CN102220859B - Oil flooding method for greatly improving recovery rate of crude oil - Google Patents

Oil flooding method for greatly improving recovery rate of crude oil Download PDF

Info

Publication number
CN102220859B
CN102220859B CN2010101471174A CN201010147117A CN102220859B CN 102220859 B CN102220859 B CN 102220859B CN 2010101471174 A CN2010101471174 A CN 2010101471174A CN 201010147117 A CN201010147117 A CN 201010147117A CN 102220859 B CN102220859 B CN 102220859B
Authority
CN
China
Prior art keywords
oil
edda
polyoxy
displacement
grams
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN2010101471174A
Other languages
Chinese (zh)
Other versions
CN102220859A (en
Inventor
沈之芹
沙鸥
李应成
李斌
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
Original Assignee
China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Petroleum and Chemical Corp, Sinopec Shanghai Research Institute of Petrochemical Technology filed Critical China Petroleum and Chemical Corp
Priority to CN2010101471174A priority Critical patent/CN102220859B/en
Publication of CN102220859A publication Critical patent/CN102220859A/en
Application granted granted Critical
Publication of CN102220859B publication Critical patent/CN102220859B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to an oil flooding method for greatly improving the recovery rate of crude oil, which mainly solves the problem of low oil flooding efficiency under the conditions of high temperature and high salt content, high use concentration and corrosion and scale depositing damage caused to the stratum and oil wells by alkali in ASP(alkali, surfactant and polymer) flooding of the oil flooding agent containing a surfactant in the prior art. The oil flooding method for greatly improving the recovery rate of crude oil comprises the following steps of: contacting underground dehydrated raw oil and an oil flooding combination under stratum water conditions that oil flooding temperature is higher than or equal to 85DEG C, the total mineralization is bigger than or equal to 16000mg/L, and Ca<2+>+Mg<2 is more than or equal to 450mg/L, and sufficiently displacing raw oil in a core, wherein the oil flooding combination comprises the following components in percents by mass: 0.01-5.0% of N,N-2-fatty acyl diamine 2 aceto- 2 polyoxyethylene ether bisulphonate, 0.01-3.0% of polymers and 92.0-99.98% of stratum water. The problem is better solved by the technical scheme, and the method can be used in the tertiary oil recovery production of oil fields.

