive and improve oil recovery factor 58.3%, again after the synthetic oil displacement agent of metaideophone 0.3pv (rock pore volume) step (d), water drive, to moisture more than 98%, record on water drive basis and can improve oil recovery factor 16.2% again.
[embodiment 4]
(a) N, the two hexadecanoyl group ethylenediamine neopentanoic acids of N-synthetic
By 422.4 grams of palmitic acids (1.65 moles), thionyl chloride 235.6 grams of (1.875 moles) and 6.3 grams of DMF, add in 1000 milliliters of four-hole boiling flasks being furnished with sealing machine stirring, thermometer, condensation pipe etc., in 80 ℃, react after 5 hours, decompression steams excessive thionyl chloride, obtains palmitoyl chloride.Another is furnished with and in 2000 milliliters of four-hole boiling flasks of sealing machine stirring, thermometer, condensation pipe, adds 45.0 grams of anhydrous ethylenediamines (0.75 mole), 225 gram 1,4-dioxane, be warming up to 60 ℃, slowly drip 187.5 grams of methyl methacrylates (1.875 moles), drip off and continue reaction 4 hours, unreacted methyl methacrylate and solvent Isosorbide-5-Nitrae-dioxane are removed in decompression, and residue is ethylenediamine dimethylated methyl propionate.With 50wt% NaOH, regulate reactant liquor PH=8～10, under vigorous stirring, slowly drip lauroyl chloride, constantly add simultaneously 50wt% NaOH with the PH that maintains reaction 8～10, after dripping off, in 70 ℃, continue reaction 4 hours, obtain N, the two hexadecanoyl group ethylenediamine dimethylated methyl propionates of N-, continuation adds 360 grams of ethanol in reaction bulb, with 50wt% NaOH, adjust PH=11～12 again, reflux 4 hours, cooling, filtration is desalted, pressure reducing and steaming ethanol, residue is neutralized to highly acid with hydrochloric acid, branch vibration layer, obtain N, 360.0 grams of the two hexadecanoyl group ethylenediamine neopentanoic acids of N-, molar yield 67.8%.
(b) N, two hexadecanoyl group ethylenediamine neopentanoic acid two APEOs (n=5) of N-synthetic
With [embodiment 1] (b); difference is with the N of 360.0 grams (0.508 moles); the two hexadecanoyl group ethylenediamine neopentanoic acids of N-substitute 306.2 grams of (0.514 mole) N; the use amount of the two dodecanoyl ethylenediamine neopentanoic acids of N-, oxirane is 223.5g (5.08 moles); the use amount of the alkali compounds of calcium is 6.6 grams; obtain N, 497.4 grams of two hexadecanoyl group ethylenediamine neopentanoic acid two APEOs (n=5) of N-, molar yield 85.3%.
(c) N, two hexadecanoyl group ethylenediamine neopentanoic acid two APEOs (n=5) disulfonates of N-synthetic
By the N of step (b) synthesized; two hexadecanoyl group ethylenediamine neopentanoic acid two APEOs (n=5) of N-497.4 grams (0.433 mole) and 103.6 grams of (2.60 moles) NaOH, 339.9 grams of (1.73 moles) 3-chlorine-2-hydroxyl propanesulfonates, 17.3 grams of TBABs, 1500 milliliters of toluene are mixed in to be furnished with mechanical agitation, in the reactor of 5000 milliliters of thermometer and reflux condensing tube, to be heated to 100 ℃ of reactions 8 hours.Cooling, neutralization, divides and removes inorganic salts, the N that alkalizes to obtain, two hexadecanoyl group ethylenediamine neopentanoic acid two APEOs (n=5) disulfonates of N-, molar yield 72.9%.To synthetic N, two hexadecanoyl group ethylenediamine neopentanoic acid two APEOs (n=5) disulfonates of N-, application U.S. Nicolet-380FT-IR spectrometer, adopts liquid-film method to carry out infrared spectrum analysis (sweep limits 4000～400cm
-1), there is all characteristic absorption peaks of Fig. 1.
