CN102220860B - Polymer-surfactant binary compound oil displacement method - Google Patents
Polymer-surfactant binary compound oil displacement method Download PDFInfo
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/588—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific polymers
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Abstract
The invention relates to a polymer-surfactant binary compound oil displacement method, which mainly solves the problems of low oil displacement efficiency and high using concentration of a surfactant-containing oil displacement agent under high temperature and high salt conditions in the prior art and the corrosion and scale deposition of a formation and an oil well due to alkali in alkali-surfactant-polymer compound flooding. By the polymer-surfactant binary compound oil displacement method, underground dehydrated crude oil is contacted with an oil displacement composition and crude oil in arock core is fully displaced under the conditions that the oil displacement temperature is more than or equal to 85 DEG C, the total mineralization of formation water is more than or equal to 16,000mg/L, and the total content of Ca<2+> and Mg<2+> in the formation water is more than or equal to 450mg/L, wherein the oil displacement composition comprises the following components in percentage by mass: (1) 0.01 to 5.0 percent of N,N-difatty acyl diamine dimethylpropanoic acid dipolyoxyethylene ether disulfonate, (2) 0.01 to 3.0 percent of polymer, and (3) 92.0 to 99.98 percent of formation water. Through the technical scheme, the problems are well 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 poly-table binary combination flooding method.
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 that faces has one, and imbalance between supply and demand is outstanding, and the oil demand amount is more large, 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, to satisfy human wants, must research and development improve petroleum recovery technology, tertiary oil recovery (EOR) can make oil recovery factor improve 6～20% by the intensified oil reduction measure again, even more.
Chemical flooding is an important method that improves recovery ratio.Surfactant flooding is considered to improve by a relatively large margin a kind of chemical agent of recovery ratio, applied widely, tool development prospect.No matter surfactant is as host or as the auxiliary agent displacement of reservoir oil, all plays immeasurable effect to increasing substantially recovery ratio.Polymer displacement of reservoir oil tech is a kind of method of important raising oil recovery, compares with general water drive, and polymer displacement of reservoir oil can accelerate oil recovery process, improves economic benefit, and Processes and apparatus is simple, cost is lower.As an important technology in the chemical flooding, the 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 the problems such as the fouling of producing well pit shaft is serious, Produced Liquid difficult treatment that the adding of alkali causes occurring in the field test are so that the application prospect of ASP Oil-Displacing Technology allows of no optimist.By contrast, do not use alkali in the binary combination flooding prescription that polymer and surfactant form, the mining site operability is stronger, thereby is subject to the approval in oil field.But because need not any alkali, crude oil PetroChina Company Limited. acids active material can not be fully used, so that research and development have novel surfactant and an alkali-free binary combination flooding prescription of high surface more is imperative.
The Surfactant 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 also are the surfactants of external tertiary oil recovery consumption maximum.Because sulfonate surfactant is anionic, it and the bivalent cation (Ca in the formation 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 be fit to high saliferous, high Ca in continual exploitation research abroad
2+, Mg
2+The surfactant that the ion stratum is used comprises the research of multi-functional surfactant, Gemini surface active agent and sacrifice agent, and pays attention to the composition research of various surfactants.
The 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 are designed in same surfactant molecule, make it have the advantage of anion and non-ionic surface active agent concurrently, have complementary advantages, function admirable, therefore shown good application prospect, especially the binary composite displacement system that exists for alkali-free, not only do not avoided the obstruction of oil reservoir owing to there being the existence 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 by two hydrophilic radicals, two hydrophobic groupings and is connected and connects a base key and close the special construction compound that forms, has more good performance than conventional surfactant, make it have ultralow interfacial tension, low critical micelle concentration, low Kraff point, good lime soap dispersing power, good a series of peculiar properties such as wettability, thereby cause great concern.Gemini surfactant with interface performance and rheological characteristic is expected to replace the alkali in the ternary composite driving prescription, under rational formula system, finally realizes binary displacement system, for the chemical flooding in oil field is opened up new approach.
In the patent application at beginning of the thirties late 1920s, Degroot (De Groot) just once proposed the recovery ratio that the water soluble surfactant active helps to improve oil.
At present, the main Gemini surface active agent of domestic research and development mainly is the cation double quaternary ammonium salt type, as Chinese patent CN 1528853, CN 1817431, CN 1066137 etc. reported in succession that the bisamide type is cationic, fluorine-containing cationic type and contain the pyridine radicals cation Gemini surfactant.The absorption loss is large because cation has, the high in cost of production shortcoming, the in recent years research and development of anionic and nonionic Gemini surface active agent have also obtained increasing attention, have reported the synthetic of the asymmetric Shuangzi of a kind of anion such as Chinese patent CN 101073757.And since anionic surfactant to have salt tolerance poor, and nonionic has the poor shortcoming of temperature tolerance, so that these products can't being applied at high temperature and high salt oil deposit.
In addition, in the existing ternary composite oil-displacing system, the alkali that contains high concentration, such as NaOH, sodium carbonate etc., in use, to bringing huge injury in stratum and oil well etc., employed surfactant is difficult for being biodegradable, and human body also there is certain harmfulness, as: 1991, Zhao Guoxi was at " surfactant physical chemistry " P495; 1994, disclosed content among Liu Chengzai " surfactant the is complete works of " P35.So for 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 ultralow interfacial tension, the displacing surfactant system of Effective Raise oil recovery factor.Of the present invention this in the alkali-free situation just, be suitable for the moon of high temperature and high salt oil deposit-non-Gemini surface active agent, its preparation method, binary is compound and the application in tertiary oil recovery.