Description

Increase substantially the flooding method of oil recovery factor
Technical field
The present invention relates to a kind of flooding method that increases substantially oil recovery factor.
Background technology
Along with The development in society and economy, people are to the continuous increase of oil demand amount and the minimizing of petroleum reserves, and oil is just becoming more and more valuable as non-renewable resource.The problem that faces has one, and imbalance between supply and demand is outstanding, and the oil demand amount is big more big more, and find is fewer and feweri; Two, also left in the exhausted oil reservoir have a substantial oil.Primary oil recovery (POR) but extraction 10～25% underground crude oil, secondary oil recovery (SOR) but extraction 15～25% underground crude oil, i.e. a primary oil recovery and secondary oil recovery extraction 25～50% underground crude oil.In order to guarantee oil supply steady in a long-term, satisfy human wants that must research and development improve petroleum recovery technology, tertiary oil recovery (EOR) can make oil recovery factor improve 6～20% again by the intensified oil reduction measure, even more.
Chemical flooding is an important method that improves recovery ratio.Surfactant flooding is considered to improve by a relatively large margin a kind of chemical agent of recovery ratio, applied widely, tool development prospect.No matter 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 quicken oil recovery process, improves economic benefit, and Processes and apparatus is simple, cost is lower.As an important technology in the chemical flooding, the ternary composite driving oil tech that polymer, surfactant and alkali form has carried out some field tests in China and foreign countries, has obtained good oil displacement efficiency.But problems such as the fouling of producing well pit shaft is serious, extraction liquid difficult treatment that the adding of alkali causes occurring in the field test make ternary composite oil-displacing The Application of Technology prospect allow of no optimist.By contrast, do not use alkali in the binary combination flooding prescription that polymer and surfactant form, the mining site operability is stronger, thereby is subjected to the approval in oil field.But because need not any alkali, crude oil PetroChina Company Limited. acids active material can not be fully used, so that research and development have the novel surfactant and an alkali-free binary combination flooding prescription of high surface more is imperative.
The surfactant industrialization product of external used for tertiary oil recovery mainly contains two big classes: the one, and petroleum sulfonate is main surfactant, the 2nd, alkylbenzenesulfonate is main surfactant, this two classes surfactant raw material is all taken from crude oil, raw material sources are wide, quantity is big, thereby also are the surfactants of external tertiary oil recovery consumption maximum.Because sulfonate surfactant is anionic, it and 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 continuing the suitable high saliferous of developmental research, high Ca abroad 2+, Mg 2+The surfactant that the ion stratum is used comprises the research of multi-functional surfactant, Gemini surface active agent and sacrifice agent, and pays attention to the composite research of various surfactants.
The 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 prospects for application, especially the binary combination flooding system that exists at alkali-free, not only do not avoided the obstruction of oil reservoir owing to there is the existence of alkali, problem such as fouling and corrosion, and can form ultralow interfacial tension with crude oil.In recent years, because Shuangzi (Gemini) surfactant is to be connected base key with one and to be closed the special construction compound that forms by two hydrophilic radicals, two hydrophobic groupings, has more good performance than conventional surfactant, make it have ultralow interfacial tension, low critical micelle concentration, low Kraff point, good lime soap dispersing power, good a series of peculiar properties such as wettability, thereby cause great concern.Gemini surfactant with interface performance and rheological characteristic is expected to replace the alkali in the ternary composite driving prescription, under rational formula system, finally realizes binary displacement system, for the chemical flooding in oil field is opened up new approach.
In the patent application at beginning of the thirties late 1920s, Degroot (De Groot) just once proposed the recovery ratio that the water soluble surfactant active helps to improve oil.
At present, the main Gemini surface active agent of domestic research and development mainly is the cation double quaternary ammonium salt type, has reported in succession that as Chinese patent CN 1528853, CN 1817431, CN 1066137 etc. the bisamide type is cationic, fluorine-containing cationic and contain the pyridine radicals cation Gemini surfactant.Shortcomings such as the absorption loss is big because cation has, cost height, the research and development of anionic and nonionic Gemini surface active agent have in recent years also obtained increasing attention, have reported the synthetic of the asymmetric Shuangzi of a kind of anion as Chinese patent CN 101073757.And since anionic surfactant to have salt tolerance poor, and nonionic has the shortcoming of temperature tolerance difference, makes that these products can't being applied at high temperature and high salt oil deposit.
In addition, in the existing ternary composite oil-displacing system, the alkali that contains high concentration, as NaOH, sodium carbonate etc., in use, to bringing huge injury in stratum and oil well etc., employed surfactant is difficult for by biodegradation, and human body also there is certain harmfulness, as: 1991, Zhao Guoxi was at " surfactant physical chemistry " P495; 1994, disclosed content among Liu Chengzai " surfactant complete works " P35.So at those harsh oil reservoirs, we ought to seek a kind of under alkali-free, high temperature (formation temperature is greater than 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 effectively improves the displacing surfactant system of oil recovery factor.Of the present invention this just under the alkali-free situation, be suitable for high temperature and high salt oil deposit the moon-non-Gemini surface active agent, its preparation method, binary is compound and the application in tertiary oil recovery.
Summary of the invention
Technical problem to be solved by this invention is that the oil 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 working concentration height and the ternary composite driving and the problem of incrustation injury provide a kind of flooding method that increases substantially oil recovery factor.This method will contain N, and the composition of the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy vinethene disulfonates of N-is used for oil displacement process, have alkali-free, not have corrosion and incrustation injury, and working concentration is low, characteristics such as oil displacement efficiency height under the high temperature and high salt condition.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of flooding method that increases substantially oil recovery factor, 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, the abundant displacement of the crude oil in the rock core is come out, wherein said displacement of reservoir oil composition comprises following component by percentage to the quality:
(1) 0.01～5.0% N, the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy vinethene disulfonates of N-;
(2) 0.01～3.0% polymer;
(3) 92.0～99.98% formation water;
Wherein the general molecular formula of (1) component is:
Figure GSA00000089854200031
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 to have best hydrophilic lipophilic balance at 3～4 o'clock that carbon number adds ratio preferable range that 1 sum and EO count n, and its aqueous solution can form 10 with crude oil -3～10 -4Ultralow interfacial tension; N, the R in the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy vinethene disulfonates of N- 1Carbon number is preferably nine, 11,15 or 17, R 2Carbon number be preferably two, four or six.
This flooding method specifically may further comprise the steps:
(a) N, the preparation of N-two fatty acyl diamines:
With the carbochain number of required proportioning 10～18 aliphatic acid, thionyl chloride and N, dinethylformamide (DMF) was 70～100 ℃ of reactions 2～5 hours, excessive thionyl chloride is extracted in decompression out, it is 10～18 fat acyl chloride that the transparency liquid that obtains is the carbochain number, after adding the carbochain number and be the dilution with toluene of 10～18 aliphatic acid quality 1/2nd, be warming up to 60～90 ℃, 's 2～6 diamines by required proportioning with the carbochain number, pyridine and consumption are that the carbochain number is that slowly to splash into the carbochain number after the toluene of 10～18 aliphatic acid quality 1/2nd mixes be in 10～18 the fat acyl chloride solution, reacted 2～5 hours, and obtained the white powder solid chemical compound through post processing.Wherein, the carbochain number is 10～18 aliphatic acid, thionyl chloride and N, the mol ratio of dinethylformamide is 1: 1.0～2.0: 0.03～0.1, and the carbochain number is that 10～18 fat acyl chloride, carbochain number are that 2～6 the diamines and the mol ratio of pyridine are 2.0～4.0: 1: 1.5～3.5.
(b) N, the preparation of the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA)s of N-:
The N that step (a) is synthesized, the two carbochain numbers of N-be 10～18 fatty acyl diamines by required proportioning and NaOH or potassium hydroxide TBAB catalyst mix after, to add N, after the oxolane dilution that the two carbochain numbers of N-are 10～18 fatty acyl diamines quality 1/2nd, be heated to back flow reaction 2～8 hours, the sodium chloroacetate that adds required proportioning again continued back flow reaction 6～14 hours, got the white powder solid through post processing.Wherein, N, the two carbochain numbers of N-are mol ratio=1: 2～9: 3～9: 0.02～0.07 of 10～18 fatty acyl diamines, sodium chloroacetate, NaOH (potassium hydroxide) and TBAB.
(c) N, the preparation of the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy vinethenes of N-:
The N that step (b) is synthesized; the two carbochain numbers of N-are that 10～18 fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA)s and oxirane are 85～160 ℃ by required proportioning in reaction temperature; pressure is less than under the 0.80MPa gauge pressure condition; the alkali compounds of calcium is a catalyzer; react N, the two carbochain numbers of N-are 10～18 fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA)s, two polyoxy vinethenes.Wherein, N, the two carbochain numbers of N-are that 10～18 fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA)s and oxirane mol ratio are 1: 4～14, and catalyst amount is N, and the two carbochain numbers of N-are 0.5～5.0% of 10～18 fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) quality.
(d) dichloro-N, the preparation of the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy vinethenes of N-:
The N that step (c) is synthesized; the two carbochain numbers of N-be 10～18 fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA)s, two polyoxy vinethenes, thionyl chloride, pyridine by required proportioning 70～100 ℃ of reactions 3～10 hours; excessive thionyl chloride is extracted in decompression out; in and layering remove inorganic salts; vacuum drying gets dichloro-N, and the two carbochain numbers of N-are 10～18 fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA)s, two polyoxy vinethenes.Wherein, N, the mol ratio that the two carbochain numbers of N-are 10～18 fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA)s, two polyoxy vinethenes, thionyl chloride and pyridine is 1: 2.0～6.0: 1.0～5.0.
(e) N, the preparation of the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy vinethene disulfonates of N-:
The dichloro-N that step (d) is synthesized; the two N of N-; the two carbochain numbers of N-are that 10～18 fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA)s, two polyoxy vinethenes place reactor; the mixture and the water that add solvent ethylene glycol, sulfonating agent sodium sulfite or the sodium sulfite and the sodium hydrogensulfite of required proportioning; reacted 3～9 hours down at 90～150 ℃; get thick product N through post processing again, the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) APEO disulfonates of N-.Wherein, sulfonated reagent is the mixture of sodium sulfite or sodium sulfite and sodium hydrogensulfite; dichloro-N; the two N of N-; the mol ratio that the two carbochain numbers of N-are 10～18 fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA)s, two polyoxy vinethenes and sulfonated reagent is 1: 2.5～5.0; the ethylene glycol consumption is 8～16% of a reactant quality, and water consumption is 10～40% of a reactant quality.
(f) with the N of aequum, the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy vinethene disulfonates of N-, above-mentioned 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 ethylenediamine-N,N'-diacetic acid (EDDA) 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%.
(g) be 16000～40000mg/L, Ca with total salinity earlier 2++ Mg 2+The formation water that is 450～1000mg/L is saturated with rock core, measure the voids volume (PV) of rock core, carry out saturated with dewatered oil then, carry out the imitation oil displacement experiment test under 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 (f) with composition after, water drive is calculated the percentage that improves oil recovery factor to moisture 99%.
In the technique scheme, (a) the carbochain number is 10～18 aliphatic acid, thionyl chloride and N in the step, the mol ratio of dinethylformamide is preferably 1: 1.2～and 2.0: 0.05～0.1, the carbochain number is that 10～18 fat acyl chloride, carbochain number are that 2～6 the diamines and the mol ratio of pyridine are preferably 2.5～3.5: 1: 2～3.The reaction temperature of preparation acyl chlorides is preferably 80～95 ℃, and the reaction temperature of preparation acid amides is preferably 70～90 ℃.(b) N in the step, the two carbochain numbers of N-be the mol ratio of 10～18 fatty acyl diamines, sodium chloroacetate, NaOH (potassium hydroxide) and TBAB be preferably 1: 3～8: 4～8: 0.03～0.06.(c) N, the two carbochain numbers of N-be 10～18 fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA)s and oxirane mol ratio be preferably 1: 6～12, catalyst amount is N, N-pair of carbochain numbers are 1.0～3.0% of 10～18 fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) quality.(d) N in the step, the two carbochain numbers of N-be the mol ratio of 10～18 fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA)s, two polyoxy vinethenes, thionyl chloride and pyridine be preferably 1: 3.0～4.5: 2.0～4.0, reaction temperature is preferably 75～90 ℃, the reaction time is preferably 4～8 hours.(e) dichloro-N; the two carbochain numbers of N-be the mol ratio of 10～18 fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA)s, two polyoxy vinethenes and sulfonated reagent be preferably 1: 3～4.5; the ethylene glycol consumption is preferably 10～14% of reactant quality; water consumption is preferably 15～30% of reactant quality; reaction temperature is preferably 110～140 ℃, and the reaction time is preferably 4～8 hours.(f) by percentage to the quality, N, the consumption preferable range of the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy vinethene disulfonates of N-is 0.03～1.0%, more preferably scope is 0.1～0.3%; Above-mentioned 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.(g) 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 ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy vinethene disulfonates of N-; owing to contain aerobic ethene non-ionic group and azochlorosulfonate acid anion group simultaneously in its molecular structure; make the salt tolerant advantage of its heat resistance that has anion surfactant concurrently and non-ionic surface active agent; and the Shuangzi architectural feature of symmetry; it is low to make it have critical micelle concentration again; it is strong to reduce the interfacial tension ability; features such as anti-high salinity and particular rheological properties and viscoplasticity-viscosifying action have more good performance than conventional surfactant.Do not contain aromatic ring structure in its molecule in addition, be easier to biodegradation, therefore less to the harm of human body and environment, be a kind of green surfactant that is suitable for the used for tertiary oil recovery of high temperature and high salt oil deposit.
Adopt the flooding method that increases substantially oil recovery factor 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; with consumption is 0.1～0.3wt%N; the above-mentioned temperature-resistant anti-salt polymer of the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy vinethene disulfonates of N-and 0.1～0.2wt% forms the above-mentioned composition oil displacement agent; measure the dynamic interface tension value between 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 15.8% by (water drive improves oil recovery factor and reaches 40.8%) raising oil recovery factor through the indoor evaluation of physical analogy displacement experiment at this oil displacement agent on high temperature, the high salinity reservoir, obtain better technical effect.
Description of drawings
Fig. 1 is N, the infared spectrum of the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy vinethene disulfonates of N-.
The N of the present invention's preparation; the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy vinethene disulfonates of N-can characterize by the following method: after synthetic is purified; use U.S. Nicolet-380 FT-IR spectrometer, adopt liquid-film method to carry out infrared spectrum analysis (sweep limits 4000～400cm -1), as shown in Figure 1, be 2953cm in wave number -1, 2919cm -1, 2850cm -1Methyl and the flexible characteristic peak of methylene C-H on the alkyl chain, 1475cm appear in the place -1C-H flexural vibrations on the alkyl chain, 1634cm -1Locating strong peak is the I key band vC=O of acid amides, 1418cm -1The peak is the III key band C-N stretching, extension of acid amides in the place, 1106cm -1Locate a broad peak, this peak is that the last C-O-C asymmetric stretch of EO bands of a spectrum cause 1350cm owing to connected EO -1About the peak also to some extent broadening with grow tall, the characteristic peak of sulfonate, the symmetrical stretching vibration of S=O is at 1155cm -1About, antisymmetric stretching vibration is at 1345cm -1About, so 1116cm -1The peak at place is owing to C-O-C asymmetric stretch bands of a spectrum stack on the symmetrical stretching vibration of S=O and the EO causes 1350cm -1About the peak be because the antisymmetric stretching vibration of S=O and the vibration of skeleton carbon cause, and proved response has generated N really thus, the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy vinethene disulfonates of N-.
The present invention is further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
(a) two 12 (bay) acyl group ethylenediamine is synthetic
With laurate 300 grams (1.5 moles), thionyl chloride 267.8 grams (2.25 moles) and 4.5 gram DMF, add and be furnished with in 2000 milliliters of four-hole boiling flasks of sealing machine stirring, thermometer, condensation pipe etc., after 3 hours, decompression steams excessive thionyl chloride, obtains lauroyl chloride in 90 ℃ of reactions.When temperature is reduced to 60 ℃, add dry toluene 150 grams, after stirring, slowly drip the mixed liquor of forming by anhydrous ethylenediamine 30.0 grams (0.5 mole), anhydrous pyridine 99.0 grams (1.25 moles) and dry toluene 150 grams, the control temperature drips off and is warming up to 85 ℃ of reactions 2 hours less than 60 ℃.Cooling is filtered, and crude product gets white powder solid, molar yield 97.1% with ethyl alcohol recrystallization after the vacuum drying.
(b) N, the two dodecanoyl EDDAs of N-synthetic
Bimonthly osmanthus acyl group ethylenediamine 200 grams (0.47 mole) that step (a) is synthetic, 400 gram oxolanes, 112.8 gram (2.82 moles) NaOH and 7.5 gram TBABs; add and be furnished with in 2000 milliliters the there-necked flask of mechanical agitation, thermometer and reflux condensing tube, be heated to the backflow quaternization 4 hours.Slightly the cooling back is divided and is added the sodium chloroacetate solid that total amount is 219.0 grams (1.88 moles) for five times, keeps back flow reaction 10 hours.Cooling is neutralized to reactant liquor with hydrochloric acid and is highly acid, is cooled to room temperature, suction filtration, and to neutral, vacuum drying gets white powder solid 165.0 grams, molar yield 65.0% with distilled water washing solid.
(c) N, the two dodecanoyl EDDA two polyoxy vinethenes (n=4) of N-synthetic