(d) by the synthetic N of step (c); two hexadecanoyl group ethylenediamine neopentanoic acid two APEOs (n=5) the disulfonate 0.1wt% of N-, above-mentioned modified polyacrylamide 0.2wt% and the marine block injected water of 97.0wt% Shengli Oil Field mix and blend 2 hours, obtain a kind of high efficiency anti-magnesium ions oil displacement agent of homogeneous transparent.In 40 ℃ of temperature, salinity, be 32000mg/L, Mg
2+for 1200mg/L, Ca
2+in water for 400mg/L, the apparent viscosity that records this oil displacement agent is 16.3mPa.s; Between the marine block IFA-8 of this oil displacement agent and Shengli Oil Field well dewatered oil, form the ultralow interfacial tension of 0.0078mN/m.Apparent viscosity is by the BROODFIELD II type viscometer determining of U.S. Brookfield company, and the TX500 type rotation interfacial tensimeter that interfacial tension is produced by Texas ,Usa university is measured.
(e) first with salinity 32000mg/L, Mg
2+for 1200mg/L, Ca
2+for the injected water of 400mg/L, by rock core, (length is 30 centimetres, diameter is 2.5 centimetres, permeability is 1.5 micron 2) saturated, the voids volume (PV) of measuring rock core is 51.2%, then with the marine block IFA-8 of Shengli Oil Field well dewatered oil, carry out saturated, under 40 ℃ of constant temperature, carry out imitation oil displacement experiment test: first water drive is to moisture 94%, record water drive and improve oil recovery factor 56.0%, again after the synthetic oil displacement agent of metaideophone 0.3pv (rock pore volume) step (d), water drive, to moisture more than 98%, record on water drive basis and can improve oil recovery factor 17.5% again.
[embodiment 5]
(a) N, the two hexadecanoyl group butanediamine neopentanoic acids of N-synthetic
With [embodiment 4] (a); difference substitutes 45.0 grams of (0.75 mole) anhydrous ethylenediamines with the anhydrous butanediamine of 66.0 grams (0.75 moles), and all the other are identical, obtain N; 362.7 grams of the two hexadecanoyl group butanediamine neopentanoic acids of N-, molar yield 65.7%.
(b) N, two hexadecanoyl group butanediamine neopentanoic acid two APEOs (n=4) of N-synthetic
With [embodiment 1] (b); difference is with the N of 362.7 grams (0.493 moles); the two hexadecanoyl group butanediamine neopentanoic acids of N-substitute 306.2 grams of (0.514 mole) N; the use amount of the two dodecanoyl ethylenediamine neopentanoic acids of N-, oxirane is 173.5g (3.944 moles); the use amount of the alkali compounds of calcium is 7.4 grams; obtain N, 456.5 grams of two hexadecanoyl group butanediamine neopentanoic acid two APEOs (n=4) of N-, molar yield 85.1%.
(c) N, two hexadecanoyl group butanediamine neopentanoic acid two APEOs (n=4) disulfonates of N-synthetic
By the N of step (b) synthesized; two hexadecanoyl group butanediamine neopentanoic acid two APEOs (n=4) of N-456.5 grams (0.420 mole) and 102.9 grams of (2.57 moles) NaOH, 290.5 grams of (1.48 moles) 3-chlorine-2-hydroxyl propanesulfonates, 19.9 grams of TBABs, 1600 milliliters of toluene are mixed in to be furnished with mechanical agitation, in the reactor of 5000 milliliters of thermometer and reflux condensing tube, to be heated to 100 ℃ of reactions 10 hours.Cooling, neutralization, divides and removes inorganic salts, the N that alkalizes to obtain, two hexadecanoyl group butanediamine neopentanoic acid two APEOs (n=4) disulfonates of N-, molar yield 71.1%.To synthetic N, two hexadecanoyl group butanediamine neopentanoic acid two APEOs (n=4) disulfonates of N-, application U.S. Nicolet-380FT-IR spectrometer, adopts liquid-film method to carry out infrared spectrum analysis (sweep limits 4000～400cm
-1), there is all characteristic absorption peaks of Fig. 1.
(d) by the synthetic N of step (c); two hexadecanoyl group butanediamine neopentanoic acid two APEOs (n=4) the disulfonate 0.25wt% of N-, above-mentioned ultra high molecular weight anion-type polyacrylamide 0.1wt% and the marine block injected water of 96.5wt% Shengli Oil Field mix and blend 2 hours, obtain a kind of high efficiency anti-magnesium ions oil displacement agent of homogeneous transparent.In 65 ℃ of temperature, salinity, be 15000mg/L, Mg
2+for 600mg/L, Ca
2+in water for 200mg/L, the apparent viscosity that records this oil displacement agent is 14.9mPa.s; Between the marine block IFA-8 of this oil displacement agent and Shengli Oil Field well dewatered oil, form the ultralow interfacial tension of 0.0005mN/m.Apparent viscosity is by the BROODFIELD II type viscometer determining of U.S. Brookfield company, and the TX500 type rotation interfacial tensimeter that interfacial tension is produced by Texas ,Usa university is measured.