Summary of the invention
Technical problem to be solved by this invention is that the oil displacement agent that contains surfactant in the prior art exists under the high temperature and high salt condition oil displacement efficiency poor, the corrosion that alkali brings stratum and oil well in the high and ternary composite driving of working concentration and the problem of incrustation injury provide a kind of new poly-table binary combination flooding method.The method will contain N; the two fatty acyl group diamines neopentanoic acid two polyoxy vinethene disulfonate surfactant compositions of N-are used for oil displacement process; have alkali-free, injure without corrosion and incrustation, working concentration is low, the high characteristics of oil displacement efficiency under the high temperature and high salt condition.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of poly-table binary combination flooding method, the composition that the displacement of reservoir oil is used in displacement of reservoir oil temperature 〉=85 ℃, total salinity 〉=16000mg/L, Ca
2++ Mg
2+Under the formation water condition of 〉=450mg/L, underground dewatered oil is contacted with displacement of reservoir oil composition, with the abundant displacement of the crude oil in the rock core out, wherein said displacement of reservoir oil composition comprises following component by percentage to the quality:
(1) 0.01～5.0% N, the two fatty acyl group diamines neopentanoic acid two polyoxy vinethene disulfonates of N-;
(2) 0.01～3.0% polymer;
(3) 92.0～99.98% formation 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, displacement of reservoir oil temperature is preferably 85～90 ℃; Described formation water total salinity is preferably 16000～32000mg/L, Ca
2++ Mg
2+Be preferably 450～890mg/L; Polymer is preferably from above-mentioned temperature-resistant anti-salt polymer; The 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 polyoxy vinethene disulfonates of N-
1Carbon number is preferably nine, 11,15 or 17, R
2Carbon number be preferably two, four or six.This flooding method specifically may further comprise the steps:
(a) N, the preparation of the two fatty acyl group diamines neopentanoic acids of N-:
Be 10～18 aliphatic acid, thionyl chloride and N with the carbochain number of required proportioning, 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 that obtains is the carbochain number
1In addition with the carbon number of required proportioning be 2～6 diamines, methyl methacrylate and solvent Isosorbide-5-Nitrae-dioxane mix all with after, 40～70 ℃ of reactions 2～5 hours, the reduce pressure unreacted raw material of removal and solvent got the diamines dimethylated methyl propionate
2, regulate PH=9～10 with the sodium hydroxide solution of 50wt%, drip under the vigorous stirring
1, in 40～70 ℃ of reactions 2～6 hours, getting N again, the two carbochain numbers of N-are 10～18 fatty acyl group diamines dimethylated methyl propionates
3, the ethanol of adding aequum is regulated PH=11～12 with the sodium hydroxide solution of 50wt%, and back flow reaction 2～6 hours gets N after the acidifying, and the two carbochain numbers of N-are 10～18 fatty acyl group diamines neopentanoic acids.Wherein, preparation
1The time, the carbochain number is that the mol ratio of 10～18 aliphatic acid, thionyl chloride and DMF is 1: 1.0～2.0: 0.03～0.1; Preparation
2The time, solvent is Isosorbide-5-Nitrae-dioxane, and consumption is that the carbochain number is 3～6 times of 2～6 diamines quality, and the carbochain number is that 2～6 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 acid, the ethanol consumption was that the carbochain number is 5～10 times of 2～6 diamines quality.
(b) N, the preparation of the two fatty acyl group diamines neopentanoic acid two polyoxy vinethenes of N-:
The N that step (a) is 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 the 0.80MPa gauge pressure condition; the alkali compounds of calcium is catalyzer; react to get N, the two carbochain numbers of N-are 10～18 fatty acyl group diamines neopentanoic acids, two polyoxy vinethenes.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 polyoxy vinethene disulfonates of N-:
The N that step (b) is synthesized; the two carbochain numbers of N-are that 10～18 fatty acyl group diamines neopentanoic acids, two polyoxy vinethenes 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; reacted 3～15 hours; reaction finishes to get N by post processing, the two fatty acyl group diamines neopentanoic acid two polyoxy vinethene disulfonates of N-.Wherein, N, the mol ratio that the two carbochain numbers of N-are 10～18 fatty acyl group diamines neopentanoic acids, two polyoxy vinethenes, 3-chlorine-2-hydroxyl propanesulfonate, potassium hydroxide or NaOH and TBAB=1: 2～6: 2～8: 0.05～0.3.
(d) with the N of aequum, the two fatty acyl group diamines neopentanoic acid two polyoxy vinethene disulfonates of N-, above-mentioned temperature-resistant anti-salt polymer and formation water evenly mix, and 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 vinethene disulfonates of N-, above-mentioned temperature-resistant anti-salt polymer and the proportioning of formation water are 0.01～5.0%: 0.01～3.0%: 92.0～99.98%.
(e) first take total salinity as 16000～40000mg/L, Ca
2++ Mg
2+The formation water that is 450～1000mg/L is saturated with rock core, measure the voids volume (PV) of rock core, then carry out saturated with dewatered oil, carry out the imitation oil displacement experiment test under 85～95 ℃ of temperature: first water drive is to moisture 92%, the synthetic displacement of reservoir oil of metaideophone 0.3pv (rock pore volume) step (d) with composition after, water drive is calculated the percentage that improves oil recovery factor to moisture 99%.