With the synthetic N of step (b); the alkali compounds of two dodecanoyl EDDA 165.0 grams (0.305 mole) of N-, 2.0 gram calcium adds to be furnished with in the high-pressure reactor of condensing unit, mixing plant and gas distributor; when limit logical nitrogen limit heating is made 135 ℃; add 20 gram water, stirring reaction 1 hour.After removing moisture content, be cooled to 80 ℃, the sulfuric acid (20wt%) that slowly drips the catalyst neutralisation theoretical amount makes the compound oxidizing calcium alkoxylating catalyst reactant liquor system of high activity, high selectivity, system temperature is heated to 80～90 ℃, open vacuum system, dehydration is 2 hours under high vacuum, purges 3～4 times with nitrogen then, the system reaction temperature is transferred to 140 ℃ slowly feed 107.6 gram (2.444 moles) oxirane, controlled pressure≤0.60MPa.After the reaction end, purge system with nitrogen, the neutralization of cooling back, dehydration get N, the two dodecanoyl EDDA two polyoxy vinethenes (n=4) of N-268.5 grams, molar yield 98.5%.
(d) dichloro-N, the two dodecanoyl EDDA two polyoxy vinethenes (n=4) of N-synthetic
The N that step (c) is synthesized; the two dodecanoyl EDDA two polyoxy vinethenes (n=4) of N-268.5 grams (0.30 mole); 50.4 gram (0.63 mole) pyridine places backflow is housed; stir; in 1000 milliliters of there-necked flasks of gas absorbing device; under agitation slowly thionyl chloride 125.0 restrains (1.05 moles); 85 ℃ of reactions 6 hours; reaction finishes the excessive thionyl chloride of back pressure reducing and steaming; the residue cooling; standing demix; the upper strata is neutralized to neutrality with 15% sodium hydroxide solution; divide and remove inorganic salts; organic layer washes with water 5～6 times again; vacuum drying gets dichloro-N; the two dodecanoyl EDDA two polyoxy vinethenes (n=4) of N-243.9 grams, molar yield 87.5%.
(e) N, two dodecanoyl EDDA two polyoxy vinethene (n=4) disulfonates of N-synthetic
The dichloro-N that step (d) is synthesized; the two dodecanoyl EDDA two polyoxy vinethenes (n=4) of N-243.9 grams (0.263 mole) place autoclave; add 60 gram ethylene glycol, 80 gram water, 81.6 gram sodium sulfites (0.79 mole) and 16.6 gram sodium hydrogensulfites (0.132 mole); reaction is 6 hours under 130 ℃ of temperature; reaction finishes the back decompression distillation and boils off most of moisture; add an amount of isopropyl alcohol standing over night in the mixture; the inorganic salts that filtering is precipitated out add the further filtering inorganic salts of an amount of carrene again.Solvent is removed in decompression, gets N, two dodecanoyl EDDA two polyoxy vinethene (n=4) disulfonates of N-, and the product quality mark is 90.2%.To synthetic N, two dodecanoyl EDDA two polyoxy vinethene (n=4) disulfonates of N-are used U.S. Nicolet-380 FT-IR spectrometer, adopt liquid-film method to carry out infrared spectrum analysis (sweep limits 4000～400cm -1), have all characteristic absorption peaks of Fig. 1.
(f) with the synthetic N of step (e); two dodecanoyl EDDA two polyoxy vinethene (n=4) the disulfonate 0.15wt% of N-, above-mentioned temperature-resistant anti-salt polymer 0.15wt% and 97.0wt% Shengli Oil Field win Tuo Er district and win formation water and mix stirring 2 hours, obtain the composition that a kind of displacement of reservoir oil of homogeneous transparent is used.At 85 ℃ of temperature, salinity 32000mg/L, Ca 2++ Mg 2+In the water of 890mg/L, the apparent viscosity that records this composition is 15.5mPa.s; Said composition and Shengli Oil Field win the ultralow interfacial tension that forms 0.0008mN/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.
(g) earlier 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%, winning Tuo Er district 0-141 well dewatered oil with Shengli Oil Field then 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 (f) with composition after, water drive records on the water drive basis and can improve oil recovery factor 15.2% again to moisture 99%.
[embodiment 2]
(a) two 12 (bay) acyl group hexamethylene diamine is synthetic
With [embodiment 1] (a), difference substitutes 30.0 gram (0.5 mole) anhydrous ethylenediamines with the anhydrous hexamethylene diamine of 58.0 grams (0.5 mole), and all the other are identical, get white powder solid, molar yield 95.6% after the vacuum drying.
(b) N, the two dodecanoyl hexamethylene diamine oxalic acid of N-synthetic
Bimonthly osmanthus acyl group hexamethylene diamine 225.6 grams (0.47 mole) that step (a) is synthetic, 450 gram oxolanes, 105.3 gram (1.88 moles) potassium hydroxide and 4.5 gram TBABs; add and be furnished with in 2000 milliliters the there-necked flask of mechanical agitation, thermometer and reflux condensing tube, be heated to the backflow quaternization 3 hours.Slightly the cooling back is divided and is added the sodium chloroacetate solid that total amount is 164.3 grams (1.41 moles) for five times, keeps back flow reaction 9 hours.Cooling is neutralized to reactant liquor with hydrochloric acid and is highly acid, is cooled to room temperature, suction filtration, and to neutral, vacuum drying gets white powder solid 171.4 grams, molar yield 61.2% with distilled water washing solid.
(c) N, the two dodecanoyl hexamethylene diamine oxalic acid two polyoxy vinethenes (n=3) of N-synthetic
With [embodiment 1] (c); difference is with the N of 171.4 grams (0.288 mole); the two dodecanoyl hexamethylene diamine oxalic acid of N-substitute 165.0 gram (0.305 mole) N; the use amount of the two dodecanoyl EDDAs of N-, oxirane is 76.0g (1.728 moles); the use amount of the alkali compounds of calcium is 4.3 grams; get N, the two dodecanoyl hexamethylene diamine oxalic acid two polyoxy vinethenes (n=3) of N-240.7 grams, molar yield 97.2%.
(d) dichloro-N, the two dodecanoyl hexamethylene diamine oxalic acid two polyoxy vinethenes (n=3) of N-synthetic
The N that step (c) is synthesized; the two dodecanoyl hexamethylene diamine oxalic acid two polyoxy vinethenes (n=3) of N-240.7 grams (0.28 mole), 66.9 gram (0.84 mole) pyridines place in 1000 milliliters of there-necked flasks that backflow, stirring, gas absorbing device are housed; under agitation slowly thionyl chloride 133.4 restrains (1.12 moles); all the other operations with [embodiment 1] (d); vacuum drying gets dichloro-N; the two dodecanoyl hexamethylene diamine oxalic acid two polyoxy vinethenes (n=3) of N-218.5 grams, molar yield 87.0%.
(e) N, two dodecanoyl hexamethylene diamine oxalic acid two polyoxy vinethene (n=3) disulfonates of N-synthetic
The dichloro-N that step (d) is synthesized; the two dodecanoyl hexamethylene diamine oxalic acid two polyoxy vinethenes (n=3) of N-218.5 grams (0.24 mole) place autoclave; add 60 gram ethylene glycol, 100 gram water, 65.2 gram sodium sulfites (0.63 mole) and 13.2 gram sodium hydrogensulfites (0.10 mole); reaction is 8 hours under 110 ℃ of temperature; all the other operations with [embodiment 1] (e); get N; two dodecanoyl hexamethylene diamine oxalic acid two polyoxy vinethene (n=3) disulfonates of N-, the product quality mark is 90.0%.To synthetic N, two dodecanoyl hexamethylene diamine oxalic acid two polyoxy vinethene (n=3) disulfonates of N-are used U.S. Nicolet-380FT-IR spectrometer, adopt liquid-film method to carry out infrared spectrum analysis (sweep limits 4000～400cm -1), have all characteristic absorption peaks of Fig. 1.
(f) with the synthetic N of step (e); two dodecanoyl hexamethylene diamine oxalic acid two polyoxy vinethene (n=3) the disulfonate 0.2wt% of N-, above-mentioned temperature-resistant anti-salt polymer 0.15wt% and 96.5wt% Shengli Oil Field win Tuo Er district and win formation water and mix stirring 2.5 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 15.3mPa.s; Said composition and Shengli Oil Field win the ultralow interfacial tension that forms 0.0063mN/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.
(g) earlier 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 51.0%, winning Tuo Er district 0-141 well dewatered oil with Shengli Oil Field then 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 40.6%, again the synthetic displacement of reservoir oil of metaideophone 0.3pv (rock pore volume) step (f) with composition after, water drive records on the water drive basis and can improve oil recovery factor 15.0% again to moisture 99%.
[embodiment 3]
(a) two ten (last of the ten Heavenly stems) acyl group butanediamine is synthetic
With [embodiment 1] (a), difference substitutes 300.0 gram (1.5 moles) laurate with the capric acid of 261.0 grams (1.5 moles), anhydrous butanediamine with 44.0 grams (0.5 mole) substitutes 30.0 gram (0.5 mole) anhydrous ethylenediamines, all the other are identical, get white powder solid, molar yield 96.7% after the vacuum drying.
(b) N, the two ten acyl group butanediamine oxalic acid of N-synthetic
Two capryl butanediamine 186.1 grams (0.47 mole) that step (a) is synthetic, 400 gram oxolanes, 112.8 gram (2.82 moles) NaOH and 7.5 gram TBABs; add and be furnished with in 2000 milliliters the there-necked flask of mechanical agitation, thermometer and reflux condensing tube, be heated to the backflow quaternization 3 hours.Slightly the cooling back is divided and is added the sodium chloroacetate solid that total amount is 219.0 grams (1.88 moles) for five times, keeps back flow reaction 12 hours.Cooling is neutralized to reactant liquor with hydrochloric acid and is highly acid, is cooled to room temperature, suction filtration, and to neutral, vacuum drying gets white powder solid 152.5 grams, molar yield 63.4% with distilled water washing solid.
(c) N, two ten acyl group butanediamine oxalic acid, the two polyoxy vinethenes (n=3) of N-synthetic
With [embodiment 1] (c); difference is with the N of 152.5 grams (0.298 mole); the two ten acyl group butanediamine oxalic acid of N-substitute 165.0 gram (0.305 mole) N; the use amount of the two dodecanoyl EDDAs of N-, oxirane is 78.6g (1.788 moles); the use amount of the alkali compounds of calcium is 3.8 grams; get N, the two ten acyl group butanediamine oxalic acid of N-two polyoxy vinethenes (n=3) 225.5 grams, molar yield 97.5%.
(d) dichloro-N, two ten acyl group butanediamine oxalic acid, the two polyoxy vinethenes (n=3) of N-synthetic
The N that step (c) is synthesized; the two ten acyl group butanediamine oxalic acid of N-two polyoxy vinethenes (n=3) 225.5 grams (0.29 mole), 69.3 gram (0.87 mole) pyridines place in 1000 milliliters of there-necked flasks that backflow, stirring, gas absorbing device are housed; under agitation slowly thionyl chloride 138.2 restrains (1.16 moles); all the other operations with [embodiment 1] (d); vacuum drying gets dichloro-N; the two ten acyl group butanediamine oxalic acid of N-two polyoxy vinethenes (n=3) 209.1 grams, molar yield 88.7%.