(e) first with salinity 15000mg/L, Mg
2+for 600mg/L, Ca
2+for the injected water of 200mg/L, by rock core, (length is 30 centimetres, and diameter is 2.5 centimetres, and permeability is 1.5 microns
2) saturated, the voids volume (PV) of measuring rock core is 53.9%, then with the marine block IFA-8 of Shengli Oil Field well dewatered oil, carry out saturated, under 65 ℃ of constant temperature, carry out imitation oil displacement experiment test: first water drive is to moisture 94%, record water drive and improve oil recovery factor 60.1%, after the synthetic oil displacement agent of metaideophone 0.3pv (rock pore volume) step (d), water drive, to moisture more than 98%, record on water drive basis and can improve oil recovery factor 18.2% again again.
[embodiment 6]
(a) N, the two octadecanoyl ethylenediamine neopentanoic acids of N-synthetic
By 497 grams of stearic acid (1.75 moles), thionyl chloride 374.9 grams of (3.15 moles) and 7.5 grams of DMF, add in 1000 milliliters of four-hole boiling flasks being furnished with sealing machine stirring, thermometer, condensation pipe etc., in 95 ℃, react after 3 hours, decompression steams excessive thionyl chloride, obtains stearyl chloride.Another is furnished with and in 2000 milliliters of four-hole boiling flasks of sealing machine stirring, thermometer, condensation pipe, adds 45.0 grams of anhydrous ethylenediamines (0.75 mole), 225 gram 1,4-dioxane, be warming up to 60 ℃, slowly drip 225.0 grams of methyl methacrylates (2.25 moles), drip off and continue reaction 4 hours, unreacted methyl methacrylate and solvent Isosorbide-5-Nitrae-dioxane are removed in decompression, and residue is ethylenediamine dimethylated methyl propionate.With 50wt% NaOH, regulate reactant liquor PH=8～10, under vigorous stirring, slowly drip lauroyl chloride, constantly add simultaneously 50wt% NaOH with the PH that maintains reaction 8～10, after dripping off, in 70 ℃, continue reaction 3 hours, obtain N, the two octadecanoyl ethylenediamine dimethylated methyl propionates of N-, continuation adds 315 grams of ethanol in reaction bulb, with 50wt% NaOH, adjust PH=11～12 again, reflux 4 hours, cooling, filtration is desalted, pressure reducing and steaming ethanol, residue is neutralized to highly acid with hydrochloric acid, branch vibration layer, obtain N, 384.5 grams of the two octadecanoyl ethylenediamine neopentanoic acids of N-, molar yield 67.1%.
(b) N, two octadecanoyl ethylenediamine neopentanoic acid two APEOs (n=6) of N-synthetic
With [embodiment 1] (b); difference is with the N of 384.5 grams (0.503 moles); the two octadecanoyl ethylenediamine neopentanoic acids of N-substitute 306.2 grams of (0.514 mole) N; the use amount of the two dodecanoyl ethylenediamine neopentanoic acids of N-, oxirane is 265.6g (6.036 moles); the use amount of the alkali compounds of calcium is 5.6 grams; obtain N, 547.2 grams of two octadecanoyl ethylenediamine neopentanoic acid two APEOs (n=6) of N-, molar yield 84.2%.
(c) N, two octadecanoyl ethylenediamine neopentanoic acid two APEOs (n=6) disulfonates of N-synthetic
By the N of step (b) synthesized; two octadecanoyl ethylenediamine neopentanoic acid two APEOs (n=6) of N-547.2 grams (0.424 mole) and 101.6 grams of (2.54 moles) NaOH, 416.7 grams of (2.12 moles) 3-chlorine-2-hydroxyl propanesulfonates, 26.9 grams of TBABs, 1800 milliliters of toluene are mixed in to be furnished with mechanical agitation, in the reactor of 5000 milliliters of thermometer and reflux condensing tube, to be heated to 110 ℃ of reactions 12 hours.Cooling, neutralization, divides and removes inorganic salts, the N that alkalizes to obtain, two octadecanoyl ethylenediamine neopentanoic acid two APEOs (n=6) disulfonates of N-, molar yield 72.3%.To synthetic N, two octadecanoyl ethylenediamine neopentanoic acid two APEOs (n=6) disulfonates of N-, application U.S. Nicolet-380FT-IR spectrometer, adopts liquid-film method to carry out infrared spectrum analysis (sweep limits 4000～400cm
-1), there is all characteristic absorption peaks of Fig. 1.