In the technique scheme, (a) prepare in the step
1The time, the carbochain number be the mol ratio of 10～18 aliphatic acid, thionyl chloride and DMF be preferably 1: 1.2～2.0: 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, reaction temperature is preferably 50～60 ℃, and the reaction time 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 reaction temperature is preferably 60～70 ℃, and the reaction time is preferably 3～4 hours; Preparation N, when the two carbochain numbers of N-were 10～18 fatty acyl group diamines neopentanoic acid, it was 6～8 times of 2～6 diamines quality that the ethanol consumption is preferably the 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 the step; the two carbochain numbers of N-be the mol ratio of 10～18 fatty acyl group diamines neopentanoic acids, two polyoxy vinethenes, 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 polyoxy vinethene disulfonates of N-is 0.03～1.0%, more preferably scope is 0.1～0.3%; Above-mentioned temperature-resistant anti-salt polymer volume preferable range is 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 85～90 ℃; The formation water total salinity is preferably 16000～32000mg/L, Ca
2++ Mg
2+Be preferably 450～890mg/L.
The N of the prepared displacement of reservoir oil of the present invention in the composition; the two fatty acyl group diamines neopentanoic acid two polyoxy vinethene disulfonates of N-; owing to containing simultaneously aerobic ethene non-ionic group and azochlorosulfonate acid anion group in its molecular structure; make the salt tolerant advantage of its heat resistance that has anion surfactant concurrently and non-ionic surface active agent; and symmetrical Shuangzi architectural feature; make it have critical micelle concentration again low; reduce the interfacial tension ability strong; the features such as the rheological characteristic of anti-high salinity and uniqueness and viscoplasticity-viscosifying action have more good performance than conventional surfactant.Do not contain aromatic ring structure in its molecule in addition, be easier to biodegradation, therefore less to the harm of human body and environment, be a kind of green surfactant that is suitable for the used for tertiary oil recovery of high temperature and high salt oil deposit.
Adopt poly-table binary combination flooding method of the present invention, under the alkali-free condition, can be used for 85～90 ℃ of formation temperatures, salinity is 16000～32000 mg/litre, Ca
2+, Mg
2+The Shengli Oil Field that is 450～890 mg/litre wins Tuo Er district's formation water and crude oil; take consumption as 0.1～0.3wt%N; the above-mentioned temperature-resistant anti-salt polymer of the two fatty acyl group diamines neopentanoic acid two polyoxy vinethene disulfonates of N-and 0.1～0.2wt% forms the above-mentioned composition oil displacement agent; measure the dynamic interface tension value between this oil displacement agent aqueous solution and the Shengli Oil Field victory Tuo Er district crude oil, can reach 10
-3～10
-4The ultralow 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 physical analogy displacement experiment Lab-evaluation at this oil displacement agent on high temperature, the high salinity reservoir, obtain preferably technique effect.
Description of drawings
Fig. 1 is N, the infrared spectrum of the two fatty acyl group diamines neopentanoic acid two polyoxy vinethene disulfonates of N-.
The N of the present invention's preparation; the two fatty acyl group diamines neopentanoic acid two polyoxy vinethene disulfonates of N-can characterize by the following method: after synthetic is purified; use U.S. Nicolet-380 FT-IR spectrometer, adopt liquid-film method to carry out infrared spectrum analysis (sweep limits 4000～400cm
-1), be 2850～2950cm in wave number
-1Methyl and the flexible characteristic peak of methylene C-H on the alkyl chain, 1475cm appear in the place
-1C-H flexural vibrations on the alkyl chain 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
-1To 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 upper C-O-C asymmetric stretch of EO bands of a spectrum cause owing to having 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 vinethene disulfonates of N-.
The present invention is further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
(a) N, the two dodecanoyl ethylenediamine neopentanoic acids of N-synthetic
With laurate 300 grams (1.5 moles), thionyl chloride 267.8 grams (2.25 moles) and 4.5 gram DMF, add and be furnished with in 1000 milliliters of four-hole boiling flasks of sealing machine stirring, thermometer, condensation pipe etc., in 90 ℃ the reaction 3 hours after, decompression steams excessive thionyl chloride, obtains lauroyl chloride.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, condensation pipe, 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 Isosorbide-5-Nitrae-dioxane are removed in decompression, and residue is the ethylenediamine dimethylated methyl propionate.With 50wt% NaOH conditioned reaction liquid PH=8～10; slowly drip lauroyl chloride under the vigorous stirring; constantly add simultaneously 50wt% NaOH with the PH that keeps reaction 8～10; continue reaction 3 hours in 60 ℃ after dripping off; get N, the two dodecanoyl ethylenediamine dimethylated methyl propionates of N-continue to add 270 gram ethanol in reaction bulb; transfer PH=11～12 with 50wt% NaOH again; refluxed 4 hours, cooling, filtration is desalted; pressure reducing and steaming ethanol; residue is neutralized to highly acid with hydrochloric acid, and branch vibration layer gets N; two dodecanoyl ethylenediamine neopentanoic acid 306.2 grams of N-, molar yield 68.5%.