(e) N, two ten acyl group butanediamine oxalic acid, two polyoxy vinethene (n=3) disulfonates of N-synthetic
The dichloro-N that step (d) is synthesized; the two ten acyl group butanediamine oxalic acid of N-two polyoxy vinethenes (n=3) 209.1 grams (0.26 mole) place autoclave; add 60 gram ethylene glycol, 90 gram water, 70.6 gram sodium sulfites (0.68 mole) and 14.3 gram sodium hydrogensulfites (0.11 mole); reaction is 7 hours under 120 ℃ of temperature; all the other operations with [embodiment 1] (e); get N; two ten acyl group butanediamine oxalic acid, two polyoxy vinethene (n=3) disulfonates of N-, the product quality mark is 91.2%.To synthetic N, two ten acyl group butanediamine oxalic acid, two polyoxy vinethene (n=3) disulfonates of N-are used U.S. Nicolet-380FT-IR spectrometer, adopt liquid-film method to carry out infrared spectrum analysis (sweep limits 4000～400cm -1), have all characteristic absorption peaks of Fig. 1.
(f) with the synthetic N of step (e); two ten acyl group butanediamine oxalic acid, two polyoxy vinethene (n=3) the disulfonate 0.15wt% of N-, above-mentioned temperature-resistant anti-salt polymer 0.15wt% and 97.0% Shengli Oil Field win Tuo Er district and win formation water and mix stirring 2.5 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 14.9mPa.s; Said composition and Shengli Oil Field win the ultralow interfacial tension that forms 0.0038mN/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.
(g) earlier 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 51.2%, winning Tuo Er district 0-141 well dewatered oil with Shengli Oil Field then 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 (f) with composition after, water drive records on the water drive basis and can improve oil recovery factor 14.9% again to moisture 99%.
[embodiment 4]
(a) two 16 (palm) acyl group ethylenediamine is synthetic
With palmitic acid 320 grams (1.25 moles), thionyl chloride 178.5 grams (1.5 moles) and 4.8 gram DMF, add and be furnished with in 2000 milliliters of four-hole boiling flasks of sealing machine stirring, thermometer, condensation pipe etc., after 5 hours, decompression steams excessive thionyl chloride, obtains palmitoyl chloride in 80 ℃ of reactions.When temperature is reduced to 60 ℃, add dry toluene 160 grams, after stirring, slowly drip the mixed liquor of forming by anhydrous ethylenediamine 30.0 grams (0.5 mole), anhydrous pyridine 79.2 grams (1.0 moles) and dry toluene 160 grams, the control temperature drips off and is warming up to 75 ℃ of reactions 3 hours less than 60 ℃.Cooling is filtered, and crude product gets white powder solid, molar yield 91.3% with ethyl alcohol recrystallization after the vacuum drying.
(b) N, the two hexadecanoyl group EDDAs of N-synthetic
Two palmityl ethylenediamines 251.9 grams (0.47 mole) that step (a) is synthetic, 504 gram oxolanes, 94.0 gram (2.35 moles) NaOH and 6.0 gram TBABs; add and be furnished with in 2000 milliliters the there-necked flask of mechanical agitation, thermometer and reflux condensing tube, be heated to the backflow quaternization 6 hours.Slightly the cooling back is divided and is added the sodium chloroacetate solid that total amount is 164.3 grams (1.41 moles) for five times, keeps back flow reaction 12 hours.Cooling is neutralized to reactant liquor with hydrochloric acid and is highly acid, is cooled to room temperature, suction filtration, and to neutral, vacuum drying gets white powder solid 190.9 grams, molar yield 62.3% with distilled water washing solid.
(c) N, the two hexadecanoyl group EDDA two polyoxy vinethenes (n=5) of N-synthetic
With [embodiment 1] (c); difference is with the N of 190.9 grams (0.293 mole); the two hexadecanoyl group EDDAs of N-substitute 165.0 gram (0.305 mole) N; the use amount of the two dodecanoyl EDDAs of N-, oxirane is 128.9g (2.93 moles); the use amount of the alkali compounds of calcium is 3.8 grams; get N, the two hexadecanoyl group EDDA two polyoxy vinethenes (n=5) of N-304.9 grams, molar yield 95.3%.
(d) dichloro-N, the two hexadecanoyl group EDDA two polyoxy vinethenes (n=5) of N-synthetic
The N that step (c) is synthesized; the two hexadecanoyl group EDDA two polyoxy vinethenes (n=5) of N-304.9 grams (0.28 mole), 78.1 gram (0.98 mole) pyridines place in 1000 milliliters of there-necked flasks that backflow, stirring, gas absorbing device are housed; under agitation slowly thionyl chloride 116.7 restrains (0.98 mole); 75 ℃ of reactions 8 hours; all the other operations with [embodiment 1] (d); vacuum drying gets dichloro-N; the two hexadecanoyl group EDDA two polyoxy vinethenes (n=5) of N-271.5 grams, molar yield 85.9%.
(e) N, two hexadecanoyl group EDDA two polyoxy vinethene (n=5) disulfonates of N-synthetic
The dichloro-N that step (d) is synthesized; the two hexadecanoyl group EDDA two polyoxy vinethenes (n=5) of N-271.5 grams (0.240 mole) place autoclave; add 65 gram ethylene glycol, 110 gram water, 74.9 gram sodium sulfites (0.72 mole) and 15.1 gram sodium hydrogensulfites (0.12 mole); reaction is 7 hours under 120 ℃ of temperature; all the other operations with [embodiment 1] (e); get N; two hexadecanoyl group EDDA two polyoxy vinethene (n=5) disulfonates of N-, the product quality mark is 90.0%.To synthetic N, two hexadecanoyl group EDDA two polyoxy vinethene (n=5) disulfonates of N-are used U.S. Nicolet-380FT-IR spectrometer, adopt liquid-film method to carry out infrared spectrum analysis (sweep limits 4000～400cm -1), have all characteristic absorption peaks of Fig. 1.
(f) with the synthetic N of step (e); two hexadecanoyl group EDDA two polyoxy vinethene (n=5) the disulfonate 0.1wt% of N-, above-mentioned temperature-resistant anti-salt polymer 0.2wt% and 97.0wt% Shengli Oil Field win Tuo Er district and win formation water and mix stirring 2.0 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 16.0mPa.s; Said composition and Shengli Oil Field win the ultralow interfacial tension that forms 0.0012mN/m between the Tuo Er district 0-141 well dewatered oil.Apparent viscosity is by the BROODFIELD II type viscometer determining of U.S. Brookfield company, and interfacial tension is dripped interfacial tensimeter mensuration by the TX500 type rotation that Texas ,Usa university produces.
(g) earlier 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 52.1%, winning Tuo Er district 0-141 well dewatered oil with Shengli Oil Field then 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 40.4%, again the synthetic displacement of reservoir oil of metaideophone 0.3pv (rock pore volume) step (f) with composition after, water drive records on the water drive basis and can improve oil recovery factor 15.8% again to moisture 99%.
[embodiment 5]
(a) two 16 (palm) acyl group butanediamine is synthetic
With [embodiment 4] (a), difference substitutes 30.0 gram (0.5 mole) anhydrous ethylenediamines with the anhydrous butanediamine of 44.0 grams (0.5 mole), and all the other are identical, get white powder solid, molar yield 94.2% after the vacuum drying.
(b) N, the two hexadecanoyl group butanediamine oxalic acid of N-synthetic
Two palmityl butanediamine 265.1 grams (0.47 mole) that step (a) is synthetic, 530 gram oxolanes, 112.8 gram (2.82 moles) NaOH and 9.0 gram TBABs; add and be furnished with in 2000 milliliters the there-necked flask of mechanical agitation, thermometer and reflux condensing tube, be heated to the backflow quaternization 6 hours.Slightly the cooling back is divided and is added the sodium chloroacetate solid that total amount is 328.5 grams (2.82 moles) for five times, keeps back flow reaction 10 hours.Cooling is neutralized to reactant liquor with hydrochloric acid and is highly acid, is cooled to room temperature, suction filtration, and to neutral, vacuum drying gets white powder solid 195.6 grams, molar yield 61.2% with distilled water washing solid.
(c) N, the two hexadecanoyl group butanediamine oxalic acid two polyoxy vinethenes (n=4) of N-synthetic
With [embodiment 1] (c); difference is with the N of 195.6 grams (0.288 mole); the two hexadecanoyl group butanediamine oxalic acid of N-substitute 165.0 gram (0.305 mole) N; the use amount of the two dodecanoyl EDDAs of N-, oxirane is 101.4g (2.304 moles); get N; the two hexadecanoyl group butanediamine oxalic acid two polyoxy vinethenes (n=4) of N-282.1 grams, molar yield 94.9%.
(d) dichloro-N, the two hexadecanoyl group butanediamine oxalic acid two polyoxy vinethenes (n=4) of N-synthetic
The N that step (c) is synthesized; the two hexadecanoyl group butanediamine oxalic acid two polyoxy vinethenes (n=4) of N-281.2 grams (0.27 mole), 51.6 gram (0.65 mole) pyridines place in 1000 milliliters of there-necked flasks that backflow, stirring, gas absorbing device are housed; under agitation slowly thionyl chloride 92.8 restrains (0.78 mole); 90 ℃ of reactions 4 hours; all the other operations with [embodiment 1] (d); vacuum drying gets dichloro-N; the two hexadecanoyl group butanediamine oxalic acid two polyoxy vinethenes (n=4) of N-234.1 grams, molar yield 84.0%.
(e) N, two hexadecanoyl group butanediamine oxalic acid two polyoxy vinethene (n=4) disulfonates of N-synthetic
The dichloro-N that step (d) is synthesized; the two hexadecanoyl group butanediamine oxalic acid two polyoxy vinethenes (n=4) of N-234.1 grams (0.219 mole) place autoclave; add 60 gram ethylene glycol, 150 gram water, 87.8 gram sodium sulfites (0.85 mole) and 17.7 gram sodium hydrogensulfites (0.14 mole); reaction is 6 hours under 130 ℃ of temperature; all the other operations with [embodiment 1] (e); get N; two hexadecanoyl group hexamethylene diamine oxalic acid two polyoxy vinethene (n=4) disulfonates of N-, the product quality mark is 89.0%.To synthetic N, two hexadecanoyl group hexamethylene diamine oxalic acid two polyoxy vinethene (n=4) disulfonates of N-are used U.S. Nicolet-380FT-IR spectrometer, adopt liquid-film method to carry out infrared spectrum analysis (sweep limits 4000～400cm -1), have all characteristic absorption peaks of Fig. 1.
(f) with the synthetic N of step (e); two hexadecanoyl group hexamethylene diamine oxalic acid two polyoxy vinethene (n=4) the disulfonate 0.25wt% of N-, above-mentioned temperature-resistant anti-salt polymer 0.15wt% and 96.0wt% Shengli Oil Field win Tuo Er district and win formation water and mix stirring 2.0 hours, obtain the composition that a kind of displacement of reservoir oil of homogeneous transparent is used.At 85 ℃ of temperature, salinity 24000mg/L, Ca 2++ Mg 2+In the water of 667mg/L, the apparent viscosity that records this composition is 15.4mPa.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.