(d) by the synthetic N of step (c); two octadecanoyl ethylenediamine neopentanoic acid two APEOs (n=6) the disulfonate 0.15wt% of N-, above-mentioned modified polyacrylamide 0.15wt% and the marine block injected water of 97.0wt% Shengli Oil Field mix and blend 2.5 hours, obtain a kind of high efficiency anti-magnesium ions oil displacement agent of homogeneous transparent.In 80 ℃ of temperature, salinity, be 21000mg/L, Mg
2+for 900mg/L, Ca
2+in water for 300mg/L, the apparent viscosity that records this oil displacement agent is 14.2mPa.s; Between the marine block IFA-8 of this oil displacement agent and Shengli Oil Field well dewatered oil, form the ultralow interfacial tension of 0.0031mN/m.Apparent viscosity is by the BROODFIELD II type viscometer determining of U.S. Brookfield company, and the TX500 type rotation interfacial tensimeter that interfacial tension is produced by Texas ,Usa university is measured.
(e) first with salinity 21000mg/L, Mg
2+for 900mg/L, Ca
2+for the injected water of 300mg/L, by rock core, (length is 30 centimetres, diameter is 2.5 centimetres, permeability is 1.5 micron 2) saturated, the voids volume (PV) of measuring rock core is 51.8%, then with the marine block IFA-8 of Shengli Oil Field well dewatered oil, carry out saturated, under 80 ℃ of constant temperature, carry out imitation oil displacement experiment test: first water drive is to moisture 94%, record water drive and improve oil recovery factor 57.2%, again after the synthetic oil displacement agent of metaideophone 0.3pv (rock pore volume) step (d), water drive, to moisture more than 98%, record on water drive basis and can improve oil recovery factor 17.2% again.
[embodiment 7]
(a) N, the two octadecanoyl hexamethylene diamine neopentanoic acids of N-synthetic
With [embodiment 6] (a); difference substitutes 45.0 grams of anhydrous ethylenediamines (0.75 mole) with the anhydrous hexamethylene diamine of 87.0 grams (0.75 moles), and all the other are identical, obtain N; 398.5 grams of the two octadecanoyl hexamethylene diamine neopentanoic acids of N-, molar yield 64.8%.
(b) N, two octadecanoyl hexamethylene diamine neopentanoic acid two APEOs (n=5) of N-synthetic
With [embodiment 1] (b); difference is with the N of 398.5 grams (0.486 moles); the two octadecanoyl hexamethylene diamine neopentanoic acids of N-substitute 306.2 grams of (0.514 mole) N; the use amount of the two dodecanoyl ethylenediamine neopentanoic acids of N-, oxirane is 213.8g (4.86 moles); the use amount of the alkali compounds of calcium is 6.0 grams; obtain N, 507.6 grams of two octadecanoyl hexamethylene diamine neopentanoic acid two APEOs (n=5) of N-, molar yield 82.9%.
(c) N, two octadecanoyl hexamethylene diamine neopentanoic acid two APEOs (n=5) disulfonates of N-synthetic
By the N of step (b) synthesized; two octadecanoyl hexamethylene diamine neopentanoic acid two APEOs (n=5) of N-507.6 grams (0.403 mole) and 159.6 grams of (2.80 moles) potassium hydroxide, 392.5 grams of (2.00 moles) 3-chlorine-2-hydroxyl propanesulfonates, 26.1 grams of TBABs, 1800 milliliters of toluene are mixed in to be furnished with mechanical agitation, in the reactor of 5000 milliliters of thermometer and reflux condensing tube, to be heated to 110 ℃ of reactions 12 hours.Cooling, neutralization, divides and removes inorganic salts, the N that alkalizes to obtain, two octadecanoyl hexamethylene diamine neopentanoic acid two APEOs (n=5) disulfonates of N-, molar yield 70.6%.To synthetic N, two octadecanoyl hexamethylene diamine neopentanoic acid two APEOs (n=5) disulfonates of N-, application U.S. Nicolet-380FT-IR spectrometer, adopts liquid-film method to carry out infrared spectrum analysis (sweep limits 4000～400cm
-1), there is all characteristic absorption peaks of Fig. 1.