(b) N, the two dodecanoyl ethylenediamine neopentanoic acid two polyoxy vinethenes (n=4) of N-synthetic
With the synthetic N of step (a); the alkali compounds of two dodecanoyl ethylenediamine 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 unit, mixing plant and gas distributor; when limit logical nitrogen limit heating is made 135 ℃; add 20 gram water, stirring reaction 1 hour.After removing moisture content, be cooled to 80 ℃, the sulfuric acid (20wt%) that slowly drips the catalyst neutralisation theoretical amount makes the compound oxidizing calcium alkoxylating catalyst reactant liquor system of high activity, high selectivity, system temperature is heated to 80～90 ℃, open vacuum system, dehydration is 2 hours under high vacuum, then uses nitrogen blowing 3～4 times, the system reaction temperature is transferred to 140 ℃ slowly pass into 181.1 gram (4.116 moles) oxirane, controlled pressure≤0.60MPa.Reaction is used the nitrogen blowing system after finishing, and neutralization after the cooling, dehydration get N, the two dodecanoyl ethylenediamine neopentanoic acid two polyoxy vinethenes (n=4) of N-428.3 grams, molar yield 87.9%.
(c) N, two dodecanoyl ethylenediamine neopentanoic acid two polyoxy vinethene (n=4) disulfonates of N-synthetic
The N that step (b) is synthesized; the two dodecanoyl ethylenediamine neopentanoic acid two polyoxy vinethenes (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-chlorine-2-hydroxyl propanesulfonates, 16.3 gram TBABs, 1500 milliliters of toluene are mixed in to be furnished with mechanical agitation, in 5000 milliliters the reactor 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 get, two dodecanoyl ethylenediamine neopentanoic acid two polyoxy vinethene (n=4) disulfonates of N-, molar yield 75.8%.To synthetic N, two dodecanoyl ethylenediamine neopentanoic acid two polyoxy vinethene (n=4) disulfonates of N-are used U.S. Nicolet-380FT-IR spectrometer, adopt liquid-film method to carry out infrared spectrum analysis (sweep limits 4000～400cm
-1), have all characteristic absorption peaks of Fig. 1.
(d) with the synthetic N of step (c); two dodecanoyl ethylenediamine neopentanoic acid two polyoxy vinethene (n=4) the disulfonate 0.15wt% of N-, above-mentioned temperature-resistant anti-salt polymer 0.15wt% and 97.0wt% Shengli Oil Field win Tuo Er district victory formation water mix and blend 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 ultralow 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.
(e) first with salinity 32000mg/L, Ca
2++ Mg
2+(length is 30 centimetres to the formation water of 890mg/L, and diameter is 2.5 centimetres, and permeability is 1.5 microns with rock core
2) saturated, the voids volume (PV) of measuring rock core is 51.3%, then winning Tuo Er district 0-141 well dewatered oil with Shengli Oil Field carries out saturated, carry out the imitation oil displacement experiment test under 85 ℃ of constant temperature: first water drive is to moisture 92%, record water drive and improve oil recovery factor 40.2%, again the synthetic displacement of reservoir oil of metaideophone 0.3pv (rock pore volume) step (d) with composition after, water drive records on the water drive basis and can improve oil recovery factor 15.8% again to moisture 99%.
[embodiment 2]
(a) N, the two dodecanoyl hexamethylene diamine neopentanoic acids of N-synthetic
With [embodiment 1] (a); difference substitutes 45.0 gram (0.75 mole) anhydrous ethylenediamines with the anhydrous hexamethylene diamine of 87.0 grams (0.75 mole), and all the other are identical, get N; two dodecanoyl hexamethylene diamine neopentanoic acid 328.6 grams of N-, molar yield 67.2%.
(b) N, the two dodecanoyl hexamethylene diamine neopentanoic acid two polyoxy vinethenes (n=3) of N-synthetic
With [embodiment 1] (b); difference is with the N of 328.6 grams (0.504 mole); the two dodecanoyl hexamethylene diamine neopentanoic acids of N-substitute 306.2 gram (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; get N, the two dodecanoyl hexamethylene diamine neopentanoic acid two polyoxy vinethenes (n=3) of N-409.5 grams, molar yield 88.2%.
(c) N, two dodecanoyl hexamethylene diamine neopentanoic acid two polyoxy vinethene (n=3) disulfonates of N-synthetic
The N that step (b) is synthesized; the two dodecanoyl hexamethylene diamine neopentanoic acid two polyoxy vinethenes (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-chlorine-2-hydroxyl propanesulfonates, 16.3 gram TBABs, 1500 milliliters of toluene are mixed in to be furnished with mechanical agitation, in 5000 milliliters the reactor 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 get, two dodecanoyl hexamethylene diamine neopentanoic acid two polyoxy vinethene (n=3) disulfonates of N-, molar yield 75.5%.To synthetic N, two dodecanoyl hexamethylene diamine neopentanoic acid two polyoxy vinethene (n=3) disulfonates of N-are used U.S. Nicolet-380 FT-IR spectrometer, adopt liquid-film method to carry out infrared spectrum analysis (sweep limits 4000～400cm
-1), have all characteristic absorption peaks of Fig. 1.
(d) with the synthetic N of step (c); two dodecanoyl hexamethylene diamine neopentanoic acid two polyoxy vinethene (n=3) the disulfonate 0.2wt% of N-, above-mentioned temperature-resistant anti-salt polymer 0.15wt% and 96.5wt% Shengli Oil Field win Tuo Er district victory formation water mix and blend 2 hours, obtain the composition that a kind of displacement of reservoir oil of homogeneous transparent is used.At 90 ℃ of temperature, salinity 24000mg/L, Ca
2++ Mg
2+In the water of 667mg/L, the apparent viscosity that records this composition is 15.1mPa.s; Said composition and Shengli Oil Field win the ultralow interfacial tension that forms 0.0021mN/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.