(g) earlier 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 51.9%, winning Tuo Er district 0-141 well dewatered oil with Shengli Oil Field then 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 (f) with composition after, water drive records on the water drive basis and can improve oil recovery factor 14.6% again to moisture 99%.
[embodiment 6]
(a) two 18 (tristearin) acyl group ethylenediamine is synthetic
With stearic acid 497 grams (1.75 moles), thionyl chloride 374.9 grams (3.15 moles) and 7.5 gram DMF, add and be furnished with in 2000 milliliters of four-hole boiling flasks of sealing machine stirring, thermometer, condensation pipe etc., after 3 hours, decompression steams excessive thionyl chloride, obtains stearyl chloride in 95 ℃ of reactions.When temperature is reduced to 60 ℃, add dry toluene 249 grams, after stirring, slowly drip the mixed liquor of forming by anhydrous ethylenediamine 30.0 grams (0.5 mole), anhydrous pyridine 118.8 grams (1.5 moles) and dry toluene 249 grams, the control temperature drips off and is warming up to 70 ℃ of reactions 5 hours less than 60 ℃.Cooling is filtered, and crude product gets white powder solid, molar yield 94.7% with ethyl alcohol recrystallization after the vacuum drying.
(b) N, the two octadecanoyl EDDAs of N-synthetic
Stearic bicine diester base ethylenediamine 278.2 grams (0.47 mole) that step (a) is synthetic, 556.4 gram oxolanes, 112.8 gram (2.82 moles) NaOH and 6.0 gram TBABs; add and be furnished with in 2000 milliliters the there-necked flask of mechanical agitation, thermometer and reflux condensing tube, be heated to the backflow quaternization 4 hours.Slightly the cooling back is divided and is added the sodium chloroacetate solid that total amount is 328.5 grams (2.82 moles) for five times, keeps back flow reaction 10 hours.Cooling is neutralized to reactant liquor with hydrochloric acid and is highly acid, is cooled to room temperature, suction filtration, and to neutral, vacuum drying gets white powder solid 184.0 grams, molar yield 55.3% with distilled water washing solid.
(c) N, the two octadecanoyl EDDA two polyoxy vinethenes (n=6) of N-synthetic
With [embodiment 1] (c); difference is with the N of 184.0 grams (0.260 mole); the two octadecanoyl EDDAs of N-substitute 165.0 gram (0.305 mole) N; the use amount of the two dodecanoyl EDDAs of N-, oxirane is 137.8g (3.132 moles); the use amount of the alkali compounds of calcium is 2.9 grams; get N, the two octadecanoyl EDDA two polyoxy vinethenes (n=6) of N-300.8 grams, molar yield 93.6%.
(d) dichloro-N, the two octadecanoyl EDDA two polyoxy vinethenes (n=6) of N-synthetic
The N that step (c) is synthesized; the two octadecanoyl EDDA two polyoxy vinethenes (n=6) of N-300.8 grams (0.24 mole), 40.3 gram (0.50 mole) pyridines place in 1000 milliliters of there-necked flasks that backflow, stirring, gas absorbing device are housed; under agitation slowly thionyl chloride 100.0 restrains (0.84 mole); 90 ℃ of reactions 5 hours; all the other operations with [embodiment 1] (d); vacuum drying gets dichloro-N; the two octadecanoyl EDDA two polyoxy vinethenes (n=6) of N-253.0 grams, molar yield 82.8%.
(e) N, two octadecanoyl EDDA two polyoxy vinethene (n=6) disulfonates of N-synthetic
The dichloro-N that step (d) is synthesized; the two octadecanoyl EDDA two polyoxy vinethenes (n=6) of N-253.0 grams (0.20 mole) place autoclave; add 70 gram ethylene glycol, 80 gram water, 71.7 gram sodium sulfites (0.69 mole) and 14.5 gram sodium hydrogensulfites (0.12 mole); reaction is 5 hours under 140 ℃ of temperature; all the other operations with [embodiment 1] (e); get N; two octadecanoyl EDDA two polyoxy vinethene (n=6) disulfonates of N-, the product quality mark is 90.5%.To synthetic N, two octadecanoyl EDDA two polyoxy vinethene (n=6) disulfonates of N-are used U.S. Nicolet-380FT-IR spectrometer, adopt liquid-film method to carry out infrared spectrum analysis (sweep limits 4000～400cm -1), have all characteristic absorption peaks of Fig. 1.
(f) with the synthetic N of step (e); two octadecanoyl EDDA two polyoxy vinethene (n=6) the disulfonate 0.2wt% of N-, above-mentioned temperature-resistant anti-salt polymer 0.1wt% and 97.0wt% Shengli Oil Field win Tuo Er district and win formation water and mix stirring 2.5 hours, obtain the composition that a kind of displacement of reservoir oil of homogeneous transparent is used.At 90 ℃ of temperature, salinity 32000mg/L, Ca 2++ Mg 2+In the water of 890mg/L, the apparent viscosity that records this composition is 14.5mPa.s; Said composition and Shengli Oil Field win the ultralow interfacial tension that forms 0.0046mN/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.
(g) earlier 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 52.2%, winning Tuo Er district 0-141 well dewatered oil with Shengli Oil Field then 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 40.5%, again the synthetic displacement of reservoir oil of metaideophone 0.3pv (rock pore volume) step (f) with composition after, water drive records on the water drive basis and can improve oil recovery factor 13.9% again to moisture 99%.
[embodiment 7]
(a) two 18 (tristearin) acyl group hexamethylene diamine is synthetic
With [embodiment 6] (a), difference substitutes 30.0 gram (0.5 mole) anhydrous ethylenediamines with the anhydrous hexamethylene diamine of 58.0 grams (0.5 mole), and all the other are identical, get white powder solid, yield 96.3% after the vacuum drying.
(b) N, the two octadecanoyl hexamethylene diamine oxalic acid of N-synthetic
Stearic bicine diester base hexamethylene diamine 304.6 grams (0.47 mole) that step (a) is synthetic, 609 gram oxolanes, 210.6 gram (3.76 moles) NaOH and 7.5 gram TBABs; add and be furnished with in 2000 milliliters the there-necked flask of mechanical agitation, thermometer and reflux condensing tube, be heated to the backflow quaternization 4 hours.Slightly the sodium chloroacetate solid that adds total amount 438.0 grams (3.76 moles) for five times is divided in the cooling back, keeps back flow reaction 10 hours.Cooling is neutralized to reactant liquor with hydrochloric acid and is highly acid, is cooled to room temperature, suction filtration, and to neutral, vacuum drying gets white powder solid 185.6 grams, molar yield 51.7% with distilled water washing solid.
(c) N, the two octadecanoyl hexamethylene diamine oxalic acid two polyoxy vinethenes (n=5) of N-synthetic
With [embodiment 1] (c); difference is with the N of 185.6 grams (0.243 mole); the two octadecanoyl hexamethylene diamine oxalic acid of N-substitute 165.0 gram (0.305 mole) N; the use amount of the two dodecanoyl EDDAs of N-, oxirane is 106.9g (2.43 moles); the use amount of the alkali compounds of calcium is 3.0 grams; get N, the two octadecanoyl hexamethylene diamine oxalic acid two polyoxy vinethenes (n=5) of N-271.2 grams, molar yield 92.7%.
(d) dichloro-N, the two octadecanoyl hexamethylene diamine oxalic acid two polyoxy vinethenes (n=5) of N-synthetic
The N that step (c) is synthesized; the two octadecanoyl hexamethylene diamine oxalic acid two polyoxy vinethenes (n=5) of N-271.2 grams (0.225 mole), 72.4 gram (0.90 mole) pyridines place in 1000 milliliters of there-necked flasks that backflow, stirring, gas absorbing device are housed; under agitation slowly thionyl chloride 120.1 restrains (1.01 moles); all the other operations with [embodiment 1] (d); vacuum drying gets dichloro-N; the two octadecanoyl hexamethylene diamine oxalic acid two polyoxy vinethenes (n=5) of N-227.8 grams, molar yield 81.6%.
(e) N, two octadecanoyl hexamethylene diamine oxalic acid two polyoxy vinethene (n=5) disulfonates of N-synthetic
The dichloro-N that step (d) is synthesized; the two octadecanoyl EDDA two polyoxy vinethenes (n=5) of N-227.8 grams (0.184 mole) place autoclave; add 60 gram ethylene glycol, 90 gram water, 57.4 gram sodium sulfites (0.552 mole) and 11.6 gram sodium hydrogensulfites (0.092 mole); reaction is 7 hours under 140 ℃ of temperature; all the other operations with [embodiment 1] (e); get N; two octadecanoyl hexamethylene diamine oxalic acid two polyoxy vinethene (n=5) disulfonates of N-, the product quality mark is 87.8%.To synthetic N, two octadecanoyl hexamethylene diamine oxalic acid two polyoxy vinethene (n=5) disulfonates of N-are used U.S. Nicolet-380FT-IR spectrometer, adopt liquid-film method to carry out infrared spectrum analysis (sweep limits 4000～400cm -1), have all characteristic absorption peaks of Fig. 1.
(f) with the synthetic N of step (e); two octadecanoyl hexamethylene diamine oxalic acid two polyoxy vinethene (n=5) the disulfonate 0.15wt% of N-, above-mentioned temperature-resistant anti-salt polymer 0.15wt% and 97.0wt% Shengli Oil Field win Tuo Er district and win formation water and mix stirring 2.0 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 15.7mPa.s; Said composition and Shengli Oil Field win the ultralow interfacial tension that forms 0.0033mN/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.
(g) earlier 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 51.5%, winning Tuo Er district 0-141 well dewatered oil with Shengli Oil Field then 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 (f) with composition after, water drive records on the water drive basis and can improve oil recovery factor 15.1% again to moisture 99%.
[comparative example 1]
With [embodiment 1] (f); difference substitutes 0.15wt%N with the petroleum sodium sulfonate (Wuxi oil refinery) of 0.15wt%; two dodecanoyl EDDA two polyoxy vinethene (n=4) disulfonates of N-; all the other are identical; the apparent viscosity that records this composition is 13.8mPa.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] (g), record water drive and improve oil recovery factor 40.5%, the above-mentioned displacement of reservoir oil of metaideophone with composition after, record on the water drive basis and can improve oil recovery factor 10.3% again.
[comparative example 2]
With [embodiment 1] (f), difference substitutes the above-mentioned temperature-resistant anti-salt polymer of 0.15wt% with the super high molecular weight polyacrylamide (viscosity average molecular weigh is 2,500 ten thousand) of 0.15wt%, all the other are identical, the apparent viscosity that records this composition is 10.5mPa.s, and said composition and Shengli Oil Field win the interfacial tension that forms 0.0623mN/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] (g), 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 oil recovery factor 9.2% again