(d) by the synthetic N of step (c); two octadecanoyl hexamethylene diamine neopentanoic acid two APEOs (n=5) the disulfonate 0.2wt% of N-, above-mentioned modified polyacrylamide 0.15wt% and the marine block injected water of 96.5wt% Shengli Oil Field mix and blend 2 hours, obtain a kind of high efficiency anti-magnesium ions oil displacement agent of homogeneous transparent.In temperature 70 C, salinity, be 32000mg/L, Mg
2for 1200mg/L, Ca
2+in water for 400mg/L, the apparent viscosity that records this oil displacement agent is 14.5mPa.s; Between the marine block IFA-8 of this oil displacement agent and Shengli Oil Field well dewatered oil, form the ultralow interfacial tension of 0.0006mN/m.Apparent viscosity is by the BROODFIELD II type viscometer determining of U.S. Brookfield company, and the TX500 type rotation interfacial tensimeter that interfacial tension is produced by Texas ,Usa university is measured.
(e) first with salinity 32000mg/L, Mg
2for 1200mg/L, Ca
2+for the injected water of 400mg/L, by rock core, (length is 30 centimetres, and diameter is 2.5 centimetres, and permeability is 1.5 microns
2) saturated, the voids volume (PV) of measuring rock core is 52.7%, then with the marine block IFA-8 of Shengli Oil Field well dewatered oil, carry out saturated, under 70 ℃ of constant temperature, carry out imitation oil displacement experiment test: first water drive is to moisture 94%, record water drive and improve oil recovery factor 60.0%, after the synthetic oil displacement agent of metaideophone 0.3pv (rock pore volume) step (d), water drive, to moisture more than 98%, record on water drive basis and can improve oil recovery factor 16.3% again again.
[comparative example 1]
With [embodiment 1] (d); difference substitutes 0.2wt%N with the petroleum sodium sulfonate (Wuxi oil refinery) of 0.2wt%; two dodecanoyl ethylenediamine neopentanoic acid two APEOs (n=4) disulfonates of N-; all the other are identical; the apparent viscosity that records this oil displacement agent is 15.1mPa.s, forms the interfacial tension of 0.0483mN/m between the marine block IFA-8 of this oil displacement agent and Shengli Oil Field well dewatered oil.Apparent viscosity is by the BROODFIELD II type viscometer determining of U.S. Brookfield company, and the TX500 type rotation interfacial tensimeter that interfacial tension is produced by Texas ,Usa university is measured.
With [embodiment 1] (e), record water drive and improve oil recovery factor 59.5%, after the above-mentioned oil displacement agent of metaideophone, record on water drive basis and can improve again oil recovery factor 12.6%.
[comparative example 2]
With [embodiment 1] (d), difference be take the high molecular weight polyacrylamide (viscosity average molecular weigh is 1,500 ten thousand) of 0.15wt% and is substituted the above-mentioned ultra high molecular weight anion-type polyacrylamide (viscosity average molecular weigh is 2,300 ten thousand) of 0.15wt%, all the other are identical, the apparent viscosity that records this oil displacement agent is 12.3mPa.s, the interfacial tension of asking formation 0.0011mN/m of the marine block IFA-8 of said composition and Shengli Oil Field well dewatered oil.Apparent viscosity is by the BROODFIELD II type viscometer determining of U.S. Brookfield company, and the TX500 type rotation interfacial tensimeter that interfacial tension is produced by Texas ,Usa university is measured.
With [embodiment 1] (e), record water drive and improve oil recovery factor 59.2%, after the above-mentioned oil displacement agent of metaideophone, record on water drive basis and can improve again oil recovery factor 11.8%.