(e) first with salinity 24000mg/L, Ca
2++ Mg
2+(length is 30 centimetres to the formation water of 667mg/L, and diameter is 2.5 centimetres, and permeability is 1.5 microns with rock core
2) saturated, the voids volume (PV) of measuring rock core is 51.2%, then winning Tuo Er district 0-141 well dewatered oil with Shengli Oil Field carries out saturated, carry out the imitation oil displacement experiment test under 90 ℃ of constant temperature: first water drive is to moisture 92%, record water drive and improve oil recovery factor 39.8%, again the synthetic displacement of reservoir oil of metaideophone 0.3pv (rock pore volume) step (d) with composition after, water drive records on the water drive basis and can improve oil recovery factor 15.2% again to moisture 99%.
[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) laurate 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 vinethenes (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 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; get N, the two ten acyl group butanediamine neopentanoic acids of N-two polyoxy vinethenes (n=3) 371.6 grams, molar yield 89.5%.
(c) N, two ten acyl group butanediamine neopentanoic acids, two polyoxy vinethene (n=3) disulfonates of N-synthetic
The N that step (b) is synthesized; the two ten acyl group butanediamine neopentanoic acids of N-two polyoxy vinethenes (n=3) 371.6 grams (0.447 mole) and 100.3 gram (1.79 moles) potassium hydroxide, 263.3 gram (1.34 moles) 3-chlorine-2-hydroxyl propanesulfonates, 18.8 gram TBABs, 1500 milliliters of toluene are mixed in to be furnished with mechanical agitation, in 5000 milliliters the reactor 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 get, two ten acyl group butanediamine neopentanoic acids, two polyoxy vinethene (n=3) disulfonates of N-, molar yield 73.5%.To synthetic N, two ten acyl group butanediamine neopentanoic acids, two polyoxy vinethene (n=3) disulfonates of N-are used U.S. Nicolet-380 FT-IR spectrometer, adopt liquid-film method to carry out infrared spectrum analysis (sweep limits 4000～400cm
-1), have all characteristic absorption peaks of Fig. 1.
(d) with the synthetic N of step (c); two ten acyl group butanediamine neopentanoic acids, two polyoxy vinethene (n=3) the disulfonate 0.15wt% of N-, above-mentioned temperature-resistant anti-salt polymer 0.15wt% and 97.0wt% Shengli Oil Field win Tuo Er district victory formation water mix and blend 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 ultralow 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.
(e) first with salinity 32000mg/L, Ca
2++ Mg
2+(length is 30 centimetres to the water of 890mg/L, and diameter is 2.5 centimetres, and permeability is 1.5 microns with rock core
2) saturated, the voids volume (PV) of measuring rock core is 51.8%, then winning Tuo Er district 0-141 well dewatered oil with Shengli Oil Field carries out saturated, carry out the imitation oil displacement experiment test under 85 ℃ of constant temperature: first water drive is to moisture 92%, record water drive and improve oil recovery factor 40.1%, again the synthetic displacement of reservoir oil of metaideophone 0.3pv (rock pore volume) step (d) with composition after, water drive records on the water drive basis and can improve oil recovery factor 14.7% again to moisture 99%.
[embodiment 4]
(a) N, the two hexadecanoyl group ethylenediamine neopentanoic acids of N-synthetic
With palmitic acid 422.4 grams (1.65 moles), thionyl chloride 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, condensation pipe etc., in 80 ℃ the reaction 5 hours after, decompression steams excessive thionyl chloride, obtains palmitoyl 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, condensation pipe, 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 Isosorbide-5-Nitrae-dioxane are removed in decompression, and residue is the ethylenediamine dimethylated methyl propionate.With 50wt% NaOH conditioned reaction liquid PH=8～10; slowly drip lauroyl chloride under the vigorous stirring; constantly add simultaneously 50wt% NaOH with the PH that keeps reaction 8～10; continue reaction 4 hours in 70 ℃ after dripping off; get N, the two hexadecanoyl group ethylenediamine dimethylated methyl propionates of N-continue to add 360 gram ethanol in reaction bulb; transfer PH=11～12 with 50wt% NaOH again; refluxed 4 hours, cooling, filtration is desalted; pressure reducing and steaming ethanol; residue is neutralized to highly acid with hydrochloric acid, and branch vibration layer gets N; two hexadecanoyl group ethylenediamine neopentanoic acid 360.0 grams of N-, molar yield 67.8%.
(b) N, the two hexadecanoyl group ethylenediamine neopentanoic acid two polyoxy vinethenes (n=5) of N-synthetic
With [embodiment 1] (b); difference is with the N of 360.0 grams (0.508 mole); the two hexadecanoyl group ethylenediamine neopentanoic acids of N-substitute 306.2 gram (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; get N, the two hexadecanoyl group ethylenediamine neopentanoic acid two polyoxy vinethenes (n=5) of N-497.4 grams, molar yield 85.3%.
(c) N, two hexadecanoyl group ethylenediamine neopentanoic acid two polyoxy vinethene (n=5) disulfonates of N-synthetic
The N that step (b) is synthesized; the two hexadecanoyl group ethylenediamine neopentanoic acid two polyoxy vinethenes (n=5) of N-497.4 grams (0.433 mole) and 103.6 gram (2.60 moles) NaOH, 339.9 gram (1.73 moles) 3-chlorine-2-hydroxyl propanesulfonates, 17.3 gram TBABs, 1500 milliliters of toluene are mixed in to be furnished with mechanical agitation, in 5000 milliliters the reactor 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 get, two hexadecanoyl group ethylenediamine neopentanoic acid two polyoxy vinethene (n=5) disulfonates of N-, molar yield 72.9%.To synthetic N, two hexadecanoyl group ethylenediamine neopentanoic acid two polyoxy vinethene (n=5) disulfonates of N-are used U.S. Nicolet-380FT-IR spectrometer, adopt liquid-film method to carry out infrared spectrum analysis (sweep limits 4000～400cm
-1), have all characteristic absorption peaks of Fig. 1.