Claims (6)

1. flooding method that increases substantially oil recovery factor, 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, the abundant displacement of the crude oil in the rock core is come out, wherein said displacement of reservoir oil composition comprises following component by percentage to the quality:
(1) 0.01～5.0% N, the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy vinethene disulfonates of N-;
(2) 0.01～3.0% polymer;
(3) 92.0～99.98% formation water;
Wherein the general molecular formula of (1) component is:
Figure FSB00001073686500011
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; Described temperature-tolerant anti-salt polyacrylamide is formed by acrylamide, 2-acrylamido-2-methyl propane sulfonic acid, 2-acrylamido dodecyl sodium sulfonate and four kinds of monomer copolymerizations of pi-allyl oleyl ether, and its molar percentage is 76: 18: 5: 1.
2. the flooding method that increases substantially oil recovery factor according to claim 1 is characterized in that described displacement of reservoir oil temperature is 85～95 ℃.
3. the flooding method that increases substantially oil recovery factor 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. the flooding method that increases substantially oil recovery factor according to claim 1 is characterized in that described N, the R in the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy vinethene disulfonates of N- 1Carbon number is nine, 11,13,15 or 17.
5. the flooding method that increases substantially oil recovery factor according to claim 1 is characterized in that described N, the R in the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy vinethene disulfonates of N- 2Carbon number be two, four or six.
6. the flooding method that increases substantially oil recovery factor according to claim 1 is characterized in that described N, the R in the two fatty acyl group ethylenediamine-N,N'-diacetic acid (EDDA) two polyoxy vinethene disulfonates of N- 1Carbon number add 1 sum and the EO adduction is counted the ratio of n between 2～4.
CN2010101471174A 2010-04-15 2010-04-15 Oil flooding method for greatly improving recovery rate of crude oil Active CN102220859B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2010101471174A CN102220859B (en) 2010-04-15 2010-04-15 Oil flooding method for greatly improving recovery rate of crude oil