Claims (8)
1. a flooding method for high efficiency anti-magnesium ions, by oil displacement agent at 30～83 ℃ of displacement of reservoir oil temperature, total salinity > 8000 mg/litre, Mg
2+> 200 mg/litre, Ca
2+the MgCl of > 30 mg/litre
2under type injected water condition, underground dewatered oil is contacted with oil displacement agent, by the abundant displacement of the crude oil in rock core out, wherein said oil displacement agent comprises following component by percentage to the quality:
(1) 0.01～5.0% N, the two fatty acyl group diamines neopentanoic acid two APEO disulfonates of N-;
(2) 0.01～3.0% polymer;
(3) 92.0～99.98% injected water;
Wherein the general molecular formula of (1) component is:
In formula: R
1for C
9～C
17alkyl, R
2for C
2～C
6alkylidene, n is the adduction number of ethoxy group EO, its span is any one integer in 2～7; M is any one metal ion being selected from potassium, sodium or lithium; Polymer is selected from one or both in modified polyacrylamide or xanthans.
2. the flooding method of high efficiency anti-magnesium ions according to claim 1, is characterized in that described modified polyacrylamide is selected from ultra high molecular weight anion-type polyacrylamide or is formed by acrylamide, 2-acrylamide-2-methylpro panesulfonic acid, three kinds of monomer copolymerizations of 2-acrylamido dodecyl sodium sulfonate.
3. the flooding method of high efficiency anti-magnesium ions according to claim 1, is characterized in that described displacement of reservoir oil temperature is 40～80 ℃.
4. the flooding method of high efficiency anti-magnesium ions according to claim 1, is characterized in that the total salinity of described injected water is 10000～40000 mg/litre, Mg
2+be 300～1350 mg/litre, Ca
2+be 50～800 mg/litre, water type is MgCl
2type.
5. the flooding method of high efficiency anti-magnesium ions according to claim 2, is characterized in that described ultra high molecular weight anion-type polyacrylamide, and its viscosity average molecular weigh is 2,300 ten thousand; The modified polyacrylamide being formed by acrylamide, 2-acrylamide-2-methylpro panesulfonic acid, three kinds of monomer copolymerizations of 2-acrylamido dodecyl sodium sulfonate, its three kinds of monomer molar percentages are 80: 18: 2, its viscosity average molecular weigh is 15,000,000.
6. the flooding method of high efficiency anti-magnesium ions according to claim 1, is characterized in that described N, the R in the two fatty acyl group diamines neopentanoic acid two APEO disulfonates of N-
1carbon number is nine, 11,13,15 or 17.
7. the flooding method of high efficiency anti-magnesium ions according to claim 1, is characterized in that described N, the R in the two fatty acyl group diamines neopentanoic acid two APEO disulfonates of N-
2carbon number be two, four or six.
8. the flooding method of high efficiency anti-magnesium ions according to claim 1, is characterized in that described N, the R in the two fatty acyl group diamines neopentanoic acid two APEO disulfonates of N-
1carbon number adds ratio that 1 sum and EO adduction count n between 2～4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010261841.XA CN102373913B (en) | 2010-08-23 | 2010-08-23 | High-efficiency anti-magnesium ion oil displacement method |
Applications Claiming Priority (1)
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| CN104559987A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Amide polyoxyethylene ether sulfonate betaine surfactant |
| CN104559985B (en) * | 2013-10-28 | 2018-07-06 | 中国石油化工股份有限公司 | The displacement of reservoir oil is applied in poly- table pack object and its tertiary oil recovery |
| CN104559988B (en) * | 2013-10-28 | 2018-05-11 | 中国石油化工股份有限公司 | Beet alkali surface activator, preparation method and the application in intensified oil reduction |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4702319A (en) * | 1986-12-29 | 1987-10-27 | Exxon Research And Engineering Company | Enhanced oil recovery with hydrophobically associating polymers containing sulfonate functionality |
| CN101029224A (en) * | 2007-04-06 | 2007-09-05 | 山东大学 | Use of bi-alkyl carboxylate surface activator in triple oil recovery |
| CN101279934A (en) * | 2007-04-04 | 2008-10-08 | 中国石油化工股份有限公司 | Aliphatic acid polyethenoxy ether sulphonate and preparation thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4702319A (en) * | 1986-12-29 | 1987-10-27 | Exxon Research And Engineering Company | Enhanced oil recovery with hydrophobically associating polymers containing sulfonate functionality |
| CN101279934A (en) * | 2007-04-04 | 2008-10-08 | 中国石油化工股份有限公司 | Aliphatic acid polyethenoxy ether sulphonate and preparation thereof |
| CN101029224A (en) * | 2007-04-06 | 2007-09-05 | 山东大学 | Use of bi-alkyl carboxylate surface activator in triple oil recovery |
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