(d) with the synthetic N of step (c); two hexadecanoyl group ethylenediamine neopentanoic acid two polyoxy vinethene (n=5) the disulfonate 0.1wt% of N-, above-mentioned temperature-resistant anti-salt polymer 0.2wt% and 97.0wt% Shengli Oil Field win Tuo Er district victory formation water mix and blend 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 ultralow 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.
(e) first with salinity 16000mg/L, Ca
2++ Mg
2+(length is 30 centimetres to the formation water of 450mg/L, and diameter is 2.5 centimetres, and permeability is 1.5 microns with rock core
2) saturated, the voids volume (PV) of measuring rock core is 51.7%, then winning Tuo Er district 0-141 well dewatered oil with Shengli Oil Field carries out saturated, carry out the imitation oil displacement experiment test under 85 ℃ of constant temperature: first water drive is to moisture 92%, record water drive and improve oil recovery factor 40.5%, again the synthetic displacement of reservoir oil of metaideophone 0.3pv (rock pore volume) step (d) with composition after, water drive records on the water drive basis and can improve oil recovery factor 16.5% again to moisture 99%.
[embodiment 5]
(a) N, the two hexadecanoyl group 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 hexadecanoyl group butanediamine neopentanoic acid 362.7 grams of N-, molar yield 65.7%.
(b) N, the two hexadecanoyl group butanediamine neopentanoic acid two polyoxy vinethenes (n=4) of N-synthetic
With [embodiment 1] (b); difference is with the N of 362.7 grams (0.493 mole); the two hexadecanoyl group butanediamine neopentanoic acids of N-substitute 306.2 gram (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; get N, the two hexadecanoyl group butanediamine neopentanoic acid two polyoxy vinethenes (n=4) of N-456.5 grams, molar yield 85.1%.
(c) N, two hexadecanoyl group butanediamine neopentanoic acid two polyoxy vinethene (n=4) disulfonates of N-synthetic
The N that step (b) is synthesized; the two hexadecanoyl group butanediamine neopentanoic acid two polyoxy vinethenes (n=4) of N-456.5 grams (0.420 mole) and 102.9 gram (2.57 moles) NaOH, 290.5 gram (1.48 moles) 3-chlorine-2-hydroxyl propanesulfonates, 19.9 gram TBABs, 1600 milliliters of toluene are mixed in to be furnished with mechanical agitation, in 5000 milliliters the reactor 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 get, two hexadecanoyl group butanediamine neopentanoic acid two polyoxy vinethene (n=4) disulfonates of N-, molar yield 71.1%.To synthetic N, two hexadecanoyl group butanediamine neopentanoic acid two polyoxy vinethene (n=4) disulfonates of N-are used U.S. Nicolet-380FT-IR spectrometer, adopt liquid-film method to carry out infrared spectrum analysis (sweep limits 4000～400cm
-1), have all characteristic absorption peaks of Fig. 1.
(d) with the synthetic N of step (c); two hexadecanoyl group butanediamine neopentanoic acid two polyoxy vinethene (n=4) the disulfonate 0.25wt% of N-, above-mentioned temperature-resistant anti-salt polymer 0.15wt% and 96.5wt% Shengli Oil Field win Tuo Er district victory formation water mix and blend 2 hours, obtain the composition that a kind of displacement of reservoir oil of homogeneous transparent is used.At 90 ℃ of temperature, salinity 24000mg/L, Ca
2++ Mg
2+In the water of 667mg/L, the apparent viscosity that records this composition is 15.5mPa.s; Said composition and Shengli Oil Field win the ultralow interfacial tension that forms 0.0034mN/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.
(e) first with salinity 24000mg/L, Ca
2++ Mg
2+(length is 30 centimetres to the formation water of 667mg/L, and diameter is 2.5 centimetres, and permeability is 1.5 microns with rock core
2) saturated, the voids volume (PV) of measuring rock core is 51.6%, then winning Tuo Er district 0-141 well dewatered oil with Shengli Oil Field carries out saturated, carry out the imitation oil displacement experiment test under 90 ℃ of constant temperature: first water drive is to moisture 92%, record water drive and improve oil recovery factor 40.9%, again the synthetic displacement of reservoir oil of metaideophone 0.3pv (rock pore volume) step (d) with composition after, water drive records on the water drive basis and can improve oil recovery factor 14.1% again to moisture 99%.
[embodiment 6]
(a) N, the two octadecanoyl ethylenediamine neopentanoic acids of N-synthetic
With stearic acid 497 grams (1.75 moles), thionyl chloride 374.9 grams (3.15 moles) and 7.5 gram DMF, add and be furnished with in 1000 milliliters of four-hole boiling flasks of sealing machine stirring, thermometer, condensation pipe etc., in 95 ℃ the reaction 3 hours after, decompression steams excessive thionyl chloride, obtains stearyl 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, condensation pipe, 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 Isosorbide-5-Nitrae-dioxane are removed in decompression, and residue is the ethylenediamine dimethylated methyl propionate.With 50wt% NaOH conditioned reaction liquid PH=8～10; slowly drip lauroyl chloride under the vigorous stirring; constantly add simultaneously 50wt% NaOH with the PH that keeps reaction 8～10; continue reaction 3 hours in 70 ℃ after dripping off; get N, the two octadecanoyl ethylenediamine dimethylated methyl propionates of N-continue to add 315 gram ethanol in reaction bulb; transfer PH=11～12 with 50wt% NaOH again; refluxed 4 hours, cooling, filtration is desalted; pressure reducing and steaming ethanol; residue is neutralized to highly acid with hydrochloric acid, and branch vibration layer gets N; two octadecanoyl ethylenediamine neopentanoic acid 384.5 grams of N-, molar yield 67.1%.
(b) N, the two octadecanoyl ethylenediamine neopentanoic acid two polyoxy vinethenes (n=6) of N-synthetic
With [embodiment 1] (b); difference is with the N of 384.5 grams (0.503 mole); the two octadecanoyl ethylenediamine neopentanoic acids of N-substitute 306.2 gram (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; get N, the two octadecanoyl ethylenediamine neopentanoic acid two polyoxy vinethenes (n=6) of N-547.2 grams, molar yield 84.2%.
(c) N, two octadecanoyl ethylenediamine neopentanoic acid two polyoxy vinethene (n=6) disulfonates of N-synthetic
The N that step (b) is synthesized; the two octadecanoyl ethylenediamine neopentanoic acid two polyoxy vinethenes (n=6) of N-547.2 grams (0.424 mole) and 101.6 gram (2.54 moles) NaOH, 416.7 gram (2.12 moles) 3-chlorine-2-hydroxyl propanesulfonates, 26.9 gram TBABs, 1800 milliliters of toluene are mixed in to be furnished with mechanical agitation, in 5000 milliliters the reactor 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 get, two octadecanoyl ethylenediamine neopentanoic acid two polyoxy vinethene (n=6) disulfonates of N-, molar yield 72.3%.To synthetic N, two octadecanoyl ethylenediamine neopentanoic acid two polyoxy vinethene (n=6) disulfonates of N-are used U.S. Nicolet-380 FT-IR spectrometer, adopt liquid-film method to carry out infrared spectrum analysis (sweep limits 4000～400cm
-1), have all characteristic absorption peaks of Fig. 1.
(d) with the synthetic N of step (c); two octadecanoyl ethylenediamine neopentanoic acid two polyoxy vinethene (n=6) the disulfonate 0.2wt% of N-, above-mentioned temperature-resistant anti-salt polymer 0.1wt% and 97.0wt% Shengli Oil Field win Tuo Er district victory formation water mix and blend 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 ultralow 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.
(e) first with salinity 32000mg/L, Ca
2++ Mg
2+(length is 30 centimetres to the formation water of 890mg/L, and diameter is 2.5 centimetres, and permeability is 1.5 microns with rock core
2) saturated, the voids volume (PV) of measuring rock core is 52.1%, then winning Tuo Er district 0-141 well dewatered oil with Shengli Oil Field carries out saturated, carry out the imitation oil displacement experiment test under 85 ℃ of constant temperature: first water drive is to moisture 92%, record water drive and improve oil recovery factor 40.3%, again the synthetic displacement of reservoir oil of metaideophone 0.3pv (rock pore volume) step (d) with composition after, water drive records on the water drive basis and can improve oil recovery factor 15.2% again to moisture 99%.
[embodiment 7]
(a) N, the two octadecanoyl hexamethylene diamine neopentanoic acids of N-synthetic
With [embodiment 6] (a); difference substitutes anhydrous ethylenediamine 45.0 grams (0.75 mole) with the anhydrous hexamethylene diamine of 87.0 grams (0.75 mole), and all the other are identical, get N; two octadecanoyl hexamethylene diamine neopentanoic acid 398.5 grams of N-, molar yield 64.8%.
(b) N, the two octadecanoyl hexamethylene diamine neopentanoic acid two polyoxy vinethenes (n=5) of N-synthetic
With [embodiment 1] (b); difference is with the N of 398.5 grams (0.486 mole); the two octadecanoyl hexamethylene diamine neopentanoic acids of N-substitute 306.2 gram (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; get N, the two octadecanoyl hexamethylene diamine neopentanoic acid two polyoxy vinethenes (n=5) of N-507.6 grams, molar yield 82.9%.
(c) N, two octadecanoyl hexamethylene diamine neopentanoic acid two polyoxy vinethene (n=5) disulfonates of N-synthetic
The N that step (b) is synthesized; the two octadecanoyl hexamethylene diamine neopentanoic acid two polyoxy vinethenes (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-chlorine-2-hydroxyl propanesulfonates, 26.1 gram TBABs, 1800 milliliters of toluene are mixed in to be furnished with mechanical agitation, in 5000 milliliters the reactor 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 get, two octadecanoyl hexamethylene diamine neopentanoic acid two polyoxy vinethene (n=5) disulfonates of N-, molar yield 70.6%.To synthetic N, two octadecanoyl hexamethylene diamine neopentanoic acid two polyoxy vinethene (n=5) disulfonates of N-are used U.S. Nicolet-380FT-IR spectrometer, adopt liquid-film method to carry out infrared spectrum analysis (sweep limits 4000～400cm
-1), have all characteristic absorption peaks of Fig. 1.
(d) with the synthetic N of step (c); two octadecanoyl hexamethylene diamine neopentanoic acid two polyoxy vinethene (n=5) the disulfonate 0.15wt% of N-, above-mentioned temperature-resistant anti-salt polymer 0.15wt% and 97.0wt% Shengli Oil Field win Tuo Er district victory formation water mix and blend 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 ultralow 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.
(e) first with salinity 16000mg/L, Ca
2++ Mg
2+(length is 30 centimetres to the formation water of 450mg/L, and diameter is 2.5 centimetres, and permeability is 1.5 microns with rock core
2) saturated, the voids volume (PV) of measuring rock core is 52.0%, then winning Tuo Er district 0-141 well dewatered oil with Shengli Oil Field carries out saturated, carry out the imitation oil displacement experiment test under 85 ℃ of constant temperature: first water drive is to moisture 92%, record water drive and improve oil recovery factor 40.8%, again the synthetic displacement of reservoir oil of metaideophone 0.3pv (rock pore volume) step (d) with composition after, water drive records on the water drive basis and can improve oil recovery factor 15.9% again to moisture 99%.
[comparative example 1]
With [embodiment 1] (d); difference substitutes 0.15wt%N with the petroleum sodium sulfonate (Wuxi oil refinery) of 0.15wt%; two dodecanoyl ethylenediamine neopentanoic acid two polyoxy vinethene (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.
With [embodiment 1] (e), record water drive and improve oil recovery factor 40.2%, the above-mentioned displacement of reservoir oil of metaideophone with composition after, record on the water drive basis and can improve again oil recovery factor 10.3%.
[comparative example 2]
With [embodiment 1] (d), difference substitutes the above-mentioned temperature-resistant anti-salt polymer of 0.15wt% take the super high molecular weight polyacrylamide (viscosity average molecular weigh is as 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.
With [embodiment 1] (e), record water drive and improve oil recovery factor 40.3%, the above-mentioned displacement of reservoir oil of metaideophone with composition after, record on the water drive basis and can improve again oil recovery factor 9.1%.
Claims (7)
1. poly-table binary combination flooding method, the composition that the displacement of reservoir oil is used in displacement of reservoir oil temperature 〉=85 ℃, total salinity 〉=16000mg/L, Ca
2++ Mg
2+Under the formation water condition of 〉=450mg/L, underground dewatered oil is contacted with displacement of reservoir oil composition, with the abundant displacement of the crude oil in the rock core out, wherein said displacement of reservoir oil composition comprises following component by percentage to the quality:
(1) 0.01～5.0% N, the two fatty acyl group diamines neopentanoic acid two polyoxy vinethene disulfonates of N-;
(2) 0.01～3.0% polymer;
(3) 92.0～99.98% formation water;
Wherein the general molecular formula of (1) component is:
In the formula: R
1Be C
9～C
17Alkyl, R
2Be 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 that is selected from potassium, sodium or the lithium; Described polymer is selected from a kind of in super high molecular weight polyacrylamide, temperature-tolerant anti-salt polyacrylamide or the xanthans.
2. poly-table binary combination flooding method according to claim 1 is characterized in that described displacement of reservoir oil temperature is 85～95 ℃.
3. poly-table binary combination flooding method according to claim 1, the total salinity that it is characterized in that described formation water is 16000～40000mg/L, Ca
2++ Mg
2+Be 450～1000mg/L.
4. poly-table binary combination flooding method according to claim 1, it is characterized in that described temperature-resistant anti-salt polymer is formed by acrylamide, 2-acrylamide-2-methylpro panesulfonic acid, 2-acrylamido dodecyl sodium sulfonate and four kinds of monomer copolymerizations of pi-allyl oleyl ether, its molar percentage is 76: 18: 5: 1.
5. poly-table binary combination flooding method according to claim 1 is characterized in that described N, the R in the two fatty acyl group diamines neopentanoic acid two polyoxy vinethene disulfonates of N-
1Carbon number is nine, 11,13,15 or 17.
6. poly-table binary combination flooding method according to claim 1 is characterized in that described N, the R in the two fatty acyl group diamines neopentanoic acid two polyoxy vinethene disulfonates of N-
2Carbon number be two, four or six.
7. poly-table binary combination flooding method according to claim 1 is characterized in that described N, the R in the two fatty acyl group diamines neopentanoic acid two polyoxy vinethene disulfonates of N-
1Carbon number add 1 sum and the EO adduction is counted the ratio of n between 2～4.
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| CN103773348B (en) * | 2012-10-25 | 2016-02-10 | 中国石油化工股份有限公司 | Poly-table binary composite oil displacement agent and flooding method |
| CN106590569B (en) * | 2015-10-20 | 2019-12-10 | 中国石油化工股份有限公司 | Enhanced oil recovery method for improving recovery ratio |
| CN110791275B (en) * | 2019-11-18 | 2021-12-17 | 西安石油大学 | Salt-resistant oil displacement agent based on double-anion surfactant and preparation method thereof |
| CN111650090B (en) * | 2020-05-25 | 2021-06-01 | 中国石油大学(北京) | Polymer meter residual quantity determination method and device for compound flooding produced water |
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| GB930296A (en) * | 1959-10-01 | 1963-07-03 | Ruth A Walker | The preparation of acylamino compounds |
| 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 |
| CN101279938A (en) * | 2007-04-04 | 2008-10-08 | 中国石油化工股份有限公司 | Alkyl phenol sulfonic polyethenoxy ether sodium monosulfosuccinates and preparation thereof |
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| GB930296A (en) * | 1959-10-01 | 1963-07-03 | Ruth A Walker | The preparation of acylamino compounds |
| 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 |
| CN101279938A (en) * | 2007-04-04 | 2008-10-08 | 中国石油化工股份有限公司 | Alkyl phenol sulfonic polyethenoxy ether sodium monosulfosuccinates and preparation thereof |
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