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2010101471174A CN102220859B (en) 2010-04-15 2010-04-15 Oil flooding method for greatly improving recovery rate of crude oil

Publications (2)

Publication Number Publication Date
CN102220859A CN102220859A (en) 2011-10-19
CN102220859B true CN102220859B (en) 2013-07-31

Family

ID=44777542

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2010101471174A Active CN102220859B (en) 2010-04-15 2010-04-15 Oil flooding method for greatly improving recovery rate of crude oil

Country Status (1)

Country Link
CN (1) CN102220859B (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102277146B (en) * 2010-06-11 2013-12-25 中国石油化工股份有限公司 Composition for improving recovery ratio substantially and preparation method thereof
CN103215019B (en) * 2012-12-17 2016-06-08 江南大学 The preparation of the compound alkali-free surfactant oil displacement of a kind of alkylolamides-sulfate and application
CN105041278B (en) * 2015-06-29 2019-03-05 中国海洋石油集团有限公司 A method of improving polymer injection
CN104963668B (en) * 2015-06-29 2018-09-21 中国海洋石油集团有限公司 A method of reducing oil field Polymer Used For Oil Displacement adsorbance
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
CN107288577A (en) * 2017-08-06 2017-10-24 大庆东油睿佳石油科技有限公司 A kind of double slug type profile control agents of poly- table of low-permeability sandstone oil reservoir and its application method
CN108164465A (en) * 2017-11-22 2018-06-15 浙江大学宁波理工学院 A kind of lauric acid bis-imdazoline and its synthetic method and application

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN101029224A (en) * 2007-04-06 2007-09-05 山东大学 Use of bi-alkyl carboxylate surface activator in triple oil recovery

Also Published As

Publication number Publication date
CN102220859A (en) 2011-10-19

Similar Documents

Publication Publication Date Title
CN102220118B (en) Oil displacement composition and preparation method thereof
CN102220859B (en) Oil flooding method for greatly improving recovery rate of crude oil
CN102218282B (en) Dual-carboxylate gemini surfactant resistant to high temperature and high salt and preparation method thereof
CN102277146B (en) Composition for improving recovery ratio substantially and preparation method thereof
CN102219714B (en) N,N-dual fat acyl diamine diacetate dipolyoxyethylene ether bisulphonate and preparation method thereof
CN103032055B (en) Use the flooding method containing the cloudy non-surfactant composition of sulfonate
CN102220119B (en) Oil displacing method for reservoirs with high temperature and salinity
CN102220121B (en) Composition capable of improving recovery ratio considerably and preparation method thereof
CN102278102B (en) Binary oil driving method for high-temperature and high-salt oil reservoir
CN102220860B (en) Polymer-surfactant binary compound oil displacement method
CN102220123B (en) Oil displacement method for tertiary oil recovery
CN102277148B (en) Composition for improving recovery ratio of crude oil and preparation method thereof
CN102277147B (en) Oil displacement method for high-temperature high-salt oil reservoir
CN103031119B (en) Sulfonate-containing anionic/nonionic surfactant composition and preparation method
CN102219896B (en) N,N-difattyacyl diamino diacetoxyl dipolyoxyethylene ether dicarboxylate and preparation method thereof
CN102220120B (en) Binary compound flooding compound and preparation method thereof
CN102220124B (en) Oil displacement compound for tertiary oil recovery and preparation method thereof
CN102373913B (en) High-efficiency anti-magnesium ion oil displacement method
CN102373039B (en) Oil displacement method suitable for seawater base
CN102373046B (en) High efficiency anti-magnesium ions oil displacement agent and its preparation method
CN102373040B (en) Composition suitable for seawater-based oil displacement and its preparation method
CN102373045B (en) Seawater-based oil displacement agent and preparation method thereof
CN102373043B (en) Displacement agent suitable for MgCl2 injection water and preparation method thereof
CN102373041B (en) Oil displacement method by use of seawater base oil displacement agent
CN102373044B (en) Oil displacement method suitable for MgCl2 water-type oil displacement agent

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant